Bs Reports 2015

PHYSICOCHEMICAL AND SPECTROSCOPIC STUDIES OF
ADSORPTION MECHANISM OF VARIOUS TYPES OF

POLLUTION FROM MODEL SOLUTIONS AND WASTEWATERS
Zbigniew HUBICKI, Marek MAJDAN, Dorota KOODYSKA, Monika

WAWRZKIEWICZ, Anna WOOWICZ, Agnieszka GADYSZ-PASKA,
Magdalena MAKARSKA-BIAOKOZ, Grzegorz WJCIK,
Marzena GCA, Agnieszka LIPKE
DEPARTMENT OF INORGANIC CHEMISTRY
Development of ion exchanger production technology has been conditioned by

the need of water treatment owing to the progress of numerous branches of
industry. Ion exchangers were also applied for purification of industrial wastewaters
from which toxic components and precious noble metals were recovered. Of many
commercially available ion exchange resins, chelating ion exchangers are of
significant importance. Their characteristic feature is capability of selective sorption
of one metal ion in the presence of others. Among the chelating ion exchangers,
those of the functional bis(2-pyridylmethyl)amine groups also called
bispickoliloamine ones exhibit favourable properties. The representatives of this
type of ion exchangers are: Dowex M-4195 and Lewatit MonoPlus TP 220. For
the removal of other toxic ions and dyes low cost materials can be also used. For
example, fly ash is a residue derived from combustion of coal in furnaces of thermal
power plant. According to the World Coal Association the total world coal
production reached a record level of 7822 mln tons in 2013 that is 0.4% more than
in 2012. As the European Coal Combustion Products Association reports about 31
mln tons of fly ash was produced in Europe in 2010. According to the United States
Environmental Protection Agency the main benefits of reusing these materials are:
lower greenhouse gas emissions, reducing the use of original resources and cost of
fly ash disposal as well as improving strength and durability of the obtained
sorbents used in the environmental protection. Although the literature reports
studies on fly ash exploitation in adsorption of heavy metals from aqueous solutions
with the influence of chemical composition of fly ash, pH, temperature, phase
contact time and amount of fly ash etc. only very few papers can be found that
investigate fly ash coated by chitosan for removal of heavy metal ions.
An important issue is not only the search for low-cost sorbents for toxic
substances, but also an attempt to assess the effects of these substances from the
adsorbent, for example, forming a complex on the surface. Due to their practical
importance, the problem of uranium surface complexes has been studied. Phosphate
complexes of U(VI) formed on the surface of different sorbents such as silica,
alumina, ferrihydrite, evidently improve U(VI) sorption. The continuous variation
method can serve as a preliminary test for the evaluation of the stoichiometry of
uranium phosphates surface complexes. The approximate character of the method
is evident for pH = 6.6, when the free U(VI) hydroxy complexes are anchored on
the sorbent surface parallel to the uranyl phosphate complexes. This difficulty can
be eliminated by analyzing the intensification of uranium sorption when the system
with phosphates is compared with that without phosphates. The interaction of
(UO2)3(OH)5+ and (UO2)4(OH)7+ species with HPO42- ions is evident.
Phosphate anions evidently improve the sorption of U(VI) ions on bentonite owing
to the formation of ternary complexes among aluminol sites, U(VI) and phosphate
anions HPO42. This fact can be exploited in the construction of engineering barriers
used for the isolation of nuclear waste repository sites from the natural
environment. Deconvolution of the sorptive spectra of U(VI) results in the
presumption about the stepwise evolution of the surface complexes formation with
pH , where UO2HPO4, (UO2)3(PO4)24H2O, (UO2)3(OH)5+, (UO2)4(OH)7+ species
interact with the surface sites of bentonite. X-ray photoelectron spectroscopy allows
one to diagnose the participation of silanol and aluminol groups in the complexation
of U(VI) ions in the absence and presence of phosphates.
Characteristic spectroscopic properties of water-soluble porphyrins depending
on the parameters of the reaction environment, like the strong ability to absorption
and fluorescence, as well as the specific non-covalent interactions between this
class of substances and biologically active aromatic compounds predestine
porphyrin systems to play a role of sensors in processes with the participation of
different biologically important molecules. The illustration of such interactions is a
monitoring of -stacked complexes formed between uric acid, involved strongly in
human metabolism, and a cationic water-soluble porphyrin (5,10,15,20-tetrakis[4-
(trimethylammonio) phenyl]-21H,23H-porphine tetra-p-tosylate (H2TTMePP). Both
the spectroscopic studies (measurements with use of UV-VIS and emission
spectroscopy techniques and calculations with application of the non-linear curve-
fitting procedure based on MarquardtLevenberg algorithm from Sigma Plot,
version 9.0) and quantum-mechanic calculations (using PQS program, version 4.0)
leads to the conclusion that in the particular conditions (basic pH) H2TTMePP
porphyrin can form with uric acid 1:1 and 1:2 stacking complexes, interacting in the
mode called face-to-face. The obtained results can become a support to the idea
of a fluorescent chemosensor of uric acid, potentially useful for monitoring of uric
acid traces in aqueous environment (wastewaters treatment), studies of the diseases
associated with uric acid overproduction or for other biological and medical
purposes.
STUDIES OF ION EXCHANGERS AND SORBENTS
APPLICABILITY SORBENTS FOR REMOVAL OF NOXIOUS
SUBSTANCES FROM WATERS AND WASTEWATERS
Zbigniew HUBICKI, Marek MAJDAN, Dorota KOODYSKA, Monika

WAWRZKIEWICZ, Anna WOOWICZ, Agnieszka GADYSZ-PASKA,
Magdalena MAKARSKA-BIAOKOZ, Grzegorz WJCIK
Marzena GCA, Agnieszka LIPKE
Various sorbents such as: microporous carbonaceous Lewatit AF 5, strongly

basic anion exchange resin with gel (Dowex PSR-2) and microporous (Dowex PSR-
3) structure were applied for metal ions recovery from aqueous acidic solutions.
The batch method was used throughout the studies. The affinity and sorption
capacity of selected metal ions (Pd(II), Co(II), Cu(II), Ni(II), Zn(II)) were
estimated. A series of batch tests was carried out as a function of contact time
(1 min-4 h), and acid concentrations (0.1 6.0 M HCl 100 mg M(II)/L; 0.1-0.9 M
HCl 0.9-0.1 M HNO3 100 mg M(II)/L). Additionally, the effects of the initial
Pd(II) concentrations (100, 500, 1000 mg/L), beads size (0.4-0.8 mm), agitation
speed (120, 140, 180 pm) and adsorption temperature (298, 313, 333 K) were
analyzed. Kinetic and equilibrium studies for palladium(II) ions removal as well as
the thermodynamic parameters, and pHZPC, SEM, XRD results before and after
palladium sorption on selected sorbents were obtained. The working ion exchange
capacities of palladium were determined based on the breakthrough curves (column
method). Desorption and reuse possibilities the of above mentioned sorbents were
examined. The maximum capacity of the adsorbents was determined from the
Langmuir isotherm model at ambient temperature and was equal to 193.31 mg/g
(Lewatit AF-5), 167.18 mg/g (Dowex PSR-2) and 184.8 mg/g (Dowex PSR-3).
Kinetic studies of Pd(II) followed the pseudo-second order model. The effects of
experimental conditions such as agitation speed, temperature and bead size
distribution are slightly marked. The most effective desorption of palladium was
obtained using 0.5 M ammonium hydroxide (%D = 71.5 %) for Lewatit AF-5, 2 M
NH4OH (%D = 36.5%) for Dowex PSR-2 and 0.1 M thiourea solutions (%D =
34.76 %) for Dowex PSR-3. The process for Pd(II) sorption on Lewatit AF-5 is of
spontaneous and exothermic character. Entropy possesses negative values.
The kinetic adsorption of the cationic dye C.I. Basic Blue 3 (BB3, Fig. 1) on
the low cost sorbent - sawdust from aqueous solution was investigated in order to
identify the ability of this material to remove textile dye from wastewaters. For this
purpose a series of batch tests was carried out as a function of contact time (1-240
min) and dye initial concentration (50, 100, 200 mg/L). Kinetic studies of the dye
followed the pseudo-second order model (Fig. 2) rather than the pseudo-first order
one or intraparticle diffusion model. The pseudo-second order rate constantsk2
values decrease with the increasing initial dye concentration, whereas the initial
sorption rate h increases with the increasing amount of the dye in the system.
N
H3C +
CH3
N O N
Cl
H3C CH3
Fig. 1. C.I. Basic Blue 3.
Fig.2.Pseudo-first order (A) and pseudo-second order (B) kinetics of BB3 sorption on
sawdust from the solutions of different initial dye concentrations.
The selective ion exchangers are commonly used for selective sorption of
noble metals, but their apply for chromium(VI) was not describe up to now in the
literature. The LewatitTP 214 is the macroporousstyrene divinylbenzene ion
exchanger with thiourea groups. The kinetic and mechanism of sorption of
chromium(VI) ion were investigated. The investigations of chromium(III) and(VI)
speciation allowed to notice that chromium(VI) is reduced to chromium(III). The
reduced chromium(III) ions are not retained by thiourea groups but are transferred
from ion exchanger to external aqueous solution. Similar observation during
sorption of chromium (VI) ions on strongly basic anion exchanger were
reported[1,2]. Moreover, the DRS and FTIRATR spectroscopy method were used to
investigate reductive mechanism of sorption. The reduction process of
chromium(VI) ions is the most effective in acidic solution.
Natural adsorbent biosorbent - based powder obtained from tubers of
sunflower (collected in autumn or spring), as well as chicory and dahlia, was tested
for water purification and wastewater containing toxic elements, especially
uranium(VI), chromium(VI), cadmium(II) and nickel(II), as well as organic
compounds, for example phenol. Powdered biomaterials were used in an amount of
0.5 g per 0.1 liter of water contaminated with uranyl ions in the concentration from
510-5 to 510-4 M to obtain uranium sorption from 40 to 60%, sorption of
chromium(VI) 15 to 23%, nickel sorption from 52 to 100%, the sorption of
cadmium from 60 to 100%, and phenol from 4 to 35%
References:
[1] G. Wjcik, Z. Hubicki, P. Rusek, Przemys Chemiczny, 90 (2011) 2153.
[2] G. Wjcik, Z. Hubicki, P. Rusek, Przemys Chemiczny, 92 (2013) 82.
UTILIZATION OF CUPFERRON IN STUDY OF NEW
PROCEDURES OF GALLIUM DETERMINATION USING
ADSORPTIVE STRIPPING VOLTAMMETRY
Mieczysaw KOROLCZUK, Magorzata GRABARCZYK, Iwona RUTYNA

DEPARTMENT OF ANALYTICAL CHEMISTRY
AND INSTRUMENTAL ANALYSIS
The AdSV determination of gallium with cupferron as a complexing agent is a

very satisfactory proposition for water sample analysis. In comparison to other
adsorptive voltammetric procedures described in literature data the proposed work
distinguishes itself by a few advantages, such as the wide linear range, a low
detection limit at a short accumulation time. The determination of metal traces in
environmental water samples using adsorptive stripping techniques is normally
difficult, when surface active substances are present. Generally, in most of the
voltammetric procedures even low concentrations of organic matter limit the
applicability causing a decrease or total decay of the analytical signal. In this work,
an adsorptive voltammetric stripping procedure for direct determination of Ga(III)
using cupferron as a complexing agent in water samples containing high
concentrations of surface active substances is proposed.
The results obtained confirm that the voltammetric signal of gallium is very
sensitive to the presence of nonionic and cationic surface active substances and
their concentration equal to 0.5 mg L-1 Triton X-100 and cetyltrimethylammonium
bromide (CTAB) causes a total decay of the gallium peak current. In the case of the
anionic surfactant no interferences were observed and the presence of even 30 mg
L-1 of sodium dodecyl sulfate (SDS) didnt decrease the gallium signal.
For a fast and simple elimination of the influence caused be surface active
substances in the proposed procedure, adsorption features of Amberlite resins are
employed. Three types of Amberlite resin, XAD-2, XAD-7 and XAD-16 were used.
The preliminary experiment showed that the Ga(III)-cupferron complex was
adsorbed on all kinds of used resin, whereas in the absence of cupferron gallium
was not adsorbed on resins. Considering this, the proposed procedure had to be
carried out in two steps. In the first step the resin was added to the analysed sample
and mixed for 5 min. During this time the organic matrix of the sample was
removed through its adsorption onto the resin whereas the ions of gallium remained
in the solution. In the second step the sample was pipetted into the voltammetric
cell, a complexing agent was added and the voltammetric measurement was
performed.
As was expected, the addition of resin noticeably decreased the unwanted
negative influence of the non-ionic and cationic surfactants on the gallium peak
height. An especially positive impact of XAD-7 and XAD-16 resins was observed,
in the case of XAD-2 resin surfactant interferences were eliminated to a lesser
extent. Particularly effective elimination of interferences take places for non-ionic
surfactant, and even 20 mg L-1 of Triton X-100 and CTAB dont disturb gallium
signal if the preliminary mixing with XAD-7 or XAD-16 resin is performed. For
comparison 0.5 mg L-1 of this surfactants cause total decay of gallium peak if the
preliminary mixing with resin is not carry out.
In the adsorptive voltammetric determination of gallium using cupferron as a
complexing agent, interferences may be caused also by the competitive adsorption
of foreign ions and their complexes with cupferron on the electrode surface. The
effects of foreign ions were tested using a fixed concentration of Ga(III) equal to 5
10-8 mol L-1 and different amounts of examined ions. It was found that at least a
1000-fold excess of As(III), Ca(II), Cd(II), Co(II), Mn(II), Ni(II), Zn(II), Tl(I) and a
100-fold excess of Al(III), As(V), Cr(III), Cr(VI), Cu(II), Ge(IV), Mg(II), Pb(II),
Se(VI), W(VI) did not interfere. The 100-fold excess of the following ions, Bi(III),
Fe(III), Hg(II) and Sb(III) causes a decrease of the gallium peak current to about 75
% and In(III) to about 30 % compared to the gallium peak current recorded in the
absence of foreign ions. The considerable interferences were induced in the
presence of Mo(VI) and Se(IV) and their 5-fold excess decreased of the gallium
peak current to about 50 %.
STUDIES OF ELECTRODE PROCESSES AND
PRECONCENTRATION OF TRACE ELEMENTS AND
BIOLOGICALLY ACTIVE COMPOUNDS FOR ANALYTICAL
PURPOSES
Mieczysaw KOROLCZUK, Magorzata GRABARCZYK, Iwona RUTYNA

The purpose of the studies was the application of the in situ formed lead film
electrode for ultra-trace determination of gallium ions in water samples.
Electrochemical techniques seem to be suitable for direct metal ion determination
because they offer highly sensitive detection with low-cost portable instrumentation
and are simple, reliable and easy to use. In trace analysis of gallium, anodic
stripping voltammetry (ASV) and adsorptive cathodic stripping voltammetry
(AdCSV) are mainly used. The ASV and AdSV procedures were carried out mainly
on different mercury electrodes. The major drawback of mercury electrodes is their
high toxicity, so attempts to replace them with less toxic ones is an important
challenge. In the last few years lead film electrodes were introduced for stripping
analysis and they have been applied until today for the determination only of
selected metal ions, Co(II), Ni(II), U(VI), Pt(IV). In the present study, we used a
lead film electrode (PbFE) formed in situ to gallium determination by AdCSV.
In the previous studies we proved that cupferron forms stable complexes with
gallium and in comparison with other complexing agents, such as solochrome violet
RS, morin, ammonium pyrrolidine dithiocarbamate (APDC), pyrocatechol violet
(PCV), diethyldithiocarbamate (DDTC), alizarin red S, catechol that have been used
so far in voltammetric procedures of gallium determination provides the best
parameters, such as the widest linear range and the lowest detection limit.
Preliminary experiments confirmed that Ga(III)-cupferron complexes also adsorbed
on the in situ plated lead electrode so the optimization of experimental parameters
in the determinations, such as the composition of the supporting electrolyte,
cupferron concentration, conditions of lead film formation, potential and time of
accumulation was performed.
The measurements were performed using a solution containing analysed
sample contining Ga(III), 0.0.5 mol L-1 CH3COOH, 6 10-5 mol L-1 Pb(II), 2
10-4 mol L-1 cupferron. The determinations of Ga(III) were carried out while the
potential was changed in the following sequence: the deposition step was carried
out for 60 s at -0.7 V, during this step a lead film electrode was plated on glassy
carbon electrode and the Ga(III)cupferron complex was accumulated on the
electrode simultaneously whilst stirring the solution with a magnetic stirring bar. At
the end the stirrer was switched off, and after 5 s equilibration time, a differential
pulse stripping voltammogram was recorded, while the potential was scanned from
-0.7 V to -1.05 V at a scan rate of 20 mV s-1 and a pulse height 50 mV. The
measurements were carried out from undeaerated solutions.
Under this conditions the linear calibration curve for Ga(III) was obtained for
accumulation time of 60 s in the range from 1 10-8 to 2 10-7 mol L-1. The linear
correlation coefficient was r = 0.9985. The relative standard deviation (RSD) from
five determinations of Ga(III) at a concentration of 2 108 mol L1 was 4.4 %. The
detection limit estimated from three times the standard deviation for the lowest
studied Ga(III) concentration and accumulation time of 60 s was about 3.8 109
mol L1.
The best way to validate the new procedure using the lead film electrode as a
voltammetric sensor is its application in the analysis of certified reference material,
whose matrix is similar to the matrix of the analyzed samples. Because of the lack
of environmental water as the certified reference material containing suitable
concentrations of Ga(III), the recovery studies were carried out from a certified
reference materials SPS-WW1 Waste Water (batch 111) and SPS-SW1 Surface
Water (batch 116). The SPS-WW1 material contains 13 elements at a concentration
ranging from 20 ng mL-1 to 2000 ng mL-1, the SPS-SW1 material contains 45
elements at a concentration ranging from 0.5 ng mL-1 to 2000 ng mL-1. The samples
were analyzed after tenfold dilutions. Three replicate determinations of the samples
containing spiked gallium afforded the average recovery values between 92.8 %
and 98.8 % with relative standard deviation between 5.6 % and 6.2 %.
BIOLOGICALLY ACTIVE COMPOUNDS AND ITS
EXPLOITATION FOR ANALYTICAL PUROPSES
Ryszard DOBROWOLSKI
DEPARTAMENT OF ANALYTICAL CHEMISTRY
The world consumption of platinum is growing constantly causing the increase

of its emission to the environment. Some platinum salts are responsible for many
potential humans health risks, e.g. causing asthma, allergy and other serious health
problems. For this reason, the monitoring of the concentration of platinum in the
environment and in the biological samples is necessary. However, the determination
of platinum is still a serious analytical challenge, because its quantity in
environmental samples is low, at the around ng/kg level, and other elements are in
excess. Due to that, a preconcentration procedure is often applied to increase
concentration levels in analyzed solutions and also remove matrix interferences.
Widely used preconcentration technique is the sorption of trace elements on an ion-
exchangers.
The aim of this study was the application of micro-and mesoporous adsorbents
for enrichments and determination of chosen elements by using atomic absorption
spectrometry methods. Experimental parameters affecting the adsorption of Pt(IV)
on ions exchangers Dowex 1-X8 and Purolite S-920, such as pH of the sample
solution, contact time and interfering ions, were studied and optimized. The
possibility of platinum removing from the ion exchangers was studied using nitric
acid, hydrochloric acid and thiourea solution with respect to their concentrations.
Platinum determination in the digested environmental samples was performed by
the ions exchangers slurry and direct solid sampling technique GFAAS. For this
purpose the ion exchange resins were powdered in a mill MM2 (Retsch GmbH) at
the temperature of liquid nitrogen to the size lower than 5m.
The adsorption/desorption experiments were carried out using batch mode. In
Fig. 1. the adsorption ability of both ion exchangers towards platinum(IV) as a
function of the solution equilibrium pH is shown. The maximum Pt(IV) ions
adsorption onto Purolite S-920 was obtained in the pH range from 0.9 to 1.5,
whereas Dowex 1-X8 exhibited the highest affinity to Pt(IV) ions for pH about 1.
The effect of time on adsorption of Pt(IV) onto ions exchangers is shown in Fig. 2.
In the case of Purolite S-920 the adsorption equilibrium is attained after several
minutes, while in case of Dowex 1-X8 getting equilibrium requires about three
hours of the suspension shaking. Due to the excess of nitrates and chlorides coming
from aqua regia applied for digestion of solid materials, may influence the
adsorption ability of ions exchangers the effect of NO3- and Cl- on Pt(IV) adsorption
ability was investigated. It was observed that the adsorption of (PtCl6)2- ions
decreases as the concentration of chloride or nitrates ions in the solution increases,
which may be the result of competitive sorption between Cl, HCl2 NO3 and
H(NO3)2 type ions and platinum complex anions. Due to this effect the removing
of nitrates and chlorides from the solution by sample solution evaporation almost to
dryness before enrichment step was proposed. The maximum static adsorption
capacities determined on the basis of adsorption isotherms of Pt(IV) are 100 mg/g
for Dowex 1-X8 and 220 mg/g for Purolite S-920. Taking into account the results of
adsorption studies Purolite S-920 was selected for the Pt(IV) preconcentration from
environmental samples. It was experimentally stated that the application of
concentrated nitric, hydrochloric acids or thiourea acidic solution did not cause the
total desorption of platinum species from the surface of Purolite S-920. For this
reason that the most effective technique for determination of platinum in
environmental samples after its enrichment on Purolite S-920 is the slurry sampling
GF AAS or direct solid sampling GF AAS.
The determination of platinum by slurry sampling GF AAS technique was
carried out using AAS-3 (Carl Zeiss, Jena, Germany) atomic absorption
spectrometer equipped with a deuterium-lamp background corrector. Determination
of platinum by direct solid sampling AAS technique was carried out using ContrAA
700 high-resolution continuum-source graphite furnace atomic absorption
spectrometer (Analytik Jena, Jena, Germany).
The proposed methodology was validated by the application of certified
reference material SARM 7 and applied for platinum determination in copper shale
samples, which results are presented in Table 1.
Table 1. Results of platinum determination in real samples by slurry sampling and
direct solid GF AAS techniques after preconcentration on Purolite S-920.
Sample Certified value Slurry sampling Direct solid

SARM 7 3.7400.045 3.6940.121 3.7100.117
POLK I 0.4200.017* 0.3890.022 0.4100.019
* The value obtained from the Polish Geological Institute.
Fig.1. The pH influence on Pt(IV) Fig.2. Adsorption kinetics of Pt(IV) onto

adsorption onto ions exchangers; m=0.05 ions exchangers; m=0.05 g, V=50 mL,
g, V=50 mL, CPt(Dowex 1-X8)=4 mg/L, CPt(Dowex 1-X8)=4 mg/L, CPt(Purolite
CPt(Purolite S-920)=35 mg/L, t=90 min., S-920)=20 mg/L, pH=1, T=25
T=25 C.
EXPLOITATION FOR ANALYTICAL PURPOSES
Joanna LENIK, Cecylia WARDAK

CDs are capable of interacting with a large variety of guest molecules to form
inclusion complexes, and so they are used in the pharmaceutical, food, clothing,
cosmetic, and chemical industries [1]. The formation of inclusion complexes by
cyclodextrins can alter some physicochemical properties of the guest molecules
(e.g., electrochemical properties). CDs are also used in analytical techniques, such
as potentiometry, polarography, and voltammetry.
The aim of the researches was the application of -cyclodextrins as the active
substances of electrodes with a polymeric membrane phase with diclofenac
function. For this end, modifications of the membrane composition were studied
and a number of cyclodextrins such as: (2-hydroxypropyl)--cyclodextrin,
heptakis(2,3,6-tri-O-methyl)--cyclodextrin, and heptakis(2,3,6-tri-O-benzoyl)--
cyclodextrin were applied as new ionophores.
The basic analytical parameters (selectivity, response time, pH effect on potential,
lifetime) of the constructed ion-selective electrodes are determined. The overall
good characteristics including a wide linear range (5.0 1051 102 mol L1), a
low limit of detection (1.0 1055.0 105 mol L1), and a reproducible Nernstian
slope were obtained. In particular, the incorporation of heptakis(2,3,6-tri-O-
benzoyl)--cyclodextrin resulted in excellent electrodes with a short response time
and long lifetime (810 months). A notable advantage of the proposed electrode is
its simple and cheap construction. In addition, the proposed electrode is very easy to
use. Unlike electrodes with internal solution, it does not have to be stored in a
vertical position and does not require external solution for storage between
measurements. The electrode may be kept in air and is mechanically robust and
maintenance-free. The proposed electrode was satisfactorily applied to the
determination of diclofenac in real samples, pharmaceuticals, and urine samples.
(Table 1).
Table 1. Results obtained in the analysis of diclofenac samples by the proposed ion-
selective electrode.
Sample Taken Found n Relative RSD Confidence

mg L-1 mg L-1 Error [%] range [mg L-
1
[%] ]
Pure (Sigma) 31.8 29.9 6 1.9 3.4 29.9 1.1
100.0 100.5 6 0.5 2.2 100.5 2.3
150.0 149.8 6 0.1 2.5 149.8 2.5
Pharmaceutical 100.0 96.1 8 3.8 2.5 96.1 2.0
(Majamil)
150.0 148.3 8 1.1 4.5 148.3 5.6
(Olfen)
Urine 31.8+ 31.7 10 0.3 3.1 31.7 7.0
2,5ml urine
31.8+ 31.5 10 1.0 2.7 31.5 6.1
5 ml urine
References:
[1] H. Dodziuk, Cyclodextrins and Their Complexes, Wiley-VCh Verlag GmbhH &
Co. KGaA, Weinheim, 2006.
PRECONCENTRATION OF TRACE ELECMENTS AND
Katarzyna TYSZCZUK-ROTKO
The aim of the study was to develop voltammetric procedure for the
determination of biologically active compounds with the use of electrodes modified
with polymer and lead films.
Dopamine (3,4-dihydroxyphenylmethylamine, DA) is an important
catecholamine neurotransmitter which plays a significant role in proper functioning
of the brain. The detection of DA in nervous tissues and body fluids is a key point
in biomedical diagnoses because low concentration of this compound may result in
some diseases such as Alzheimer, Parkinson and Schizophrenia [1, 2]. However, the
significant effect of many coexisted compounds such as paracetamol, ascorbic acid
and uric acid on the DA's signal is observed [3, 4]. In this connection, the direct
detection of DA in biological samples is difficult. Paracetamol (acetaminophen,
N-acetyl-p-amino-phenol, PA) is widely used drug for the relief of fever and
various types of pains such as headaches. However, overdose of PA may cause
hepatotoxicity and nephrotoxicity [5]. In addition, the concentration of PA
significantly effects on the degree of DA neurodegeneration [6]. Therefore, the
simultaneous detection of DA and PA in different body fluids is of great
importance. For this purpose, we checked the applicability of boron-doped diamond
electrode covered with Nafion and lead films (PbF/Nafion/BDDE) to simultaneous
detection of dopamine and paracetamol.
Under the optimal analytical conditions, the calibration graph for DA on
the PbF/Nafion/BDDE in the presence of 2.5 10-5 mol L-1 PA was linear from
2.0 10-7 to 1.0 10-4 mol L-1 and obeyed the equation y = 0.213 x + 0.031, where
y is the peak current (A) and x is the dopamine concentration (mol L-1).
The correlation coefficients (R2) was 0.9993. The calibration graph for PA in the
presence of 1.0 10-5 mol L-1 DA was linear from 5.0 10-7 to 1.0 10-3 mol L-1
and obeyed the equation y = 0.031 x - 0.207, where y is the peak current (A) and
x is the paracetamol concentration (mol L-1). The correlation coefficients (R2) was
0.9969. The detection and quantification limits of DA and PA estimated from 3 and
10 times the standard deviation (n = 5) for the lowest determined concentration
of dopamine and paracetamol divided by the slope of the linear regression equation
are equal to 1.5 10-7 and 5.1 10-7 mol L-1 as well as 2.2 10-7 and 7.3 10-7 mol
L-1, respectively.
The proposed procedure was successfully applied to the determination of PA in
some commercial pharmaceuticals as well as to the simultaneous determination of
DA and PA in human urine, whole blood and serum samples directly without any
separation steps.
References:
[1] P.M. Ndangili, O.A. Arotiba, P.G.L. Baker, E.I. Iwuoha, Journal of
Electroanalytical Chemistry, 643 (2010) 77.
[2] C. Avendano, G. A. Angeles M.T.R. Silva, G.R. Pina, R.M. Romo,
M.P. Pardave, Journal of Electroanalytical Chemistry, 609 (2007) 17.
[3] M. Liu, Q. Chen, C. Lai, Y. Zhang, J. Deng, H. Li, S. Yao, Biosensors and
Bioelectronics, 48 (2013) 75.
[4] H. Beitollahi, A. Mohadesi, S. Mohammadi, A. Pahlavan, H. Karimi-Maleh,
A. Akbari, Journal of Molecular Liquids, 169 (2012) 130.
[5] F.L. Martin, A.E. McLean, Drug and Chemical Toxicology, 21 (1998) 477.
[6] C.J. Locke, S.A. Fox, G.A. Caldwell, K.A. Caldwell, Neuroscience Letters, 439
(2008) 129.
Agnieszka NOSAL - WIERCISKA

The electrochemical properties of metal ions depend on the composition and

concentration of supporting electrolyte. The metal cations in aqueous solution show
strong interactions with water molecules. The dehydration steps play a big role in
the deposition reactions.
The studies concerning the reduction process of Bi(III) in chlorates (VII)
solution of different water activity point at strong interactions between a depolarizer
ion and water molecules [1,2]. According to Lovri et al. [2] the reduction of Bi(III)
includes three partial dehydration steps. The studies conducted in 1 8 moldm-3
chlorates (VII) [3] point at the significant role of water activity in Bi(III)
electroreduction process. The values of kinetic parameters determined in the
examined solutions point at the slight influence of supporting electrolyte
concentration on the kinetics of Bi(III) electroreduction in 1 3 moldm-3 chlorates
(VII), whereas in 4 8 moldm-3 chlorates (VII) the values of determined kinetic
parameters point at significant increase of reversibility of Bi(III) ion
electroreduction with the increase of chlorates (VII) concentration.
The influence of protonation on the electroreduction of Bi(III) ions in chlorates
(VII) solutions of different water activity using voltammetric and impedance
methods was examined.
The results of the kinetic parameters correlation lead to the statement that the
changes in the amount of chloric (VII) acid against the amount of its sodium salt in
the supporting electrolytes of the low water activity have a significant influence on
the rate of Bi(III) ions electroreduction [4].
The increase of the concentration of chloric acid sodium salt, as well as the chloric
(VII) acid alone within the particular concentration of the supporting electrolyte
inhibits the process of Bi(III) ions electroreduction. It should be associated with the
reorganization of the structure of the double layer connected with the slow
dehydration inhibited by ClO 4 ions. The standard rate constants ks values with the
increase of the chlorates (VII) concentrations for all the solutions examined of
chlorates (VII) confirms the catalytic influence of the decrease of water activity on
the process of Bi(III) ions electroreduction. The multistage process is confirmed by
the not rectilinear
lnkf = f (E) dependences. Assuming that the process of Bi(III) electroreduction is
multi-stage and the transfer of individual electrons proceeds consecutively, hence at
the less positive potentials the process rate is controlled by the transfer of the first
electron. It occurs presumably in the outer Helmholtz plane or within the one water
molecule from the electrode surface [4].
References:
[1] . Komorsky Lovri, M. Lovri and M. Branica, J. Electrochem. Soc.,
140(1993) 1850.
[2] M. Lovri and M. Branica, Indian J. Chem., 29A (1990) 435.
[3] A. Nosal Wierciska, Electrochim. Acta, 92 (2013) 397.
[4] A. Nosal Wierciska, M. Grochowski, M. Winiewska, K. Tyszczuk Rotko,
S. Skrzypek, M. Brycht, D. Guziejewski, Electrocatalysis, 6 (2015) 315.
Jolanta NIESZPOREK, Dorota GUGAA-FEKNER, Dorota SIEKO

Adenine (a purine derivative) is one of five nitric bases constituting DNA,

RNA and some coenzymes e.g. NAD. Acetic buffers of pH 3 and pH 5 were used as
the base electrolytes in this study. The influence of the acetic buffers pH on the
adsorption of adenine on mercury electrode was investigated. The systems were
characterized by the measurement of differential capacity, zero charge potential
(Ez), and surface tension at this potential. Fig. 1 presents differential capacity-
potential curves of the double layer Hg / acetic buffer solutions of pH 3 and 5
extrapolated to zero frequency.
26 26
Cadenina/M Cadenina/M
0.00000 0.00000
24 0.00005 0.00005
0.00010 24 0.00010
0.00030 0.00030
22 0.00050 0.00050
0.00080 0.00080
0.00090 22 0.00090
20 0.00100 0.00100
0.00200 0.00200
0.00300
C/F.m-2
C/F.m-2
18 20
16
18
14
16
12
10 14
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000 1200 1400
-E[mV] -E[mV]
(a) (b)
Fig. 1 Extrapolated differential capacity curves of the double layer Hg/acetic buffer pH 3 (a)
and pH 5 (b) in the presence of various concentrations of adenine.
The highest changes of differential capacity appeared in pH 5 acetic buffer

solutions containing adenine.
Table 1. The values of zero charge potential, Ez vs. Ag/AgCl electrode and surface
tension, z at Ez for the system Hg/acetic buffer pH 3 and pH 5 in the presence of
various concentrations of adenine.
pH 3 pH 5
c [mol/dm3] z z
-Ez [mV] -Ez [mV]
[mNm-1] [mNm-1]
0.00000 453.9 376.0 467.9 398.0
0.00005 465.4 395.0 472.8 387.5
0.00010 465.4 393.8 462.2 397.0
0.00030 455.5 387.9 462.2 392.3
0.00050 456.4 384.6 462.2 398.3
0.00080 451.0 379.8 457.3 417.1
0.00090 449.9 378.6 457.3 419.0
0.00100 448.3 377.7 450.7 421.6
0.00200 445.8 374.3 448.3 424.3
The Ez value changes show a mechanism in which adenine molecules adsorb

on their aromatic chain side on the electrode surface in the pH 5acetic buffer
whereas in the pH 3 acetic buffer adenine adsorption differs and depends on the
electrode potential.
Moreover, we examined the electroreduction of Zn2+ in NaClO4 as a
supporting electrolyte in the presence of anionic surfactants of various molecular
sizes on a mercury electrode. The results of measurements carried out at different
temperatures concerning the kinetic process of the electroreduction of Zn2+ in the
presence of sodium 1-decanesulfonate and sodium 1-octanesulfonate showed the
two-step character of the electrode process and accelerating influence of both
surfactants on the kinetics of the investigated electrode process.
In comparison to sodium 1-octanesulfonate the accelerating effect of sodium 1-
decanesulfonate was stronger. While considering the Zn2+ reduction mechanism
four models were used: EE, CE, IA, and IE.
MUTUAL INFLUENCE OF THE n-OCTYL- -D-
GLUCOPYRANOSIDE AND THE SODIUM DODECYLSULFATE
ON THEIR ADSORPTION AND AGGREGATION PROPERTIES
Anna ZDZIENNICKA, Bronisaw JACZUK, Joanna KRAWCZYK,

