Synthesis and Characterization of Novel Photoactive

Polymer Poly(vinyl alcohol)-graft-Poly(vinyl naphthalene)

MONIKA RYMARCZYK-MACHAL- , SZCZEPAN ZAPOTOCZNY,1 MARIA NOWAKOWSKA
Faculty of Chemistry, Jagiellonian University, 30-060 Krakow, Ingardena 3, Poland

Received 22 December 2005; accepted 10 February 2006

DOI: 10.1002/pola.21396
Published online in Wiley InterScience (www.interscience.wiley.com).

A copolymer of poly(vinyl naphthalene) grafted onto poly(vinyl alcohol)

has been synthesized with nitroxide-mediated controlled radical polymerization. By
separating the processes of the generation of grafting sites and polymerization, we
can avoid the formation of the homopolymer. Because of its architecture, the polymer
is soluble in water, despite the high content of hydrophobic groups. The naphthalene
chromophores tend to aggregate, forming hydrophobic microdomains in an aqueous
solution. Those aggregates exist in a very constrained environment that leads to extraordinarily large redshifts of both the absorption and emission of the polymer. The
C 2006
polymer acts as an efcient photosensitizer in photoinduced electron transfer. V

ABSTRACT:

Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 26752683, 2006

Keywords: controlled radical polymerization; uorescence; graft copolymers; photosensitizers; water-soluble polymers

INTRODUCTION
Controlled radical polymerization (CRP) is a very
convenient method for the synthesis of macromolecules of a required architecture. It makes possible
the synthesis of a variety of well-dened copolymers: statistical, block, graft, and branched.1 Amphiphilic copolymers have attracted considerable
attention because of their wide range of practical
applications, such as drug delivery,2,3 stabilization
of colloidal particles,2,3 and solubilization of hydrophobic compounds.2,3 They are able to form micelles because of the collapse of the hydrophobic
core in hydrophilic media.
There is a demand for a simple and versatile
synthesis strategy for amphiphilic copolymers of
different architectures, particularly grafted ones,
because, to ensure high efciency of solubilization
and controlled or sustained release of solubilized
Correspondence to: M. Nowakowska (E-mail: nowakows@
chemia.uj.edu.pl)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 26752683 (2006)
C 2006 Wiley Periodicals, Inc.
V

compounds, it is important to have a micelle with

a stable hydrophobic core. It is believed that the
core is better stabilized by many short arms than
by one long block.
CRP techniques have been recently used for
the synthesis of well-dened graft amphiphilic
copolymers.2,3 The traditional approaches use
common radical initiators, which are able to generate radicals on the existing polymer backbone,
forming starting sites for polymerizing comonomers. A disadvantage of the classical method is
the lack of control and formation of homopolymers, whereas CRP often requires complex procedures for macroinitiator/functional monomer formation or premodications of the polymers. We
combine here the ease of the free-radical graftingfrom technique and the molecular control offered
by nitroxide-mediated radical polymerization. By
separating the processes of the generation of
grafting sites and polymerization, we can avoid
the formation of the homopolymer.
Recently, we have demonstrated that nitroxide-mediated living radical polymerization is an
attractive method for the synthesis of block
2675

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RYMARCZYK-MACHAL

amphiphilic copolymers.46 We are interested in

the synthesis of photoactive amphiphilic copolymers because of their applications as photosensitizers.7,8 Biodegradable polymers of this type are
particularly interesting because they are not
harmful to the environment.9,10 This report deals
with the synthesis and characterization of a graft
photoactive amphiphilic copolymer based on biodegradable poly(vinyl alcohol) (PVA) and containing grafted poly(vinyl naphthalene) (PVNp) short
chains.