Katarzyna SZYMCZYK
DEPARTMENT OF INTERFACIAL PHENOMENA
Surfactants are amphiphilic compounds which are widely applied in many

industries and everyday life [1-3]. Commercially available surface active agents are
mainly chemically synthesized or derived from petroleum feedstock [4]. The
increasing pollution of the environment by synthetic surface active agents has
become a significant problem and that is why natural surfactants are intensively
studied. Of specific interest are biocompatible surfactants including sugar ones and
biosurfactants. The sugar surfactants are well assimilated by skin and mucous
membranes, exhibit low toxicity and very good biodegradability. What is more,
they are effective compounds in oil contaminants washing clean and can solubize
hydrocarbons and chloroorganic compounds. Though sugar surfactants application
expands, the literature does not provide enough information about their adsorption
or aggregation properties in various systems. Particularly in the literature there is
lack of information dealing with the mutual influence of sugar surfactant and
synthetic ones on their adsorption and aggregation properties. It is known that in
practice there are rather used the mixtures of surfactants than single ones. The
mixture of surfactants can reduce high water surface tension to a greater extent than
simple surfactants because of synergetic effect in the adsorption and aggregation
processes. Therefore, the aim of the research was to investigate the adsorption and
micellization properties of the n-octyl- -D-glucopyranoside (OGP) and sodium
dodecylsulfate (SDDS) mixture by the measurements of surface tension, density
and viscosity of aqueous solutions of this mixture at constant concentration of OGP
or SDDS. The measured values of the surface tension were compared to those
calculated from the Fainerman and Miller equation of state [5] as well as to the
hypothetical one. The obtained results were analyzed with regard to adsorption at
the water-air interface and micellization of OGP in the presence of SDDS and vice
versa. On the basis of this analysis, the Gibbs surface excess concentration of the
particular surfactants at the water-air interface, the Gibbs surface free energy of
adsorption and micellization, the composition of the surface layer, the apparent and
partial molar volumes of OGP and SDDS were determined. The Gibbs surface free
energy of adsorption was calculated on the basis of the critical micelle
concentration (CMC) and the surface tension values at this concentration as well as
by using the Langmuir equation. The composition of the surface layer was
compared to that of hypothetical one as well as to that in the bulk phase. In turn,
apparent and partial molar volumes were discussed in the light of the volume of
surfactant molecules on the basis of the length and angle of the bonds. On the basis
75 1.0015
6 1-5 1-10 b) c)
70 7 70 11
20
1.0010
8 12
9 13
65
(mN/m)
10
(mN/m)
14 1.0005
60 11 60
12 19
(g/cm )
3
15
1.0000
LV
LV
55 13
Surface tension,
Surface tension,
50 50 16
Density,
0.9995
14 18
45 16
15 17 0.9990
16 17 14
40 40 18
17 1-12
19 20 0.9985 15
35
18-20 13
30 30 0.9980
-8 -7 -6 -5 -4 -3 -2 -7 -6 -5 -4 -3 -2 -1 0.000 0.002 0.004 0.006 0.008 0.010
logarithm of SDDS concentration, logC1 logarithm of OGP concentration, logC2 SDDS concentration, C1 (M)
1.12
1.0015 d) e) f)
17 1.10
15 20 1.10 17
1.0010
15
1.08
1.0005 1-14 1.08
(mPa s)
(mPa s)
(g/cm )
3
1.0000 1.06
19 1.06
Viscosity,
Viscosity,
0.9995 1-13
Density,
1.04
1.04
0.9990 18 18 18,19
16
16 14 1.02
0.9985 1.02
17 1-13 16
1.00 14
0.9980 15
1.00
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.000 0.005 0.010 0.015 0.020 0.00 0.01 0.02 0.03 0.04 0.05 0.06
OGP concentration, C2 (M) SDDS concentration, C1 (M) OGP concentration, C2 (M)
Fig. 1. Isotherms of the surface tension (a, b), density (c, d) and viscosity (e, f) of aqueous
solutions of SDDS and OGP mixture at the constant concentration of SDDS (C 1) (b, d,
f) and OGP (C2) (a, c, e).
of the measurements and thermodynamic consideration it can be stated that the

changes of the surface tension of aqueous solutions of OGP and SDDS mixture as a
function of SDDS or OGP concentration at the low constant value of SDDS or OGP
concentration can be predicted by the values of the surface tension for single
surfactant solution as well as by the Fainerman and Miller equation. The synergetic
effect in the reduction of water surface tension by the OGP and SDDS mixture was
found. The composition of the surface layer at the water-air interface is different
from the composition of the surfactant in the bulk phase. The isotherm of
adsorption of OGP and SDDS mixture at the water-air system is of the Langmuir
type. The Gibbs surface free energy of adsorption of SDDS and OGP mixture can
be determined on the basis of its CMC. There is no straight linear dependence
between the CMC of OGP and SDDS mixture and its composition in the bulk
phase.
References:
[1] J.M. Rosen, Surfactants and Interfacial Phenomena, 3rd ed., Wiley Interscience,
New York, 2004.
[2] T.F. Tadros, Applied Surfactants: Principles and Applications, Wiley-VCH,
Weinheim, Germany, 2005.
[3] K. Holmberg, B. Jnsson, B. Kronberg and B. Lindman, Surfactants and
Polymers in Aqueous Solution, John Wiley & Sons Ltd, England, 2002.
[4] T.D. Renfro, W. Xie, G. Yang and G. Chen, Rhamnolipid Surface
Thermodynamic Properties and Transport in Agricultural Soil., Colloids Surf. B,
115 (2014) 317-322.
[5] V.B. Fainerman, R. Miller, Thermodynamics of adsorption of surfactants at the
fluid interfaces, in Surfactants Chemistry, Interfacial Properties and
Application, Studies in Interface Science, V.B. Fainerman, D. Mbius and R.
Miller (Eds.), Vol. 13, Elsevier, 2001, p. 99-188.
ANALYSIS OF TERNARY LANGMUIR AND LANGMUIR-
BLODGETT MONOLAYERS OF LIPIDS
Magorzata JURAK, Lucyna HOYSZ, Emil CHIBOWSKI,

Agnieszka Ewa WICEK, Aleksandra SZCZE, Konrad TERPIOWSKI
Domain formation in model membranes has been intensively studied since the
hypothesis of lipid rafts was put forward [1]. Rafts are defined as nanoscale regions
of biological membranes that take part in important cellular processes and signaling
pathways. Model membranes, such as the lipid Langmuir monolayers at the air-
water interface and the solid supported Langmuir-Blodgett monolayers, offer the
possibility of understanding how phase separation and domain formation can be
regulated by the lipid components [2]. A number of lipid mixtures have been used
to mimic the biophysical properties of rafts in membrane. Introducing cholesterol
modifies the membrane physical stability by altering its fluidity, permeability and
dielectric properties [3].The separation of ordered areas from the disordered (uid)
regions is a natural consequence of specic intermolecular interactions and lattice
deformation. The formation of such domains can be controlled by the lipid
composition. Moreover, the domain structure can be changed by preferential
hydrolysis of the phospholipids by interfacially activated enzymes [4].
A surface thermodynamic analysis was applied to the experimentally measured
surface pressure area per molecule (-A) isotherms of mixed Langmuir monolayer
films formed by 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-
dioleoyl-sn-glycero-3-phosphocholine (DOPC) and cholesterol (Chol) to
quantitatively describe the phase miscibility of these physiologically important
ternary mixtures at the air-water interface. Then, by means of the Langmuir-
Blodgett technique the investigated films were transferred onto the hydrophilic
mica plates at the surface pressure of 35 mN/m. Wettability of the model
membranes was investigated via contact angle measurements of three probe liquids
(water, formamide and diiodomethane). The contact angles allowed evaluation of
the total surface free energy and its components (Lifshitz-van der Waals component
SLW, electron-donor S- and electron-acceptor S+ parameters) for mixed systems
based on the theoretical approach proposed by van Oss et al. (LWAB) [5].
The obtained results show the existence of attractive interactions between
phospholipid DPPC/DOPC and Chol in the whole range of the studied surface
pressures and molar ratios which can be proved by negative values of the excess
free enthalpy of mixing Gexc (Fig. 1A). As previously reported the DPPC/DOPC
mixture exhibits positive values of Gexc ( Gexc>0) indicating that interactions
between hetero-molecules are less attractive (or more repulsive) than between
homo-molecules [6]. These interactions increase with the surface pressure, and a
phase separation takes place. Because the attraction between molecules in the
DPPC/DOPC/Chol is stronger than in the respective DPPC/DOPC or Chol
monolayers, one may conclude that the ternary systems are more stable, and the
stability of the films increases with the surface pressure. The most stable system
was obtained, when DPPC/DOPC/Chol were mixed at the 1:1:2 molar ratio, i.e. at
xChol=0.5. On the other hand the ternary DPPC/DOPC/Chol system clearly shows
phase separation [7]. The phase diagram of this ternary system, typically displays a
two-phase coexistence region of the liquid-disordered and liquid-ordered phases.
The liquid-ordered state in the model membranes can be considered as certain
equivalent of rafts. It is likely that the major driving force for phase separation or
domain formation in DPPC/DOPC/Chol is very unfavourable interaction between
DPPC and DOPC. Incorporation of Chol to the DPPC/DOPC monolayers causes
their condensation leading to increase in density of lipid molecules and their
ordering, thus improving the film stability.
500 60
A Surface free energy and its components
S
tot
B
LW
0 50 S
-
Excess free enthalpy of mixing
S
-500 40 +
, mN/m S
5
2
-1000
, mJ/m
Gexc, J/mol
10 30
15
-1500
S
20 20
25
-2000
30
10
35
-2500 40
0
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
DPPC/DOPC Chol molar ratio, xChol Chol DPPC/DOPC Chol molar ratio, xChol Chol
Fig. 1. Excess free energy of mixing ( Gexc) (A) and surface free energy (Stot) and its
components (SLW, S-, S+) calculated from the LWAB approach (B) versus the composition plots
for the ternary mixed monolayer DPPC/DOPC/Chol.
The interactions between different lipids in the films deposited on the mica
surface reflect the membrane properties (Fig. 1B). The films wettability and the
apparent surface free energy as well as its components strongly depend on the
monolayer composition, phase behaviour and ordering of molecules as well as
different affinity of Chol for both phospholipids (DPPC and DOPC).
The presented results can be helpful to design the film surfaces with targeted
properties which would potentially have practical applications.
References:
[1] K. Simons and E. Ikonen, Nature, 387 (1997) 569.
[2] S.L. Veatch and S.L. Keller, Biochim. Biophys. Acta, 1746 (2005) 172.
[3] W.-T. Li, Y.-M. Yang and C.-H. Chang, Colloids Surf. B, 66 (2008) 187.
[4] A.C. Simonsen, Biophys. J., 94 (2008) 3966.
[5] C.J. van Oss, M.K. Chaudhury and R.J. Good, Chem. Rev., 88 (1988) 927.
[6] M. Jurak and E. Chibowski, Colloids Surf. B, 75 (2010) 165.
[7] P.F.F. Almeida, Biochim. Biophys. Acta, 1788 (2009) 72.
TRANSFORMATION OF CHLOROGENIC ACID IN PRESSURIZED
LIQUID EXTRACTION CONDITIONS
Dorota WIANOWSKA, Rafa TYPEK, Andrzej L. DAWIDOWICZ

DEPARTAMENT OF CHROMATOGRAPHIC METHODS
Chlorogenic acids (CQAs) are naturally occurring quinic acid conjugates of

caffeic acid found in all higher plants. Coffee beans and mate are most frequently
mentioned as plant products remarkably rich in CQAs. A new research interest in
CQAs, their properties, and natural occurrence, results from scientific studies which
have shown that regular coffee consumption (with its chlorogenic acids content)
reduce the risk of type 2 diabetes by up to 67% and push up levels of homocysteine,
an amino acid that has been associated with artery-clogging atherosclerosis.
Although the mentioned biomedical CQAs properties are largely unproven new
applications of chlorogenic acids are suggested in pharmaceuticals, foodstuffs, food
additives, and cosmetics.
The analytical procedures of the plant constituents determination, involve the
application of a sample preparation methods to fully isolate and/or pre-concentrate
the analyzed substances from the plant matrix. Most formulas of plant analysis
mainly involve the application of long-lasting liquid extraction methods such as
Soxhlet extraction, maceration, and extraction under reflux. In the past several
years, researchers have been focused on the so-called supported extraction
techniques, which allow for the full recovery of the components of interest from the
sample matrix in short time. One of them is pressurized liquid extraction (PLE),
regarded as a leading method of effective and quick sample preparation, especially
in plant samples analysis.
Fig. A presents the exemplary chromatogram of the methanolic extract of
trans-5-CQA obtained in the 20 min PLE process. Its analysis shows that two
compounds are present in the methanolic PLE extract of trans-5-CQA:
cis-5-O-caffeoylquinic acid (cis-5-CQA) (peak 2) and
4-O-caffeoylquinic acid (4-CQA) (peak 1).
According to [1], trans-5-CQA heated under reflux in MeOH transforms to:
cis-5-CQA;
the methanolic adducts of trans-5-CQA (5-CQA-3-OMe) and
methyl esters of trans-5-CQA (est-Me-5-CQA).
The comparison of the above presented results proves that the transformation of
trans-5-CQA in the PLE conditions, using MeOH as extractant, is different than
that observed for trans-5-CQA heated under reflux.
Chromatogram of the methanol/water PLE
extract of trans-5-CQA (Fig. B) proves
that six compounds is formed from trans-
5-CQA in the PLE extracts:
diastereoizomeric pair (1S,3R,4R,5R)-
5-[3-(3,4-dihydroxyphenyl)-3R/S-
hydroxypropanoyl]-1,4,5-
trihydroxycyclohexanecarboxylic acid
(5-CQA-3R/S-OH)(peak 3/4);
4-CQA (peak 1);
cis-5-CQA (peak 2);
5-CQA-3-OMe (peak 5) and
est-Me-5-CQA (peak 6).
It is worth mentioning that the same
transformation products are formed during
the heating of trans-5-CQA
methanol/water solutions under reflux [1].
Chromatogram of buffered
methanol/water PLE extracts of trans-5-
CQA (Fig. C) shows that trans-5-CQA is
transformed to six compounds:
4-CQA (peak 1);
cis-5-CQA(peak 2);
3-O-caffeoylquinic acid (3-CQA)
(peak 7);
5-CQA-3-OMe (peak 5);
est-Me-5-CQA (peak 6);
methyl ester of caffeic acid (est-Me-
CA) (peak 8).
Exemplary chromatograms of 5-CQA

PLE extract obtained using:
methanol (A),
metanol/water (B), and
methanol/buffer, pH 6 (C)
as extractant.
In the light of [1], apart from the above derivatives, eight more trans-5-CQA
transformation products is formed in methanol/buffer solutions heated under reflux.
Thus, the difference in the number of the trans-5-CQA derivatives formed in PLE is
clearly seen. The significantly lower number of trans-5-CQA derivatives in PLE
extracts probably results from the short duration time of the PLE process.
[1] A. L. Dawidowicz, R. Typek, Food Chem. 167 (2015) 5260.

APPLICATION OF MECHANOCHEMICAL, HYDROTHERAL
AND MICROWAVE PROCESSES FOR PREPARATION
OF CHOSEN CATALYSTS AND ADSORBENTS
Jadwiga SKUBISZEWSKA-ZIBA, Barbara CHARMAS

DEPARTMENT OF CHROMATOGRAPHIC METHODS
Comparison of surface properties of silica xero- and hydrogels hydrothermally

modified using mechanochemical, microwave and classical methods
The aim of the work was to prepare the silica samples of different porous
structure and surface chemistry using microwave radiation (MWT) or mechanical
energy (MChT) treatment of micro-mesoporous silica gel with high specific surface
area (642 m2/g) which was prepared by sol-gel method from tetraethoxysilane
(TEOS). Wet gel as well as dried xerogel were used as starting materials. The
silicas synthesized via the classical hydrothermal treatment (HTT) were used as the
reference samples. It was interesting to compare the effects of modification by the
above mentioned ways. Of great interest were the changes in the structure of pores
and skeletons of starting materials modified under different conditions as well as
concentration of various surface and interglobular OH groups.
The initial silica samples of gel or xerogel were modified by three
different ways. (i) Hydrothermal treatment (HTT) was carried out in a classical steel
autoclave at 260 oC and pressure of saturated steam for 3 hours. (ii) Microwave
treatment (MWT) was performed in a high pressure microwave reactor
(Plazmatronica, Poland) for 0.5 h at temperatures 175, 225 or 260 oC. (iii) The
mechanochemical treatment (MChT) was carried out using the planetary mill
Pulverisette 7 (Fritch, Germany) (milling vessel and balls composed of Si 3N4, dball =
10 mm), at different rotation speeds - 250, 450, 460 or 850 rpm, and different time
of milling - 0.5, 1 or 1.5 h. The samples were characterized using the N2 adsorption-
desorption, TG/DTG analysis, SEM and FTIR methods.
On the basis of obtained results it was concluded that:
Mechanochemical treatment (MChT) of silica hydrogel gives the possibility
of obtaining silica paste of tixotropic character. Such property allows the formation
of granules, e.g. by extrusion, which is the important factor from the point of view
of silicas preparation for different applications.
Porous structure of initial xerogel (sample SiO2-ini) is mainly microporous
and no hysteresis loop is observed on the adsorption isotherm. However, depending
on the form of initial silica subjected to modification (gel or xerogel) and a kind of
heat energy supplied to the system (classical HTT, MWT or MChT) the hysteresis
loops of adsorption isotherms have various shapes.
Fig.1 SEM pictures of MChT treated silica hydrogel, during the 0.5 h at different rotational
speeds: 250 rpm (a), 450 rpm (b), 650 rpm (c). Magnifications x 2000 (upper images) and x
25000 (bottom images).
During HTT modification, both in the case of gel or xerogel, quite wide
pores of regular cylindrical shape are formed. But, for silicas modified using
microwaves (MWT) the presence of regular and irregular forms of cylindrical
pores, even in the form of bottles can be stated.
For the samples milled in the form of hydrogel with the increasing rotation
speed, open uniform mesoporous structure with the specific surface area 750-800
m2/g develops. Meanwhile increase in the duration time causes reorganization of
the structure towards microporosity development. During milling at a low rotational
speed (250 rpm) the reconstruction of porous structure is poor.
During MChT at a high rotation speed (850 rpm) and small quantity of
water (in air) the mesoporous structure is formed. But milling at a large
concentration of water (suspension) microporous silica is created with a small
number of mesopores.
A careful analysis of the images taken by scanning electron microscopy
SEM allowed us to confirm the conclusions drawn on the basis of the results of
nitrogen adsorption-desorption concerning structural characteristics of studied
silicas that by the increasing the grinding speed (up to 650 rpm) the diameters of the
globules making up the structure of the resulting silicas become smaller (Fig.1).
References:
[1] J. Skubiszewska-Ziba, S. Khalameida, V. Sydorchuk, Comparison of surface
properties of silica xero- and hydrogels hydrothermally modified using
mechanochemical, microwave and classical methods, Colloids and Surfaces
submitted
CHROMATOGRAPHIC AND SPECTROSCOPIC PROCEDURES IN
ANALYSIS OF ORGANIC, BIOACTIVE COMPOUNDS
Andrzej L. DAWIDOWICZ, Irena CHOMA, Jadwiga SKUBISZEWSKA-

ZIBA, Dorota WIANOWSKA, Barbara CHARMAS, Rafa TYPEK, Micha
DYBOWSKI, Piotr BOROWSKI, Magorzata OLSZOWY,
Katarzyna BERNACIK
DEPARTAMENT OF CHROMATOGRAPHIC METHODS
Rutin transformation during its analysis involving extraction process for sample
preparation
Rutin (quercetin-3-O-rutinoside) is one of the most popular phenolic compounds
found in various plant species. Its miscellaneous biological activity and, especially,
the ability to inhibit blood plates aggregation (which makes blood thinner and
improves circulation in the blood circulation system), causes permanent interest in
its properties and natural occurrence.
Liquid-solid extraction is the most popular method for rutin isolation from plants.
We found that at least 23 compounds (rutin transformation and degradation
products and their methyl derivatives) were formed from rutin during its simulated
and real extraction from elderberry flower by methanol and methanol/water
mixtures [1]. They are:
2-(3,4-dihydroxyphenyl)-5,7-dihydroxy-3-[(2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-
(hydroxymethyl)oxan-2-yl]oxychromen-4-one (isoquercitrin) Peak 7
2-(3,4-dihydroxyphenyl)-5-methoxy-7-hydroxy-3-[(2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-
(hydroxymethyl)oxan-2-yl]oxychromen-4-one (methyl-isoquercitrin) Peak 18
2-(3,4-Dihydroxyphenyl)-5,7-dihydroxy-3-[[(2S,3R,4R,5R, 6S) -3,4,5-trihydroxy-6-methyl-2-
tetrahydropyranyl]oxy]-4-chromenone (quercitrin) Peak 9
2-(3,4-Dihydroxyphenyl)-5-methoxy-7-hydroxy-3-[[(2S,3R,4R,5R,6S)-3,4,5- trihydroxy-6-
methyl-2-tetrahydropyranyl]oxy]-4-chromenone (methylquercitrin) Peak 20
2-(3,4-dihydroxyphenyl)-5-methoxy-7-hydroxy-3-[(2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-
[[(2R,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxymethyl]oxan-2-yl]oxychromen-4-
one (methyl-rutin) Peak 23
2-(3,4-Dihydroxybenzoyl)-2,4,6-trihydroxy-1-benzofuran-3(2H)-one (DTB) Peak 5
2-[(3,4-Dihydroxyphenyl)carbonyl]-4,6-dihydroxy-2-methoxy-1-benzofuran-3(2H)-one
(methyl-DTB) Peak 22
Oxo(2,4,6-trihydroxyphenyl)acetic acid (OTA) Peak 1
Methyl oxo(2,4,6-trihydroxyphenyl) acetate (methyl-OTA) Peak 12
2-[Carboxy(3,4-dihydroxyphenyl)methoxy]-4,6-dihydroxybenzoic acid (CDA) Peak 4
2-[1-(3,4-Dihydroxyphenyl)-2-methoxy-2-oxoethoxy]-4,6-dihydroxybenzoic acid
(methyl-CDA) Peak 15
2-[(3,4-Dihydroxybenzoyl)oxy]-4,6-dihydroxybenzoicacid (DDA) Peak 3
Methyl 2-[(3,4-dihydroxybenzoyl)oxy] -4,6-dihydroxybenzoate (methyl-DDA) Peak 14
4,6-Dihydroxy-1-benzofuran-2,3-dione (DBD) Peak 2
6-Hydroxy-4-methoxy-1-benzofuran-2,3-dione (methyl-DBD) Peak 13
7-(3,4-Dihydroxyphenyl)bicyclo[4.2.0]octa-1,3,5,7-tetraene-2,4,8-triol (DBOT) Peak 6
7-(3,4-Dihydroxyphenyl)-8-methoxybicyclo[4.2.0]octa-1,3,5,7-tetraene-2,4-diol
(methyl-DBOT) Peak 17
3,5-Dihydroxy-2-[methoxy(oxo)acetyl]phenyl-3,4-dihydroxybenzoate (DPD) Peak 8
5-Hydroxy-3-methoxy-2-[methoxy(oxo)acetyl]phenyl 3,4-dihydroxybenzoate (methyl-DPD) Peak 19
2-(3,4-Dihydroxyphenyl)-3,5,7-trihydroxy-4H-chromen-4-one (quercetin) Peak 10
2-(3,4-Dihydroxyphenyl)-5,7-dihydroxy-3-methoxy-4Hchromen-4-one (methyl-quercetin) Peak 21
2-(3,4-Dihydroxyphenyl)-1-benzofuran-3,4,6-triol (DBT) Peak 11
2-(3,4-Dihydroxyphenyl)-3-methoxy-1-benzofuran-4,6-diol (methyl-DBT) Peak 16
Fig. 1 Exemplary chromatograms of methanolic (A), methanol/water (75/25 v/v) (B) and
methanol/phosphoric buffer (pH=6.5) (75/25 v/v) (C) solution of rutin and
methanolic (A), methanol/water (75/25 v/v) (B) and methanol/phosphoric buffer
(pH=6.5) (75/25 v/v) (C) extract of elderberry flower, all heated under reflux for 3
h. Peak numbers correspond to compound numbers reported in the above set of
compounds.
Twelve of them (marked in bold see the set of compounds) have not been reported
yet. We observed that the amount of each formed compound depends not only on
the extraction time, alcohol concentration and extractant pH but also on the
components of plant matrix from which rutin was extracted.
Separation, identification and investigation of antioxidant ability of plant extract

components using TLC, LC-MS and TLC-DPPH
Polyphenols are one of the biggest group of higher plant secondary metabolites. On
the grounds of their wide range of biological activity, polyphenols contained in
fruits, vegetables, spices, wines, beverages (tea, coffee, juice) are very important
part of daily human diet. Above all, they are natural antioxidants possessing redox
properties acting as radical scavengers, reducing agents and hydrogen donators.
Furthermore, many other physiological properties have been attributed to them:
anti-inflammatory, antiviral, antimicrobial, anti-allergic, anti-cancer as well as
antiulcer and antidiarrheal.
Many analytical methods, including chromatographic techniques, have been
used for separation and determination of flavonoids and phenolic acids. Among
them, the most often used, is high performance liquid chromatography (HPLC) [2].
Recently, development and popularity of effect directed analysis (EDA), and in
particular, direct bioautography (DB), gives new possibilities for TLC separations.
Thin-layer chromatography direct bioautography (TLC-DB) is a hyphenation in
which the separation step is performed using (HP)TLC, while searching for
compounds of given properties (antioxidant, enzymatic, antiestrogenic,
antimutagenic, antibacterial or antifungal) is done using proper biological detection
directly on the TLC plate [3]. This hyphenation affords several advantages, such as
fast results, reduction in time-consuming sample preparation steps, and what is the
most important, direct access to the separated target compounds on the (HP)TLC
plate. TLC-DB plays an important role in identification of antioxidants and radical
scavengers in natural samples. This can be assessed using stable 2,2-diphenyl-1-
picrylhydrazyl (DPPH) radical (TLC-DPPH) or 2,2-azino-bis(3-
ethylbenzothiazoline-6-sulphonic acid) (ABTS) radical (TLC-ABTS+) [4].
Ten common phenolic compounds (seven flavonoids and three phenolic acids)
from five plant extracts i.e. Hypericum perforatum L., Matricaria recutita L.,
Achillea millefolium L., Thymus vulgaris L. and Salvia officinalis L. were separated
using optimized TLC conditions and visualized using NP/PEG reagent. Antioxidant
properties of components of the extracts were assessed using TLC-DPPH directly
on the TLC plate. Nine from ten analyzed polyphenols were proved to be radical-
scavengers. LC-MS analysis allowed to confirm the presence of target compounds
identified earlier by TLC and additionally of four other compounds (caffeic acid
and apigenin in St. John wort as well as apigenin and apigenin 7-O-glucoside in
sage). They have not been identified by TLC, probably because of low
concentration of these compounds in the plant samples.
Spectroscopic and calorimetric studies of water bound in lactic acid bacteria
Lactic acid bacteria (LAB), as well as yeast cells, used in the food industry can
be stored in a freeze-dried state. Freeze-drying (lyophilisation) is widely used to
preserve thermo-sensitive active ingredients such as proteins or microorganisms.
Freeze-dried microorganisms contain a small amount of residual intracellular water.
The addition of water, sugar solution, milk or other nutrient media to them and
increasing the temperature to an optimal one lead to renewal of bacterial activity.
The activity of water (or nutrient media) in the mentioned processes depends on the
amounts of water because at low content of bound (structured) water, the solubility
of nutrients (as well as other compounds) in this water is low. The stronger the
bonding of interfacial water, the lower the activity of this water as a solvent.
In this regard the aim of the work was to study the characteristics of water
bound to lactic acid bacteria (freeze-dry) depending on the water content, presence
of a solute (trifluoroacetic acid - TFAA), changes in the dispersion media (air,
CDCl3, dimethylsulfoxide, n-decane), and presence of solid particles (thermal silica
TS 100 or silylated silica gel Sipernat 50 - Evonic Germany). The study was
performed using low-temperature 1H NMR spectroscopy, DSC, cryoporometry,
infrared spectroscopy, microphotography and thermogravimetry methods.
On the basis of obtained results it was shown that the structural and
thermodynamic characteristics of intracellular liquids (water and organics) in lactic
acid bacteria depend strongly on their contents and temperature, especially below
freezing points of these liquids. This is due to significant changes in the properties
of strongly and weakly liquids bound to bacteria in comparison with the bulk liquid.
Penetration of small organic molecules (e.g. TFAA, chloroform) into LAB can be
inhibited by particles of silica TS 100 encapsulating bacteria. In similar samples but
without TS 100, TFAA penetration into bacteria occurs that is observed as
appearance of corresponding 1H NMR signals of waterTFAA mixture absent in the
presence of TS 100.
Fig. 2 DSC thermograms of (a) cooling and (b and c) heating runs of LAB samples at
different amounts of added water (a and b): 0 (curves 1), 0.1 (2), 0.2 (3), 0.3 (4), 0.5 (5-run
1, 6-run 2) and 0.7 (7) g/g, and (c) LAB interacting with silylated silica at CSi50s = 0.3
(curve 1), 0.4 (curves 2 and 3) and 0.5 (curves 46) g/g in various surroundings; (d) Pore
size distributions calculated using DSC thermoporometry for samples (a) 4 (curve 1 in (d)),
5 (2), 6 (3), 7 (4), and (c) 1 (curve 5 in (d)), 2 (6 in (d)), and 4 (7 in (d)). Microphoto (insert
in (c), scale bar 10 mm) of freeze-dry LAB sample [5].
There were strongly and weakly bound waters determined from their changes
in the Gibbs free energy. Strongly and weakly associated waters were identified by
changes in the chemical shifts of the proton resonance for hydroxyls participating in
hydrogen bonds. Changes in the characteristics of water bound to LAB depend on
the water content, dispersion medium and co-adsorbate types, and the presence of
silica. Several types of water were found in wetted LAB. There are, at five types of
intracellular and extracellular waters. There are: (1) strongly bound intracellular
water (frozen at T < 260 K), which can be in states of weakly (WAW) or strongly
(SAW) associated water; (2) weakly bound intracellular and extracellular water
(frozen at 260 <T< 273 K), which can be both WBW and SBW; (3) extracellular
bulk water, which does not interact with bacteria. It can be observed in diluted
suspensions of bacteria. The presence of both SBW and WBW results in diminution
of the heat effects on cooling/heating of wetted LAB, since the values of H for
these waters are much smaller than that for bulk water.
A low content of intracellular water prevents its crystallisation, therefore sharp
freezing exotherm and melting endotherm are absent for LAB at hydration degree
lower than 2 g/g when the bulk water is absent (Fig. 2). For storage of LAB, both
hydrophilic agglomerated silica TS 100 and silylated silica gel Sipernat 50 can be
used for microencapsulation of lactic acid bacteria without destroy of them.
Determination of vibrational spectra of chlorogenic acid

5-O-Caffeoylquinic acid (5-CQA, chlorogenic acid) is one of the major
chlorogenic acids present in many fruits, vegetables and herbs. A series of
complementary spectroscopic studies supported by theoretical calculations were
done. In particular, the calculations of vibrational spectra (IR and Raman) of 5-
CQA were carried out at the B3LYP/6-311++G(d,p) computational level. To obtain
reliable assignment of the observed bands the vibrational harmonic wavenumbers
[6,7] were scaled with the aid of the multiparameter effective scaling frequency
factor (ESFF) [8-10] method using our home-made ESFF program. The results
were published in one of the leading journals devoted to food chemistry,
biochemistry, microbiology, technology and nutrition [11].
The optimized structure (B3LYP/6-311++G**) is shown in Fig. 3. Note that
the hydrogen bonding was not taken into account, and for this reason the
assignment of bands corresponding to vibrations of motifs not involved in hydrogen
bond formation was made.
Fig. 3. The optimized structure of 5-CQA
Very good agreement between the theoretical scaled and experimental

wavenumbers of 5-CQA was obtained. The root-mean square (RMS) deviation for
the assigned IR bands is equal to 10.4 cm-1. This value indicates that the calculated
vibrational spectrum is of high quality. The RMS deviation in the range 10-11 cm1
is typical of the multi-parameter scaling of a high quality harmonic wavenumbers.
The band assigned to the stretching C=O vibrations of the carboxylic group is
located at 1733 (calc.), 1725 (IRKBR) and 1723 (IRATR) cm-1. The next band [1704
(calc.), 1687 (IRKBR), 1687 (IRATR) and 1689 (Raman) cm-1] is due to the stretching
C=O vibrations of the ester group. These two modes are very pure in that the
contribution from only one group is above 80%. The next band at the 1629 (calc.),
1640 (IRKBR), 1638 (IRATR) and 1630 (Raman) cm-1 band is assigned to the
stretching vibration of the C=C fragment (nearly 50%); this time it is coupled with
some other local vibrations (Table 1). The bands derived mainly from stretching
vibrations of the aromatic ring are present in the range of 1603-1530 (calc.), 1613-
1530 (IRKBR), 1613-1529 (IRATR) and 1604-1515 (Raman) cm-1. Below that range
one can hardly find group vibrations the normal modes are either strongly
delocalized over the entire molecule, or the contributions from a particular local
coordinate does not exceed 25%. Such a behavior is typical of a fingerprint range. It
turned out that there are only a few vibrations that can be attributed a status group
vibration, but only in one case the contribution exceeds 50% (for band at 1443 cm
1
; IRKBr). This is demonstrated in Table 2, which shows the assignment of bands in
the range of 1200-1400 cm-1.
Table 2. Theoretical and experimental wavenumbers of 5-CQA along with the

bands assignment in the range of 1200-1400 cm-1. X denotes a general second-row
atom (C or O) and two and three letter symbols refer to the bond lengths and
valence angles, respectively.
IRKBr IRATR Raman
Theor. contributions (PED) detailed description
exp. exp. exp.
1204 1202 1202 23% XX(s,c)+59% XXH+16% torsions 40%(C-O-H)
1255 26% XX(s,c)+50% XXH+20% torsions delocalized
1260 1252 1250 45% XX(s,c)+42% XXH delocalized
1265 1257 41% XX(s,c)+42% XXH delocalized
1275 72% XXH 45%(C-O-H)
1281 1289 1289 1284 64% XX(s,c)+29% XXH 37%(C-O)
1303 19% XX(s,c)+54% XXH+19% torsions not considered
1305 51% XXH+26% torsions delocalized
1308 1304 1303 42% XX(s,c)+39% XXH delocalized
1318 54% XX(s,c)+32% XXH delocalized
1338 79% XXH not considered
1344 36% XX(s,c)+37% XXH not considered
1352 1358 1362 73% XX(s,c)+23% XXH mainly Ar asym. stretch
1367 1372 27% XX(s,c)+38% XXH+31% torsions delocalized
1385 1382 36% XX(s,c)+41% XXH+17% torsions 23%(C-O-H)
1382
1388 27% XX(s,c)+49% XXH+21% torsions 18%(C-O-H)+15%(C-O-H)
1398 26% XX(s,c)+41% XXH+29% torsions 16%(C-C)+16%(C-O-H)
References:
[1] A.L. Dawidowicz, R. Typek, K. Bernacik, Food Analytical Methods 9 (2016)
213224 DOI: 10.1007/s12161-015-0170-2.
[2] C. Proestos, N. Chorianopoulos, G. Nychas, M. Komaitis, J. Agric. Food Chem.
53 (2005)11901195
[3] I.M. Choma, W. Jesionek, Effect-directed biological detection: Bioautography.
In Instrumetal Thin-Layer Chromatography, C.F. Poole, ed. Elsevier,
Amsterdam, 2014.
[4] W. Jesionek, I.M. Choma, B. Majer-Dziedzic, I. Malinowska, J. Liq.
Chromatogr. Rel. Technolog. 37 (2014), 28822891.
[5] V.M. Gun'ko, V.V. Turov, T.V. Krupska, M.D. Tsapko, J. Skubiszewska-Ziba,
B. Charmas, R. Leboda, Effects of strongly aggregated silica nanoparticles on
interfacial behaviour of water bound to lactic acid bacteria, RSC Advances, 5
(2015) 77347739
[6] E. B. Wilson, Jr., J. C. Decius, P. C. Cross, Molecular Vibrations. The Theory
of Infrared and Raman Vibrational Spectra, Dover Publications, Inc., New York,
1955.
[7] S. Califano, Vibrational States, John Wiley & Sons, London, 1976.
[8] P. Borowski, M. Fernndez-Gmez, M. P. Fernndez-Liencres, T. Pea Ruiz,
Chem. Phys. Lett., 446 (2007) 191198.
[9] P. Borowski, J. Mol. Spectr., 264 (2010) 6674.
[10] P. Borowski, J. Phys. Chem. A, 116 (1012) 38663880.
[11] E. Bajko, M. Kalinowska, P. Borowski, L. Siergiejczyk, W. Lewandowski,
LWT Food Science and Technology, 65 (2016) 471479.
SOLUBILIZATION OF PROPYL GALLATE MOLECULES IN THE
SDS MICELLES MOLECULAR DYNAMIC STUDY
Mateusz DRACH, Jolanta NARKIEWICZ-MICHAEK

DEPARTMENT OF THEORETICAL CHEMISTRY
Solubilization phenomenon has attracted attention and interest of many

researchers over decades. This attention is due to a broad range of solubilization
applications in biological, pharmaceutical and industrial processes. For instance the
activity of antioxidants used to protect foods and biological systems depends on
their localization in different phases of the protected system.
In this work, the all atom molecular dynamic simulations of sodium
dodecylsulphate (SDS) micelles in the presence of synthetic antioxidant propyl
gallate (PG) are presented. The simulations were performed for the systems with
different solubilizate to surfactant ratios (1:6, 1:3, 1:2) using GROMACS 4.07
package [1,2] and the NPT ensemble. The temperature was maintained at 300 K by
applying the Nose-Hoover thermostat whereas the pressure was held constant at 1
bar using the Parinello-Rahman barostat.
Fig. 1. Density distributions for various Fig. 2. Time evolution of the sodium ion
atoms and groups of atoms with respect to number at r < 2.5 nm and r < 3.5 nm.
the SDS micelle COM (center of the mass).
Fig. 3. Density distributions for various Fig. 4. Time evolution of the number of
atoms and groups of atoms with respect to solubilized propyl gallate molecules and
the SDS/PG micelle COM. The ratio of sodium ions at r < 3.5 nm. The ratio of
solubilizate to surfactant was 1:2 solubilizate to surfactant was 1:2
The all atom (AA) model was used to describe surfactant molecules. The
parameters for this system were taken from the CGenFF potential [3,4]. The water
molecules were represented by the SPC/E potential. The starting configurations for
the investigated systems were prepared using PACKMOL package [5].
The results can be summarized as follows:

The computational model employed by us is able to reproduce experimental
results of SDS micelle structure in water. The micelle is approximately
spherical with the mean radius of about ~2.5 nm
The sodium ions mainly reside close to the aggregate surface. About 30 Na +
ions are placed at the distance less than 2.5 nm from SDS COM and 45 Na+
ions at the distance less then 3.5 nm. It means that. ~50-75% of micelle
charge is screened by counterions.
The solubilized PG molecules are located in the external part of SDS
micelle. They penetrate SDS micelle to the fifth carbon in the surfactant
alkyl chain.
In the investigated systems with the SDS:PG ratio equal to 6:1, 3:1 and 2:1,
the amount of solubilized PG has only a minor effect on the micelle shape
and counterion binding.
References:
[1] H. J. C. Berendsen, D. van der Spoel and R. van Drunen, Computer Physics
Communications, 91 (1995) 43-56.
[2] B. Hess, C. Kutzner, D. van der Spoel, and E. Lindahl, Journal of Chemical
Theory and Computation, 4 (2008) 435-447.
[3] K. Vanommeslaeghe, E. Hatcher, C. Acharya, S. Kundu, S. Zhong, J. Shim, E.
Darian, O. Guvench, P. Lopes, I. Vorobyov, A. D. MacKerell Jr., J. Comput.
Chem., 31 (2010) 671-690.
[4] W. Yu, X. He, K. Vanommeslaeghe, A. D. MacKerell Jr., J. Comput. Chem., 33
(2012) 2451-2468.
[5] L. Martnez, R. Andrade, E.G. Birgin and J. M. Martnez, J. Comput. Chem., 30
(2009) 2157-2164.
HYDROPHOBIZATION OF MESOPOROUS SILICA MATERIALS
VIA SILYLATION WITH HEXAMETHYLDISILAZANE
Mariusz BARCZAK
DEPARTMENT OF THEORETICAL CHEMISTRY
For many applications including adsorption, catalysis, drug delivery systems,

gas chromatography, fabrication of low k dielectric silica, the surface of silica
should be preferably hydrophobic. However, mesoporous silica materials based on
tetraethoxysilane are usually hydrophilic which results in the deterioration of their
properties with time [1]. The hydrophilicity is attributed to the presence of the
silanols (SiOH) which are also a principal bonding site on silica. Thus, by
replacing hydrogen in the surface silanol groups by a hydrolytically stable group,
hydrophobic silica materials can be obtained.
Hexamethyldisilazane (HMDS) is one of the frequently used silylating agents.
The presence of basic nitrogen makes it highly reactive towards silica silanols [2].
As it can be seen from the overall reaction presented in Fig. 1, hydrophobization is
achieved via silylation, i.e. silanol groups are reacted to yield trimethylsilyl groups.
Thus, the HMDS-based silylation process is chlorine-free, making it possible to
react with the surface silanol groups without liberating hazardous by-products [3].
In the present research the influence of HMDS treatment on the structural and
chemical properties of SBA-15 mesoporous silica was investigated.
Fig. 1. The overall reaction between the silanol groups and HMDS
Mesoporous silica materials were synthesized as in [4]. In a model synthesis,
2g of P123 was dissolved in 60 ml of 2M HCl and 12 ml of deionized water under
stirring at 40C. After 12 h of stirring a 20 mmol of TEOS was added and the
resulting mixture was stirred for 24 h and aged at 100C for next 24 h. The white
solid was washed with deionized water, filtered and dried at 70C. The template
was removed by calcination at 550C during 5h. Subsequently, the HMDS
functionalization was performed according to the following procedure. 0.4g of the
sample was mixed with 30 ml of toluene and 1 ml of HDMS and kept for 2h under
reflux. Both materials (i.e. pristine and HMDS-treated) were characterized by
nitrogen sorption measurements (using NOVA 1200e sorptometer made by
Quantachrome) and transmission FTIR spectroscopy (using FT/IR-6200
spectrometer made by Jasco) to investigate structural and chemical changes
induced by the silylation treatment.
The isotherms of both samples are presented in Fig. 2. As it can be seen, the
silylation treatment induces severe changes in porous structure. The BET specific
surface area decreases from 889 m2/g to 532 m2/g, the average mesopore size
decreases from 8.76 nm to 7.93 nm, the total pore volume from 1.13 cm3/g to 0.78
cm3/g and the micropore volume from 0.26 cm3 to 0.11 cm3. Of course, the reason
for all these changes is the replacing silanol groups by bulky trimethylsilyl groups.
Fig. 2. Nitrogen sorption Fig. 3. FTIR spectra of the samples studied

isotherms of the studied samples
Apart from morphological changes chemical changes occur upon HMDS

treatment, which is evidenced by the FTIR spectra presented in Fig. 3. The wide
and intensive band extending from 3700 cm-1 to 2700 cm-1 corresponds to the O-
H-vibrations of some adsorbed water. This band and that located at 1630 cm-1
corresponding to the bending vibrations of water are noticeably diminished after
silylation. This testifies that the silylated silica is less favorable to adsorb water. At
the same time, the absorption bands related to the asymmetric and symmetric C-H
stretching modes of methyl in the TMS- groups (at 2960 cm-1, 2920 cm-1 and
2850 cm-1) appear. Also the appearance of the absorption band at 1260 cm-1
coming from the symmetric deformation of Si-CH3 bonds is observed. The presence
of these bands testifies that the trimethylsilyl groups were successfully attached to
the silica surface during treatment with HMDS.
To summarize, the silylation of SBA-15 mesoporous silica via treatment with
HMDS was investigated. This method turned to be a simple and effective tool to
transform the surface silanol groups into trimethylsilyl ones. In this way,
hydrophobicity of mesoporous silicas can be tuned for desired applications.
References:
[1] A. M. Kartal, C. Erkey, The Journal of Supercritical Fluids, 53 (2010) 115.
[2] W. Hertl, M. L. Hair, The Journal of Physical Chemistry, 76 (1971) 2181.
[3] S.Fruehauf et al., Mater. Res. Soc. Conf. Proc. ULSI XVII, pp. 287-294.
[4] M. Barczak, et al., Adsorption, 16 (2010) 457.
PREPARATION AND INVESTIGATION OF CATALYTIC
SYSTEMS IN THE REACTIONS INVOLVING CARBON OXIDES,
HYDROCARBONS AND THEIR OXYGEN CONNECTIONS
Tadeusz BOROWIECKI, Marcin CICHY, Wojciech GAC,

Magdalena GRELUK, Andrzej MACHOCKI,
Sylwia PASIECZNA-PATKOWSKA, Marek ROTKO,
Janusz RYCZKOWSKI, Grzegorz SOWIK, Witold ZAWADZKI
DEPARTMENT OF CHEMICAL TECHNOLOGY
Preparation and analysis of catalytic materials for the process of removal

(oxidation) of soot from Diesel exhaust gases
The main aim of this study was obtaining and analysis of potentially active
Co-Ce catalysts for soot oxidation from diesel exhaust gases. The catalytic
materials were prepared by a co-precipitation method, slowly adding the aqueous
solution of ammonium carbonate to the solution containing appropriate amounts of
Co and Ce acetates. After filtration, the obtained catalyst precursors were dried at
120oC (2 h) and calcined at 400oC or at 500oC (2 h). The obtained catalysts contain
different amounts of Co and Ce (determined by the XRF) but always in the oxide
form: Co3O4 and CeO2 (confirmed by the XRD). The activity of Co-Ce catalysts
was measured in the tight contact using model soot (Printex U) and the reaction
mixture containing 10 vol.% of O2. The obtained results demonstrate that the Co-Ce
catalysts are much more active than single-component catalysts containing Co or
Ce. Moreover, a crucial is also the molar ratio of Co:Ce, because the highest
activity in the process of soot oxidation demonstrates the Co-Ce catalyst containing
significantly more Ce than Co. Further studies will be conducted.
The effect of impregnation medium on activity of ceria-supported cobalt catalysts
for ethanol steam reforming
The goal of this study was to assess the effect of using methanol, ethanol and
propanol as the impregnation solvent in the preparation of cobalt catalysts
supported on ceria in the ethanol steam reforming (SRE).
The catalysts, prepared by support impregnation with cobalt nitrate solutions
were characterized using various characterization techniques including nitrogen
adsorption, hydrogen chemisorption, XRF, XRD and TPR. The reaction of ethanol
conversion with water was carried out under atmospheric pressure in a fixed-bed
continuous-flow quartz reactor over the catalyst (0.1 g; 0.15-0.3 mm) reduced in
situ with hydrogen at 400C for 1 hour, prior to the reaction.
The type of solvent used to dissolve cobalt precursor in order to obtain cobalt
based catalysts on ceria influences on: cobalt dispersion, ethanol conversion in
steam reforming of ethanol, and selectivity of ethanol conversion in SRE.
It does not influence on reducibility of obtained oxide forms of catalysts.
the optimum temperature of 540C is the lower one which simultaneously enables
to achieve total conversion of ethanol, the high production of hydrogen, the lack of
acetaldehyde among reaction products, small concentration of carbon monoxide.
Hydrogenation of carbon oxides is an important route for the production of
valuable chemicals, alkanes, alkenes, alcohols, ethers. The aim of the studies was
synthesis of novel nanostructured iron-manganese catalysts. The catalysts were
prepared by the impregnation of high surface area silica mesoporous supports. It
was found that the prepared manganese ferrites were strongly dispersed in silica
pores and exhibited a superparamagnetic behavior. Studies evidenced that the size,
reducibility and magnetic properties of nanocrystallites can be tailored by variation
of precursor loading and changes of annealing temperature.
In 2015 research concerning steam reforming of glycerol was continued.
Series of catalysts, was evaluated for possible use in glycerol conversion to
synthesis gas. Physiochemical properties of four nickel catalysts with different
amount of active metal (2.5%, 5%, 7.5% and 10%) supported on non-stoichiometric
hydroxyapatite, were characterized by such techniques as: XRD, XRF (amounts of
nickel), hydrogen chemisorption (active surface area), nitrogen adsorption (total
surface area), by the electron microscopy methods and TPR.
Catalysts have been tested in glycerol steam reforming reaction using
down-flow quartz reactor. 10 mg sample was load into reactor and, previously to
measurement, reduced in hydrogen flow. Reforming reaction was conducted in
temperature range 650-800oC (in 50oC, 60 min steps) under atmospheric pressure.
Glycerol:water mixture with S/C = 3:1 was delivered to reactor by syringe pump.
Received products stream was divided into gaseous and liquid phases. Gas phase
was chromatographically analyzed for contents of: H2, CO, CO2, CH4 and C2H6. In
liquid phase content of unreacted glycerol was determined.
Received results show, that catalysts activity and stability increase with
increasing amounts of Ni, but only up to 7.5 wt. %. Further increase, to 10 wt. %,
causes drop in catalyst activity. The highest values, both glycerol conversion and
selectivity to hydrogen, were obtained in 800oC for catalyst with 7.5 wt.% Ni. The
same object shows the best stability during 10 hours-long test.
Long term stability tests in stem reforming of methanol (SRM) on Pd based
catalyst was performed. The aim of the study was to investigate the activity and
selectivity changes during SRM process at 210oC as well as after simulated
shutdown-start up cycles in the presence of air. The catalysts were tested after short
(1h) and long (5h) activation in pure hydrogen stream, at low (350oC) and higher
(400oC) temperatures as well as after low (250oC) and high (400oC) calcination
temperatures. SRM process was conducted for at least 120 h and interrupted by
simulated shutdown-start up cycles. After each shutdown-start up cycle the catalysts
reveal initial activity loss and increase of carbon monoxide selectivity. For
investigated catalysts self activation phenomenon in SRM was proved. The
catalysts with higher Pd content reveal good activity, selectivity, stability and
resistance to deactivation during shutdown-start up cycles in the SRM. It was found
that an increase of calcination and reduction temperature of catalyst improves its
selectivity, stability and resistance to deactivation during shutdown-start up cycles
in the SRM, however, it decreases catalyst activity.
OPTIMIZATION OF MUNICIPAL WASTE MANAGEMENT
SYSTEMS INCLUDING METHODS FOR MECHANICAL-
BIOLOGICAL (MBP) WASTE TREATMENT
Adam LESIUK
Municipal solid waste management system in Poland from 2013 was built on
the waste management plants. The waste management plants must be implemented
by the technology based on mechanical-biological treatment (MBP) of municipal
waste [1,2]. Number of waste management plants in Poland that use the MBP is
over 100 installations, but in the Lublin province only 6. According to the law, only
waste that has been processed (recovery processes, including recycling,
fermentation or composting) may be directed to the storage. The result is a so-called
waste stream, secondary raw materials, which should be directed to recovery. The
mass of the municipal waste stream (glass, plastics, metals, paper) led to recovery
also depends on the morphological composition of waste.
The aim of the study was to compare the morphological composition of mixed
waste produced by residents of cities with a population that is different, it is Lublin
(big city) and Radzy Podlaski (small city). The studies of the morphological
composition of waste was carried out in one year, a waste was sorted into 10 groups
of ingredients. The following table (Table 1) shows the morphology of mixed waste
generated in cities.
Table 1. Morphological composition of mixed waste generated in selected cities in

the Lublin province.
Morphological composition of mixed

Component waste [%]
Radzy Podlaski Lublin
paper 5.9 5.75
plastics 14.6 11.30
glass 6.4 6.19
metals 2 1.24
composite packaging 7.6 0.54
wood 0.3 0.44
textiles 7.3 2.86
organic waste 52.60 66.15
WEEE 0.50 0.60
other wastes 2.80 4.93
The research shows that the morphological composition of municipal waste
differs from each other slightly. The waste in Lublin includes 13% more organic
fraction than in Radzy Podlaski. This is the result of an effective system of
selective collection where a large mass of material is collected separately. The
waste produced in Lublin also includes several times less waste tetrapak type. In the
case of the other components of their content they are at a similar level.
References:
[1] Ustawa z dnia 14 grudnia 2012 r. o odpadach (Dz.U. 2013 poz. 21).
[2] Krajowy Plan Gospodarki Odpadami 2014, Warszawa 2010.
INFLUENCE OF CATIONIC POLYACRYLAMIDE ADSORPTION
ON THE ELECTROKINETIC PROPRTIES OF
CHROMIUM(III) OXIDE POLYMER SOLUTION SYSTEM
Stanisaw CHIBOWSKI, Magorzata WINIEWSKA, Elbieta GRZDKA,

Jacek PATKOWSKI, Teresa URBAN, Magorzata PASZKIEWICZ
DEPARTMENT OF RADIOCHEMISTRY AND COLLOID CHEMISTRY
The effects of solution pH and cationic group contents in polyacrylamide

(PAM) macromolecules on the polymer adsorption mechanism on chromium(III)
oxide surface were studied. Additionally, the polymer adsorption influence on the
surface charge density and zeta potential of solid particles was determined.
Polymers belonging to the polyacrylamides group are often used because of
their lower sensitivity to temperature and being prone to self-association. Moreover,
they can be easily modified using the copolymerization reaction, which provides a
wide range of their applications. In many cases the PAM macromolecules stabilize
the colloidal dispersion by the steric effect or form polymeric bridges between the
colloidal particles leading to their destabilization. This polymer is very often used
because of its high efficiency, low cost and not large requirements for its quality.
Chromium(III) oxide is one of the most frequently used dye in the industry. It
is applied for coloring glass, concrete, ceramic, plastic or leather. It is also used as a
catalyst for organic syntheses. Cr2O3 is a very popular colorant in the production of
banknotes and green ink. It is also used as an ingredient in cosmetics (eyeshadow)
and dye in bronzers, lipsticks and cheek rose. Due to the wide application of
chromium oxide(III) in industry, its increased amount can be found in wastewaters.
Cr2O3 has an intense green colour, and even its low concentrations can inhibit light
penetration to greater depths of water. This can lead to oxygen deficiency caused by
disruptions in the process of photosynthesis carried out by aquatic plants and algae.
Therefore it is important to look for new ways to remove coloured substances from
wastewaters. One of them can be adsorption of macromolecules (i.e. ionic
polyacrylamide) on the solid particle surfaces, making their removal much simpler.
The BET specific surface area of used Cr2O3 was equal to 7.12 m2/g and the mean
grain size of the solid particles in water was 265 nm.
Applied cationic PAM (Fig. 1) was obtained by copolymerization reaction of
acrylamide with cationic monomer (i.e. containing the quaternary amine group).
Four samples of polymer differing with molecular weight (7 000 and 8 500 kDa)
and cationic groups content (20, 35, 50 and 80%) were used in experiments. The
pKb values of PAM solutions were determined by the potentiometric titration
technique. At pH 3 and 6 the polymeric macromolecules are totally dissociated,
whereas at pH 9, the dissociation degree is in the range 88.8-92.6%.
All experiments were carried out at 25oC in the solution of sodium chloride
with the concentration (1 10-2 mole/dm3), which played role of supporting
electrolyte.
CH2 CH CH2 CH
C O C O
Cl-
NH2 n O CH3
CH2 CH2 N+ CH3
CH3 m
Fig. 1. Adsorbed amounts of PAM 8.5_20% ( ) on the Cr2O3 surface and chemical formula
of cationic polyacrylamide.
Fig. 2. Surface charge density ( 0) and zeta potential ( ) of Cr2O3 particles in the absence
and presence of cationic PAM. CPAM=1 ppm.
For all examined systems adsorption of cationic polyacrylamide on the solid

surface increases with the increasing pH (Fig. 1). This is due to the changes in
polymer-surface electrostatic interactions (degree of PAM macromolecules
ionization, sign and surface charge density of the metal oxide). The macromolecules
of cationic PAM contain two types of functional groups. There are: nonionic amide
groups that do not dissociate in aqueous solution and specified amounts of cationic
groups. The used adsorbent is characterized by the pHpzc (pzc - point of zero charge)
equal to 6. Thus, in the pH range lower than 6, the Cr2O3 surface charge is positive,
which is the reason for the electrostatic repulsion between the charged polymer
chains and adsorbent (the smallest polymer adsorption).
The adsorption of cationic polyacrylamide results in a noticeable reduction in
the surface charge density of the solid compared to the system without PAM in the
pH range higher than pHpzc (Fig. 2). A different situation is observed in the case of
zeta potential changes, where the presence of the PAM adsorption layer around the
solid particles causes a significant increase in the value of the electrokinetic
potential (Fig. 2). This is due to the occurrence of positive charges originating from
the functional groups of adsorbed PAM macromolecules in the slipping plane.
These groups are located in the loop and tail structures of polyacrylamide chains
bounded with the surface.
INVESTIGATION OF ADSORPTION OF INORGANIC AND
ORGANIC SUBSTANCES IN MICELLAR, OXIDE AND
ENVIRONMENTAL DISPERSE SYSTEMS
Adam W. MARCZEWSKI*, Magorzata SCZKOWSKA*,**,

Anna DERYO-MARCZEWSKA**, Magdalena BACHNIO**
Stanisaw CHIBOWSKI*, Elbieta GRZDKA*, Wadysaw JANUSZ*,
Andrzej KOMOSA*, Jolanta ORZE*, Magorzata PASZKIEWICZ*,
Jacek PATKOWSKI*, Marek RESZKA*, Ewa SKWAREK*,
Marta SZYMULA*, Teresa URBAN*, Magorzata WINIEWSKA*,
Jerzy JABOSKI*
*DEPT. OF RADIOCHEMISTRY AND COLLOID CHEMISTRY
**DEPT. OF PHYSICOCHEMISTRY OF SOLID SURFACE
Adsorption of organic substances in aqueous solution is a very important

phenomenon for the environment as well for wastewater and tap water treatment .
Of the many factors affecting adsorption equilibria and kinetics, temperature is
relatively rarely investigated. The temperature changes have mostly, but not only
seasonal character. In some cases its influence may be both advantageous and
disadvantageous. In this report effect of temperature on adsorption equilibrium and
kinetics of two selected phenoxy pesticides is shown [1].
Static measurements of 4-chlorophenoxyacetic acid (4-CPA) adsorption on
experimental RIB carbon (Norit) from water solutions at 298 and 318 K were
performed [1]. Data was analyzed by using Generalized Langmuir (GL) isotherm
optimization showed, that data may be best described by using Generalized
Freundlich (GF), a special case of GL equation, with low heterogeneity parameter
m = 0.26 and 0.21, correspondingly. It confirmed high energetic heterogeneity
typical for microporous activated carbons. Moreover, decrease of adsorption
magnitude (equilibrium constant K decreased approx. 4x upon temperature
increase) confirmed negative value of free enthalpy of adsorption (Fig. 1).
4 6
ln(Kco) = 6519/T - 16.37

ln(Kco)
3
a [mmol/l]
2
4-CPA/RIB (25C)
GF (25C) 4
1
4-CPA/RIB (45C) Van't Hoff plot
GF (45C) ln(KCo) 4-CPA/ RIB
4-CPA / RIB
0 3
0 0.5 1 1.5 2 0.0031 0.0032 0.0033 0.0034
c [mmol/l] 1/T [K-1]
Fig. 1. Equilibrium isotherms and Vant Hoff plot for 4-CPA/RIB [1].
Kinetic measurements were performed for adsorption of 4-CPA and 3-bromo-
phenoxypropionic acid (3-BrPP) on RIB carbon over 278 - 328 K temperature
range [1]. For both systems increase of adsorption rate with temperature was
observed, which may be easily attributed to the increase of diffusion rates (Fig.2).
1.0
1.0 5C 5C (4-exp fit) 15C m-exp (15C)
c/co 15C 15C (3-exp fit) 25C m-exp (25C)
25C 25C (5-exp fit) c/co0.8 35C (a) m-exp (35C (a))
0.8
35C 35C (4-exp fit) 35C (b) m-exp (35C (b))
45C 45C (4-exp fit) 55C m-exp (55C)
0.6 55C 55C (4-exp fit) 0.6
0.4 0.4
3-BrPP /RIB
0.2 0.2
4-CPA / RIB
0.0 0.0
0 20 40 60 80 100 0 20 40 60
t1/2 [min1/2] t1/2 [min1/2]
Fig. 1. Adsorption kinetics for 4-CPA and 3-BrPP on RIB carbon from aqueous solution.
Solid lines are m-exp optimized kinetics [1].
However, analysis of data by using Bangham plot and intraparticle diffusion

model (IDM) [2] showed, that the simple IDM is insufficient as it could not
reproduce the initial linear dependence of adsorption on time. Thus mixed-order
equation MOE [3] (semi-empirical, mathematically identical to Langmuir kinetic
equation IKL [4], unifies first and second order kinetic equation) , fractal like MOE
(f-MOE, includes solid fractality effects) [5], McKays pore diffusion model (PDM)
[6] and empirical multi-exponential (m-exp) equation [1,3-5] were used they
allow for the initial adsorption ~ time linearity. All those equations fitted data better
than IDM, however, the best fit overall was always obtained for m-exp (with 3 to 5
exponent terms) [1].
For analysis of temperature dependences of adsorption kinetics Arrhenius and
Eyring plots were used, which require the values of rate constants that may be
obtained by data optimization. However, such constants depend on the model or
equation and as such are not unequivocal. Thus we decided to use adsorption half-
time t1/2 instead [1]. This quantity may be determined experimentally, may also be
easily calculated from optimized equation parameter (e.g. for PSOE it is reciprocal
to the rate coefficient). We found that the activation energies determined by using
log t1/2 vs. 1/T are very close to the average of the Arrhenius and Eyring plots [1].
References:
[1] A.W. Marczewski, M. Sczkowska, A. Deryo-Marczewska, M. Bachnio,
Adsorption (2016) in press.
[2] J. Crank, Mathematics of diffusion, Oxford University Press, London 1954.
[3] A.W. Marczewski, Appl. Surf. Sci., 256 (2010) 5145.
[4] A.W. Marczewski, Langmuir, 26 (2010) 15229.
[5] A.W. Marczewski, A. Derylo-Marczewska and A. Slota, Adsorption, 19 (2013)
391-406.
[6] G. McKay, M. El Geundi, M.M. Nassar, Proc. Safety Environ. Prot., 74 (1996)
277-288.
SYNTHESIS AND INVESTIGATIONS OF NEW COORDINATION
COMPOUNDS
Agata BARTYZEL, Beata CRISTVO, Wiesawa FERENC, Halina

GUCHOWSKA, Renata YSZCZEK, Liliana MAZUR, Agnieszka
OSTASZ, Dariusz OSYPIUK, Iwona RUSINEK, Zofia RZCZYSKA,
Justyna SIENKIEWICZ-GROMIUK
DEPARTMENT OF GENERAL AND COORDINATION CHEMISTRY
The aim of our investigations was the synthesis and characterization of new
coordination compounds of desired physico-chemical and biological properties.
This purpose was accomplished in several aspects connected with synthesis and
investigations of new ligands (Schiff base: 2,2-{(1,3-propanediyl)bis[nitrile(2-
hydroxyphenyl)methylidene]}diphenol, (benzylthio)acetic acid, N1-acyl-
amidrazones) and preparation of their metal complexes as well as synthesis of
heteronuclear complexes with the Schiff base (N,N-bis(2,3-dihydroxybenzylidene)-
1,3-diaminopropane), metal complexes with different carboxylic acids (4-bromo-
phenoxyacetic acid; 4-oxo-4-{[3-(trifluoromethyl)phenyl]amino}but-2-enoic acid;
benzene-1,3,5-triacetic and 4,4-biphenyloxodiacetic acids). The synthesis and
investigations of trimethoprim and p-xylylene-bis(thioacetic) acid salt were also
conducted. Due to determination of structures and properties of the investigated
compounds, several methods such as: X-ray single crystal and powder diffraction
techniques, TG-DSC, TG-FTIR, FT-IR, 1H and 13C NMR, Raman, UV-VIS, XPS,
DFT, biological and magnetic were applied.
The symmetrical Schiff base 2,2-{(1,3-propanediyl)bis[nitrile(2-
hydroxyphenyl)methylidene]}diphenol in the zwitterionic keto form crystallizes in
the monoclinic system, space group P21/c. Its complexes with Ni(II) and Cu(II) ions
crystallize in monoclinic system, space group P21/n. The metals are coordinated by
a pair of phenolate O and imine N atoms of the Schiff base and in the case of
copper also by O atom from the solvent molecules. They lose solvents over 50C.
Degradation and combustion of complexes are observed above 200C.
(Benzylthio)acetic acid was synthesized from benzyl chloride and thiourea as
substrates. The crystal structure of acid is characterized by four types of
intermolecular interactions: OH O; C H O, C H S and stacking CH phen
interaction which are effective in crystal packing. The obtained material is
thermally stable up to 150C.
Four linear N1-acylamidrazones synthesized in the equimolar reaction of N3-
substituted amidrazones with appropriate acid anhydrides exist in their amide-
hydrazone form with respect to the hydrazone C=N bond. The central amidrazone
moiety has a cis configuration. They form binuclear complexes [Cu2L2]4H2O and
[Cu2(HL)2Cl2]2C2H5OH as well as 3-D coordination polymer [CuL(H2O)]nnH2O.
The complexes are air-stable and they do not disintegrate in DMSO. In cytotoxicity
research, the studied complexes exhibited moderate in vitro cytotoxic effect against
HL-60, MCF-7, HT-29 and CX-1 cancer cell lines.
The new heteronuclear 3d-4f complexes of the formula
[Cu4Ln2(H2L)4(NO3)4(H2O)3](NO3)2nsolv (Ln=Sm, Eu, Tb, Ho and Er; H2L -
dianion of N,N-bis(2,3-dihydroxybenzylidene)-1,3-diaminopropane; nsolv = 9H2O;
3H2OCH3COOHCH3OH; 3.5H2O2MeOH, 7.5H2O; 2MeOH) crystallize in the
triclinic system, space group P-1. The hexanuclear cationic moiety is built up of
two [CuII2LnIII] units linked by a nitrato ion. The Cu(II) and Ln(III) ions are bridged
by two phenoxo O atoms from the Schiff base with Cu...Ln and Cu...Cu separations
ca. 3.5 and 7.0 , respectively. The CuII4LnIII2 (Ln=Tb, Ho, Er) complexes exhibit
weak ferromagnetic interactions between 3d and 4f metal centers.
4-bromophenoxyacetic acid reacts with M(II) ions (M=Co, Ni, Cu and Zn)
forming the complexes ML2nH2O (n=2 for Cu, 3 for Mn, Ni, Zn and 4 for Co). The
carboxylate groups act as a bidentate chelating or bridging ligand. All the
complexes obey the Curie-Weiss law showing the paramagnetic properties in the
ranges of 77303 K and 4300 K. In their molecules, the ferro- or antiferromagnetic
interactions occur. 4-oxo-4-{[3-(trifluoromethyl)phenyl]amino}but-2-enoic acid
forms with Mn(II), Co(II), Ni(II) and Cu(II) ions crystalline complexes ML 2nH2O,
(n=2 for Cu and Co; n=3 for Mn and Ni). The carboxylate groups act as a bidentate
ligand. The Cu(II) complex shows the tetragonal pyramid coordination
environment. In air, at first they dehydrate and next decompose to the oxides. The
intermediate products are oxyfluorides. The magnetic susceptibility of compounds
at 76303K and 1.8300K reveal them to obey the Curie-Weiss law exhibiting the
paramagnetic properties and ferromagnetic interactions.
The crystal structure of trimethoprim and p-xylylene-bis(thioacetic) acid salt
belongs to the triclinic P-1 space group. The asymmetric unit of supramolecular
complex contains protonated trimethoprim cation as well as one and half of
hydrogen bonded p-xylylene-bis(thioacetate) anion. The trimethoprim is protonated
at atom N1 of the pyrimidine moiety, which is evident from the increase in the
internal angle at N1 (C22-N1-C19) from 115.46(5) in neutral trimethoprim to
119.38(3) in the cation. Lanthanide(III) benzene-1,3,5-triacetates LnL (36)H2O,
where Ln=La, Nd, Eu, Tb, Ho, Tm and Lu crystallize in the monoclinic or triclinic
systems. They form stable anhydrous complexes after the dehydration. The values
of dehydration energy increase with the increasing atomic number of Ln(III) from
28 to 35 kJ/mol. The XRDP investigations of the compounds in situ at 30C and at
250C indicate that the crystalline frameworks are maintained despite removal of
water. The complexes undergo decomposition over 350C to suitable oxides. The
carboxylate groups chelate Ln ions as can be deduced from their XPS electronic
spectra. The new ligand 4,4-biphenyloxodiacetic acid (H2bpoda) form with Li(I),
Na(I) and K(I) ions coordination polymers of the formulae: Li2bpoda 4H2O,
Na2bpoda 2H2O, Na2bpoda 4H2O and K2bpoda. Chemical nature of the metal ions
strongly influences on the coordination numbers and coordination modes of bpoda
ligand. They form 2-D or 3-D coordination polymers. Coordination through both
carboxylate groups occurs and only for the Li complex, side chain oxygen does not
take part in metal bonding.
SYNTHESIS AND PROPERTIES OF POLYMERS
Barbara GAWDZIK, Andrzej BARTNICKI, Marta GROCHOWICZ, Jerzy