EXPERIMENTAL
Materials
PVA [weight-average molecular weight (M w)
14,000 g/mol, degree of hydrolysis 98.5100%;
BDH Chemicals, Ltd., Poole, England], (VNp,
95%, Aldrich, puried by column chromatography), 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1oxy (HTEMPO; free radical, 98%; Aldrich), perylene (Pe; Aldrich; gold label, 99.9%), iron(II) sulfate heptahydrate (>99.5%, Merck), hydrogen
peroxide (30% solution, analytical grade; POCH,
Gliwice, Poland), 10-camphorsulfonic acid (anhydrous, 98%; Aldrich), HCl (30% solution, spectroscopic-grade; POCH), NaOH (p.a.; POCH),
dimethyl sulfoxide (DMSO; high-performanceliquid-chromatography-grade; POCH), methanol
(high-performance-liquid-chromatography-grade;
POCH), and cyclohexane (p.a.; POCH) were used
as received. Triethanol amine (TEA; 98%; Aldrich)
was distilled in vacuo. 4,40 -Bipyridinium-1,10 -bis
(trimethylene sulfonate) (SPV) and [6-(N,N-dimethylamino)]-1-(40 -cyanophenyl)-3-phenylpyrazolo[3,
4-b]-quinoline (PQ) were prepared according to
the procedures described in the literature.11,12
Deionized water was used to prepare all the
solutions.
Apparatus
Ultravioletvisible (UVvis) absorption measurements were performed with an HP 8452 diodearray spectrophotometer. 1H NMR spectra were
measured in a DMSO-d6 solution with a Bruker
AMX 500 spectrometer, and IR spectra were
measured in KBr pellets with a Bruker IFS 48
spectrometer. Steady-state uorescence spectra
and lifetimes were measured at room temperature with an SLM-Aminco 8100 spectrouorometer with a 450-W xenon lamp as a light source.
The structures of the compounds used as probes in

Scheme 1. Structures of the compounds used in the

studies.

the uorescence studies are shown in Scheme 1.

Gel permeation chromatography (GPC) analyses
of the polymers were carried out with a Waters
chromatograph with diode-array UVvis and refractive-index detectors. Separation was achieved
with a Waters Ultrahydrogel linear column with
a 0.05 M NaCl aqueous solution as an eluent. A
Malvern Nano ZS light scattering apparatus working at a scattering angle of 1738 was used for
dynamic light scattering (DLS) measurements.
Data analysis was carried out with software provided by Malvern.
Polymer Synthesis
The synthesis of the copolymer was performed in
two steps (see Scheme 2). In the rst step, PVA
was modied by the reaction between HTEMPO
and radicals generated on the polymeric chains
with Fentons reagent.1315 The resulting macroinitiator, PVA-graft-HTEMPO, was subsequently
used in the CRP of the 2-vinyl naphthalene (VNp)
monomer.
To graft HTEMPO onto PVA chains, the redox
initiator, Fentons reagent (a mixture of H2O2 and
FeSO4), was applied. It generated hydroxyl radicals according to the following reaction:
HO
OH Fe2 HO OH
Fe3

The  OH radicals could abstract hydrogen atoms

from a polymeric chain, and this resulted in
the formation of radicals located on carbon
atoms.16 These radicals rapidly reacted with stable HTEMPO radicals, which did not react with
radicals generated on oxygen atoms.17 The reaction was carried out at room temperature in an
aqueous solution. The mixture contained the
reagents PVA (1.25 g), HTEMPO (0.73 g), H2O2
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NOVEL PHOTOACTIVE POLYMER

2677

Scheme 2. Copolymer synthesis.