KSIOPOLSKI, Anna KULTYS, Magorzata MACIEJEWSKA, Joanna
OSYPIUK-TOMASIK, Beata PODKOCIELNA, Maciej PODGRSKI,
Andrzej PUSZKA, Magdalena ROGULSKA, ukasz SZAJNECKI,
Magdalena SOBIESIAK, Marta WORZAKOWSKA
DEPARTMENT OF POLYMER CHEMISTRY
Naphthalene derivatives, due to their unique luminescent properties, have been

investigated and used as fluorophores of luminescent materials, polymer light-
emitting diodes, photo-voltaic and optical devices etc. Polynaphthalenes with
different linkages in 1,4-, 1,5-, 2,6- and 2,7- positions have been used as conducting
polymers [1].
The focus of the present study is on new compounds derived from 2,7-(2-hydroxy-
3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) [2]. The copolymers were
synthesized using different comonomers: methyl methacrylate (MMA), 2-
hydroxyethyl methacrylate (HEMA), butyl acrylate (BA), divinylbenzene (DVB),
styrene (ST) and N-vinyl-2-pyrrolidone (NVP) [3]. These comonomers were chosen
because of their different chemical character, which depended on the presence of
aromatic or aliphatic substituents in their structure. The choice of the comonomers
was also dictated by the fact that they are active solvents, which makes
polymerization easier. Moreover, their spatial distribution in the structure enables
modification of the luminescent properties of polymers and, most importantly,
prevents interaction between polymer chains that would otherwise result in
agglomeration, which, in turn, would worsen luminescence.
To summarize, we present new polymeric naphthalene derivatives, which in future
have a chance to find application in the preparation of different luminophores. The
chemical structure of 2,7-NAF.DM was confirmed by NMR, GC-MS and elemental
analysis. Their luminescent properties were studied in terms of quantum efficiency
( abs), which was shown to change in the range of 5090% depending on the type
of comonomer. It was found that the green-emitting species in these polymers can
be excited directly by low-energy (400520 nm) photoirradiation. These materials
can be applied in the liquid or solid states in the form of powders, films or
monoliths [4].
The seed polymerization performed with 4-vinylpyridine (4VP) and

trimethylpropane trimethacrylate (TRIM) monomers led to monodisperse
microspheres with porous structure which is permanent in both dry and swollen
state [5]. CHN elemental analysis has confirmed that 4VP monomer was
incorporated into copolymer networks. Additionally, ATR-FTIR analysis has also
shown that 4VP units are present in prepared copolymers. The in-plane vibrations
of 4VP aromatic ring (C=N and C=C vibrations) occur at 1599 cm-1 and 1558 cm-1
in the FTIR spectra, and bands intensities increase with the increasing amount of
4VP in the copolymeric networks. Despite of the protocol of seed polymerization
has been extensively studied earlier, to obtain the porous microspheres of 4VP and
TRIM monomers with uniform sizes it should be modified. In the course of our
research it was found that the molecular weight of used polystyrene seed particles
had a crucial impact on the size and shape of obtained final polymeric particles.
Applying PS microspheres with Mw exceeded 2300 Da, 4VP-TRIM particles
initially had a spherical shape, but with the increasing polymerization degree the
spheres collapsed and finally particles in the form of discs were obtained. In the
presented research the PS microspheres with Mw equal to 19500 Da were chosen to
prepare spherical 4VP-TRIM copolymers. Simultaneously, it was also known that
PS molecular weight can play an important role in the forming of porous structure
of final particles produced during seed polymerization. The use of low molecular
weight PS could lead to copolymers with low surface area. The average sizes and
the coefficient of variation (CV) for all types of particles were characterized. It was
found that the particles average diameters are dependent on the comonomer
composition. With the increasing amount of the crosslinking agent in the
comonomer mixture the particles average diameter decreases. This observation is
understandable since when a larger amount of crosslinking monomer is used, the
more crosslinked and rigid network is formed.
References:
[1] T. Mori, M. Kijima, European Polymer Journal, 45 (2009) 1149.
[2] B. Podkocielna, B. Gawdzik, Applied Surface Science 256 (2010) 2462.
[3] B. Podkocielna, A. Lipke, B. Gawdzik , M. Majdan, Polymers for Advanced
Technologies, 26 (2015) 176.
[4] M. Maciejewska, Polymers for Advanced Technologies, 26 (2015) 85.
[5] M. Grochowicz, . Szajnecki, B. Gawdzik, Adsorption Science and Technology,
33 (2015) 609.
CHARACTERISTICS OF THE MESOSTRUCTURED CELLULAR
SILICA FOAMS SYNTHESIZED WITH THE USE OF NaY ZEOLITE
Stanisaw PIKUS, Magorzata SKIBISKA, Aleksander PADEWSKI

DEPARTMENT OF CRYSTALLOGRAPHY
The aim of the study was the synthesis of materials with varying amounts of
micro and mesopores. Such materials may show several interesting properties
useful in many application areas. . For the synthesis of these materials as a source of
micro-pore zeolite is often used. So far obtained similar materials with a zeolite by
a two-step synthesis (mixing, coating of mesoporous materials for zeolite) were
realized [1I. An example of this systems is the zeolite/ mesopores materials
preparated by Zhang at al [2]. In the present study hybrid silica materials were
synthesized by direct synthesis method of MCF (Mesostructured Cellular Foam)
and we used a single-stage synthesis according to the scheme set out in Figure 1
Hydrolysis and
condensation TEOS
Fig. 1. The synthesis of MCF with using of zeolite NaY .

.
Textural properties of zeolite Y/MCF materials were presented in Table 1. For
these materials observed typical IV adsorption/ desorption isotherms with H1
hysteresis loop in the p/po range of 0.5~ 1.0. The H1 hysteresis is typical for
materials with mesopores in which is occurred the capillary condensation and have
large pore with narrow size distributions.. As a result we were received materials
with different ratio of micro/mesopores. We get materials with better acidity and
hydrothermal stability than mesoporous materials and larger mass transfer than
zeolite [3].The BET surface area is changing with increasing the amount of zeolite
Y for samples between 672 to 320 m2/g. The same result we observed in the case of
micropores (90-250 m2/g). By incerasing TMB/P123 from 0.5 to 1.0 the surface
area incerases from 320 to 672 m2/g. Similar trends are observed for the
micropores. The addition of TMB caused growth the pore volume.
Table 1 Textural properties of investigated composites.
Zeolit Pore Volume Pore Size distribution

TMB SBET Smic
NaY SAMPLE Vt Vmic (t-plot) Dh Dmo (NLDFT)
(cm3) (m2/g) (m2/g)
(g) (cm3/g) (cm3/g) (nm) (nm)
0.5 KJO1 567 201 1.48 0.098 10.4 1.4
1.0 1.16 KJO2 468 171 1.03 0.087 8.8 1.5
1.5 KJO3 320 90 0.9 0.046 11.3 1.6
0.5 KJO4 632 207 1.55 0.099 9.8 1.4
1.0 2.31 KJO5 671 250 1.57 0.121 9.3 1.6
1.5 KJO6 672 125 1.66 0.065 9.9 1.7
The materials synthesized in the same manner but without the addition of
zeolite have much less micropores, usually they specific area are about 60-80 m2/g.
This results of prepared materials can be the basis for the development of
production technology of MCF mesoporous foams with very high concentration of
micropores next to many existing mesopores.
Studies by XRD showed that the obtained materials are entirely amorphous,
this means that the zeolite has been decomposed during the synthesis. Despite this
the evident effect of the addition of the zeolite on the amount of micropores in the
resulting materials MCF are visible; the number of micropores increases several
times
The presence of a large number of micropores may increase the adsorptive
capacity of the materials, especially in sorption of metal cations. An additional
advantage of this method is the ability to control the process of synthesis and
physicochemical properties of materials by selection of appropriate parameters of
the synthesis and the possibility of chemical modification.
References:
[1] P.Van Der Voort, P. I. Ravikovitch, K. P. De Jong, A. V. Neimark, A. H.
Janssen, M. Benjelloun, E. Van Bavel, P. Cool, B. M. Weckhuysen, E. F.
Vansant, Chem. Commun. (2002) 1010-1011.
[2] X.Zhang, F. Zhang, X.Yan, Z. Zhang, F. Sun, Z. Wang, D. Zhao, J.
Porous Mater., 15 (2008) 145-150.
[3] K. R. Kloetstra, H. W. Zandbergen, J.C. Jansen and H. van Bekkum,
Microporous Mater., 6 (1996) 287.
N,N-DISUBSTITUTED THIOUREA DERIVATIVES
Anna E. KOZIO
Anna BIELNICA, Marta STRUGA
WARSAW MEDICAL UNIVERSITY
The thiourea fragment represents an important synthon which is responsible

for numerous biological activities, particulary antimicrobial, antiviral, anticancer,
cytotoxic and anti-inflammatory. Both N-alkyl and N-aryl-thiourea analogues have
displayed anticonvulsant acivity, and nitrogen-containing heterocyclic substituents
cause inhibitory effect for the HIV reverse transcriptase. The other molecular
components of biologically important compounds are 1,2,4-triazole and 2-
aminothiazole. The first is often included into potent antifungal and antibacterial
agents, as well as anti-inflammatory, antioxidant and analgesic agents. The database
of biologically active substances reveals the extensive use of the aminothiazole
moiety in numerous applied drugs (eg. sulfatiazole, cetraxone, aztreonam, riluzole).
Two groups of new N,N-disubstituted thiourea derivatives (Fig. 1) were
synthetized; the molecular structure of group A combines 1,2,4-triazole and
thiourea groups with aryl substituents (R), while the group B contains 1,3-thiazole,
thiourea and aryl. The compouds were tested for biological activity, and some of
them show antimicrobial, antiviral, cytotoxic and/or pharmaco-logical activity [1,2].
Of special importance is their tuberculostatic activity.
H H H H
N N N N
N R S
R
N
S N S
N
A B
Fig. 1. Formulae of disubstituted thiourea derivatives.
Considering the fact that such activity results from non-covalent inter-
molecular interactions, the association patterns in solid were analyzed.
The X-ray crystallography was applied to determine molecular and crystal
structure. The results indicated that a type of thiourea conformers observed in the
crystal structure depends on the combination of the substituents (Fig. 2). Further,
the orientation of the N-H and C=S bonds influences motifs formed by hydrogen
bonds, especially those between the thiourea units, C=S...H-N.
Fig. 2. Conformers of 1-benzyl-3-(4H-1,2,4-triazol-4-yl)thiourea (A1) and 1-benzyl-3-(1,3-
thiazol-2-yl)thiourea molecules (B1).
The presence of 1,3-thiazole group causes rigid trans, cis conformation of the
thiourea fragment for all molecules B. These conformers are stabilized by the
intramolecular N-H...N hydrogen bond. The conformation of molecules A is not
restricted and resulting pattern of non-bonded contacts is variable; the hydrogen
bonds are formed between two thiourea groups or thiourea..triazole (Fig. 3). While
main association motif for the molecules B is thiourea...thiourea dimer.
Fig. 3. Catemeric pattern of molecules A1 and molecular dimer of B1.
References:
[1] A. Bielenica, E. Kdzierska, S. Fidecka, H. Mauszyska, B. Mirosaw, A.E.
Kozio, J. Stefaska, S. Madeddu, G. Giliberti, G. Sanna, M. Struga Synthesis,
antimicrobial and pharmacological evaluation of thiourea drivatives of 4H-1,2,4-
triazole Letters in Drug Design & Discovery, 12, (2015) 263 276.
[2] J. Stefaska, G. Nowicka, M. Struga, D. Szulczyk, A.E. Kozio, E.
Augustynowicz-Kope, A. Napirkowska, A. Bielenica, W. Filipowski, A.
Filipowska, A. Drzewiecka, G. Giliberti, S. Madeddu, S. Boi, P. La Colla, G.
Sanna, Animicrobial and anti-biofilm activity of thiourea derivatives
incorporating a 2-amino-1,3-thiazole scaffold, Chemical and Pharmaceutical
Bulletin, 63, (2015) 225 236.
STUDIES ON FACTORS AFFECTING
THE PROCESS OF CHEMICAL EDUCATION AND ITS RESULTS
Ryszard M. JANIUK
DEPARTMENT OF CHEMICAL EDUCATION
Didactic of chemistry, similarly to didactics other natural science subjects,

have been exploring the factors which affect the process and effects of education in
this subject. The didactics of particular science subjects started to emerge as
scientific disciplines several decades ago, with the establishment of pertinent
scientific journals and organisations. Nowadays, in several developed countries,
such as the USA, the UK, Germany, or France, the didactics of science subjects
have developed greatly within their general disciplines.
As far as the Polish context is concerned, what stimulated the development of
these didactics was the fact that in the 1970s units specialising in educating teachers
were established in most institutions of higher education. At the time, several
initiatives supporting the development of chemistry education were launched, and
in 1989, thanks to the change in the political system, it became possible to increase
international collaboration. However, in the past decade or so, the state of education
in chemistry and other natural science subjects has deteriorated [1]. This is due to
formal difficulties which make it impossible for specialists in natural science
education to develop their expertise and a reluctance to cooperate on the part of the
persons working in the education system [2].
As any other aspect of modern society, education needs to undergo reforms at
times. The success of any reform in education is to a great extent dependent upon
whether or not teachers accept its goals, feel that the changes that are being
proposed are necessary, as well as actively support and implement the reform.
The reform of natural science education implemented in September 2012 in
Polish upper-secondary schools completely changed the way natural science
subjects are taught. The manner in which the reform was implemented was
criticised by several stakeholders, and the opinions expressed by teachers once the
reform was introduced were unfavourable as well. In order to verify these critical
views and determine to what extent teachers of natural science subjects in Polish
upper-secondary schools identified with the reform two years after it was
introduced, a study involving 191 teachers who mainly taught chemistry was
conducted.
The surveys conducted as part of the study [3] showed that most of the
teachers were familiar with the aims of the reform but did not accept them. It was
difficult for the teachers to name the benefits of the reform, whereas they were able
to mention several problems it had caused. The respondents said they had not
changed the way they worked in line with the aims of the reform and declared they
had a negative attitude to other future reforms. According to the respondents, other
teachers held similar views regarding the reform. This would mean that Polish
natural science teachers do not feel accountable for the reform and do not identify
with it; on the contrary, they have distanced themselves from it. This situation raises
serious concerns about the effects the reform will have in the short and long term.
References:
[1] R. M. Janiuk et al., Raport o stanie dydaktyk przedmiotw przyrodniczych in:
Spoeczne znaczenie wiedzy przyrodniczej, 2002, pp.169 - 182
[2] R. M. Janiuk Krtka historia dydaktyki chemii w Polsce. in: Streszczenia. 58.
Zjazdu PTChem. Gdask 2015, p. 422
[3] R. M. Janiuk. Identyfikowanie si nauczycieli szk ponadgimnazjalnych z
reform edukacji przyrodniczej. in: Z chemi ku przyszoci, Wydawnictwo
UMCS, Lublin 2015, pp.55-72.
HIGH BIREFRINGENT MICROSTRUCTURED SIDE HOLE
OPTICAL FIBER WITH SQUEEZED LATTICE
Krzysztof POTURAJ, Grzegorz WJCIK, Aleksander WALEWSKI,

Lidia CZYEWSKA, Janusz PDZISZ, Jarosaw KOPE, Wiesaw
PODKOCIELNY, Magorzata GIL, Andrzej GORGOL, Pawe MERGO
LABORATORY OF OPTICAL FIBERS TECHNOLOGY
Sensing characteristics of MOFs depend on internal microstructure [1], which

means that the development of new microstructured fibers with predefined features
is limited mostly by technological processes. The fiber internal microstructure is
usually arranged in a hexagonal lattice with air holes of a cylindrical shape and
different size. In 2001 Steel and Osgood [2] presented an extensive numerical study
of the fiber with elliptical holes obtained by one-directional squeezing of a typical
hexagonal lattice. It has been shown in this work that increasing the area of
elliptical holes elevates the phase modal birefringence and its dispersion in the long
wavelength range.
The first side-hole fiber with elliptical holes in the cladding was made of
PMMA [3]. The microstructure in this fiber was squeezed by two large air holes
placed symmetrically on both sides of the microstructured region, similarly to
conventional side-hole fiber reported for the first time in [4]. The first silica side-
hole fiber with a squeezed lattice presented in [5] showed a very high group
birefringence |G| = 5.5 103 at 1.55 m.
The mSHF reported in this work was made using the modified stack and draw
method. In the first step, the microstructured part of the preform was stacked of
silica rods and cylinders and drawn using a standard approach. In the next step, the
cladding of the preform was milled on both sides of the microstructure.
Subsequently, the preform was overcladded with a new silica glass cylinder to
obtain two large side-holes. During a drawing processes, the pressure applied to
large holes was greater than in microholes, which resulted in squeezing the central
microstructured region in the y-direction, figure 1. The geometrical parameters of
the fabricated fiber measured along the x- and y-axes are gathered in Table 1. The
dimensions and shapes of the cladding holes vary over the fiber cross-section.
Therefore, in table 1, we present the values of the ellipse axes in x- and y-directions
averaged for the first circle of holes.
Measurements of the phase modal birefringence were conducted using the
well-known lateral-force method. The other fiber parameters, like the group
birefringence and the sensitivity to pressure and temperature, were measured in the
setup based on the Sagnac interferometer. The measuring loop consisted of the
investigated fiber of the length L = 360 mm, which was spliced with two arms of a
single-mode fiber coupler of a type X with the coupling ratio of 50:50. The splices
were protected by the 30 mm long stainless steel needles filled with epoxy. A part
of the Sagnac interferometer containing the mSHF was placed inside a
pressure/temperature chamber. We formed a small loop on a single mode fiber and
tuned the polarization state in the Sagnac interferometer by tilting it. The 3rd arm of
the Xcoupler was supplied with a broadband light source (supercontinuum), while
the 4th arm was connected to the optical spectrum analyzer to register the output
signal.
Fig. 1. Scheme of the mSHF with indicated geometrical parameters (a), SEM images of the
microstructured region (b) and the entire fiber cross-section (c).
Tab. 1. Geometrical parameters of the microstructured side-hole fiber averaged for
the first circle of holes.
An elliptical shape of the cladding holes results in high phase and group modal
birefringence, equal respectively to B = 3.33 104 and
4
G = 6.62 10 at 1.55 m. Thanks to a large diameter of the side-holes
located in the solid part of the cladding, the fiber polarimetric sensitivity to
hydrostatic pressure was increased two times compared to earlier reports and equals
Kp = 25.6 rad MPa1 m1 at 1.55 m. Moreover, the fiber has a very low
polarimetric sensitivity to temperature KT = 9.18 103 rad K1 m1 at 1.55
m, thus allowing for hydrostatic pressure measurements with little cross-sensitivity
to temperature.
References:
[1] C.M. Jewart et al, Opt. Express, 18 (2010) 2565764.
[2] M.J. Steel and R. M. Jr., Osgood J. Lightwave Technol., 19 (2001) 495503.
[3] M. A. van Eijkelenborg et al., Opt. Fiber Technol., 9 (2003) 199209.
[4] H.M. Xie et al., Ulrich R., Opt. Lett., 11 (1986) 3335.
[5] F. Beltrn-Meja, et al., Opt. Lett. 35 (2010) 5446.
SORPTION OF DICLOFENAC AND NAPROXEN ONTO MWCNT IN
MODEL WASTEWATER TREATED BY H2O2 AND/OR UV
Boena CZECH, Patryk OLESZCZUK

DEPARTMENT OF ENVIRONMENTAL CHEMISTRY
The application of oxidation processes such as UV and/or H2O2 will change the
physicochemical properties of carbon nanotubes (CNT). It may affect the sorption
affinity of CNT to different contaminants and then affect their fate in the
environment. In the present study the adsorption of two very common used
pharmaceuticals (diclofenac and naproxen) onto CNT treated by UV, H2O2 or
UV/H2O2 was investigated. The adsorption isotherms were obtained using a batch
equilibration technique at 23 1 C using 40 - mL Teon centrifuge tubes filled
with background solution. The suspension pH was maintained at 7.0 0.2. CNT (2
mg) were placed in the background solution for 24 h and then, the pharmaceutical
solutions in methanol were added. Initial DCF and NPX concentrations were in the
range of 1.2525 mgL-1. The volume percentage of methanol was kept below 0.05
% to minimize cosolvent effects. Upon equilibration (5 d), the solutions were
centrifuged (3500 rpm, 30 min) and ltrated (0.45 m) to separate the CNT from
the supernatant.Four different adsorption models (Freundlich, Langmuir, Temkin,
Dubinin-Radushkevich) were tested. The best fitting of experimental data was
observed for Freundlich or Langmuir model. The significant relationships between
Q calculated from Langmuir model with O% and dispersity were observed.
Fig. 1. Sorption isotherms of diclofenac (a) and naproxen (b) on pristine and treated by UV
and/or H2O2 multiwalled carbon nanotubes.
Kinetics of diclofenac and naproxen followed mainly pseudo-second order

indicating for chemisorption limiting step of adsorption. The data showed that the
mechanism of sorption was physical or chemical depending on the type of CNT
modification.
The increasing production and thus consumption of CNT can result in their
greater release into the environment. According to predictions, WWT plants will be
CNT receiver. From there, they will be further transferred into the environment
together with activated sludge or treated water. Both during the processes of water
and WWT themselves and in the environment, CNT can undergo transformations.
Not only will their surface properties change, such as porosity or total surface area,
but also their surface charge and aggregation ability which determine the fate of
CNT in the environment. As a result of increased aggregation, CNT will not be
transported, but their accumulation in activated sludge may produce as-yet-
unknown threats. In turn, decreased aggregation of CNT will result in their easier
mobility and transport in water for large distances. Changed properties of the
structure, dispersion and aggregation or also the ability to adsorb or desorb other
contaminants will affect biotransformation.
THE CONCENTRATION AND CHANGES OF FREELY
DISSOLVED POLYCYCLIC AROMATIC HYDROCARBONS IN
BIOCHAR-AMENDED SOIL
Patryk OLESZCZUK, Marcin KUMIERZ

DEPARTMENT OF ENVIRONMENTAL CHEMISTRY
The use of biochar in agriculture is becoming more and more common [1].
This is due to many benefits that these materials bring. However, there is wide
research that demonstrates that in their composition biochars may contain numerous
organic and inorganic contaminants [2-5]. Polycyclic aromatic hydrocarbons
(PAHs) are an example of this type of contaminants that are commonly found in
biochars [5]. These compounds are particularly dangerous due to their mutagenic,
cancerogenic and toxic nature. The presence of polycyclic aromatic hydrocarbons
(PAHs) in biochars puts into doubt their environmental use. The aim of this study
was to determine the freely dissolved (Cfree) PAHs content in soil amended with
biochar in a long-term field experiment. This experiment was carried out for 851
days. Biochar was added to the soil at a rate of 30 and 45 t/ha. The addition of
biochar to the soil resulted in a decrease in 13 Cfree PAHs by 25 and 22%, in the
soil with the addition of biochar at the rate of 30 and 45 t/ha, respectively (Fig. 1).
As far as individual PAHs are concerned, in most cases a reduction in Cfree was also
observed (from 3.6 to 66%, depending on the biochar rate).
12
0.08
0 t/ha
30 t/ha
10 45 t/ha
0.06
Cfree content [ng/L]
Cfree content [ng/L]
8 0.04
6 0.02
0.00
4 5-ring 6-ring
0
13PAHs 3-ring 4-ring 5-ring 6-ring
Fig. 1. The concentration of 13 Cfree PAHs in control soil and biochar-amended soil at the
beginning of the experiment. Error bars represent standard deviation error (SD, n = 3
extractions).
During the first 105 days of the experiment, the content of 13 Cfree in the
biochar-amended soil significantly decreased by 26% (30 t/ha) and 36% (45 t/ha).
After this period of time until the end of the experiment, no significant changes in
Cfree were observed, regardless of the biochar rate. However, the behavior of
individual PAH groups differed depending on the number of rings and experimental
treatment. Ultimately, after 851 days of the experiment the content of 13 C free
PAHs was lower by 29% (30 t/ha) and 35% (45 t/ha) compared to the beginning of
the study as well as lower by 40% (30 t/ha) and 42% (45 t/ha) than in the control
soil. The log KTOC coefficients calculated for the soil-amended soils were higher
immediately after adding biochar and subsequently they gradually decreased,
indicating the reduced strength of the interaction between biochar and the studied
PAHs.
Due to the growing interest in the use of biochars, efforts should make to
obtain the best possible characteristics of these materials. While many studies have
demonstrated their positive environmental effect, there is still scarce information on
risks associated with the presence of organic and inorganic contaminants in biochar.
The present study shows that biochar with a PAH content that meets the proposed
standards does not cause a significant increase in Cfree PAHs (thus those that are
responsible for the toxic effect and which can bioaccumulate). What is more, it
causes a significant decrease in native Cfree PAHs. Therefore, in spite of the
increase in the total PAH content after biochar amendment, as observed in the
previous study, Cfree PAHs do not pose a risk.
Nevertheless, the issue concerning the persistence of binding of PAHs by
carbon and the possible release of these compounds from biochar remains
unexplained. Over the study period, no significant increase in Cfree PAHs was
observed, but the decreasing log KTOC coefficients and the increasing percentage of
Cfree PAHs in the total PAH content may suggest the weakening of the binding of
PAHs by the biochar. But, as suggested previously, it is difficult to determine
whether the observed changes are associated with the desorption of native PAHs
occurring in soils or PAHs introduced with the biochar.
References:
[1] A.D. Igalavithana, Y.S. Ok, A.R.A Usman, M.I. Al-Wabel, P. Oleszczuk, S.S.
Lee, The Effects of Biochar Amendment on Soil Fertility. Agricultural and
Environmental Applications of Biochar: Advances and Barriers, Edition: SSSA
Special Publication 63, Publisher: Soil Science Society of America, Inc (2015).
[2] A. Freddo, C. Cai, B.J. Reid, Environ. Pollut. 171 (2012) 1824.
[3] S.E. Hale, J. Lehmann, D. Rutherford, A.R. Zimmerman, H.P.H. Arp, G.
Cornelissen, Environ. Sci. Technol., 46 (2012) 28302838.
[4] P. Oleszczuk, I. Joko, M. Kumierz, J. Hazard. Mater., 260 (2013) 375382.
[5] A. Zieliska, P. Oleszczuk, Biomass Bioenergy, 75 (2015) 235244.
DIRECT CONVERSION OF TERTIARY PHOSPHINE OXIDES TO
PHOSPHINE-BORANES USING BH3 IN THE PRESENCE OF A
LEWIS ACID
Sylwia SOWA, Anna FLIS, K. Micha PIETRUSIEWICZ

DEPARTMENT OF ORGANIC CHEMISTRY
Several methodologies have been developed for synthesis of phosphines

through the reduction of P=O bond.[1] However, high sensibilty of free phosphines
towards oxidation and water make them most often difficult to handle during
isolation steps. A good alternative consists of a direct transformation of P=O bond
in a more convenient P-BH3 functionality which is considered as a practical
phosphine equivalent.[2] Such transformations involving BH3 as reducing agent
have some precedents but they are limited in scope.[3] Moreover, such direct P=O
to P-BH3 transformations in acyclic tertiary phosphine oxides were only possible
with the use of NaBH4 as reductant and after some modifications of the starting
phosphine oxides.[4] Therefore, we have become interested in expanding the use of
BH3 in reduction of acyclic tertiary phosphine oxides by adding Lewis acid to the
reaction mixture. Recently, Lewis acids were described a useful additives for P=O
bond reductions using silanes.[5]
We started our investigation by testing different Lewis acids combined with
BH3-THF in reduction of a model cyclic phosphine oxide 1. The results are
presented in Table1.
Table 1
BH3-THF (3 equiv.)
Lewis acid
P P
Ph O toluene, conditions Ph BH3
1 2
Entry Lewis acid (equiv.) Conditions Isolated yield (%)
1 B(OMe)3 (3 equiv.) 60 C, 24 h 12
2 BF3-THF (3 equiv.) 60 C, 24 h 0
3 Yb(SO3CF3)3 (0.1 equiv.) rt, 48 h 22
4 Ti(Oi-Pr)4 (0.15 equiv.) rt, 55 min. 37
5 Ti(Oi-Pr)4 (0.15 equiv.) rt, 4 h 37
6 Ti(Oi-Pr)4 (0.5 equiv.) rt, 55 min. 50
7 Ti(Oi-Pr)4 (3 equiv.) rt, 40 min. 98
It turned out that Ti(Oi-Pr)4 was the most effective of the tested Lewis acids
and secured transformation of 1 to the corresponding phosphine borane 2 in
decidedly shorter reaction times and lower temperature as compared to the reported
reductions of 1 by BH3-THF alone, i.e., 2 days heating at 80 oC.3a Use of Ti(Oi-Pr)4
in substoichiometric amounts did not allow to attain full conversion of 1. Instead, it
was found most practical to use 3 equivalents of reducing agent together with 3
equivalents of Ti(Oi-Pr)4 with which full conversion of 1 to 2 was achieved at room
temperature in 40 minutes. Evaluation of this reducing system in reduction of
acyclic tertiary phosphine oxides is briefly summarized in Table 2.
Table 2
O BH3-THF (3 equiv.) BH3

Ti(Oi-Pr)4
P R''
P R''
R' toluene, conditions
R'
3 4
R R Lewis acid (equiv.) Conditions Yield (%)

(NMR/Isolated)
Ph Ph Ti(Oi-Pr)4 (3 equiv.) 80 C, 24 h 100/91
Me Me Ti(Oi-Pr)4 (1 equiv.) 60 C, 20 h 59/44
i-Pr i-Pr Ti(Oi-Pr)4 (3 equiv.) 80 C, 48 h 100/80
t-Bu CH2OMe Ti(Oi-Pr)4 (3equiv.) 80 C, 48 h 94/56
As can be seen from the data collected in Table 2, acyclic phosphine oxides
were more resistant to reduction under studied conditions. Attempts to lower Lewis
acid input resulted in incomplete conversions even at elevated reaction
temperatures.
References:
[1] (a) F.Hein, K. Issleib, H. Rabold, Z. Anorg. Chem. 287 (1956) 208;
(b) H.Fritzsche, F. Korte Chem. Ber., 97 (1964) 1988; (c) K. Naumann, G. Zon,
K. Mislow, J. Am. Chem. Soc., 91 (1969) 7012.
[2] T. Imamoto, T. Kusumoto, N. Suzuki, K. Sato, J. Am. Chem. Soc., 107 (1985)
5301.
[3] (a) G. Keglevich, M. Fekete, T. Chulunbaatar, A. Dobo, V. Harmat, L. Toke, J
Chem. Soc., Perkin Trans. I, (2001) 4451; (b) M. Stankevic, K. M.
Pietrusiewicz, Synlett, 7 (2003) 1112; (c) M. Kwiatkowska, G. Krasiski, M.
Cypryk, T. Cierpia, P. Kiebasiski, Tetrahedron Asymmetry, 22 (2011) 1581.
[4] K. V. Rajendran, D. G. Gilheany, Chem. Commun., 48 (2012) 817.
[5] (a) T. Coumbe, N. J. Lawrence F. Muhammad, Tetrahedron Lett., 35 (1994)
625; (b) M. Berthod, A.Favre-Reguillon, J. Mohamad, G. Mignani, G.
Docherty, M. Lamaire, Synlett 10 (2007) 1545; (c) Y. Li, L.-Q. Lu, S. Das, S.
Pisiewicz, K. Junge, M. Beller, J. Am. Chem. Soc., 134 (2012) 18325; (d) Y. Li,
S. Das, S. Zhou, K. Junge, M. Beller, J. Am. Chem. Soc., 134 (2012) 9727.
STRUCTURE AND PHASE TRANSITIONS OF DIBLOCK
COPOLYMERS ADSORBED ON SOLID SUBSTRATES
Edyta SYK, Wojciech RYSKO, Pawe BRYK

DEPARTMENT FOR THE MODELLING OF
PHYSICO-CHEMICAL PROCESSES
We use grand canonical Monte Carlo simulation in conjunction with multiple

histogram reweighting, finite size scaling and hyperparallel tempering to investigate
the structure and phase behaviour of monolayers of diblock copolymers. While the
order-disorder transition (ODT) in such systems is already well understood, the
complete phase diagrams of chain molecules (including the gas phase) were not
determined. The model used in our study consists of chain molecules arranged on
the square lattice and we consider both fully flexible and rod-coil polymer models.
The A subunit can be flexible or rigid, while B subunit is always flexible. The
segments interact via the short range nearest-neighbour attractive interactions with
the energy parameters u AA , u BB and u AB . The phase behaviour is determined as a
function of the chain length M and for few selected values of the interaction
parameters. In order to restrict somewhat large parameter space we consider only
the chains with equal number of segments in each of the subunits, M A M B .
In [1] we have studied the case where u AA u BB 1 , and u AB 0 . In such
case the interaction energy between the unlike segments is weakened, relative to the
interaction energies between the segments of the same type. This gives rise to a
microphase separation and formation of the ordered polymer structures. For short
chains we have found that the ordered, lamellar phase consists of the fully stretched
chains (the so-called strong segregation regime). The order-disorder phase
transition is strongly first-order. The phase diagram consists of a binodal with a
critical point and a triple point. The phase behaviour changes with an increase of the
chain length. For long enough chains the entropy loss associated with stretching the
chains is too big and cannot be overcome by the energy gain associated with the
formation of the ordered phase. Consequently, while the chains still form the
lamellar phase, the chains are not fully stretched anymore (the so-called weak
segregation regime). The order-disorder transition becomes second order and the
corresponding phase diagram comprises of a gas-disordered liquid binodal with a
critical point, and a -line terminated by a critical end-point. We have also
discovered non-monotonous behaviour of the critical density and critical chemical
potential of the gas-disordered liquid versus the chain length. When one subunit
becomes completely stiff, then the weak-segregation regime ordered phase
comprises of the mutually interdigitating rigid parts (the so-called hockey-puckey
phase). The phase diagram in this case also consists of the -line, which in this
case joins the critical point of the gas-disordered liquid phase transition in a
tricritical point.
In [2] we have studied the case where u AB 1 and with either u AA 1 and
u BB 0 , or u AA 0 and u BB 1 . In this case the interaction energy between the
unlike segments is enhanced with respect to the energy between some of the
segments of the same type. Such a set of the interaction parameters promotes the
number of contacts between the segments of the different kind. This leads to
washing out of the ordered phase for the case of the fully flexible diblock
copolymers, and the corresponding phase diagram comprises only of the gas-
disordered liquid binodal ending in a critical point. However, if one of the subunits
is stiff we observe the formation of a novel ordered phase. Simulational snapshot is
shown in Fig.1(a). It is easy to notice that the flexible part of the chain is also
stretched out (as in the strong segregation regime), the chains are bent in the middle
and arranged in a chessboard-like pattern (hence its name hairpin chessboard
phase). This novel phase has not been observed previously. The phase diagram
consists of a binodal and a triple point with ODT being of the first order. However,
since the triple point increases more rapidly with the chain length than the critical
point, for long enough chains the phase diagram becomes that of a swan-neck
topology (cf. Fig1(b)).
Fig.1. (a) Simulational snapshot showing the hairpin chessboard-like ordered phase of
heteronuclear rod-coil diblock copolymers. (b) The phase diagram for heteronuclear rod-coil
diblock copolymers with M A M B 8 showing the swan-neck topology [2].
Our study demonstrates a deep connection between the structure of a molecule

and its phase behaviour. Depending on the architecture of a molecule and its
interactions the phase diagram can be either first or second order with various forms
of the ordered phases. Particularly important is the existence of the rigid parts of a
molecule. In such an instance one may observe the formation of some novel phases.
References:
[1] E. Syk, W. Rysko, and P. Bryk, J. Chem.Phys., 141 (2014) 044910.
[2] E. Syk, W. Rysko, and P. Bryk, J.Phys.: Condens. Matter, 27 (2015) 415101.
ONE-POT SYNTHESIS OF TWO DIFFERENT HIGHLY
POROUS SILICA MATERIALS
Patrycja KRASUCKA, Wojciech STEFANIAK, Agnieszka KIERYS

Jacek GOWOREK
DEPARTMENT OF ADSORPTION
Silica particles of well-defined morphology and size are of considerable

interest due to many applications in industry and catalytic processes. For such
applications, it is desirable to control the particle size, porosity and surface
properties. Sol-gel synthesis is widely used in preparation of regularly shaped silica
species of controlled morphology. Starting from Stobers et.al. [1] synthesis of
monodisperse silica particles, many new methods for producing high quality silica
spheres have been developed until the present [2].
In the course of the past five years, we have proposed the synthesis of a
polymer-silica composites and silica gels with spherically shaped particles. The
silica component was introduced into polymer by swelling in silica gel precursor
TEOS [4]. The porosity of final material was determined by transformation of silica
precursor into silica gel in solution of adjusted pH.
Here we report a new synthesis method, which combines the swelling of
preformed porous polymer XAD7HP particles in silica precursor (tetraethoxysilane,
TEOS) at presence of cetyltrimethylammonium bromide (CTAB). All materials were
characterized by scanning electron microscopy (SEM), transmission electron
microscopy (TEM) and nitrogen adsorption method.
For illustrative purposes Fig. 1 presents the initial polymer beads, composite
beads and internal structure of silica particles. In Table 1 are given basic porosity
parameters for most representative sample presented in Fig.1.
Specific surface area and total pore volumes for composite as well as silica are
relatively high what proves the good mixing of both components in the composite
and successful transformation of silica precursor into silica gel.
Table 1. Parameters characterizing the porosity of the received samples obtained

from nitrogen adsorption/desorption isotherms at 77K: SBET specific surface are,
Vp total pore volume, Di pore diameter at the peak of PSD [3].
SBET Vp D1 D2
Sample
[m2/g] [cm3/g] [nm] [nm]
XAD7 458 0.56 3.8 9.4
XADSi 141 0.39 3.8
SiO2 736 1.62 2.5 7.8
MCM-41 1073 1.12 4.2
As a conclusion one can state that the method of the preparation of highly
porous silica gel on the basis of polymer template by swelling in tetraethoxysilane
at the presence of surfactant produces highly porous spherical silica particles. The
TEOS molecules migrate entirely the interior of polymer particles. The
transformation of silica precursor in swollen polymer particles at the presence of
surfactant is different, in comparison to the synthesis without surfactant, and is
accompanied by the partition of TEOS between polymer and the bulk solution. As a
result, two separate solid phases are formed.
a) b) c)
d) e) f)
Fig. 1. SEM images of Amberlite XAD7HP and derivative beads (a), polymer-silica
composite XADSi (b), SiO2 after calcination of the composite (c), core of silica bead after
calcination at different magnifications (d, e) and silica shell of the same sample (f) [4].
The first one consists of the polymer-silica composite and the second one is
composed of the fine particles of MCM-41 silica. It should be mentioned that
depending on the composition of reacting solution, especially the amount of TEOS
and CTAB, the microparticles of MCM-41 exhibit differentiated morphology from
a rod like particles to spherical particles. The concentration of surfactant in the
reacting mixture influences strongly the morphology of MCM-41 material. The
amount of CTAB in the bulk solution affects the proportion of small pores to large
mesopores in silica samples derived from the composite after calcination.
References:
[1] W. Stober, A. Fink, J. Colloid Interface Sci., 26 (1968) 62-69.
[2] S. Polarz , B. Smarsly, J. Nanosci. Nanotechnol., 2 (2002) 581-612.
[3] P. Krasucka, W. Stefaniak, A. Kierys, J. Goworek, Micropor. Mesopor. Mater.
221 (2016) 14-22.
BIOPOLYMERS AS A TEMPLATE FOR POLYMER-SILICA
COMPOSITES AND SILICA MATERIALS
Andrzej SIENKIEWICZ, Agnieszka KIERYS, Jacek GOWOREK

Silica gel is a well-known inorganic material that due to its chemical and
physical properties has found many applications in industry and catalysis. Porosity
of SiO2 depends on conditions of synthesis (i.e. pH, micelles, temperature, etc.).
Increasing awareness of environment pollution creates demand for green chemistry
procedures for manufacturing porous silica materials of desired morphology and
pore structure. Recently a new family of silicas prepared by hard templating is
intensively studied. A combination of the specific properties of two chemically
different porous solids provides an unique opportunity to develop the new area of
nano-technology. In our approach instead of employing micellar structures as a
template for silica preparation (as it is in recently popular MCM-41 and SBA-15
materials), natural biopolymer agar was used. Agar along with nonionic surfactant
pluronic F127 has been reported as a hybrid template for ordered mesoporous silica
preparation [1]. Agar consists mainly of agarose and thus can be considered as a
pure biopolymer which dissolves in water above 80oC and forms gel when cooled
down below 40oC.
Silica sample has been prepared in hot (80oC) agar (1% w/w) solution (30 ml)
with addition of ammonia (pH=11). After cooling down the solution of agar to
50oC, tetraethyl orthosilicate (TEOS) has been dropwisely added. The gelation time
of agar and silica is slightly differentiated. The solution has been left in 40 oC for
16h and subsequently stored in room temperature for 72h. The gelated sample has
been dried at 90oC for 6h and calcined at 550oC for 6h. The idea was to perform
hydrolysis and condensation of silica gel in the free spaces between agarose chains
just before they transform to gel. During the synthesis viscosity of 1% agar solution
remains constant [2]. Presented conditions should enable silica species to penetrate
agar solution and in consequence form silica gel structures resembling free spaces
between agarose chains.
Fig. 1. SEM image, nitrogen adsorption (filled points)/desorption (empty points)
isotherm (a) and pore size distribution (b) for material under study.
SEM image indicates that silica condenses in two forms: one in the bulk
creating spherically shaped particles and the second one creating in the vicinity of
agarose chains relatively smooth surfaces. In Fig 1 it can be seen that on the surface
of silica quite regular structures are present (paler parallel lines in the picture).
Their existence can be related to the roughness of agar strands present in the
solution with empty spaces between them. Approximate length of this lines
resembles pores in agar network, reported elsewhere [3]. During the synthesis,
TEOS hydrolysis and condensation occur between the agarose chains.
Low temperature nitrogen adsorption/desorption experiment reveals that
obtained silica gel has relatively large specific surface area SBET=278 m2/g. Pore
volume is equal 0,66 cm3/g with bimodal distribution of pores (80 , 185 ). Shape
of hysteresis of nitrogen adsorption isotherms may be determined by slit-like shape
of the pores. As a conclusion one can state that agar has potential to be efficient
templates for controlled porous silica preparation. Preparation of mesoporous SiO2
materials with usage of biopolymers needs further research.
References:
[1] J. Jiu, K. Kurumada, L. Pei and M. Tanigaki, Colloid Surface B., 38 (2004) 121-
5.
[2] E. Fernandez, D. Lopez, C. Mijangos, M. Duskova-Smrckova, M. Ilavsky and
K. Dusek, J Polym Sci Pol Phys., 46 (2008) 322-8.
[3] J. Rahbani, A. Behzad, N. Khashab and M. Al-Ghoul, Electrophoresis, 34
(2013) 405-8.
STUDIES OF THE PROCESSES OF HERBICIDE REMOVAL FROM
AQUEOUS SOLUTIONS ON MICROPOROUS ACTIVATED
CARBONS
Anna DERYO-MARCZEWSKA, Magdalena BACHNIO,

Adam W. MARCZEWSKI*
DEPARTMENT OF PHYSICOCHEMISTRY OF SOLID SURFACE
*DEPARTMENT OF RADIOCHEMISTRY AND COLLOID
CHEMISTRY
Phenoxyalkanoic acid derivatives, having chlorine-substitutions at the ortho-,

meta-, and para-positions on the aromatic ring are widely used as herbicides and
synthetic plant growth regulators. Due to wide application in agriculture, and high
solubility in water, phenoxyalkanoic acids easily enter surface or ground waters
through natural drainage or infiltration.
In this work the role of porous structure of carbon adsorbent is considered
taking into account adsorption equilibrium and kinetics of selected chlorophenoxy
herbicides. The pesticides selected for the studies are: 4-chlorophenoxyacetic acid
(4-CPA) and 2-(4-chlorophenoxy)-2-methylpropionic acid (CFA). Preparation of
adsorbents were as follows: the external granule layers of extruded activated carbon
(type AG from Gryfskand, Poland) were gradually removed by abrasion (33 and
66%wt.) in a spouted bed. Initial granule was denoted as G0, after 33%wt. abrasion
as G33, after 66%wt. abrasion as G66. The porosity of the samples was
characterized by low-temperature nitrogen adsorption. The decrease of adsorption
values observed for the samples obtained by successive removing of external layers
from the carbon granules suggests differentiation of their porosity. The parameters
for G0 (SBET=800 m2/g, Sext=75 m2/g, Vt=0.44 cm3/g, Vmic+mez=0.32 cm3/g), G33
(SBET=770 m2/g, Sext=73 m2/g, Vt=0.40 cm3/g, Vmic+mez=0.29 cm3/g), G66 (SBET=740
m2/g, Sext=60 m2/g, Vt=0.37 cm3/g, Vmic+mez=0.28 cm3/g) were obtained. The process
of removing of external carbon layers richer in secondary micropores and
mesopores leads to a decrease of adsorption capacity of granules by increasing the
share of mesopore-poor granule cores. Surface chemistry (surface oxygen content)
was determined by thermogravimetry measurements. It was stated that oxygen
content slightly decreases in order G0>G33>G66.
The adsorption isotherms of pesticides from aqueous solutions were measured
by using a static method. The adsorption isotherms of both herbicides on the
carbons are differentiated; the adsorption values decrease successively from the
carbon G0, G66 to G33. It is well correlated with the changes of pore structure of
adsorbents: values of specific surface areas and pore volumes for these fractions.
Exceptions are 4-CPA (G33) and CFA (G33) systems for which the adsorption
values are the lowest values although the porous structure parameters characterizing
this carbon are better than for the carbon G66. Solubility of 4-CPA and CFA are:
957 mgdm-3 and 582 mgdm-3, and hydrophobicity determined by log P: 1.85 and
2.84, respectively. Regarding these parameters we can conclude that there is no
clear correlation between solubility/hydrophobicity and the values of adsorption for
the studied systems. This is also confirmed by the differentiated values of
adsorption reduced by a solubility parameter of the individual compound, which
clearly demonstrate that solubility/hydrophobicity is not the main factor
determining the adsorption process in the studied systems.
The adsorption kinetics was studied by applying UV-Vis spectrophotometer
with a flow cell. The concentration vs. time and the adsorption vs. time profiles
were calculated from the obtained spectra. Very good correlation between
experimental data and multi-exponential equation was obtained. Good fitting
quality is confirmed by SD(a) values. Comparing the adsorption rate constants,
logk, for 4-CPA and CFA we can find higher values for 4-CPA which indicate
easier accessibility into carbon micropores due to a symmetrical structure and lower
spatial dimension of this adsorbate. Generally, the process of pesticide adsorption
on microporous carbons in the initial stage is proportional to the adsorbate
concentration but further stages of the process proceeds much slower and are
controlled by a rate of diffusion of adsorbate molecules into the internal space of
pore structure of carbon granules.
Table 1. Parameters of Langmuir-Freundlich equation characterizing adsorption

systems.
Carbon Adsorbate am m,n logk SD(a)
4-CPA 2.258 0.522 0.699 0.137
G0
CFA 2.063 0.646 0.695 0.097
4-CPA 1.730 0.722 1.024 0.119
G33
CFA 1.631 0.905 0.713 0.067
4-CPA 1.767 0.684 1.077 0.052
G66
CFA 1.385 1 1.062 0.070
Fig. 1. Comparison of adsorption kinetics for 4-CPA on activated carbons at co-ordinates:

concentration ~ time and concentration ~ square root of time. Lines correspond to the fitted
multi-exponential equation.
SYNTHESIS, MODYFICATIONS AND STUDIES OF PROPERTIES
OF MATERIALS WITH DIFFERENTIATED STRUCTURAL AND
SURFACE CHARACTERISTICS WITH REGARD TO
APPLICATIONS IN SORPTION PROCESSES
Anna DERYO-MARCZEWSKA, Magdalena BACHNIO, Agnieszka

CHRZANOWSKA, Magorzata ZIENKIEWICZ-STRZAKA, Dariusz
STERNIK, Magorzata SCZKOWSKA, Adam W. MARCZEWSKI*
*DEPARTMENT OF RADIOCHEMISTRY AND COLLOID
CHEMISTRY
Dyes belong to a group of toxic pollutants of our environment characterized by

stability to light and oxidizing agents and resistance to biodegradation. These limits
the usefulness of some traditional methods for treatment of dye-containing sewage.
Thus, the problem of their removal from waters and wastewaters is important and
extensively investigated [1]. The adsorption process with usage of carbon materials
is regarded as an effective technique in the treatment of dye containing wastewaters
[2]. Widely applied microporous activated carbons are materials characterized by
high adsorption effectiveness, however, they can not be used in the case of
adsorbates with large molecular sizes. Moreover, the sorption processes in
micropores are slow even for low-molecular substances.
In the present paper the kinetics of dye adsorption is studied for three
mesoporous carbons of divergent porosity synthesized by the method of
impregnation of mesoporous silicas with carbon precursor and by the direct
synthesis [3] and for the microporous activated carbon RIAA (Norit). The kinetic
profiles were measured for adsorption of selected cationic and anionic dyes
(methylene blue, methyl red, crystal violet, methyl orange) from aqueous solutions
[4]. The experimental data were analyzed with regard to find some correlations
among adsorption effectiveness and rate, and structure and surface properties of
adsorbent, and adsorbate characteristics.
In Table 1 the porosity characteristics for the studied carbons are presented.
Table 1. The values of parameters characterizing porous structure of synthesized

carbons calculated from nitrogen adsorption/desorption isotherms
SBET Vt Vmic Sext D
Carbon
[m2/g] [cm3/g] [cm3/g] [m2/g] [nm]
RIAA 1468 0,80 0,31 792 2,18
W34 908 0,75 0,03 841 3,29
W79 679 0,71 0,08 510 4,19
W40 313 0,34 0,06 198 4,32
Analysing the values of parameters presented in Table 1 one can find that the
studied carbons are differentiated with regard to specific surface area, SBET, total
pore, Vt, and micropore, Vmic, volumes, external surface area, Sext, and pore size, D.
From potentiometric titration measurements the surface charge density was
established and the point of zero charge was estimated: for RIAA, W40 and W79
pHpzc is in the range 8.3-9.2, for W34 pHpzc=3.6.
0,05 0,05
0,045 0,045
0,04 BM (W40) BM (W40) c(t) (3-exp) 0,04 BM (RIAA) BM (RIAA) c(t) (3-exp)
c [mmol/l]
CM (W40) CM (W40) c(t) (3-exp) CM (RIAA) CM (RIAA) c(t) (3-exp)
c [mmol/l]
0,035 OM (W40) OM (W40) c(t) (3-exp) 0,035 OM (RIAA) OM (RIAA) c(t) (3-exp)
FK (W40) FK (W40) c(t) (3-exp) FK (RIAA) FK (RIAA) c(t) (3-exp)
0,03 0,03
0,025 0,025
0,02 0,02
0,015 0,015
0,01 0,01
0,005 0,005
0 0
0 2000 4000 6000 8000 10000 12000 0 2000 4000 6000 8000 10000 12000
t [min] t [min]
Fig 1. Comparison of adsorption kinetics for methylene blue (BM), methyl red (CM),
methyl orange (OM), and crystal violet (FK) on mesoporous W40 and microporous RIAA
carbons (lines optimized multi-exponential equation).
Analyzing the effect of porosity on the process of dye adsorption on the

studied carbonaceous materials one can find the important role of pore sizes and
specific surface area. Adsorption was more effective and faster on mesoporous
carbons with higher pore diameters and/or higher surface area. The adsorption rate
increased in the range RIAA, W40, W79, W34. The microporous activated carbon
RIAA was less effective adsorbent towards all dyes as a result of small pore sizes;
part of them was inaccessible for large adsorbate molecules, the diffusion processes
were very slow. The mesoporous carbon W34 occurred to be the best adsorbent;
this may be connected with its largest specific surface area and total pore volume,
and the lowest fraction of micropores in total porosity. Comparing various dyes
adsorption on different carbons one can observe that methylene blue has the
strongest affinity towards all adsorbents; in experimental conditions nondissociated
BM molecules (pKa>12) interacted strongly with hydrophobic carbonaceous
surface; the adsorption processes were faster in comparison to other materials.
References:
[1] R.C. Bansal, M. Goyal, Activated Carbon Adsorption, CRC Press, Boca Raton
2005.
[2] Y. Al Degs, M. Khraisheh, Water Res., 34 (2000) 927.
[3] A. Derylo-Marczewska, A.W. Marczewski, Sz. Winter, and D. Sternik, Appl.
Surf. Sci., 256 (2010) 5164.
[4]. A. Derylo-Marczewska, A.W. Marczewski, I. Skrzypek, S. Pikus, M. Kozak,
Appl. Surf. Sci., 252 (2005) 625.
PREDICTION OF LIPOPHILIC AND BIOLOGICAL
PROPERTIES OF 1,2,3-TRIAZOLES BY HPLC TECHNIQUE
WITH RP-18 STATIONARY PHASE
Magorzata JANICKA, Katarzyna STPNIK,

Irena MALINOWSKA, Marek STUDZISKI
DEPARTMENT OF PLANAR CHROMATOGRAPHY
Chromatographic behaviour of biologically active fused 1,2,4-triazinones were

investigated using HPLC technique on RP-18 stationary phase and different organic
modifiers, i.e., acetonitrile, methanol and dioxane. Retention parameters in pure
water, i.e., log kw values, evaluated by linear extrapolation of experimental retention
relationships as well as o indices were analyzed as lipophilicity descriptors of
compounds and applied to predict their in silico biological descriptors relevant to
optimal pharmacokinetics profile. The following pharmacokinetic descriptors:
fraction unbounded in brain (fu,brain), oral bioavailability (%F), permeability and
intestinal absorption in jejunum (Caco-2), skin permeation (log Kp) and blood/brain
concentration (log BB) were calculated by ACD/Percepta software. Partition
lipophilicity parameters (log P) and solubility indices (expressed as log S values) of
compounds investigated were obtained from an internet software ALOGPS 2.1.
Our investigations showed HPLC approach as a good technique for
investigating the lipophilicity and solubility of 1,2,4-triazinones. Experimental
chromatographic lipophilicity indices (log kw values) derived with the most suitable
linear model for methanolwater mobile phases showed significant correlation with
calculated log P and log S values (Fig. 1).
Fig. 1. log P vs. log kw and log S vs. log kw relationships.

Results of the PCA-based approach showed the similarities of the
chromatographic partitioning parameters and properties relevant to
pharmacokinetics. Furthermore, predictive relationships with high statistical quality
were found between the in silico pharmacokinetic descriptors and the
chromatographic parameters log kw (derived with the linear model for methanol
water and dioxanewater systems). Statistically significant curvilinear relationships
were described between some pharmacokinetic descriptors (fu, brain), %F (Fig. 2) and
Caco-2 permeability predictors) and the extrapolated lipophilicity indices (log kw),
showing optimal values of lipophilicity for optimum bioavailability.
1 2 3
log kw MeOH log kw DX compounds
110 group I
group II
100 group III
90
80
%F
70
60
50
40
30
20
1 2 3 4 5
Fig 2. %F vs. log kw relationships.
On the other hand, statistically significant log Kp and log BB versus log kw
correlations were found to be linear, suggesting that with increasing log kw values
higher brain and skin penetration can be expected. Considering the results obtained
in the studies we can conclude that LC-18 HPLC column should be recommended
for modeling the pharmacokinetic properties of drug candidates, i.e., their intestinal
absorption, their abilities to crossing bloodbrain barrier or their oral
bioavailability.
SPECIAL PURPOSE SUBSIDY TO
CONDUCT RESEARCH AIMED AT
DEVELOPING YOUNG SCIENTISTS AND
DOCTORAL STUDENTS
SPECTROSCOPIC AND BIOCATALYTIC CHARACTERIZATION
OF PORPHYRINS INTERCALATED IN SILICA GEL IN THE
PRESENCE OF SURFACTANTS
Agnieszka LIPKE
The sol-gel process is a chemical synthesis technique that is used for

preparation of gels, glasses and ceramic powders. This low temperature method
enables obtaining optically transparent silica matrices doped with various
porphyrins. Upon encapsulation, porphyrin molecules retain their spectroscopic
properties and biological activity. The advantages of sol-gel matrices, i.e. thermal
and chemical stability and open-porous structure give the immobilized compounds
applications such as efficient heterogeneous catalysts, sensors in analytical
chemistry and solid luminescent materials.
The aim of presented studies was the investigation of -pinene transformation
using porphyrin compounds as catalysts. Silica materials doped with selected
porphyrins (2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine (OEP),
hematoporphyrin IX (HmP), protoporphyrin IX (PPIX) and 6,7-Bis[3-(N -tert-
butyloxycarbonyllysine methyl ester)]-1,3,5,8-tetramethyl-2,4-divinylporphyrin [1])
were obtained using sol-gel technique. In the case of each compound the addition of
surfactant (hexadecyltrimethylammonium bromide (HDTMA), sodium dodecyl
sulphate (SDS), Triton (R) X-100) was applied The aim of surfactants addition was
to reduce the leaching of porphyrin molecules, increase their stability inside silica
matrix and enhance the efficiency of biotransformation reaction.
The spectroscopic characterization of the obtained gels was elaborated. UV-
Vis absorption, emission and excitation spectra were recorded to monitor the
porphyrin molecules modifications due to the presence of various surfactants. The
observed variations are the evidence of the agglomeration and protonation changes
of porphyrin moieties in different systems. Singlet oxygen generated as a result of
catalyst irradiation was the main oxidizing agent and its phosphorescence intensity
was the basis for the selection of samples for biotransformation reactions.
Based on chromatographic analysis, it was found that the main products of
photooxidation of -pinene are pinocarveyl hydroperoxide, trans-pinocarveol,
pinocarvone and myrtenal (Fig.1). A similar profile of final products was obtained,
but differing in the percentage of each the terpenoid compound. Oxidation reaction
occurs with the participation of singlet oxygen or/and oxygen radicals, generated by
protonated porphyrin molecules.
Fig.1. The example model chromatogram of the products of -pinene biotransformation
using visible light-excited octaethylporphine in SiO2 in the presence of HDTMA.
References:
[1] M. Trytek, A. Lipke, M. Majdan, S. Pisarek and D. Gryko, Eur. J. Org. Chem.,
9 (2013) 1653.
DETERMINATION AND SPECIATION ANALYSIS OF HEAVY
METALS IONS BY STRIPPING VOLTAMMETRY USING DOUBLE
DEPOSITION AND STRIPPING STEP
Iwona RUTYNA
Adsorptive stripping voltammetry (AdSV) is a very useful technique for the

determination of many metal ions in environmental samples at trace and ultratrace
levels. Its high sensitivity is ensured by the preconcentration step, during which
determined metals are accumulated onto the surface of the working electrode. The
study described below concern the decrease of the detection limit in stripping
voltammetry of cobalt(II) owing to the application of the double deposition and
stripping steps. The procedures of these ions determination were performed in the
voltammetric cell with two built-in working electrodes that differed significantly in
their surface areas.
The Co(II) determination procedure consists of the following steps:
The sample was pippeted to the voltammetric cell and the following reagents
were added: 3 mL 1 mol L-1 ammonia buffer + 1.5 mL 5 mol L-1 NaNO2 + 75 L
10-2 mol L-1 Pb(NO3)2 + 60 L 5 10-2 mol L-1 nioxime. The sample was adjusted
to 30 mL with water. Firstly the potential of -1.45 V for 10 s was applied to the first
electrode in order to plate a new lead film on a glassy carbon substrate. The
accumulation of Co-nioxime complex at the first electrode with large surface area
was carried out at -0.7 V for 120 s from the stirred solution. Stirring was performed
using a magnetic stirring bar. Next the stirring was stopped, the stirrer was directed
near the wall of the vessel using a stir bar retriever placed outside the cell and the
electrode was moved near the second electrode (microelectrode) and the
accumulated Co(II)-nioxime complex was stripped simultaneously by applying the
potential of -0.1 V V for 20 s. The first electrode was disconnected and the potential
of -1.45 V for 20 s and then -0.7 V for 120 s was applied to the second electrode in
order to plate a lead film on the microelectrode surface and then to perform the
second accumulation step at this electrode. Then, a square wave voltammogram was
recorded at a frequency of 200 Hz, while the potential was changed from -0.7 to -
1.3 V. The amplitude and the potential step were equal to 50 and 4 mV,
respectively. The measurements were carried out from undeaerated solutions. After
each measurement a conditioning step of 30 s at 0.3 V (with solution stirring) was
used to remove the target metals from both working electrodes before the next
measurement.
The procedure optimization
The pH of the supporting electrolyte was changed from 7 to 10 by addition of
H2SO4 or NH4OH. The cobalt peak current was observed to attain the maximal
value when pH of the supporting electrolyte was equal to 8.3 and so this value was
chosen for further study. The main parameter influencing the lead film formation
was the concentration of Pb(II) ions added to the sample solution. The influence of
Pb(II) concentration was optimized and for further studies Pb(II) concentration of
2.5 10-5 mol L-1 was chosen. The influence of complexing agent concentration on
Co(II) peak current was studied in the range from 5 10-6 to 4 10-4 mol L-1. For
further studies the nioxime concentration of 1 10-4 mol L-1 was chosen. The
optimum accumulation conditions were found to be -0.7 V for 300 s and -0.7 V for
120 s at the first and second electrode, respectively. The calibration graph for Co(II)
in the optimized conditions was linear in the range from 2 10-11 to 1 10-9 mol L-1
with the linear correlation coefficient r = 0.999. The relative standard deviation
from five determinations of Co(II) at a concentration of 1 10-10 mol L-1 was 5.1 %
(n =). The detection limit estimated from 3 times the standard deviation of low
Co(II) concentration was about 8 10-12 mol L-1 and it is so far the lowest detection
limit obtained for Co(II) using mercury-free electrodes. The interference of foreign
ions was studied for a solution containing Co(II) at a concentration of 5 10 -10 mol
L-1. The results indicate that for 100-fold excess of Zn(II), Fe(III), Ni(II), Cu(II),
Mo(VI) and 1000-fold excess of Cl-, PO43- and NO3- the interference on Co(II)
signal was not observed.
The proposed procedure was used for Co(II) determination in certified
reference material NASS-5 seawater (certified value for cobalt was equal to 0.011
0.003 g L-1) . Determinations were carried out using the method of standard
additions. The obtained result of 0.012 g L-1 with a standard deviation 6.1% (n =
3) confirmed the accuracy of the proposed method and indicates that this procedure
can be used for Co(II) determination in natural water samples.
Fig.1. Square wave stripping voltammograms obtained using: a) the second electrode for
accumulation of 120 s from unstirred solution; b) as a) but from stirred solution; c) double
accumulation for 300 and 120 s at the first and the second electrode, respectively.
Concentration of Co(II) was 2 10-9 mol L-1.
THE USE OF NEW CONSTRUCTION VOLTAMMETRIC
ELECTRODES FOR THE DETERMINATION AND SPIECIATION
OF TOXIC ELEMENTS BY STRIPPING VOLTAMMETRY
Mateusz OCHAB
A solid lead electrode was applied for Mo(VI) determination by adsorptive

stripping voltammetry. Molybdenum is one of the micronutrient needed for growing
of plants and animals. In human body molybdenum is an ingredient of many
enzymes involved in the metabolism of carbohydrates and fats, it is also needed for
the proper assimilate iron. High concentration of Mo(VI) can be toxic and leads to
molybdenosis. Sings of molybdenosis in animals include osteoporosis, anemia,
anorexia and leads to copper deficiency: both of these elements are biological
antagonists.
Stripping voltammetry method belongs to the most sensitive analytical
methods and can be used for determinations the various forms of the element in the
sample including molybdenum. Very important issue in the voltammetric method is
the selection of the working electrode, wherein the material has an effect on the
available range of potential and also on the limit of quantification. For many years
molybdenum have been determinated on mercury electrodes. However, the toxicity
of metal mercury and mercury salts obliges scientists to receive more
environmentally friendly electrodes. So far the lead and bismuth film electrode
were used [1-2], in where the metal was deposited on a carbon support before or
during analysis. The aim of the project was to develop and use a new type of
microelectrodes made of metallic lead. The advantage of the proposed electrode is
the absence of metal salt solutions for the deposition of film. Furthermore,
elimination of the metal film forming step, reduces the measurement time. A
constructed electrode was applied for Mo(VI) determination by adsorptive stripping
voltammetry. A solid lead electrode has been applied for adsorptive stripping
voltammetric determination of trace concentrations of molybdenum in the presence
of Alizarin S as a complexing agent. For determination of Mo(VI), acetate buffer
was used as a main component of the supporting electrolyte. The effect of the pH of
the supporting electrolyte was investigated in the range from 3.5 to 5.5 from
solution containing 6 10-7 mol L-1 Alizarin and 3 10-8 mol L-1 Mo(VI). On the
basis of results the pH 4.6 0.05 was chosen for study. Next the concentration of
the acetate buffer was changed from 0.02 to 0.25 mol L-1 in solution containing 2
10-8 mol L-1 Mo(VI). It was found that the current of Mo(VI) peak increases as the
concentration of the acetate buffer increases to 0.1 mol L-1 and then decreases. The
influence of the accumulation potential on the Mo(VI) stripping peak current was
examined in the range from -0.55 to -0.70 V from solution containing 6 10-7 mol
L-1 Alizarin and 3 10-8 mol L-1 Mo(VI). The obtained results are shown in Fig. 1.
An accumulations potential of -0.59 V was used for further measurements. To
choose the optimal concentration of Alizarin S, concentration of ligand was
changed from 0 to 5 10-6 mol L-1 from solution containing 2 10-8 mol L-1
Mo(VI). For study Alizarin S concentration of 6 10-7 mol L-1 was chosen.
Under the conditions, a linear relationship between the reduction peak current
of the Mo(VI)-Alizarin S complex and the concentration of Mo(VI) was obtained as
shown in Fig. 2. The calibration graph for accumulation time of 150 s was linear
from 2 10-9 to 5 10-8 mol L-1 and obeyed the equation y = 8.35x 11.48, where y
and x are the peak current (nA) and Mo(VI) concentration (nmol L-1) respectively.
The correlation coefficient r2 was 0.9985. The standard deviation at Mo(VI)
concentration of 1 10-8 mol L-1 was 3.4% (n = 5). The solid lead electrode was
applied for Mo(VI) determination in certified reference material NASS-5. Certified
value of Mo(VI) in NASS-5 was 9.6 1 g L-1. The obtained results for CRM
obtained with the proposed method was 10.3 g L-1 and is in agreement with those
certified. The analytical parameters such as the detection limit and separation of
analytical signals obtained at the solid lead electrode are comparable to those
obtaied at a lead film electrode while better than those reported for bismuth film.
-1 a
b
i/ A
c
d
-1.2
-1.4
-1.6
f
-1.8
-0.6 -0.8 -1
E / V (vs. Ag/AgCl)
Fig. 1.Influence of accululation potential on the Fig. 2. Square wave voltammograms