(0.12 g), and FeSO47H2O (0.1 g) in the molar ratio

(with respect to the PVA mer) of 1:0.1:0.12:0.012.
The solution pH was adjusted to 4 with hydrochloric acid, and the total volume of the reaction
mixture was 30 mL. The mixture was stirred
under nitrogen for 3 h and then heated to 40 8C to
remove the excess of hydrogen peroxide. The
formed ferric cations were precipitated with
NaOH, and the product was removed by ltration. The solution was then dialyzed against
water and subsequently freeze-dried.
Resulting PVA-graft-HTEMPO (0.25 g) was then
reacted with VNp (0.25 g) in a DMSO (10 mL)
solution in the presence of camphorsulfonic
acid (0.01 M) as a rate-accelerating additive.5
That nitroxide-mediated polymerization was performed under nitrogen at 130 8C for 6 h. The
product, the graft copolymer PVA-graft-PVNp
(see Scheme 2), was puried by dialysis against
DMSO and water followed by extraction with
cyclohexane to remove residuals of the nonreacted monomer. The puried copolymer was subsequently freeze-dried.
Solubilization Procedure
The molecules of the hydrophobic probe compounds were solubilized in an aqueous solution of
the copolymer by the slow injection of microliter
quantities of the probe solution (concentration
 10
3 M in methanol) into milliliter quantities
of the copolymer aqueous solution (polymer concentration  0.1 g/dm3). The mixture was shaken
for 5 min, equilibrated in the dark for at least 2 h,
and subsequently purged with nitrogen to remove
the residues of the organic solvent.
Irradiation
The samples were irradiated in a Rayonet photochemical reactor (model RPR-100) equipped with
lamps (24 W each). The intensity
16 RPR-3500A
of the incident light produced by one lamp was
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola

approximately (1.55)  1016 photons s
1 cm
3,

as stated by the manufacturer.

RESULTS AND DISCUSSION

Polymer Synthesis and Characterization
The synthesis of the PVA-graft-HTEMPO macroinitiator was conrmed by spectroscopic methods (IR and 1H NMR) and elemental analysis.
The degree of substitution (DS) of HTEMPO
in PVA was found to be equal to 0.04 6 0.01
(with respect to PVA mers), as determined by elemental analysis and 1H NMR (see Fig. 1). The
nitroxide radicals mostly combined with the radical sites formed by the subtraction of protons from

CH

groups, as can also be concluded from the NMR spectrum of PVA-graftHTEMPO (see Fig. 1). There is a substantial
decrease in the intensity of the band at 3.9 ppm
(assigned to polymeric

CH

groups) in comparison with the one at 1.4 ppm (assigned to
polymeric

CH2

groups) after HTEMPO is
attached to PVA, even if one takes into account
the contribution of 16 protons of HTEMPO18,19 in
the broad resonance centered at 1.4 ppm. This
may be explained in terms of the higher stability
of tertiary radicals in comparison with secondary
ones, which are formed after proton abstraction.
The three peaks in the range of 4.34.8 ppm are
assigned to polymeric

OH groups, which differ
in their stereoisomeric position.20 The intensities
of those bands are substantially reduced in the
case of PVA-graft-HTEMPO, probably because of
the residual acid content (from the reaction mixture), which has been reported to reduce the
hydroxyl proton resonances.21 The intensity of
those bands is recovered in the spectrum of PVAgraft-PVNp.
The GPC chromatogram of PVA-graft-HTEMPO
is virtually identical (not shown) to the one of
PVA. That was expected because of the small

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RYMARCZYK-MACHAL

Figure 1. 1H NMR spectra of PVA, PVA-graft-HTEMPO, and PVA-graft-PVNp in

DMSO-d6 solutions.

degree of polymer modication and hydrophilic

character of the attached radicals (no change
in the polymer conformation). Thus, the GPC
results primarily indicate the lack of fragmen-

tation of PVA during its reaction with Fentons

reagent.
The presence of naphthalene (Np) groups in
the PVA-graft-PVNp copolymer has been conJournal of Polymer Science: Part A: Polymer Chemistry
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NOVEL PHOTOACTIVE POLYMER

rmed with spectroscopic methods and GPC analysis. The IR spectrum of PVA-graft-PVNp (not
shown) displays clear bands at 840, 914, and
1650 cm
1, which can be assigned to the stretching vibration of C