Mo(VI) peak current from 0.1 mol L-1 acetate obtained in the course of Mo(VI)
buffer + 6 10-7 Alizarin S + 3 10-8 mol L-1 determination in supporting
Mo(VI). Accumulation time 150 s. electrolyte and increasing
concentration of Mo(VI): a) blank; b)
2 10-9; c) 5 10-9; d)
1 10-8; e) 2 10-8; f) 5 10-8 mol L-
1
. Accumulation at -0.59 V for 150 s.
References:
[1] K. Tyszczuk, M. Korolczuk, Analytica Chimica Acta, 624 (2008) 232-237.
[2] J. Wang, S. Thongngamdee, D. Lu, Electroanalysis 18 (2006) 59-63.
THE APPLICATION OF MESOPOROUS ORGANOSILICA
ADSORBENTS FOR ANALYSIS OF TRANSITION ELEMENTS
USING CHOSEN ATOMIC SPECTROMETRY METODS
Joanna DOBRZYSKA
Although the application of platinum in areas such as technology, medicine,

and jewellery is still increasing, a main source of its emission into the environment
are undoubtedly catalytic converters used in vehicles to control the emission of
exhaust gases. Convertors slowly undergo destruction and release platinum group
metals from the supporting matrix. The emitted platinum can be accumulated in
tissues exerting the negative impact on human health. Therefore, the content of
platinum in environmental samples should be monitored. The low concentration of
Pt in environmental samples forced to use the preconcentration step in analytical
procedures, for which application ordered mesoporous organosilica materials seem
to be perfectly suited, due to high thermal stability, high pore volumes, large
mesopores and relatively thick pore walls.
The purpose of this study was the synthesis of the thiolfunctionalized SBA-15
of various morphology and the application of the synthesized materials for the
adsorption of Pt(IV) ions. The modified SBA-15 materials were synthesized using
sol-gel method. In order to synthesize material S1 2g of Pluronic 123 was dissolved
in 60 mL of 2M HCl and 11 mL of deionized water. The mixture was stirred at
40C for 8h, then 18 mmol of tetraethoxysilane (TEOS) was added into solution.
After 15 minutes 2 mmol of 3-mercaptopropyltrimethoxysilane was added
dropwised. The mixture was stirred for 24h at 40C and aged for 48h at 100C. The
obtained materials were washed with deionized water, filtered and dried at 70C.
Finally, three-time extraction with ethanol at 70C was carried out. The above
procedure was modified and used for the preparation of four materials differing in
morphology and porous structure. The synthesis modifications included: a) the
addition to the reaction mixture of 2,3 mL of 1,3,5- trimethylbenzene about 2 hours
before TOES (material S2) b) the addition to the reaction mixture of 0,54 mmol of
ZrOCl2 just before TOES (material S3), c) the addition to the reaction mixture of
0,54 mmol of ZrOCl2 10 minutes after MPTMS (material S4).
The microscopic studies indicates that the addition of the ZrOCl 2 to the
reaction mixture causes the decrease of the sizes of the synthesized particles, what
is illustrated in Figure 1.
Fig.1. Particles size distribution for S1 and S3
The effect of pH on the Pt(IV) adsorption onto synthesized materials and the
adsorption kinetics were investigated and illustrated in Figure 2 and 3, respectively.
In the case of the material synthesized without ZrOCl2 the highest adsorption
capacities were observed for initial pH values between 1.5 and 3. Above this range
the small but visible decrease of adsorption was observed, contrary to the
adsorption systems containing the sorbents synthesized in the presence of ZrOCl2,
for which the adsorption affinity towards Pt(IV) is extremely high and does not
change with the pH over the range. As presented in Figure 3 the decrease of the
particle size does not influence significantly on the adsorption rate. Moreover, the
presence of the ZrOCl2 in the sorbents structure (which was confirmed by XPS)
causes the increase of the time needed for the establishing the adsorption
equilibrium state. However, the 90% efficiency of adsorption was reached after 8
hours of stirring for all studied sorbents.
Due to the wide range of the pH for which the effective adsorption occurs and the
extremely high adsorption capacities reaching 350 mg/g, materials S3 and S4 were
chosen as the most promising sorbents for the Pt(IV) ions enrichment form water
and digested environmental solid samples before slurry sampling GF AAS
technique determination.
Fig.2. Impact of pH on Pt(IV) adsorption Fig.3. Kinetics of Pt(IV) adsorption onto

onto thiolfunctionalized SBA-15; m = 0.05 thiolfunctionalized SBA-15; m = 0.05 g, V
g, V = 50 mL, t = 24 h, T = 25C, = 50mL, T = 25C, cinitial,S1,S2 = 20 mg/L,
cinitial,S1,S2 = 50 mg/L, cinitial,S3,S4 = cinitial,S3,S4 = 100 mg/L, pHinitial,S1,S2 =
100 mg/L 2.30, pHinitial,S3,S4 =3
SURFACE PROPERTIES INVESTIGATION OF HYDROPHOBIC
POLYMER/SILICA FILMS DEPOSITED ON GLASS SURFACE
Diana RYMUSZKA, Konrad TERPIOWSKI, Lucyna HOYSZ

The surfaces of the constructive materials, for example glass used in solar
panels or photovoltaic cells, are frequently covered by special layers as the
protection against harmful influence of atmospheric factors [1,2]. Such coats are
widely used also on the concrete surfaces, polymers or painted surfaces as
protective films for water and frost [1]. The surfaces of lens with reflective coats
have to be cleaned very often and because of that on their surface hydrophobic
layer, so called clean coat, has to be deposited as the protection against
contamination. Then the glass surface becomes smoother and contamination is
attracted to the drop of water created on the surface which makes its removal easier.
Unfortunately, support coverage with hydrophobic layer is very often
problematical due to low adhesion and because of that using plasma technique for
surface modification is reasonable [3,4]. This technique provides an alternative to
traditional methods of surface modification by wet chemical cleaning, etching,
cross linking or functionalization and is fast and ecological.
The aim of the study was preparation and investigation of polymer/silica film
surface properties composed of poly(methyl methacrylate) (PMMA) and silanized
silica with different surface fraction coverage with trimethylsilyl groups, ( ,
0.53 1.00) deposited on air activated plasma glass surface. Plasma treatment was
used for adhesion improvement between the PMMA/silica film and glass support.
Wettability was investigated based on the water contact angle measurements using
the sessile drop method (Digidrop GBX Contact Angle Meter, France). Contact
angle hysteresis (CAH) approach was used for determination of apparent surface
free energy from the measured contact angles. Morphology of obtained
nanocomposites was investigated with the help of high distributive field emission
scanning electron ion microscope (FE SEM) (Quanta 3D FEG, FEI).
It was found that the contact angles measured for the PMMA/silica films
whose values were over 90 (Fig. 1) the surface free energy calculated from the
CAH approach was lower than 30 mJ/m2, which is much lower than its value for the
glass covered only by PMMA, leads to the conclusion that the obtained films are
hydrophobic.The most hydrophobic film was obtained in the case of using silica
with the surface fraction coverage with trimethylsilyl groups 0.63. Using silica as a
filler in polymers very often leads to mechanical properties improvement of
organic inorganic nanocomposites [5].
140 60
advancing
130
A) receding B)
120
2
50
Apparent surface free energy, mJ/m

110
Water contact angle, deg.
100
40
90
80
70 30
60
50
20
40
30
10
20
10
0 0
PMMA PMMA/silica PMMA/silica PMMA/silica PMMA/silica PMMA PMMA/silica PMMA/silica PMMA/silica PMMA/silica
=0.53 =0.63 =0.86 =1.00 =0.53 =0.63 =0.86 =1.00
Fig. 1. Advancing and receding contact angles of water (A) and apparent surface free
energy calculated from the contact angle hysteresis (CAH) approach (B) of PMMA/silica
films deposited on the plasma activated glass surface.
On the other hand, the SEM images showed that silica particles are
homogeneously dispersed in the PMMA/chloroform solution and silica aggregates
were not observed (Fig. 2). Introducing hydrophobic groups on the silica surface
prevents its particles from the aggregation and leads to better hydrophobic
properties of nanocomposites.
PMMA/silica =0.53 PMMA/silica =0.63 PMMA/silica =0.86 PMMA/silica =1.00
Fig. 2. SEM images of PMMA/silica films deposited on the plasma activated glass surface.
References:
[1] Y. Akamatsu, K. Makita K and H. Inaba, Sol Gel Sci. Technol., 19 (2000) 387.
[2] J.S. Kim, J.K. Park, Y.J. Baik and W.M. Kim, Korean Phys. Soc. 61/9 (2012)
1467.
[3] H. Jung, B. Gweon, D.B. Kim and W. Choe, Plasma Process. Polym., 8 (2011)
535.
[4] W.S. Kang, H.S. Kim and S.H. Hong, Thin. Solid. Films, 518 (2010) 6578.
[5] S. Zhou, L. Wu, W. Shen and G. Gu, Mat. Sci., 39 (2004) 1593.
STUDIES OF STRUCTURE AND PROPERTIES OF MODIFIED
LIPID LAYERS
Magorzata JURAK
Lauryl gallate (LG) is n-alkyl ester of gallic acid widely used as a food
additive. It reduces cell damage induced by hydroxyradicals and hydrogen
peroxides. Moreover, the pharmacological antimicrobial activity of this compound
was also described [1]. The head-and-tail structure of LG may affect cellular
membranes by changing their integrity and fluidity. This activity can be correlated
with the direct interactions of gallates with the components of biological
membranes. The formation of lipid domains is a key process by which
biomembranes function. However, the influence of lauryl gallate (LG) on stability
and fluidity of the membrane, especially heterogeneous, is poorly understood. On
the other hand, the membrane functionality is determined by the
hydrophilic/hydrophobic balance which results from molecular interactions between
lipids and water (and also other liquids). Water is the external medium of most
biological systems. Therefore studies of interactions of molecules building the cell
membranes with the surrounding water are of particular interest especially for
practical purposes in development of biosensors, biocompatible implants or targeted
drug delivery.
Accordingly, the effect of lauryl gallate on the interactions and phase
behaviour of lipidic constituents of biological membranes: 1,2-dipalmitoyl-sn-
glycero-3-phosphocholine (DPPC); 2-oleoyl-1-palmitoyl-sn-glycero-3-
phosphocholine (POPC); 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC); 1,2-
dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DPPG); and cholesterol (Chol),
was examined in the binary (DPPC/LG, POPC/LG, DOPC/LG, DPPG/LG,
Chol/LG) and ternary mixtures (DPPC/DOPC/LG, DPPC/DPPG/LG,
DPPC/Chol/LG, DPPG/Chol/LG), by monitoring differences in the shape of the
compression isotherms at the air-water interface. The Brewster angle microscope
(BAM) was used for direct visualization of substructures with a long range
orientational order. The nonideality of these mixed systems was expressed in the
excess area (Aexc)-composition. To explore the magnitude of these interactions, the
thermodynamic stability of the mixed monolayers was examined via the excess
(Gexc) and total (Gmix) free enthalpy of mixing. To determine the state of films
and to get information on the molecular ordering in the monolayer, the compression
modulus was calculated. Then the binary mixed monolayers, as well as ternary
DPPC/DOPC/LG were deposited on mica by means of the Langmuir-Blodgett
technique. The wetting properties of the obtained layers were determined from the
contact angle measurements of chosen liquids, and applying the theoretical models
for the surface free energy and its components evaluation proposed by van Oss,
Good, Chaudhury (LWAB) and Chibowski (CAH). Moreover, the biomimetic
membranes on a solid surface were probed by atomic force microscopy (AFM).
With this technique a detailed view of the stability, morphology, and submicron
length structure of the lipid films with an antioxidant was obtained. One issue of
interest was the fidelity of molecular structure and phase state in the Langmuir-
Blodgett (LB) films as compared to the Langmuir films of the same material. The
aim of the investigations was comparison of the molecular properties of LB with the
Langmuir films using the AFM and BAM techniques.
It was found that LG exhibits better affinity for zwitterionic phospholipids
which additionally depends on saturation/unsaturation of the hydrocarbon chains.
The most favourable stoichiometry occurs for the mixed monolayers of LG with
unsaturated phospholipids. Moreover, the study showed that LG influences the
model membrane rigidity and organization. The effect was more pronounced for
saturated than unsaturated phospholipids. A strong fluidizing effect on DPPG and
phase separation were found. Conversely, unsaturated membrane uidity was
proved to be maintained by LG. Thus, LG was considered to localize preferentially
in the interior regions of unsaturated lipid layers keeping the membrane fluidity.
The transfer of a compressed lipid interfacial film onto a mica support evidently
preserved most of the structural features associated with degree of condensation of
the films, including formation and growth of condensed lipid domains. Moreover,
the obtained results indicated that stability and permeability of the binary and
ternary films deposited on mica were determined by the kind of lipid and
stoichiometry of the mixed monolayers. These were revealed in the contact angles
and the surface free energy as well as its components changes. Strong attractive
interactions between the components imply formation of densely packed and
ordered monolayers. POPC (or DOPC) and LG form less condensed mixed
monolayers which are more accessible to the liquid molecules than the DPPC/LG
model system. Hence, the smaller contact angles are measured and in consequence,
the higher surface free energy is determined. The apolar Lifshitz-van der Waals
interactions do not change much with the LG content. The electron-acceptor
interactions are weak or none, thus the electron-donor interactions are mainly
responsible for interfacial interactions. The agreement between the structure of the
floating monolayers and those covering the mica plates proved that supported films
retained the same morphology as the original Langmuir films at the air-water
interface, even if they were transferred at high surface pressure of 35 mN/m. Thus,
as demonstrated in this study, BAM and AFM provided complementary and
effective structural characterizations of the monomolecular films.
It is believed that the results provide better understanding of organization
structure of the lipid films and their interactions with the surrounding environment.
They may be helpful to get insight into LG behaviour as antibacterial, antiviral, and
antitumour agents in living systems.
References:
[1] I. Kubo, K. Fujita, K. Nihei and N. Masuoka, Bioorg. Med. Chem., 11 (2003)
573.
INFLUENCE OF SHORT-CHAIN ALCOHOL ON CRITICAL
MICELLE CONCENTRATION OF ANIONIC + CATIONIC
SURFACTANT MIXTURE
Magdalena BIELAWSKA, Bronisaw JACZUK,

Anna ZDZIENNICKA
Short-chain alcohols are commonly used organic additives which modify

surface, volumetric and wetting properties of the aqueous solutions of surfactants
[1]. Despite plenty of literature data, their influence on the critical micelle
concentration (CMC) of surfactants in aqueous solutions has not been sufficiently
explained yet. For that reason, the CMC changes of the mixture of two classical
surfactants: anionic sodium dodecylsulfate (SDDS) and cationic
hexadecyltrimethylammonium bromide (CTAB) in the mixed water + short-chain
alcohol (ethanol or propanol) solvent were investigated by the surface tension
measurements (ring method and maximum bubble pressure one) at 293 K. The mole
fraction of CTAB in the mixture with SDDS in the solution was equal to 0.2.
It turned out that similarly to the water + alcohol solutions of anionic +
nonionic or cationic + nonionic surfactant mixture [2, 3], SDDS and CTAB form
micelles only in the range of alcohol concentration in which it is present in the
monomeric form in the bulk phase. In the range of alcohol concentration lower than
its critical aggregation concentration (CAC), the turbidity of the solution initially
increases with the increasing concentration of SDDS and CTAB mixture and with
the further increase of surfactant mixture concentration the solutions become
transparent. It can be connected with the formation of colloidal aggregates of SDDS
and CTAB and then with the micelle formation by this mixture. Over alcohol CAC,
much higher solubility of SDDS and CTAB mixture was observed. Such solutions
are transparent, but in the range of high surfactant mixture concentration, the
crystalline precipitate appears. It probably means that over alcohol CAC, CTAB
and SDDS do not form micelles.
Ethanol at its concentration equal to 1.07 M decreases CMC of SDDS and
CTAB mixture and behaves as a co-surfactant. It can be related to its adsorption in
the palisade layer of the micelle and decreasing repulsive interactions between ionic
surfactant heads (those with the same-sign charges). Ethanol at its concentration
equal to 1.07M causes the increase of CMC of the surfactant mixture and behaves
as co-solvent. This can be connected with the reduction of the dielectric constant of
the solution as well as its polarity.
From the dynamic surface tension measurements, it results that over the
alcohol CAC the surface tension of the solution decreases with the surface age (t)
until it reaches the value obtained for the aqueous solutions of a pure short-chain
alcohol at the same concentration. It probably results from the competitive
adsorption of surfactants and alcohol at the solution-air interface. The CMC of
SDDS and CTAB mixture decreases with the increasing surface age. This can be
connected with the formation of the saturated monolayer of surfactants and alcohol
at the solution-air interface at the lower concentration of SDDS and CTAB mixture.
Table 1. The changes of CMC of SDDS and CTAB mixture under the influence of a
short-chain alcohol.
Alcohol Alcohol concentration, C2 (M) Surface age, t (s) CMCSDDS+CTAB (mM)

- 40 10.62
-
- 100 10.55
40 6.36
EtOH
100 4.91
1.07
40 31.85
PrOH
100 25.36
Fig.1. The critical micelle concentration of SDDS and CTAB mixture in its aqueous solution
without alcohol (curve 1) and with ethanol at ethanol concentration (C 2) equal to 1.07
M (curve 2) vs. the surface age (t).
References:
[1] M.J. Rosen, Surfactants and Interfacial Phenomena, Wiley-Interscience,
New York, 2004.
[2] M. Bielawska, B. Jaczuk, A. Zdziennicka, Colloids Surf., A, 480 (2015) 270.
[3] M. Bielawska, B. Jaczuk, A. Zdziennicka, J. Mol. Liq., 211 (2015) 324.
ADSORPTION AND AGGREGATIONS PROPERTIES OF TRITON
X-100 AND RHAMNOLIPID MIXTURE
Diana MAKO, Anna ZDZIENNICKA, Bronisaw JACZUK

Triton X-100 (TX-100) and rhamnolipid (RL) are very interesting surfactants
because of their unique properties and wide practical applications. TX-100 is a
typical representative of nonionic surfactants belonging to the alkyl polyethylene
oxide family used to solubilize membrane phospholipids, DNA extraction and to
purify membrane-bound proteins and enzymes without a loss of their biological
activity [1-3]. It is applied in almost every type of liquid, paste, and powdered
cleaning compound, ranging from heavy-duty industrial and agrochemical products
to gentle detergents [4]. In turn, RL which is a biosurfactant is characterized by
high surface activity, specificity of action, temperature stability and resistance to pH
changes in a whole range. It undergoes biodegradation more readily and is less
toxic. Owing to such properties biosurfactants are more and more widely applied in
various fields of industry, among others, in cosmetic, agricultural, textile, cellulose
and stationary ones. They are also exploited in crude oil mining as well as in
remediation and detoxification of soil. It is known that in practice the mixtures of
different kinds of surfactants are more commonly used than individual ones. In
many cases the mixtures of surfactants show the synergetic effect in the reduction
of water surface tension and micelle formation. In the literature it is difficult to find
the data dealing with the adsorption and aggregation properties of the RL mixed
with another surfactant. Proper mixture of RL and synthetic surfactant can be
interesting not only from the theoretical but also practical points of view. Therefore,
the purpose of our studies was to determine the adsorption and aggregation
properties of TX-100 and RL mixtures. For this purpose the surface tension, density
and viscosity of aqueous solutions of this mixture at constant concentration of RL
or TX-100 were measured. The measured values of the surface tension were
compared to those calculated from the Joos equation [5] as well as to determined on
the basis of the surface tension of aqueous solutions of individual surfactants. From
the surface tension isotherms the Gibbs surface excess concentration of the TX-100
and RL, the composition of surface layer and Gibbs standard free energy of
adsorption at the water-air interfaces were determined. In turn, on the basis of
surface tension, density and viscosity isotherms the CMC of surfactants mixture
was estemated. From the density isotherms the apparent and partial molar volume
of TX-10 and RL were also determined. These volumes were compared to those
calculated by suing the size of the TX-100 and RL molecules. The obtained results
and their analysis allow us to state that there is good agreement between the
measured values of surface tension of RL and TX-100 mixtures and those
calculated from the Joos equation if the concentration of one component of the
mixture is consistent with the unsaturated monolayer in the absence of another.
75 50
70
65
60 40
(mN/m)
(mN/m)
55
50
1
45 30
LV
LV
40
1
Surface tension,
Surface tension,
35
30 20
25
20
2
15
10
10 2
5
a)
0 b)
0
-8 -7 -6 -5 -4 -3 -2 -8 -7 -6 -5 -4 -3 -2
logarithm of TX-100 concentration logarithm of TX-100 concentration
Fig. 1. Isotherms of the surface tension (a, b) of aqueous solutions of RL and TX-100
mixture at the constant concentration of RL equal to 0.0002 mg/dm3 (a) and 5 mg/dm3
(b). Curve 1 correspond to the measured values, curve 2 to those calculated from the
Joos equation.
It should be also stated that there is the synergetic effect in the reduction of
water surface tension and micelle formation at proper concentration and
composition of the RL and TX-100 mixture. The composition of this mixture in the
surface layer at the water-air interface is different from that in the bulk phase. The
isotherm of adsorption of TX-100 and RL mixture at the water-air interface is
Langmuir type. Good agreement is observed between the apparent and partial
molar volumes of surfactants obtained from the density isotherms and those
calculated on the basis the size of these surfactants molecule and proper distance
between the surfactant and water molecules.
References:
[1] C. Tandford, J.A. Reynolds, Characterization of membrane proteins in detergent
solutions, Biochim. Biophys. Acta, 457 (1976) 133.
[2] A. Levitzki, Reconstitution of membrane receptor systems, Biochem. Biophys.
Acta, 822 (1985) 127.
[3] A.A. Ribeiro, E.A. Dennis, Motion in nonionic surfactant micelles and mixed
micelles with phospholipids. A carbon-13 spin-lattice relaxation study on p-tert-
octylphenylpolyoxyethylene ethers, J. Phys. Chem., 80 (1976) 1746.
[4] J.M. Rosen, Surfactants and Interfacial Phenomena, 3rd edition, Wiley
Interscience, New York 2004.
[5] P. Joos, Thermodynamics of mixed monolayers, Bull. Soc. Chim. Belges, 76
(1967) 591.
SYNTHESIS AND CHARACTERIZATION OF SILICA MATERIALS
SUSCEPTIBLE TO MAGNETIC FIELD
Karolina GDULA
DEPTARTMENT OF THEORETICAL CHEMISTRY
In the past two decades, an increased development in the field of nanomaterial

science has been achieved. Nowadays, so-called core-shell nanostructures are of
great interest among many research groups. Such objects can deliver many
interesting properties, which cannot be ensured by singular particles. Core-shell
hybrid nanomaterials can be composed of different core materials, which possess
many interesting properties, such as: magnetic [1], luminescent [2], fluorescence
[3], and so on. Especially, superparamagnetic iron oxide nanoparticles (SPIONs)
are promising materials for many applications, such as: magnetic resonance
imaging (MRI) [4], hyperthermia [5], targeted drug delivery systems in cancer
treatment [6], and more recently, as magnetically removable catalysts [7] and
adsorbents [8]. However, there is a need to modify their surface by covering such
particles by outer layers (shells), e.g. silica or polymer. Such treatment leads to
improve their biocompatibility and biodegradability, and prevent aggregation.
In this work, we present characterization of magnetic silica nanostructures,
functionalized with amine groups. In order to obtain functionalized polysiloxanes
with magnetic properties, the two-step reaction, was carried out. The aqueous
suspension of magnetite (Fe3O4) as magnetic core was synthesized according to the
co-precipitation of ferrous and ferric salts (in molar ratio: Fe2+/Fe3+=1/2) in a basic
medium, which is detailed described in [9]. An amine/silica shell was obtained onto
magnetite employing a modified sol-gel method reported by Melnyk et al [10]. This
method is based on hydrolysis and condensation of TEOS and a proper functional
monomer (having amine groups), in the presence of catalyst.
Three materials, differing in number and structure of amine groups built in the
adsorbent structure, were synthesized. The resulting samples were labeled as
follows: Fe3O4/TEOS/APTES A, Fe3O4/TEOS/TMPED DA,
Fe3O4/TEOS/BTMPA BA. The synthesized materials were characterized by
several analytical techniques. The presence and content of amine groups were
measured by FT-IR spectroscopy and acid-base titration, respectively. Specific
surface areas were measured by nitrogen/adsorption desorption isotherms.
The amount of amine groups built in the structure of each adsorbent were:
1.83, 2.66 and 1.89 mmol/g for A, DA and BA, respectively. The values of specific
surface area, were: 144, 176 and 29 m2/g for A, DA and BA, respectively.
In the Figure 1, FT-IR DRIFT spectrum for the sample BA is shown. In the
spectrum, intense and broad absorption band, in the region 550-580 cm1,
corresponds to (FeO), can be observed. In addition, an intense absorption band
with high-frequency shoulder in the region of 1000-1200 cm1, which is
characteristic of the as(SiOSi) stretching vibrations, is present. Two low-intensity
absorption bands belonging to s,as(NH) of amino groups at 3270-3370 cm1, are
observed.
Fig.1. FT-IR DRIFT spectra of the BA sample.
It was proved, that the sol-gel method leads to obtain materials with high
content of amine groups built into their surfaces (in the range 1.8-2.7 mmol/g). IR
results, obtained from FT-IR spectroscopy, clearly show that the surface of the
synthesized Fe3O4 particles is coated by silica layer with amine functional groups.
Thanks to their nanometer size and surface properties (especially, the presence
of amine groups which can ensure the electrostatic interaction between surface of
adsorbent and molecules of adsorbate), the obtained nanocomposites can be
considered as promising adsorbents for metal ions and bioorganic compounds from
water solutions.
References:
[1] T. Hyeon, Chem. Commun., 9 (2002) 927.
[2] M. Mahmoudi, S. Sant, B. Wang, S. Laurent, T. Sen, Adv. Drug Deliv. Rev., 63
(2011) 24.
[3] O.G. Tovmachenko, C. Graf, D.J. van den Heuvel, A. van Blaaderen, H.C.
Gerritsen, Adv. Mater., 18 (2006) 91.
[4] T. Schlorf, M. Meincke, E. Kossel, C.C. Gluer, O. Jansen, R. Mentlein, Int. J.
Mol. Sci., 12 (2011) 12.
[5] S. Laurent, S. Dutz, U.O. Hafeli, M. Mahmoudi M, Adv. Colloid Interface Sci.,
166 (2011) 8.
[6] S. Laurent, M. Mahmoudi, Int. J. Mol. Epidemiol. Genet. 2 (2011) 367.
[7] J. Lee, Y. Lee, Youn, H. Bin Na, T. Yu, H. Kim, S.M. Lee, Y.M. Koo, J.H.
Kwak, H.G. Park, H.N. Chang, M. Hwang, J.G. Park, J. Kim, T. Hyeon, Small
4 (2008) 143.
[8] S.C.N. Tang, I.M.C. Lo, Water Res., 47 (2013) 2613.
[9] Z. Ma, Y. Guan, H. Liu, J. Magn. Magn. Mater., 301 (2006) 469.
[10] I.V. Melnik, Y.L. Zub, B. Alonso, N.V. Abramov, P.P. Gorbik, Glass. Phys.
Chem. 38 (2012) 96.
AMINE MODIFIED MESOPOROUS SILICA MATERIALS
PROPERTIES EXAMINATION BY FT-IR SPECTROSCOPY
Tomasz OLEJNIK
Many scientists trying to functionalized porous silica materials in order to

improve their properties or enhance their uses. The functional groups may be
attached to these materials both during their synthesis by co-condensation or by
grafting for ready silica materials. More often used method is co-condensation
method, due to the smaller number of steps during the preparation and more
uniform distribution of functional groups on the surface. In addition the one-step
method allows introduce more modifying groups without closing the pores. The
post-synthesis method consists in treating calcined mesoporous organosilanes
containing desirable functional groups which are covalently attached to the silanol
groups present on the surface of the pores.
The aim of this study was to obtain a modified amino silica materials SBA-15,
and then attempt to introduce the metal to the crystal lattice thus modified silica
materials, during their synthesis. The second objective was to compare the physical
and chemical properties of synthesized systems by BET, AAS, FT-IR methods and
to determine the optimal conditions for the synthesis of amine-modified materials
such as SBA-15.
Fig. 1. Functionalization of mesoporous silica surface by amino groups and nickel atom
connection.
During preparation I prepared 6 samples (1B-6B) of SBA-15 mesoporous

silica materials, in which the surface was modified by amino groups. Surface
modifying component of samples 1B-3B was: APTES (3-
aminopropyltriethoxysilane) and the sample 4B-6B TMPED (N-(2-aminoethyl)-3-
aminopropyltriethoxysilane). In each subsequent sample in the series increased the
amount of modifier. Then prepared the next 6 samples (1Ni-6Ni) in which nickel
ions are introduced at the stage of synthesis and in the presence of amine modifiers:
APTES and TMPED. The source of nickel ions was Ni(NO3) 6H2O.
Table 1. The weight ratio of TEOS to APTES or TMPED in prepared samples.
Sample The weight ratio of Sample The weight ratio of TEOS
number TEOS to APTES number to TMPED
1B 19 : 1 4B 19 : 1
2B 18 : 2 5B 18 : 2
3B 17 : 3 6B 17 : 3
1Ni 19 : 1 4Ni 19 : 1
2Ni 18 : 2 5Ni 18 : 2
3Ni 17 : 3 6Ni 17 : 3
Table 2. Surface area of the received Table 3. The nickel content in the
materials. examined samples.
No BET Average pore No g /g % Ni on the
Ni adsorbent
surface diameter [] adsorbent
area [m2/g] 1Ni 0.0309 3.1
B1 830.5 115.0 2Ni 0.0794 7.9
B2 436.1 43.7 3Ni 0.1221 12.2
B3 550.1 27.5 4Ni 0.0751 7.5
B4 498.8 63.4 5Ni 0.0799 8.0
B5 340.2 63.8
6Ni 0.1674 16.7
B6 38.5 47.8
Ni1 802.1 60.9
Ni2 802.3 58.6
Ni3 734.1 57.0
Ni4 776.3 59.6
Ni5 771.3 50.1
Ni6 597.4 54.3
Fig. 2. FT-IR/PAS spectrum of the 4B-6B

samples, the range 2000-4000 cm-1.
Conclusions:
All prepared materials are
mesoporous (as reference
material SBA-15) which results
from the analysis of the
adsorption isotherm and pore size distribution.
The specific surface area decreases with increasing weight ratio of
TEOS/modifier.
FT-IR/PAS spectroscopy is an excellent tool for observing:
amino group introduced during synthesis,
connect to the metal ions with functional groups of modifier,
efficiency of template and modifier removal by calcination.
MICROSCOPIC CHARACTERIZATION OF MONO- AND
BIMETALLIC CATALYSTS FOR STEAM REFORMING OF
METHANOL AND ETHANOL
Grzegorz SOWIK
In the steam reforming of ethanol/methanol, a catalyst plays an important role

in achieving complete and selective ethanol/methanol conversion. The performance
of catalytic materials is usually governed by precise atomic structure and
composition of very specific catalytically active sites. Therefore, structural and
chemical characterization at the atomic scale becomes a vital requirement in order
to identify structureperformance relationships existing in heterogeneous catalyst
systems. It has been well proved that the performance of heterogeneous catalysts
depends on a number of parameters, including particle shape and size, catalyst
surface structure, local composition and chemical bonding, interaction between
support surface and metal particle, and evolution of these key parameters during
catalyst synthesis, application and regeneration.
In recent years, the characterization of heterogeneous metal catalysts have
been greatly improved by the use of modern chemical-physical research methods,
such as electron microscopy. It is currently very dynamically growing and effective
technique, used in studies of heterogeneous catalysts.
The aim of this study was preparation and characterization of the mono- and
bimetallic supported catalysts by using electron microscopy (TEM/STEM). The
first catalyst, composed of palladium, chromium and zinc oxides was prepared by
incipient wetness impregnation method. TEM and STEM images and EDS maps
(Fig.1.) show very good dispersion of palladium particles on zinc and chromium
oxides. The images of the catalyst show good homogenization of individual phases.
The average crystallite size of the palladium active phase, determined on the basis
of TEM and STEM images, was 5 nm. The second catalyst, containing nickel and
potassium (promoter) on the ceria support was prepared by the impregnation
method. EDS maps (Fig.2.) from this catalytic system show very good dispersion of
potassium and nickel on the support. The average crystallite size of the nickel active
phase (in the oxide form), was equal to 4.6 nm. Microscopic studies showed that
both, incipient wetness impregnation and simple impregnation methods, lead to
good dispersion of the active phase and promoter on the support in the
monometallic and bimetallic catalytic systems.
A A
B daverage = 4.6 nm
daverage = 5 nm C
Fig. 1. (A) TEM and (B) STEM Fig. 2. (A) STEM image, EDS maps and (B)
images with EDS maps, (C) particles size distribution in the nickel-based
palladium-zinc alloy particles size catalyst with ceria support and promoted with
distribution in thePd-ZnCrOx catalyst. potassium.
STEAM REFORMING OF ETHANOL OVER HIGH SURFACE
AREA Co-BASED CATALYSTS. INVESTIGATION OF CHANGES
IN CATALYSTS SURFACE STATE AND CATALYSTS
SELECTIVITY
Sylwia TURCZYNIAK
The depletion of fossil fuel resources force to reduce consumption of energy

obtained from non-renewable natural gas and petroleum. However, increasing
demands for energy and concern about environment, are driving forces to seek
alternative energy sources. In recent years, much effort has been devoted to studies
of catalysts for hydrogen production [1]. Among few possible ways of hydrogen
production (i.e. reforming of hydrocarbons, electrolysis, photolytic and biological
conversion) [2], the ethanol steam reforming (ESR) seems to be very attractive.
Cobalt supported catalysts have become one of the most promising candidates
due to comparable activity for efficient C-C bond cleavage, in the ESR at medium
temperatures range [3], to catalyst based on noble metals, at the same time their
price is lower. Disadvantages of cobalt catalysts such as sintering or deactivation
owing the coke formation can be limited by selection of a suitable support. The
previous part of this project has concerned the low surface area catalysts (M)
supported on oxides with different oxygen storage capacity: AOx and BOx. The pre-
reduced catalysts (M-Co/AOx and M-Co/BOx) were characterized using quasi-in
situ XPS under the ESR for the EtOH:H2O = 1:12 mol/mol. The research showed
that the catalysts exhibited tendency to the coke formation. It is well known that
high-surface area supports result in higher cobalt dispersion [3]. Therefore the
nano-catalysts (N) should exhibit higher catalyst activity, selectivity (towards H2,
CO2) and stability.
The nano-catalysts supported on nano-AOx and BOx oxides were prepared by
the impregnation method, characterized and denoted as N-Co/AOx and N-Co/BOx.
The catalysts pressed into pellets were mounted on the sample holder and placed in
the UHV chamber. The catalysts were pre-reduced and subjected to the EtOH:H2O
vapours at 420C. During the reaction the products distribution was analysed on-
line by the Micro GC.
The obtained results showed that on the surface of both N-Co/AOx and N-
Co/BOx catalysts the Co(0) was the main cobalt component. The introduction of the
reaction mixture caused the catalysts oxidation. The oxidation state of cobalt active
phase after the first hour of the ESR was very similar in both cases. However, it was
found that the catalyst supported on AOx oxide showed higher resistance to the
formation. Moreover, the relative selectivity of this catalyst towards CO2 was
slightly higher than in the case of the N-Co/BOx.
420 C
100
90 N-Co/AOx
Products distribution (%)

80 H2
70
60
50
40
30
CH4 CO2
20 CO
10
0
10 15 20 25 30 35 40 45 50 55 60
Time on steam (min)
Fig. 1. Gas phase products distribution under the ESR obtained over Co/AO x catalyst
(EtOH/H2O = 1/12 mol/mol, T = 420C).
The detailed studies of the ESR over the abovementioned catalysts are the
subject of the publication which is under preparation. The obtained results allow to
explain the role of the support in Co oxidation under the ESR and the influence of
the Co oxidation state on catalysts relative selectivity towards the most desirable
products.
References:
[1] H. Song, L. Zhang, R. B. Watson, D. Braden, U. S. Ozkan, Catal. Today, 129
(2007) 346.
[2] O. Bickov, P. Straka, Int. J. Hydrogen Energy, 37 (2012) 11563.
[3] A. Machocki, A. Denis, W. Grzegorczyk, W. Gac, Appl. Surf. Sci., 256 (2010)
5551.
SYNTHESIS AND EXAMINATION OF PROPERTIES OF
PALLADIUM SUPPORTED ZINC OXIDE CATALYSTS OBTAINED
BY MICROEMULSION METHOD
Justyna PAWLONKA
The structural and surface properties of support, crystallite size, and dispersion
of the active phase significantly affect the activity and selectivity of the catalysts.
The microemulsion method is one of the few methods which received
nanomaterials have a narrow crystallite size distribution and high surface area. The
most important advantage of the method is the ability to control the size of particles
formed by modifying the composition of the microemulsion. Micelles are the
specific nanoreactors, which due to continuous thermal movements, collide with
each other. The result is to replace the content of the micelles and the reaction
(reduction and / or co-precipitation), depending on the content of the micelles.
Microemulsion method has gained of interest for catalysts preparation just recently.
This method enables in easy way the control the reversed micelles, and thereby the
particle size or shape by changing the water-to-surfactant molar ratio (W0). The
microemulsion method might be used for preparation of materials with a suitable
chemical composition and distribution of the species with control on nanometer
level, different porosity or specific surface area [1].
The aim of the studies was determination of the influence of water to-
surfactant molar ratio on the properties of palladium supported zinc oxide catalysts.
All catalysts were prepared by the microemulsion method. Microemulsion
consist out of cyclohexane, n-butanol, aqueous solution of metal salts and cationic
surfactant (CTAB). Characterization of the catalyst was done with XRF, X-Ray
diffraction (XRD), low-temperature nitrogen adsorption. High Resolution
Transmission Electron Microscopy was used to determine the shape and size of the
crystallites. Catalysts were reduced in situ with H2 at 350C for 1 h prior to the
reaction.
Physicochemical properties of catalysts are presented in Table 1.
Table 1. Physicochemical properties of catalysts.

Average PdZn
Palladium
2 pore average
Catalyst SBET (m /g) content
diameter crystallite
(wt.%)
(nm) size (nm)
Pd/ZnO-1 26.0 23.9 4.67 4.2
Pd/ZnO-2 15.2 22.3 5.79 4.5
Pd/ZnO-3 23.9 20.3 4.76 3.6
The results of the steam reforming of methanol carried out over palladium-zinc
oxide catalysts show that obtained catalysts were active in methanol steam
reforming reaction and show almost full conversion of methanol at the temperatures
below 400C The highest activity and good selectivity to H2 was observed for the
catalyst Pd/ZnO-3. It is noticed that catalytic performance can be influenced by the
crystallite size.
Fig. 1. Aactivity and selectivity of the methanol steam reforming over catalysts
(H2O/CH3OH = 1.5 mol/mol).
References:
[1] M. Boutonnet, S. Lgdberg, E.E. Svensson, Current Opinion in Colloid &
Interface Science, 13 (2008) 270286.
COBATL CATALYSTS WITH MANGANIUM SUPPORT FOR
STEAM REFORMING OF ETHANOL
Bogna BANACH
Providing an clean and secure renewable energy source is one of the key
challenges facing mankind nowadays. Hydrogen is potentially an ideal energy
carrier, as it is non-polluting, oxidized yields only water. Nevertheless, many
challenges must be overcame for hydrogen to be used broadly in a sustainable
future energy system. To achieve the greatest benefit for the environment a low
cost, low polluting and low-carbon intensive process for hydrogen production from
renewable sources needs to be developed. The ethyl alcohol seems to be a highly
realistic candidate as a chemical carrier of hydrogen. Currently bioethanol is
produced by the fermentation of sugar cane, corn grains and other starch-rich
materials. Technology focusing on the production of ethanol from lignocellulosic
biomass open up the possibility for the utilization of low-cost biomass (agricultural
wastes and forests residues, such as straw, grasses, corn stover, wood). In this way,
food could be produced along with bioethanol from agricultural sources [1].
Though there are several possibilities of gaining hydrogen from bioethanol the one
which was used in this work is the steam reforming of ethanol (SRE). Catalyst for
SRE in order to gain high hydrogen selectivity must be able to: (i) dehydrogenate
ethanol, (ii) break C-C bonds, (iii) reform C1 products to generate hydrogen. The
final hydrogen efficiency of the SRE will depend on the intensity and the state of
the equilibrium of the water gas shift reaction H2O + CO H2 + CO2 as well as
successful inhibition of non-selective transformations of ethanol to acetaldehyde,
ethylene, methane, acetone and other by-products which are formed in side
reactions [2].
The aim of our studies was to find the optimal temperature for SRE process
over series of new catalysts with cobalt active phase. The effectiveness of the
process of hydrogen formation, i.e. ethanol conversion, its selectivity and hydrogen
yield, was also investigated.
All catalysts were prepared by the co-precipitation method. Characterization of
the catalyst was done with XRF, low-temperature nitrogen adsorption, hydrogen
chemisorption. The SRE effects were measured at 420C in the reaction mixture
(H2O/EtOH molar ratios equal to 21/1) as an equivalent for fermentation broth for
48h. All catalysts were reduced in situ with H2 at 400C for 1 h prior to the reaction.
Table 1. Physicochemical properties of catalysts series.
Catalyst SBET (m2/g) Average pore diameter (nm) Cobalt content (wt.%)
A-0 102 9.9 22
A-1 95 10.6 22
A-2 97 10.3 22
The results of the steam reforming of ethanol carried out over modified cobalt-
rich catalysts show that modifying agent allowed to carry out SRE process at
temperature as low as 420C. Also increase of modifier content led to improvement
of catalyst activity and selectivity.
Fig. 1. Effect of modification on activity and selectivity of the SRE over new catalysts
(EtOH/H2O = 1/21 mol/mol, T = 420C).
The presented results show that the modifying agent allowed to limit
acetaldehyde formation and elimination of acetone from reaction products. At
420C temperature the conversion of ethanol was complete (for sample A-2). Also,
the hydrogen and carbon dioxide formation was minimalize for A-2 sample.
References:
[1] S. Pariente, N. Tanchoux, F. Fajula, G. Centi, S. Perathoner, Bioethanol:
Production and Pathways for Upgrading and Valorization, in: Catalysis for
Renewables: From Feedstock to Energy Production (G. Centi, R.A. van Santen,
Eds.), Chapt. 9, Wiley-VCH (2007) 183.
[2] B. Banach, A. Machocki, Appl. Catal., A., 505 (2015) 173.
PREPARATION AND STUDIES ON SUPPORTED COBALT
CATALYSTS FOR STEAM REFORMING OF ETHANOL
Magdalena GRELUK
Approximately 80% of the present world energy demand comes from fossil
fuels. Unlike fossil fuels, hydrogen gas (H2) burns cleanly, without emitting any
environmentally pollutants. In addition, H2 is also abundantly available in the
universe and posses the highest energy content per unit of weight (i.e. 120.7 kJ/g)
compared to any of the known fuels [1]. Therefore, hydrogen is considered to have
a bright future as a source of clean energy, mainly through its use as fuel in fuel-cell
systems, which are described as continuously operating batteries; one of the
cleanest and greenest sources of electrical energy. Currently, there are four basic
methods in common use for hydrogen production i.e., water electrolysis
gasification, partial oxidation reactions and steam reforming reactions [2]. At
present steam reforming of hydrocarbons, i.e. natural gas, is the most commonly
used and generally the most economically competitive method for hydrogen
production. However, there is growing interest in the search for effective
alternatives to produce renewable hydrogen cleanly and safely. Among the various
feedstocks, ethanol is very attractive because of its relatively high hydrogen
content, availability, non-toxicity, and storage and handling safety. More
importantly, ethanol can be produced renewably by fermentation of biomass
sources, such as energy plants, agroindustrial wastes, forestry residue materials, and
organic fraction of municipal solid waste [3]. Steam reforming is the most widely
used method to convert ethanol to hydrogen [2]. Different base metals (Ni, Co and
Cu) and noble metals (Pd, Pt, Rh and Ru have been tested for ethanol conversion
reactions. Since cobalt is a much less costly alternative to noble metals, cobalt
based catalysts have been extensively studied for steam reforming of ethanol.
Recent studies indicated that the activity of cobalt catalysts depended on the
numbers of active sites after the reduction, while the active site numbers should be
determined by the metallic cobalt particle size, loading amount, dispersion and
reduction degree. Synthesis of highly dispersed cobalt catalysts requires strong
interaction between the support and the cobalt precursor, which forms fine CoO and
Co3O4 clusters. It is considered that solvents used to dissolve cobalt precursors have
a remarkable effect on the interaction between cobalt and support [4]. Ho et al. [5]
observed ethanol as a solvent of impregnation instead of water for the catalysts
obtained from cobalt nitrate improved the dispersion of supported and retained a
high extent of reduction of the cobalt phase.
In light of above points, the goal of this study was to assess the effect of using
methanol, ethanol and propanol as the impregnation solvent in the preparation of
cobalt catalysts supported on ceria in the ethanol steam reforming of ethanol.
The catalysts, prepared by support impregnation with cobalt nitrate solutions
were characterized using various characterization techniques including nitrogen
adsorption, hydrogen chemisorption, X-ray fluorescence., X-ray diffraction (XRD)
and temperature-programmed reduction (TPR). The reaction of ethanol conversion
with water was carried out under atmospheric pressure in a fixed-bed continuous-
flow quartz reactor over the catalyst (0.1 g; 0.15-0.3 mm) reduced in situ with
hydrogen at 400C for 1 hour, prior to the reaction.
Physicochemical properties of both catalysts are presented in Table 1.

A(MeOH) B(EtOH) C(PrOH) D(H2O)
2
SBET (m /g) 34.6 35.7 35.2 31.2
Pore volume (mL/g) 0.12 0.17 0.20 0.10
Average pore size (nm) 12.9 18.6 21.9 11.8
Cobalt surface area (m2/gcat) 9.6 7.7 6.1 5.1
2
Cobalt surface area (m /gCo) 116.1 85.8 66.1 55.6
Aver. Co crystallite size (nm) 16.4 19.4 21.4 25.3
Co content (% wag.) 8.30.3 9.00.3 9.20.3 9.20.3
The type of solvent used to dissolve cobalt precursor in order to obtain cobalt
based catalysts on ceria influences on:
- cobalt dispersion, according to the order:
A(MeOH) > B(EtOH) > C(PrOH) > D(H2O)
- ethanol conversion in steam reforming of ethanol, according to the order:
- selectivity of ethanol conversion in steam reforming of ethanol, according
to the order:
It does not influence on reducibility of obtained oxide forms of catalysts. the
optimum Temperature of 540C is the lower one which simultaneously enables to
achieve total conversion of ethanol, the high production of hydrogen, the lack of
acetaldehyde among reaction products, small concentration of carbon monoxide.
References:
[1] A. Haryanto, S. Fernando, N. Murali, S. Adhikari, Martin, B. Pierre, C. March,
Energy & Fuels, 19 (2005) 2098-2106.
[2] A. Bshish, Z. Yaakob, B. Narayanan, R. Ramakrishnan, A. Ebshish, Chemical
Papers, 65 (2011) 251-266.
[3] M. Ni, D.Y.C. Leung, M.K.H. Leung, Int. J. Hydrogen Energ., 32 (2007) 3238-
3247.
[4] Y. Zhang, Y. Liu, G. Yang, S. Sun, N. Tsubaki, Appl. Catal. A: Gen., 321
(2007) 79-85.
[5] S.W. Ho, M. Houalla, D.M. Hercules, J. Phys. Chem., 94 (1990) 6396-6399.
THE SURFACE STATE AND CATALYTIC PERFORMANCE
OF COBALT-BASED CATALYSTS
UNDER THE STEAM REFORMING OF ETHANOL
Sylwia TURCZYNIAK
The great interested in Co-based catalysts designed for the ethanol steam
reforming (ESR) was a driving force for series of studies of the role of Co oxidation
state under the reaction conditions. So far, techniques like XRD, XAS [1], APPES
and ex-situ [3] and quasi- in situ [3] XPS were employed; however, limitations of
each technique still leave many questions for researchers. Hypothesis that Co(0) is
the most active form of cobalt slowly loses its support, since the presence of both:
Co(0) and Co(II) under the ESR was confirmed [5-6]. Nowadays, it is expected that
both forms of Co are important for the ESR; however, their specific role is still
under discussion. Real catalytic systems are rather complicated, therefore not only
the state of cobalt but also the oxidation state of the support should be examined. In
the previous project low- and high-surface area oxides: AOx and BOx have been
selected for catalysts preparation. The catalysts were prepared by the impregnation
method and denoted as Co/AOx and Co/BOx respectively. It was found that the low-
surface area catalysts were not resistant to the coke formation under the ESR
(EtOH/H2O = 1/12 mol/mol, T = 420C) therefore high-surface area catalysts were
promoted with potassium (KCo/AOx and KCo/BOx) and characterized by XRD,
XRF, XPS and chemisorption method. It was expected that the addition of alkali
metal will improve catalysts activity, selectivity and stability in the ESR.
The aim of this research was (i) to determine the surface composition after
catalysts reduction and under the reaction conditions, (ii) to examine the oxidation
state of cobalt, the supports and potassium under the ESR.
The results of quasi-in situ XPS studies over the reduced samples indicate that
on the surface of both catalysts Co(0) was the dominating form of cobalt however,
some amounts of Co(II) were present. Higher concentration of cobalt oxide species
was found on the KCo/BOx. The reduction procedure did not influence significantly
on the supports oxidation state. Only slight changes that could indicate for the
support reduction were observed in the case of KCo/AOx. The position of the K 2p
clearly indicated to the presence of K-O species. So far published studies did not
allowed to determine if potassium exists on the surface as KOx or K2CO3. Since the
presence of both: oxygen adsorbed species (on the base of O 1s) and carbonates
(basing on the C 1s spectra) were confirmed, both forms could be expected.
After the ESR (EtOH/H2O = 1/12 mol/mol, T = 420C, ptotal = 1atm, t = 1h) it
was found that the determination of cobalt oxidation state of KCo/AOx was
impossible. The main components on the surface were oxygen and potassium. This
showed that in the case of this catalyst, potassium significantly increased the
surface oxygen mobility. The presence of these two components may also suggest
formation of K-O adlayer which is responsible for the increase of the catalyst
resistance for the coke formation. Surprisingly, the XPS spectra collected for the
KCo/BOx did not provide similar conclusions. The amount of the surface adsorbed
oxygen species (assigned in literature to the OH groups) increased; however, the
change of the atomic percentage coverage (at.%) of the surface by potassium was
significantly lower. In the case of the KCo/AOx the difference between potassium
at.% on the surface of the sample after the ESR and after reduction was 17% while
for the KCo/BOx it was only 2%. This clearly shows for higher potassium mobility
on the surface of the KCo/AOx.
The percentage contribution of Co(II) in the Co 2p spectrum for the KCo/BOx
was around 41%, therefore showing significant Co oxidation under the ESR. To
determine cobalt oxidation state for the KCo/AOx 15 min ESR was carried out. The
results have shown lower oxidation of cobalt than in the case of KCo/BOx. The
position and shape of characteristic peaks on the XPS spectrum for the element B
did not provide the information about the change of the oxidation state, while the
spectrum for the element A clearly confirmed reduction.
The obtained results provide new information about the state of the catalysts
surface under the ESR and may indicate that depending on the support potassium
invokes different changes on the surface. It is very probable that the nature and
stability of potassium species may influence on catalysts stability and higher CO2
selectivity under the ESR. The paper with more detailed description and conclusion
is under preparation.
References:
[1] I.I. Soykal, H. Sohn, U.S. Ozkan, ASC Catal., 2 (2012) 2335.
[2] S.-W. Yu, H.-H. Huang, C.-W. Tang, C.B. Wang, Int. J. Hydrogen Energy, 39
(2012) 20700.
[3] E. Varga, Z. Ferencz, A. Oszk, A. Erdoheyi, J. Kiss, J. Mol. Catal., A 397
(2015) 127
[4] J. Llorca, J.A. Dalmon,, P.R. de la Piscina, N. Homs, Appl. Catal. A, 243 (2003)
261.
[5] W. Luo, A. Asthagiri, Catal. Sci. Technol., 4 (2014) 3379.
[6] A.M. Karim, Y.Su, M.H. Engelhard, D.L. King, Y. Wang, ACS Catal., 1 (2011)
279.
SYNTHESIS AND EXAMINATION OF PROPERTIES OF
BIMETALLIC CATALYST FOR METHANOL STEAM
REFORMING
Justyna PAWLONKA
The development of fuel cell technology for electricity generation resulted in

increased interest in the process of hydrogen production by the steam reforming of
methanol. The promising properties have been evidenced for bimetallic palladium-
zinc catalysts in this reaction. The synthesis of bimetallic catalysts with controlled
crystallite size and high dispersion is one of the major challenges. Based on
previous research, it appears that the preparative conditions have a great influence
on the properties of catalysts. Among the methods, which gives possibility of good
control of particle size is synthesis in reversed micelles. It can be achieved by
simple adjustment of the amount particular microemulsion components and
synthesis conditions. The easiest and the most popular way is changing the amount
of surfactant, resulting in the change of micelles diameters, which are the kind of
nanoreactors. The aim of the studies was to determine the influence of synthesis
conditions on the surface and structural properties of bimetallic palladium-zinc
catalysts.
Palladium supported zinc oxide catalysts were prepared by microemulsion
method. Palladium or palladium zinc alloy catalysts were prepared using reversed
micelles. Microemulsion consisted out of cyclohexane, isopropanol, aqueous
solution of metal salts and Triton-X-100 as surfactant. The synthesis was carried out
under different molar ratio of water-to-surfactant. The species after reduction by
hydrazine were deposited on commercial zinc oxide. The properties of catalysts
were investigated by X-ray fluorescence (XRF), X-Ray diffraction (XRD) and low-
temperature nitrogen adsorption methods. Catalysts were additionally reduced in
situ with H2 at 350C for 1 h prior to the reaction of steam reforming of methanol.
XRD studies showed that both palladium and palladium-zinc alloy phases
were present in Pd/ZnO catalysts. For PdZn/ZnO catalysts, simultaneous reduction
of Pd and Zn species was performed in microemulsion and Pd phase was not
observed. This suggests that only PdZn alloy species were formed and remained in
the samples after thermal treatment in the inert gas atmosphere. Direct reduction of
palladium and/or zinc in microemulsion by such strong reducing agent as hydrazine
led to development of large of Pd and PdZn crystallites. Hence the catalysts showed
relatively low activity in methanol steam reforming reaction. In spite of this,
PdZn/ZnO catalysts showed higher activity than Pd/ZnO catalysts, activated after
synthesis.
Average PdZn Pd
Palladium
SBET pore average average
Catalyst content
(m2/g) diameter crystallite crystallite
(wt.%)
(nm) size (nm) size (nm)
Pd/ZnO-1 3.3 37.8 4.37 33.0 33.3
Pd/ZnO-2 8.9 14.3 4.36 31.1 34.1
Pd/ZnO-3 2.4 28.2 4.38 47.3 91.4
Pd/ZnO-4 11.8 16.4 4.37 25.3 34.8
PdZn/ZnO-1 6.6 31.6 1.90 25.9 -
PdZn/ZnO-2 6.9 24.3 4.42 45.2 -
PdZn/ZnO-3 8.6 19.0 1.85 30.7 -
PdZn/ZnO-4 8.0 26.3 3.73 29.2 -
Nearly full conversion of methanol was observed only for PdZn/ZnO-1

catalyst at the temperature of 420oC. Satisfactory selectivity to hydrogen was
observed for PdZn/ZnO-1and PdZn/ZnO-4 samples with palladium zinc alloy.
Fig. 1. Activity and selectivity of the catalysts in methanol steam reforming reaction
(H2O/CH3OH = 1.5 mol/mol).
SELECTIVITY AND ACTIVITY STUDY OF SUPPORTED
COBALT-NICKEL CATALYSTS IN THE STEAM REFORMING OF
ETHANOL
Grzegorz SOWIK
The steam reforming (SR) of ethanol C2H5OH + 3H2O 6H2 + 2CO2 is a

very effective way to obtain hydrogen from liquids, easy to transport and storage.
Ethanol can be produced from renewable raw materials (e.g. biomass). In the SR of
ethanol, a catalyst plays an important role in achieving complete and selective
ethanol conversion. Depending on the catalyst, reaction conditions and the method
of preparing of the catalyst, the conversion of ethanol and hydrogen production are
significantly different. In contrast to the highly active catalytic systems of noble
metals proposed for in the SR of ethanol, supported Ni and Co catalysts are less
costly alternative. Polymetallic heterogeneous catalysts, consisting mostly of
bimetallic metals nanoparticles on inorganic oxide supports, allow us to obtain good
results (due to increased activity and selectivity towards desired products, long
service life, prevention of the formation of a deposit of carbon or sintering) through
positive effects resulting from the interaction between two metals.
The aim of the studies was determination of the relationship between
conversion of reactants and selectivity of the SR of ethanol process and its
temperature and determination of the stability of K promoted Co-Ni catalytic
systems in the SR of ethanol by testing under isothermal (420C) conditions.
The catalysts containing from 0-10% of Ni and 0-10% of Co and promoted
with K were prepared by two-step impregnation of the CeO2 support. Before testing
selectivity and activity, catalysts were reduced with hydrogen directly in the reactor
at 400C. The activated nanomaterials were used in the SR of ethanol (the ratio of
reactants was 12 mole of water/1 mole of ethanol) to obtain hydrogen.
Studies show that the lowest temperature for complete ethanol conversion over
all Co-Ni catalysts is 420C (Fig. 1). At the initial phase of testing all catalysts
provides 100% conversion of ethanol (Fig. 2). After 24 hours of work in the SR of
ethanol only the catalyst with Ni active phase provide 100% conversion of ethanol.
All catalysts showed high selectivity for hydrogen (Fig. 3). The catalysts with a
significant amounts of Ni were more selective to methane than those with a smaller
(<2.5%) Ni amount. Significant amounts of acetaldehyde and acetone were formed
on the catalysts with predominant content of Co. The highest initial yield of
hydrogen 5.5 mol H2/mol EtOH and carbon dioxide 1.6 mol CO2/mol EtOH
provided the catalyst with the Co active phase, but after 24 hours, the yields
dropped to 1.75 mol H2/mol EtOH for hydrogen and to 0.4 mol CO2/mol EtOH for
carbon dioxide (Figs. 4 and 5). The most stable system was proved to be the catalyst
containing 10% of Ni. The hydrogen yield over that catalyst do not changed during
24 hours of the SR of ethanol and was equal to 4.5 mol H2/mol EtOH.
Fig. 1. Initial EtOH and H2O conversions in the SR

of ethanol on K promoted catalysts with different
contents of Co and Ni at 350 600C
Fig. 2. Conversion of ethanol and water in Fig. 3. Selectivity of SR of ethanol at 420C

the SR of ethanol at 420C on K promoted on K promoted catalysts with different
catalysts containing different amounts of Co contents of Co and Ni.
and Ni.
Fig. 4. Hydrogen yield in the SR of ethanol Fig. 5. Carbon dioxide yield in the SR of
at 420C on K promoted catalysts containing ethanol at 420C on K promoted catalysts
different amounts of Co and Ni. containing different amounts of Co and Ni.
STUDY OF TEMPERATURE DEPENDENCES OF ADSORPTION
KINETICS ORGANICS FROM AQUEOUS SOLUTIONS
Magorzata SCZKOWSKA
DEPTARTMENT OF RADIOCHEMISTRY AND COLLOID
CHEMISTRY
Organic aromatic compounds are commonly used in many branches of

industry. These substances are generally toxic, stable and soluble in water.
Therefore, the problem of removing these compounds from waters and wastewaters
is important and still investigated. Highly efficient technology for the removal of
toxic substances are adsorption method using activated carbon [1-2]. Adsorption is
multistage process. Efficiency of this process is depends on properties of the
adsorbent and adsorbate (surface charge adsorbent, pore size, specific surface area,
particle size of the adsorbate, the differences in solubility), the environment of the
process (pH), the presence of co-adsorbates and temperature.
The main aim of this study was to investigate the influence of temperature on
the rate of adsorption for selected organics (phenols, nitrophenols, chlorophenols,
dyes, pesticides, sufactants) from aqueous solution.
Measurements of adsorption kinetics of 3-nitrophenol (3-NPh, Sigma-Aldrich)
on activated carbon GAC (Norit; SBET=900 m2/g, Vt=0.52 cm3/g, Vmic=0.2 cm3/g)
for wide range of temperatures.
The application of measurement methodology allowed to gain high-quality
experimental data. Changes concentration and adsorption in time were analyzed by
using several empirical equations and kinetics models. The equations applied
included first and second order (FOE, SOE), mixed order (MOE) [3-6], Langmuir
kinetics (IKL) [5,7], intraparticle diffusion (IDM) and pore diffusion model (PDM)
as well as multi-exponential (m-exp) equation [3-7].
The transformation of the kinetic data allows to estimate the fitting parameters
to the above empirical equations and kinetic models. This makes, it possible to
determine that the process of adsorption of a given model. Therefore, one may
specify an effect of temperature changes on kinetics and mechanism of adsorption.
Such a detailed analysis of experimental data allows for a deeper knowledge and
understanding of the mechanism of adsorption of toxic substances on microporous
carbon adsorbents. The acquired information is of great importance in the
optimization of water treatment technology and wastewater by adsorption using
activated carbon.
On the basis of the experience can be concluded that the temperature is very
important factor in controlling the whole process of adsorption.
Fig. 1. Adsorption kinetics of 3-NPh on the activated carbon GAC at 278, 288, 298, 308,
318 K. All kinetics curves are fitted by multi-exponential equation (m-exp).
References:
[1] S. Chiron, A. Fernandez-Alba, A. Rodriguez, E. Garcia-Clavo, Water Res.
34 (2000) 366.
[2] L. Clausen, I. Fabricius, L. Madsen, J. Environ. Qual. 30 (2001) 846.
[6] A.W. Marczewski, A. Derylo-Marczewska, A. Slota, Adsorption,
19 (2013) 391.
[7] A.W. Marczewski, J. Colloid Interface Sci., 361 (2011) 603.
EXPERIMENTAL ANALYSIS OF ADSORPTION KINETICS IN
MULTICOMPONENT SYSTEM
Magorzata SCZKOWSKA
DEPTARTMENT OF RADIOCHEMISTRY AND COLLOID
CHEMISTRY
Big leap forward many countries around the world resulted in a significant
increase in the risk of emission of toxic substances. Among the large group of these
substances are aromatic organic compounds, among them: pesticides, dyes, phenols,
surfactants, and pharmaceuticals. These substances are generally soluble in water
and consequently easily migrate into the environment. In the era of intensive
development of the industry it is becoming a serious problem the presence of large
quantities of the above-mentioned compounds in water and wastewater. This in turn
created the need to develop technologies aimed at the total elimination or
minimization of the concentration of toxic substances from natural waters and
sewage. It turns out that a very efficient purification of fluids is adsorption using
activated carbon as an adsorbent. The presence of different kinds of aromatic
organic compounds of natural origin or synthetic may significantly affect the course
of treatment technologies by adsorption. It is therefore important to determine
mutual interference in the process of adsorption between substances found in water
and wastewater [1-2].
The main aim of this study was experimental analysis of the adsorption
kinetics in multicomponent systems.
Measurements of adsorption kinetics of methylene blue (MB; Sigma-Aldrich)
and 4-nitrobenzoic acid (4-NBA, Merck) on activated carbon GAC (SBET=900 m2/g,
Vt=0.52 cm3/g, Vmic=0.2 cm3/g) in single and multi-component systems were
studied. The concentrations of the solutions were chosen to be measured without
additional dilution.
The application of measurement methodology allowed to receive high-quality
experimental data. Profiles concentration ~ time and adsorption ~ time were
analyzed by using several empirical equations and kinetics models. The equations
applied included first and second order (FOE, SOE), mixed order (MOE) [3-6],
Langmuir kinetics (IKL) [5,7], intraparticle diffusion (IDM), pore diffusion model
(PDM) and multi-exponential (m-exp) equation [3-7].
Analysis of the kinetic data allows to determine the fitting parameters to the
above empirical equations and kinetics models. This makes, it possible to verify
that the process of adsorption of a given model. Therefore, we can determine the
impact of the presence of other substances on the rate and mechanism of adsorption.
Such a detailed analysis of experimental data allows for a deeper knowledge and
understanding of the mechanism of adsorption of aromatic organic compounds on
microporous carbon adsorbents. The obtain information is of great importance in
the optimization of water treatment technology and wastewater by adsorption using
activated carbon.
On the basis of this study can be concluded that the presence of competing
substances is of great importance in controlling the whole adsorption process.
Fig. 1. Comparison of adsorption kinetics of MB and 4-NBA on GAC in single and multi-
component systems, 328 K. All kinetics curves are fitted by multi-exponential equation (m-
exp).
References:
[1] S. Chiron, A. Fernandez-Alba, A. Rodriguez, E. Garcia-Clavo, Water Res.
34 (2000) 366.
[2] L. Clausen, I. Fabricius, L. Madsen, J. Environ. Qual. 30 (2001) 846.
[6] A.W. Marczewski, A. Derylo-Marczewska, A. Slota, Adsorption,
19 (2013) 391.
[7] A.W. Marczewski, J. Colloid Interface Sci., 361 (2011) 603.
THE ALBUMIN ADSORPTION INFLUENCE ON THE
ELEKTROKINETIC PROPERTIES OF THE ZIRCONIA
SUSPENSION
Katarzyna SZEWCZUK-KARPISZ
Protein adsorption strongly affects the electrokinetic properties of colloid

system, i.e. surface charge density and zeta potential of the solid particles.
Knowledge of these parameters in the protein presence can be highly helpful in the
interpretation of adsorption mechanism as well as the system stability. Moreover,
based on them the determination of the electrical double layer structure is possible
[1].
The surface charge density was appointed by the potentiometric titration
method. In this examination the solid surface charge is determined based on the
difference in base volume added to the suspension containing polymer and
supporting electrolyte solution in order to achieve a specific pH value. The
measurements were conducted using the computer program titr_v3 developed by
W. Janusz [2] and the apparatus consisting of: teflon thermostated vessel, water
thermostat RE 204 (Lauda), glass and calomel electrodes (Beckman Instruments),
pHmeter PHM 240 (Radiometer), automatic microburette Dosimat 765 (Metrohm),
PC and printer. Figure 1 shows the dependence of solid surface charge density in
the absence and presence of albumins on the solution pH value.
Fig.1. The zirconia surface charge density in the absence and presence of albumins.
The point of zero surface charge (pHpzc) of zirconia was equal to 6. This means that
at pH 6, the surface charge density is close to 0. Under these conditions, the
concentrations of ZrO- and ZrOH2+ groups on the adsorbent surface are identical.
The albumin adsorption changes the pHpzc value and the surface charge density
slightly. In the albumin presence, regardless of the biopolymer type and
concentration, a little decrease in the surface charge was observed. This is probably
due to the interaction of the -ZrOH surface groups with the protonated amino
groups of the macromolecules (-NH3+).
Zeta potential of the zirconia particles was determined by the
microelectrophoresis method using a Zetasizer Nano ZS (Malvern Instruments). In
this measurement colloidal particles move in the electric field of the electrophoretic
cell. The potential reading is made automatically when the particle movement is
compensated for by the applied voltage. Figure 2 presents the obtained results.
Fig. 2. Zeta potential of zirconia particles in the BSA presence as a function of the protein
concentration.
The measurements indicate that the zirconia isoelectric point (pHiep) is 6. Thus, at
pH 6 the charge of the ZrO2 slipping plane is equal to 0. The biopolymer adsorption
affects the pHiep and electrokinetic potential values of the solid particles. In the
albumin presence, the ZrO2 pHiep point approaches the isoelectric point of proteins
(about 5). This is the result of coating the entire zirconia surface by the adsorbate
macromolecules.
References:
[1] K. Szewczuk-Karpisz, M. Winiewska, Int. J Environ. Sci. Technol. 12 (2015)
2947.
[2] W. Janusz, Electrical double layer at metal oxide-electrolyte interface in
interfacial forces and fields theory and applications, M. Dekker, New York,
1999.
ADSORPTION OF ANIONIC AND CATIONIC POLYAMINO ACID
COPOLYMERS ON THE SILICA SURFACE
Iwona OSTOLSKA
Polyamino acids are a group of synthetic polymers whose backbone is made