H and C
C bonds in aromatic groups of Np. The composition of PVAgraft-PVNp was determined on the basis of its 1H
NMR spectrum in a DMSO solution. A wide band
in the range of 79 ppm, characteristic of aromatic protons, has been observed for the copolymer (see Fig. 1). In addition to this band, another
narrow band appears at 5.4 ppm, which can be
assigned to the aromatic proton(s). The observed
large upeld shift should be attributed to the
shielding effects of neighboring naphthyl groups
in a polymer chain with restricted internal rotation. The so-called ring current effect22 has been
reported and fully elaborated for a similar vinyl
aromatic polymer, poly(vinyl carbozole),23 as well
as large aromatic systems forming aggregates in
solution.24 It is here for the rst time observed for
the Np-containing polymer. It suggests an extraordinarily constrained macromolecular conformation, which forces the chromophores to be
tightly packed.
According to the integration of the signals of aromatic and aliphatic protons, the copolymer contains 5 mol % of Np moieties. It is, however, difcult to determine the exact content of Np on the
basis of a comparison of these signals as the
response of the aromatic protons in the NMR
spectrum may be signicantly reduced by the
strong interactions between the chromophores (as
discussed previously). When we measured the
NMR spectra in D2O, no signals of aromatic protons were observed, and this implies the complete
collapse of the hydrophobic domains. DMSO as a
nonselective solvent should promote the decoiling
of PVA-graft-PVNp macromolecules and reduce
their aggregations, but mutual interactions
between the polymeric chromophores are not
totally eliminated (as discussed previously). The
residual water content in the sample (see the
band at 3.4 ppm) may also play a role. The
response of aliphatic protons in macromolecular
systems may be treated quantitatively because of
similar relaxation times, whereas the intensity of
aromatic resonances may be very strongly
reduced because of the restricted mobility of bulky
groups. Thus, taking into account only NMR signals of aliphatic protons of PVA and PVNp parts,
we could determine the real DS of Np chromophores to be 0.30 6 0.05 with respect to PVA mers.
Taking into account DS of HTEMPO in the preJournal of Polymer Science: Part A: Polymer Chemistry
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2679

Figure 2. GPC chromatograms of PVA and PVAgraft-PVNp.

cursor polymer (DS 0.04), we could estimate the

average length of PVNp branches in PVA-graftPVNp to be about 8 mers. The molecular mass of
the copolymer could be estimated to be Mw 
28,000 g/mol on the basis of the molecular mass of
parent PVA. The value of Mw of the copolymer
doubled with respect to PVA, and this is consistent with the 1:1 weight ratio of PVA to VNp in the
polymerization mixture.
Figure 2 shows the GPC traces of PVA and the
grafted PVA copolymer. They differ considerably.
The longer retention time observed for PVA-graftPVNp suggests that its polymer chain adopts a
compact conformation in an aqueous solution and
that its hydrodynamic volume is smaller than the
one of the parent PVA polymer. The effect is similar to the one observed earlier for other amphiphilic copolymers.5,17 The GPC measurements,
carried out for PVA-graft-VNp with the refractive-index detector and UV detector (absorption
wavelength 276 nm, which is characteristic
of Np chromophores) simultaneously, indicate
clearly that the system consists of one polymer,
not a mixture. The trace recorded by the UV detector is somewhat wider then the one measured
with refractive-index detection. The effect may be
due to the different chromophore content for a
given molar mass of the PVA precursor. It broadens the total distribution monitored by the detector, which is sensitive to the number of chromophores.
The electronic absorption spectrum of PVAgraft-PVNp in an aqueous solution shows absorption bands with maxima at about 280 and 320 nm
(very attened one) characteristic of Np chromo-

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RYMARCZYK-MACHAL

Fluorescent Probe Studies

Figure 3. Electronic absorption spectra of PVA and

PVA-graft-PVNp in water and Np in methanol solutions.

phores (see Fig. 3). The spectrum also shows the

tail extended to the longer wavelengths. That
conrms the existence of strong, mutual interactions between Np groups and the formation of
aggregates absorbing at lower energies than isolated chromophores. This conclusion is also supported by the measurements of uorescence spectra [see Fig. 4(A)]. Interestingly, the emission
spectra are structured, and so they do not originate from the Np excimer. One can obtain the uorescence emission upon the excitation of the
polymeric chromophores even at wavelengths
longer than 450 nm. On the basis of these experimental observations and literature data,2527 we
have assigned that observed emission to the molecular aggregates present in our samples. That
assignment is supported by the observation that
uorescence decreases signicantly for the polymer in a DMSO solution [see Fig. 4(B)], which is
a better solvent for PVNp chains. A detailed explanation of the reported unusual uorescence response of the polymer is beyond the scope of
this article and is under intensive experimental
and theoretical investigations (publication in
preparation).
DLS studies indicate the existence of aggregates in an aqueous solution of PVA-graft-PVNp.
The observed objects are relatively large, with an
average hydrodynamic diameter equal to 255 nm,
and this suggests that intermolecular associations occur in an aqueous solution. These aggregates, however, were not observed during GPC
analysis, and this suggests that they exist only in
an aqueous solution.