up of individual amino acid monomers linked by a peptide bond. As naturally
occurring amino acid molecules are used in the synthesis, the prepared polymers
exhibit a number of important properties relevant to medicine, pharmacy and
environmental protection. First of all, the macromolecules are characterized by
complete biodegradability. The polymeric chains can be decomposed by enzymes
hydrolyzing the peptide bond, and the final products may be included in the life
cycle of the organism. Secondly, the polyamino acids are non-toxic and
biocompatible with human body, therefore their use does not induce an immune
response [1].
The solution pH impact on the adsorption process of the block copolymers on
the colloidal silica surface was investigated. All polymeric chains consist of the
poly(ethylene glycol) (PEG) fragment and the suitable ionic polyamino acid
segment (poly-L-lysine or poly-L-aspartic acid). The analyzed substances are
characterized by different polymer chain structures but have similar average
molecular weight. Adsorption measurements were conducted by the static method.
The polymer concentration after the adsorption process was estimated by using the
UV-Vis Spectrometer (Cary 100, Varian) at a wavelength of 210 nm. This
wavelength was chosen after the UV-Vis absorption tests [2].
In the case of the copolymers containing the anionic fragment derived from
poly(L-aspartic acid) - ASP-b-PEG and ASP-b-PEG-b-ASP, the adsorption is
observed only at pH 3 and 7.6. In the alkaline solution the electrostatic repulsion
forces between the totally dissociated ASP segments and the silica surface preclude
the block copolymer macromolecules binding. The adsorption isotherms analysis
indicates the marked differences in the adsorption amount of both compounds. This
is related to the conformation which the adsorbed polymer chains adopt on the silica
surface. In the acidic medium, the poly(ethylene glycol) block can form a numerous
hydrogen bonds with both positively charged and amphoteric adsorbent surface
species. Due to the low dissociation degree of the carboxylic groups belonging to
the anionic polyamino acid chains (=16%), the electrostatic interactions
contribution into the adsorption process is insignificant. A higher amount of ASP-b-
PEG adsorbed macromolecules (in comparison to the symmetric ASP-b-PEG-b-
ASP) is a consequence of the longer nonionic chain presence in the macromolecule.
Simultaneously, a PEG block can decrease repulsion by screening the charges
coming from the neighboring adsorbed ASP segments. This phenomenon does not
occur in the system containing the triblock copolymer (the PEG fragment is too
short). Therefore the adsorption of ASP-b-PEG-b-ASP on the colloidal silica is
driven by the interactions between the polyamino acid segments and the solid.
Despite the compact ASP chains conformation, the triblock copolymer
macromolecule takes up more space on the SiO2 surface compared to the diblock
polymer.
Fig.1. The zirconia surface charge density in the absence and presence of albumins.
Adsorption of the copolymers containing the poly(L-lysine) chain on the silica

surface is shown in Figure 1. The presented data point out that the solution pH is the
key factor influencing the both polymer blocks binding mechanism. At pH 4 the
amount of adsorbed macromolecules is small compared to those obtained in the
alkaline medium (adsorption at pH 3 is not observed). In order to understand
precisely the polymer chains adsorption at the silica aqueous solution interface,
the interactions between various segments of the copolymer and the solid surface
should be analyzed. At acidic pH all amino groups originated from the poly(L-
lysine) fragment undergo ionization which is a direct reason for the expanded
spatial conformation of the polyamino acid chains. The LYS segments are linked to
the adsorbent mainly through the hydrogen bridges and a small number of the
electrostatic interactions. Due to the lack of groups capable of electrolytic
dissociation, the nonionic PEG block is adsorbed on account of hydrogen bonds
formation. Therefore the observed changes in the cationic copolymers adsorption
amount are related to the modification of the two structural units length ratio.
References:
[1] F. Rypek, J. Pytela, R. Kotva, V. karda, I. Cifkov, Macromol. Symp., 123
(1997) 9.
[2] X. Wang, B.I. Lee, L. Mann, Colloids Surf. A, 202 (2002) 71-80.
THE MODIFICATION OF POLYMERIC MICROSPHERES WITH
THE USE OF RAFT POLYMERIZATION
Marta GROCHOWICZ
DEPARTMENT OF POLYMER CHEMISTRY
Surface modification of microspheres aimed at achieving their shell-

functionalization is an interesting tool for modifying their properties. In general,
two different approaches can be mentioned, the grafting to and the grafting from
approach [1]. In the grafting to technique a reactive terminal group on a functional
polymer chain reacts with the activated surface of microspheres. The already
attached chains lead to a steric hindrance for following chains to diffuse to the
surface. Such an approach suffers from low grafting rates. The benefit of the
grafting to technique is that usually the reactive groups necessary to achieve the
grafting to process do not dictate the kind of polymer chemistry employed,
allowing a great versatility of polymers to be immobilized on the particles surface.
Moreover, the employed linear polymer can be thoroughly characterized before the
conjugation (with regard to molecular weight, polydispersity or functionality). As a
polymerization method for obtaining polymeric chains, reversible addition-
fragmentation polymerization is often used. The dithioester moiety of a RAFT
agent serves two purposes. Initially, the dithioester moiety functions as a RAFT
agent for obtaining polymer chains of predetermined molecular weight carrying
RAFT end groups; subsequently these dithioester functionalities can be employed
as a reactive heterodienophile in heteroatomic Diels Alder cycloaddition reaction
(HDA) with a functionalized diene.
The aim of the project was the functionalization of surface of copolymeric
microspheres obtained with glycidyl methacrylate (GMA) and 1,4-
dimethacryloyloxybenzene (1,4DMH) with the use of linear polymeric chains of
poly(geranyl methacrylate) which were obtained via RAFT polymerization.
Copolymeric microspheres poly(GMA-co-1,4DMH) with permanent porous
structure and monodisperse particle diameters were obtained via radical
polymerization of methacrylate monomers: functional glycidyl methacrylate and
crosslinking agent 1,4-dimethacryloyloxybenzene. Seed polymerization was chosen
as an efficient method for the preparation of such particles. Microspheres which
were subjected to the further chemical modification possessed diameters about
8,61 m (RSD 2,47%); the surface area (SBET) equal 236 m2/g, the pore volume
Vp = 0.25 m3/g, and the pore diameters were in the range suitable for mesopores.
The selected poly(GMA-co-1,4DMH) microspheres which possessed in their
structure epoxide groups were reacted with sodium cyclopentadienide which is a
derivative of the one of the most reactive dienes in the DielsAlder reactions [2].
The chemical modification of such prepared microspheres was carried out with
HDA reaction. As a dienophile the RAFT poly(geranyl methacrylate) chains were
used. The grafting to approach was chosen for grafting polymeric chains with
well-defined properties on the surface of the microspheres. Linear poly(geranyl
methacrylate) chains were synthesized by RAFT polymerization. This
polymerization method allows controlling the molecular weight of the polymer
being obtained, and, through the use of a chain transfer agent (CTA), introduces
thiocarbonyl groups on the polymer chain ends. The selection of a suitable CTA
compound occurred problematic. In the course of the study, it was found that
pyridine-2-carbodithioic acid methyl ester is the appropriate CTA. This compound
was obtained according to the Scheme 1 [3].
PhSO2Na
cat. Pr 4NBr 1. S 8 / t-BuOK, 3h
+ PhSO2Me
CH3CN, DBU 2. MeI, 1h SMe
o
80 C, 24h N O N
N
Cl Ph S
HCl S
O
Scheme 1. Synthetic route of CTA.
H3C
S
+ HDA
H3C S N
n H3C
S
S N
O
O
functional H3C
CH3 poly(GMA-co-14DMH) n
O
H3C CH3 O
H3C
RAFT-poly(GM)
H3C CH3
poly(GM)-graft- poly(GMA-co-14DMH)
Scheme 2. The modification reaction of microspheres.
As a result of RAFT polymerization poly(GM) were obtained and they were

characterized by different number average molecular weight (Mn) in the range of
1800 Da to 5500 Da, with the value of MW/Mn equal about 1.09. RAFT-poly(GM)
macromolecules with Mn = 2800 Da possessing thiocarbonyl groups on the chain
ends were reacted with polymeric microspheres by hetero Diels Alder reaction
according to the Scheme 2. The ATR-FTIR and CP/MAS 13C NMR analyses of
microspheres before and after modification confirmed that HDA reaction was
successfully performed.
References
[1] L. Barner, Adv. Mater, 21 (2009) 2547
[2] M. Grochowicz, P. Pczkowski, B. Gawdzik, Adsorpt. Sci. Technol., 33 (2015)
677.
[3] I. Abrunhosa, M. Gulea, S. Masson, Synthesis, 6 (2004) 928.
THIOUREA DERIVATIVES AS SUPRAMOLECULAR SYNTHONS
Oleksandra SAVCHENKO
The molecular and crystal structure of new groups of N,N-disubstituted

thiourea derivatives was investigated. In the analyzed molecules one of the
substituents (R1) at thiourea was 4-methoxyphenyl, 2-furanmethyl, 1,3-benzo-
thiazole, 1-benzylpiperidin-4-yl, 3-trifluoromethyl or 3-chloro-4-nitrophenyl
fragment, while the other substituent (R2) was an aryl group.
Two symmetrically independent molecules are present in the crystal structure
of one derivative of 1,3-benzothiazole - 13, thus in the solid state 30 conformers are
observed.
Different conformations of the N-H bonds of thiourea group are adopted
(trans, trans or cis, trans), depending on the orientation and type of substituents R1
and R2. Differences in the molecular conformation coexist with various
intermolecular interactions and patterns of packing in the crystal.
R1 R2
1 -phe-2-CF3
O 2 -phe-3-CF3
H3C 3 -phe-2-F
4 -phe-3-F
R
5 -phe-2-Cl
6 -phe-3-Cl-4-Cl
7 -phe-2-F
8 -phe-2-Me-5-Cl
NH NH 9 -phe-3-Cl-4-F
R 10 -phe-3-Cl-4-Cl
O R1 R2
11 -phe-4-Cl
12 -phe-4-I
S 13a -phe-4-Me (A)
N
13b -phe-4-Me (B)
R
14 -phe-2-F
S
15 -C4H7
16 -phe-2F
R 17 -phe-2-Cl
18 -phe-3-Cl-4-F
N 19 -phe-4-Cl
20 -phe-3-Br
21 -phe-4-Br
F3C 22 -C7H11
23 -CO-phe
24 -phe-4-OMe
R 25 -phe-3-Cl-4-F
Cl 26 -CH2-CH=CH2
27 -C7H11
O2 N R 28 -phe
29 -phe-4-Me
The amine NH and C=S of the thiourea fragment are involved in the
intermolecular N-H...S hydrogen bonds. In all the analyzed crystal structures this
type of hydrogen bond is formed. A specific pattern of non-covalent interactions
depends on the molecular conformations.
The centrosymmetric dimer R22(8) is stabilized by the pair of N-H...S
hydrogen bonds, for the conformers cis, trans, while ten derivatives (2, 6, 8, 9, 10,
16, 17, 22, 24 and 25) having the trans, trans conformations form chains.
The most interesting intermolecular contacts are interactions between the
molecules of halo-derivatives (1, 5 and 7). In their crystal structures the N-H...X (X
= F, Cl) hydrogen bonds are formed. The donors are the thiourea NH groups and the
acceptors are the covalently bonded halogen atoms.
PLASTICS AS CARRIERS OF ORGANIC CONTAMINANTS IN
AQUEOUS ENVIRONMENT. PHYSICO-CHEMICAL AND
ECOTOXICOLOGICAL ASPECTS
Aleksandra BOGUSZ
DEPARTAMENT OF ENVIRONMENTAL CHEMISTRY
The constantly growing consumption of plastics and intensified emission of

PAHs to the environment raise more and more concerns. Out of the 25 million tons
of waste polymer plastics as much as 38% is stored in dumps (legal or uncontrolled)
where they undergo slow processes of degradation and can be transported by winds
beyond the area of the dumps causing the contamination of ecosystems. Intensified
transport of waste plastics may also be the effect of violent weather phenomena.
Studies conducted in California waters indicate that the amount of plastic wastes
with diameters < 4.75 mm increased drastically from 10 particles of plastics /m3 to
60 particles of plastics /m3 after a storm. In that manner increasing amounts of
waste plastics migrate to natural waters where they undergo further degradation and
enter into interactions with chemical substances present in a given reservoir. It is
worth emphasising the fact that waste plastics, contaminants and aquatic organisms
occur in the same trophic zones, the pelagic zone and the benthic zone. Therefore,
the occurrence of interactions between them is unavoidable. From the viewpoint of
environmental protection it is, therefore, necessary with what strength microplastics
bind organic contaminants, and thus whether the process in irreversible, precluding
secondary contamination of ecosystems or liberation of those contaminants to living
organisms.
Thus, the primary objective of this project was the determination of the level
of impact of organic contaminants from waste plastics in the context of threats that
those materials and the contaminants contained in them may cause for the
environment. The recognition of the force and range of those interactions will not
only permit the identification of mechanisms and factors affecting that process but
it will also allow the estimation of the risk related with the migration of
contaminants of that type for aquatic organisms and for humans.
The purpose of ageing was the simulation of natural conditions occurring in
the environment, which would permit the recreation of real processes to which
polymers might be subject. The selected polymers were incubated in natural water
for the purpose of determination of the effect of natural water conditions (presence
of various components of water, aquatic organisms, etc.) on the extent of ageing of
plastics.
For the experiment polyethylene (PE) and poly(ethylene terephthalate) (PET)
were selected and incubated from June of 2015 in water collected from karst lake
Firlej. After six months of incubation the polymer probes were collect to check the
level of ageing. For this purpose, polymers were investigated by FTIR and
adsorption/ desorption of nitrogen techniques. Results of FTIR analysis are
presented in Fig 1. Polymers after incubation (PE1, PET1) had the same spectra as
polymers before incubation (PE0, PET0). It can be concluded that time period (6
months) was too short to degradation of plastics and did not involve the desired
changes in the structures of materials. Results obtained in case of second analysis,
adsorption/desorption of nitrogen were also not satisfying. In case of polyethylene
and poly(ethylene terephthalate) the BET surface was 0.03 and 0.25, 0.0002 and
0.12 m2g-1 for plastics before and after ageing, respectively.
Fig 1. Results of FTIR analysis of studied polymers.
Obtained results did not allow to continue the experiment and the incubation
of plastics is still carrying on. The next steps of experiment, such adsorption of
phenanthrene and ecotoxicological test on Daphnia magna, will be proceeded after
next six months of incubation. After that time the changes in polymers structures
should be visible.
DECONSTRUCTION OF TRIPHENYLPHOSPHINE DERIVATIVES
A SIMPLE METHOD OF THE SYNTHESIS UNSYMMETRICAL
SUBSTITUTED TERTAIRY PHOSPHINES
Jolanta PISKLAK, Marek STANKEVI, K. Micha PIETRUSIEWICZ

DEPARTMENT OF ORGANIC CHEMISTRY
Organophosphorus compounds possessing aryl groups at phosphorus are very

common molecules in organic chemistry. The high availability of arylphosphorus
species creates a situation in which it is necessary to invent possible pathways to
modify these compounds. With a developed method in hand, synthesis of new P-
aryl-substituted compounds could be achieved by simple replacement of aryl
substituents. Phenyl or aryl groups are regarded as substitution-resistant although
aryl substituents in arylphosphine oxides could be replaced through reductive
cleavage of P-aryl bond with alkali metal. [1] Except a few observations,
nucleophilic substitution of phenyl (aryl) group in arylphosphorus compounds has
never been a subject of intensive research studies. [2]
This project is an attempt to synthesize P-stereogenic compounds starting from
triphenylphosphine oxide. The substitution one of three phenyl group in such
substrate led to formation of tertiary diphenylphosphine derivatives which could be
modified in second step giving rise P-stereogenic tertiary phosphine oxides.
The aim of the present research project is to develop a method for preparation
of P-chiral tertiary phosphine derivatives. For this purpose, directed ortho-
metallation strategy was chosen as a method of desymmetrization of Ph2P(O)
moiety in tertiary diphenylphosphine derivatives.
At first we have synthesized series of alkyldiphenylphosphine oxides starting
with triphenylphosphine oxide (Scheme 1). [3]
O O
P P
RLi R
THF -78 C to rt
R= t-Bu 76%
s-Bu 86%
n-Bu 97%
Me 89%
TMSCH2 80%
Scheme 1
The step is based on the selective deprotonation of only one phenyl group in
diphenyl(t-butyl)phosphine oxide followed by an addition of the electrophile
(Scheme 2).
O I O
1. s-BuLi
P P
2. I2
THF,
1. -78 C to r.t., 30 min.
2. -78 C to r.t., 1 h
57%
Scheme 2
ortho-Deprotonation of one of the phenyl groups in diphenyl(t-

butyl)phosphine oxide with a strong base followed by an addition of iodine led to
the formation of the desired unsymmetrically substituted tertiary phenyl(o-
iodophenyl)(t-butyl)phosphine oxide.
These experiments show that the formation of tertiary phosphine oxides
possessing chirality center at phosphorus atom can be easily obtained through
desymmetrization procedure using directed ortho-metallation strategy.
References:
[1] E. R. N. Bornancini and R. A. Rossi, J. Org. Chem., 55 (1990), 2332.
[2] B. Schaub, T. Jenny and M. Schlosser, Tetrahedron Lett., 25 (1984), 4097; T.
Shimada, H. Kurushima, Y.-H. Cho and T. Hayashi, J. Org. Chem., 66 (2001),
8854.
[3] M. Stankevi, J. Pisklak and K. Wodarczyk, Tetrahedron, 2016, 72, 810.
SOLID DISPERSION OF DICLOFENAC SODIUM WITHIN
POLYMER-SILICA COMPOSITE AS MULTIPARTICULATE
MATRIX SYSTEMS
Agnieszka KIERYS
Oral products among the drug delivery systems account for 60 % of the US
pharmaceutical market value [1]. Among oral products, multiparticulate controlled
release systems have been proposed since they offer a number of advantages [2].
The system consists of a multiplicity of small discrete units which are filled into
gelatin capsules or compressed with added excipients into tablets for administration.
One of highly promising materials for manufacturing of such multiparticulate
formulations are polymeric particles modified by inorganic component [3, 4]. Thus,
in the present paper the modification of a polymer carrier loaded with a high dose of
drug by silica gel is presented. The drug chosen for this study is diclofenac sodium
a non-steroidal anti-inflammatory drug (NSAID) with analgesic and antipyretic
properties which is served to reduce pain in the long-term treatment of degenerative
diseases. The polymeric drug carrier selected for this study is Amberlite XAD7HP
(P-X7), commercially available, food grade macroporous resin. This acrylic
polymer is allowed to alimentary use by the U.S. Food and Drug Administration,
Code of Federal Regulation Title 21. Silica gel was produced by transformation of
silica precursor (tetraethoxysilane, TEOS) introduced into solid dispersion of drug
within polymer matrix (P-Drug) in the presence of the vapor mixture of H2O and
HCl or H2O and NH3 of desired composition at ambient temperature.
Fig. 1. XRD patterns (a) and

DSC curves (b) of the
investigated samples.
On the basis of the X-ray

diffraction experiment, it
may be concluded that
the introduction of the
drug changes the
arrangement of the
polymeric species, and,
in consequence, the broad
peaks (centered at about
2 = 7, 14 and 41; Fig.
1a) indicating the amorphous nature of the polymer matrix P-X7 simply disappear
[5]. Although the content of diclofenac sodium in P-Drug is high and reaches about
20 %, its XRD pattern has drug diffraction peaks of low intensity. It may indicate
that the drug exists partially as an amorphous nanodispersion within the polymer
network, next to the diclofenac sodium polycrystals, which occupy the interior of
the pores. After the deposition of the silica gel within P-Drug under basic condition
two broad peaks appear at the XRD pattern of P-Drug-VB (Fig. 1b); the first one
seems to have origins in the polymer matrix, while the peak at about 22 is
associated with the amorphous silica gel [6]. By contrast, the sharp diffraction peak
of diclofenac sodium almost disappears. Hence, it may be expected that formation
of silica gel accompanies the conversion of the drug into an amorphous form.
Similar conclusions can be drawn from DSC analysis (Fig. 1b). On the other hand,
from the analysis of the XRD patterns, it may be concluded that sodium chloride
exists in P-Drug-VA, since sharp diffraction peaks at 2 = 31.7, 45.4 and 56.4
are clearly visible (Fig. 1a). Such transformation of the drug at the acidic
environment of synthesis of P-Drug-VA is highly probable, since it is a salt of weak
organic acid which performs the function of the base in the reaction with vapors of
the strong acid.
Fig. 2. Diclofenac sodium release kinetics
from investigated samples. In the figure, the
lines are provided for convenience.
Taking into consideration the release

profiles of diclofenac sodium (Fig. 2), it
may be noticed that the maximum of 96
% of diclofenac sodium is released from
P-Drug, whereas the efficiency of the
drug desorption from the P-Drug-VA is
much lower. It should be enmphasized
that the pure diclofenac sodium completely releases within first 30 minutes. The
analysis of P-Drug-VA desorption curves, and especially their segments after 7 h,
which are raising, indicate that the release of the drug is not completed. Thus, it
may be said that the remaining part of the drug in P-Drug-VA, which did not desorb
within 24 hours in the phosphate buffer at pH 6.8, is as a poorly soluble acidic form
of diclofenac. An entirely different situation occurs for P-Drug-VB. Firstly, the
degree of burst release is successfully diminished (Fig. 2) and the rate of drug
release is significantly modified, with 79 % released in 7 h. The observed changes
in the drug release rate are related not only to the silica species deposited within P-
Drug-VB, but also to the structural modification of drug arising during SiO2
deposition.
References:
[1] Colombo P., Sonvico F., Colombo G., Bettini R., Pharma. Res., 26 (2009) 601-611.
[2] Tuleu C., Andrieux C., Boy P., Chaumeil J.C., Int. J. Pharm., 180 (1999) 123-131.
[3] Kierys A., ACS Appl. Mater. Inter., 6 (2014) 14369-14376.
[4] Kierys A., Kasperek R., Krasucka P., Zimmer L., Poleszak E., Goworek J., RSC
Adv., 5 (2015) 94067-94076.
[5] Sil A., Sharma R., Ray S., Surf. Coat. Tech., 271 (2015) 201-206.
[6] Chen X., Jiang J., Yan F., Tian S., Li K., RSC Adv., 4 (2014) 8703-8710.
SYNTHESIS AND PHYSICO-CHEMICAL CHARACTERIZATION
OF SILVER-CARBON NANOCOMPOSITES
Magorzata ZIENKIEWICZ-STRZAKA
Nanoparticles are becoming significant components in a wide range of

applications, technological solutions and future projects because of their rare and
significant physical and chemical properties. Based on nanoscale elements the
nanocomposite materials as well as other hybrid structures are designed and
produced. Nanocomposites are a carrier where nanoparticles have been added for
improving actual properties or functionality of the existing material. In this work
silver nanoparticles were introduced to the microporous carbon matrix and obtained
hybrid materials were characterized and next applied as a template for adsorption of
heterocyclic organic compounds (nitrogenous bases) as models of biomolecules.
The phenomenon of interaction between biomolecules and metal nanoparticles is an
interesting subject which merges several scientific disciplines in the field of
chemical and biological science.
As a carrier material, the highly porous activated carbon RIAA (Norit n.v.,
Amersfoort, Netherlands) was applied. The specific surface area of the adsorbent
was 1440 m2/g while a total pore volume was 0.80 cm3/g. More than half of the
pores in the material falls on micropores. The specific surface area of micropores
was 1040 m2/g and micropore volume about 0.49 cm3/g. After deposition of the
silver nanoparticles and adsorption of nitrogenous bases the significant changes of
the porous structure of activated carbon were observed. It should be emphasized
significant reduction of specific surface area and reduction of the availability of
micropores due to their blocking by larger particles. The BET specific surface area
decreased to 1230 m2/g, and pore volume to 0.74 cm3/g. Surface area and volume of
micropores was also lower (666 m2/g, 0.35 cm3/g). Systematic decrease of the
concentration of investigated substances during adsorption process is visualized on
UV-Vis spectra as a decreasing absorbance. The adsorption signal at a wavelength
of 270 nm correspond to the nitrogenous bases while absorption signal of silver
nanoparticles was recorded at higher wavelengths, i.e. 420 nm.
Fig. 1. Example of the UV-Vis spectra recorded during the process of adsorption
nitrogenous bases and colloidal silver on a microporous activated carbon.
The comparison of kinetic curves for adsorption of nitrogen bases in the
presence of colloidal silver at different temperatures were performed (Fig. 2.).
Temperature dependences illustrate the existence of differences in the adsorption
rates depending on the process temperature. Adsorption of adenosine runs the
fastest at 40C and the slowest at lower temperature (10C). Increase of adsorption
process rate at higher temperature is especially visible in the initial stage of the
process. In the case of uracil, rates of adsorption at temperatures 10C and 25C are
comparable. As in the previous case, the rate is the highest at the highest
temperature. The kinetic data were fitted by the multi-exponential kinetic equation.
The quality of fitting was illustrated by received standard deviations. These
parameters for adenosine were estimated as SDC/c0 = 0.55%, 0.42% and 0.46%,
and in the case of uracil SDC/c0 = 0.28%, 0.28% and 0.19% for the temperatures
10C, 25C and 40C, respectively.
Fig. 2. Comparison of adsorption kinetics for investigated systems at the co-ordinates:

concentration ~ time. Lines correspond to the fitted multi-exponential equation.
After contacting the silver nanoparticles with nitrogenous base (especially

uracil) almost immediate change of the color of solution from yellow to red was
observed. The Transmission Electron Microscopy analysis (TEM) confirmed that
this phenomenon may be related to the change of morphology of silver particles.
The resulting AgNP/uracil system contained silver in the form of mixture:
spherical, hexagonal, longitudinal and triangular particles with sizes from 10 to 20
nm. For comparison, solution of AgNP after contact with adenosine, as well as
initial solution of AgNP contained clearly spherical nanoparticles with dimensions
from 5 nm to 10 nm. Similar effect of interaction between nitrogenous bases (other
than uracil) and metallic nanoparticles was also confirmed in the literature.
In conclusion, significant difference in the rates of adsorption depending on the
temperature conditions were observed. The properties of silver nanoparticles (size
and shape) were changed after contact with nitrogenous bases (especially uracil).
Periodic measurements of the UV-VIS spectra of heterocyclic organic compounds
in the presence of other accompanying substances which generate well-defined UV-
VIS signals is a good method to describe the adsorption process on the selected
adsorbents. The presented results are an introduction to the study of the behaviour
of biological substances in the presence of other substances and nanomaterials.
DETERMINATION OF BIOLOGICAL ACTIVITY OF ORGANIC
COMPOUNDS BY THE USE OF IN VITRO
AND IN SILICO METHODS
Katarzyna STPNIK
Biological activity is a very extensive notion describing any influence which a

substance may have on a living organism with its tissues and organs. Biologically
active compounds comprise numerous groups of substances which have e.g.
antifungal, antibacterial, ecotoxic, genotoxic, mutagenic, carcinogenic qualities.
Permeation through biological membranes is the main condition under which a
given compound may have any influence. Therefore, the processes of permeation
through biological membranes and other numerous barriers are the object of interest
in the field of biological activity research; among the typically biological barriers
there are: skin, blood-brain barrier, blood-bearing barrier, blood-ocular barrier,
blood-retinal barrier, etc.
Research on biologically active compounds including pharmacologically
active substances is usually led by the use of in vivo methods. However, mostly
due to economical and ethical reasons, in recent years, there is a growing need of
applying new, alternative methods, especially in silico or in vitro methods. In silico
methods involve computer simulations connected with the particular fields of
biological activity with the use of mathematical models constructed on the basis of
experimental data. In vitro methods are led in systems imitating biological
environment. One of the in vitro methods which describe biological activity of
many compounds is micellar chromatography, MLC (especially Biopartitioning
chromatography, BMC). BMC (MLC) micelle is generally recognized as a
biological membrane model.
To estimate the biological activity of the compounds tested, the significant
bioactivity descriptors should be determined in silico or in vitro. These descriptors
concern such processes as: blood-brain barrier permeation, skin permeation,
jejunum absorption, Caco-2 absorption (Caco-2 is cell line imitating human
intestine epithelium), toxicity (expressed as the expected effect on organisms
tested), ecotoxicity, mutagenicity, genotoxicity, human serum albumin binding and
many others, equally important.
In the study the determination of the free ampicillin fraction in drug-protein
systems was carried out.
The free ampicillin fraction in drug-human serum albumin (HSA) systems has
been determined using two analytical methods: micellar and adsorption.
Previous reports in the field of micellar chromatography indicate the possibility of
its application in the research on the degree of drug binding to the protein but not in
the research on free drug fraction.
In research on free drug fraction in standard solution of the HSA, the use of
micellar chromatography with direct sample injection (DSI) was presented for the
first time.
The micellar method involved the direct injection of the protein-drug solutions
and pure drug solutions (without the existence of HSA) to the chromatographic
system.
The optimized MLC systems were used in the evaluation of the influence of
the type of surfactant in mobile phase (using the same stationary phase) and the
type of stationary phase (using the same mobile phases) on free drug fraction.
The examination of the influence of the used type of surfactant and the type of
stationary phase on the free drug fraction in standard solutions of the HSA is the
first report of this kind.
The adsorption method of the free drug fraction determination is well known
and described in literature. Therefore, this method has been used as a comparative
method in relation to the micellar method. At the stage of adsorption process, two
adsorbents (VP-DVB, VP-TRIM) have been utilized. After the completion of the
adsorption process, different analytical techniques: RP-HPLC and
spectrophotometric analyses have been used.
The attempt to create a new, undescribed in literature method of determining
the concentration of free drug fraction was made. This new method is a
combination of micellar and adsorption methods. It involves the adsorption of the
drug on a suitable adsorbent. After centrifugation of the adsorbent and protein,
concentration of the free drug fraction was determined by the use of micellar
chromatographic systems.
The obtained results of the concentration of free drug fraction using the new
method (micellar after adsorption) were significantly different from the results
obtained by the use of adsorption method: RP-HPLC and spectrophotometric
analyses. However, it does not have to necessarily mean that the new method is
ineffective in determining the concentration of the free drug fraction. In the
presented case, the optimization process of chromatographic MLC systems was led
before the adsorption process. It is very probable that optimization process should
be performed after the completion of the adsorption process. The type of the
adsorbent used can be connected with solubilization in micelles present in micellar
environment. Moreover, in the case of MLC method with DSI, the same system
used in the micellar method after adsorption: 0.06M SDS + 20% v/v ACN; RP-8e,
was not likewise satisfactory.
Therefore, it can be concluded that both: the micellar method after
adsorption as well as MLC with DSI method need prior optimization of
chromatographic systems. It is necessary to compare in this context the results of
the free drug fraction concentration with proper values obtained using other well-
known methods.
DETERMINATION OF BIOLOGICAL ACTIVITY OF ORGANIC
COMPOUNDS BY THE USE OF CHROMATOGRAPHIC METHODS
Katarzyna STPNIK
To determine biological activity of compound by means of in vitro and/or in

silico methods, steric, electronic and lipophilic parameters of the molecule must be
taken into account. Many researchers in their experiments base on the assumptions
of the Hansch model obtaining values of actual descriptors of biological activity
close to those obtained under in vivo conditions. It is widely recognized that the
Hansch approach initiated research on the quantitative relationship between the
structure of a compound and its biological activity, QSAR.
Biological data of all different kinds can be used in the QSAR approach. The
Hansch analysis correlates the biological activity values with physicochemical
properties by linear, linear multiple or nonlinear regression analysis; thus, the
Hansch analysis is indeed a property-property relationship model. It is sometimes
called the linear free energy-related (LFER) approach therefore Abraham
parameters are frequently used in the interpretation and prediction of retention data
in diverse chromatographic modes.
According to a multi-parameter Hansch approach to a number of biochemical
issues, biological activity of a compound is conditioned by its physicochemical
properties, mainly by its lipophilicity. The Hansch analysis can be used to describe
complex biological data where several different transport processes and equilibria
contribute to the overall structure-activity relationship. Correspondingly, all
different kinds of biological activities have been correlated with the linear free
energy-related parameters using the Hansch analysis.
To determine biological activity of compound by means of in vitro and/or in
silico methods, steric, electronic and lipophilic parameters of the molecule must be
taken into account. Many researchers in their experiments base on the assumptions
of the Hansch model obtaining values of actual descriptors of biological activity
close to those obtained under in vivo conditions.
In silico methods involve computer simulations connected with the particular
fields of biological activity with the use of mathematical models constructed on the
basis of experimental data. In vitro methods are led in systems imitating biological
environment. One of the in vitro methods which describe biological activity of
many compounds is micellar chromatography, MLC (especially Biopartitioning
chromatography, BMC). BMC (MLC) micelle is generally recognized as a
biological membrane model.
To estimate the biological activity of the compounds tested, the significant
bioactivity descriptors should be determined in silico or in vitro. These descriptors
concern such processes as: blood-brain barrier permeation, skin permeation,
jejunum absorption, Caco-2 absorption (Caco-2 is cell line imitating human
intestine epithelium), toxicity (expressed as the expected effect on organisms
tested), ecotoxicity, mutagenicity, genotoxicity, human serum albumin binding and
many others, equally important.
In the study the determination of the free ampicillin fraction as well as
percutaneous absorption have been investigated using different chromatographic
methods including MLC, BMC, ISRP, IAM, etc. The micellar method involved the
direct injection of the protein-drug solutions and pure drug solutions (without the
existence of HSA) to the chromatographic system. The optimized MLC systems
were used in the evaluation of the influence of the type of surfactant in mobile
phase (using the same stationary phase) and the type of stationary phase (using the
same mobile phases) on free drug fraction.
The study recognized that micellar with DSI method can be successfully
applied in the determination of the concentration of free drug fraction as well as
percutaneous absorption, provided the appropriate optimization of the MLC
systems. As before, it is necessary to compare the value of the free drug fraction
concentration obtained using MLC with the appropriate values obtained using other
well-known methods. The system consists of CTAB and RP-8e column which
proved to be the most useful in the evaluation of the concentration of the free
ampicillin fraction in HSA solutions (the obtained values were the most similar to
the values obtained by the use of adsorption method: RP-HPLC and
spectrophotometric analyses).
The obtained results of the determination of different biological activity

descriptors indicate that various chromatographic methods can be treated like a
screening tool especially in the first stage of the research. Due to a large number of
chemical substances in everyday use, high costs and long time of investigations on
their toxicity estimation as well as ethical aspects connected with experiment on
animals, it is necessary to apply a fast and inexpensive methods of determination of
toxic substances and develop methods alternative to those in vivo of the preliminary
determination of potential toxic properties of studied substances. One of the
methods alternative to the in vivo ones is micellar chromatography, particularly
BMC which combined with the in silico methods can be used for preliminary
screening estimation of compounds biological activity.

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