The hydrophobic microdomains of the polymeric

clusters were further characterized with uorescent molecular probes that could be solubilized in
the interior. Typical uorescent probes, such as
pyrene or 6-propionyl-2-(dimethylamino)naphthalene (PRODAN), could not be used here
because of the spectral overlap between the emission and absorption spectra of the probes and the
polymer. Thus, we nally used PQ, a new probe
that absorbs and emits in the visible spectral
region. The position of the maximum in the emission spectrum of the probe is strongly polaritydependent. Thus, the emission spectrum of the
PQ probe solubilized in an aqueous solution of
the copolymer was compared with its emission
spectra in several organic solvents.28 A broadening of the spectrum suggests that the probe molecules experience the heterogeneous microenvir-

Figure 4. Fluorescence emission spectra of PVAgraft-PVNp in (A) water and (B) DMSO at different
excitation wavelengths.
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NOVEL PHOTOACTIVE POLYMER

Figure 5. Steady-state emission spectrum of PQ

solubilized in an aqueous PVA-graft-PVNp solution
(excitation wavelength 460 nm). The spectrum was
deconvoluted into three Gaussian bands, with the
emission maxima, relative contributions, and halfwidths given in the legend.

onments of various polarities. The polarity of the

microenvironments is comparable to that of (1)
toluene [maximum wavelength (kmax) 513 nm],
(2) THF (kmax 547 nm), and (3) methanol (kmax
579 nm), as determined from the deconvoluted
spectrum of PQ (see Fig. 5). The results indicate a
strong hydrophobic character of the polymeric
domains, which seem to be densely packed, thus
excluding all water molecules from their interior.
One may assign the long wavelength emission of
PQ to the molecules residing in the polymeric
phases of higher polarity (PVA phases) and at the
interfaces.

2681

region) excited indirectly by the polymeric chromophores. (Fig. 6). The apparent low efciency of
energy transfer may also be partially the result of
a lower Pe loading in the polymeric domains due
to their very dense packing.
Photoinduced electron transfer was carried out
with SPV as an electron acceptor. It was assumed
that the possible charge-separation process would
be enhanced by the fact that the Np chromophores acting as electron donors were aggregated
in the polymeric domains and the water-soluble
SPV molecules resided preferably in the surrounding aqueous environment, making back
electron transfer less probable. To check whether
the process of electron transfer from the excited
Np chromophores/aggregates is thermodynamically possible, the driving force (DG0) for that
process should be determined. It should be
emphasized that the energy transfer from Np to
SPV should be neglected as it is unfavorable
because of the differences between the energy levels of the molecules [singlet excited-state energies
based on the respective absorption spectra:
ES(SPV) 4.97 eV31 and ES(Np) 3,99 eV32].
DG0 for the photoinduced electron transfer in a
polar solvent and at a relatively large donor
acceptor separation can be calculated with the
RehmWeller equation:33
red


G0 Eox
D
EA
E
C

where Eox
D is the oxidation potential of the donor
[Eox
(Np)
2.29 eV],34 Ered
D
A is the reduction poten-

Energy and Electron-Transfer Studies

As shown previously, PVA-graft-PVNp forms in
an aqueous solution hydrophobic domains with
unusual spectral characteristics. The clusters
that form may work as energy traps for the
absorbed light energy, and so it is unlikely that
the polymeric chromophores can support efcient
migration and transfer of this energy to solubilized molecules of an acceptor. On the other hand,
the clusters of aromatic compounds act as efcient electron donors,29,30 and that process may
be used to use the copolymer as a photosensitizer.
The energy transfer from polymeric chromophores to solubilized Pe molecules was observed,
but the process was indeed not very efcient, as
can be judged from the relatively low intensity of
the Pe emission (three bands in the 400500-nm
Journal of Polymer Science: Part A: Polymer Chemistry
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Figure 6. Fluorescence emission spectra of Pe solubilized in an aqueous PVA-graft-PVNp solution (polymer concentration 0.25 g dm
3) excited directly (excitation wavelength 410 nm) and indirectly via polymeric Np chromophores (excitation wavelength
280 nm).

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RYMARCZYK-MACHAL

wavelength 350 nm) not absorbed by SPV. The

role of the sacricial donor is to reduce Np,
thereby restoring the photosensitizing ability of
the polymer. SPV
was indeed efciently formed
in the system studied.

CONCLUSIONS

Figure 7. Changes in the absorption spectra of an

aqueous PVA-graft-PVNp/SPV/TEA system after various
irradiation times (polymer concentration 1 g/dm3,
SPV concentration 8.57  10
4 M, TEA concentration
1.14  10
3 M, irradiation wavelength 350 nm).
The inset shows the kinetics of the photoinduced electron transfer. The molar absorbance coefcient of SPV

(e602nm 12 800 M
1 cm
1)38 was used to calculate the
concentration of the radical formed in the solution after
various irradiation times.

30
tial of the acceptor [Ered
E*
A (SPV)
0.37 eV],
is the energy of the electronically excited state of
the donor [E*(Np) 3.9 eV],32,35 and C is an electrostatic correction term (C 0.1 eV in polar solvents). Using these values, we can nd that in
our system DG0
1.34 eV. Because the oxidation potential of aromatic aggregates should be
lower than the one for the isolated chromophore,36 the estimated value of DG0 is rather the
highest limit for our system, and the real value of
DG0 may be even larger. This indicates that the
process of electron transfer between the polymeric Np chromophores and SPV is thermodynamically feasible and may be schematically
described as follows:

Np SPV ! Np SPV

In fact, the efcient quenching of the polymer

emission by SPV was observed (data not shown).
The charge separation in that system can be easily followed with UVvis spectroscopy because
the radical anion SPV
formed in that process
displays a characteristic absorption spectrum
with maxima at 396 and 600 nm.37 Figure 7
shows the absorption spectra for the aqueous
PVA-graft-PVNp/SPV solution in the presence of
the so-called sacricial donor, TEA, after various
times of irradiation with the light (irradiation

A novel graft amphiphilic copolymer containing

Np chromophores, PVA-graft-PVNp, has been
synthesized via nitroxide-mediated radical polymerization. By separating the processes of the
generation of grafting sites and polymerization,
we can avoid the formation of the homopolymer.
This simple synthetic approach can be easily
applied to other water-based polymeric systems.
GPC and spectroscopic measurements have conrmed the highly compact conformation of the
synthesized graft copolymer in an aqueous solution. Fluorescence spectra of the copolymer in an
aqueous solution display bands that can be assigned to the aggregates of the chromophores.
The photophysical properties of PVA-graft-PVNp,
especially its capability of efcient electron transfer, look promising for its application as a biodegradable polymeric photosensitizer. The formation of aromatic aggregates mimics antenna systems. The unusual photophysical effects observed
for the synthesized copolymer are currently being
subjected to intensive experimental and theoretical studies in our laboratories.
Financial support of this research project from the Polish Committee for Scientic Research (grant No PBZKBN-1100/T09/2004/27) is gratefully acknowledged.
The authors are grateful to Barbara Jachimska from
the Institute of Catalysis and Surface Chemistry of
the Polish Academy of Sciences for the dynamic light
scattering measurements and Andrzej Danel of the
Department of Chemistry of the Agricultural University of Krakow for the synthesis of the [6-(N,N-dimethylamino)]-1-(40 -cyanophenyl)-3-phenylpyrazolo[3,4-b]quinoline probe.

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