Accepted Manuscript

Title: New Technique in Starch Nanoparticles Synthesis

Author: Manal A. El-Sheikh

PII: S0144-8617(17)30899-8
DOI: http://dx.doi.org/10.1016/j.carbpol.2017.08.033
Reference: CARP 12640

To appear in:

Received date: 4-2-2017

Revised date: 5-8-2017
Accepted date: 8-8-2017

Please cite this article as: & El-Sheikh, Manal A., New
Technique in Starch Nanoparticles Synthesis.Carbohydrate Polymers
http://dx.doi.org/10.1016/j.carbpol.2017.08.033

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
New Technique in Starch Nanoparticles Synthesis

Manal A. El-Sheikh

Textile Research Division, National Research Centre, 12311, Dokki, Giza, Egypt.

Highlights
A new technique for the preparation of starch nanoparticles was adapted.
The new technique is based on the dual effect of sodium hydroxide and
glycerol.
Combination between mechanical and chemical processes.
FTIR, XRD, TGA and TEM were used to characterize the starch
nanoparticles.
Ease of the process and eco-friendly chemicals.
Combination between the mechanical and the chemical processes.

Abstract
Starch nanoparticles (StNPs) were previously prepared using severe
mechanical, physical and/or chemical conditions that takes too long time to produce a
little yield of uncontrolled large size of StNP. The current work presents a new
technique for the synthesis of StNPs based on the combination between sodium
hydroxide and glycerol in aqueous medium during the synthesis process while the
precipitation of the StNPs is performed under homogenization at ambient conditions.
The new technique is based on three assumptions: 1) the dual impact of sodium
hydroxide and glycerol on the swelling and gelatinization of starch as a pre-stage of
the synthesis of (StNPs1), 2) the dual impact of glycerol and cooking of starch on the
swelling and gelatinization of starch as a pre-stage of the formation of (StNPs2), and
3) the precipitation under homogenization at ambient conditions and its effect on
breaking the H- bonds of the starch molecule in both StNPs1 and StNPs2. The
importance of this technique arises from the ease of the process, the eco-friendly
chemicals and the combination between the mechanical and chemical processes. NS
(native starch), StNPs1 and StNPs2 were characterized using FTIR, XRD, TGA and

1
TEM. TEM of StNPs1 showed a well-defined round particles uniformly distributed
with size of about 62.5 nm. StNPs2 showed a non-specific shape starch particles.

Keywords: Starch Nanoparticles; Tween 80; Sodium hydroxide; Glycerol; Cooking;

Homogenization; Precipitation; FTIR; XRD; TGA; TEM.

1. Introduction
Because it is, naturally occurring polymer, abundant, produced with low cost,
biodegradable and biocompatible, starch is one of the most promising polymers for
applications in many fields. Both starch and starch derivatives are used efficiently as
reducing and capping agent in the synthesis of metal nanoparticles (El-Naggar, 2015;
El-Sheikh, 2013; El-Sheikh, 2014; El-Sheikh, 2015; El-Sheikh et al., 2013; El-Sheikh
& Ibrahim, 2014; Hebeish et al., 2014a; Hebeish et al., 2013; Hebeish et al., 2016).
Compared with starch particles, starch nanoparticles (StNPs) have shown much more
attention because of their unique properties. Properties of StNPs are completely
different from that of the bulk material due to greater surface area per mass (Chin et
al., 2011; El-Feky et al., 2015; El-Naggar, 2015; El-Naggar et al., 2015; Hebeish et
al., 2013, 2014b; Qin et al., 2016). One of the most promising applications of StNPs is
in the pharmaceutical field (El-Feky et al., 2015; El-Naggar, 2015; El-Naggar et al.,
2015). For its ability to convert poorly soluble, poorly absorbed and labile
biologically active substance into promising deliverable drugs, StNPs can carry drugs
to the target or control the release of the drug in the body. In return, the latter offers
reduction of dosing frequency, better therapeutic control, reduction of side effects,
and, consequently, better patient performance (El-Feky et al., 2015; El-Naggar et al.,
2015; Simi & Emilia Abraham, 2007; Xie et al., 2013; Yang et al., 2014).
Mechanical, physical and chemical methods, including various techniques
such as supercritical fluid extraction, solvent evaporation, precipitation and emulsion
crosslinking, were all employed in the synthesis of nanoparticles. Mechanically, less
than 400 nm StNPs were obtained by reactive extrusion of crosslinked plasticized
starch followed by grinding and high speed dispersion in water (Giezen et al., 2000;
Wildi et al., 2011). Among physical tools, high-pressure homogenization (Shi et al.,
2011) is used together with increased number of water/oil system in the presence of
crosslinking agent and more than one surfactant at high temperature, are employed in

2
the synthesis of StNPs. Chemical methods employed in the synthesis of StNPs focus
on chemically opening the starch structure. Once the starch structure is opened and
dispersed, by the application of alkali, acid or enzymes, the formation of the hydrogen
bonds can be accelerated through which StNPs formed. In acid hydrolysis of starch,
StNPs with small nanoparticles size is obtained (Angellier-Coussy et al., 2009).
However, this method takes too long time and produces low yield of StNPs. The
precipitation of soluble starch in ethanol in presence urea, as a stabilizer, is another
chemical method used for StNPs synthesis. This method showed many drawbacks
including large amounts of solvent used for StNPs precipitation, the uncontrolled
particle size formation and the large size of StNPs produced (400-600 nm) (Chin et
al., 2011; Liu et al., 2009). Recently, Hebeish et al (Hebeish et al., 2014b) modified a
solvent displacement method by using aqueous sodium hydroxide solution as the
solvent medium and ethanol as the non-solvent one in presence of Tween80
surfactant. The process proved its validity for producing spherical StNPs with average
size of 103 nm in good dispersion without consuming much solvent in the
precipitation of StNPs.
Decades ago, glycerol is known to be an effective starch plasticizer and one of
the ingredients added to size formulations of cotton yarns. Gelatinization and swelling
of starch in glycerol is well documented by many researchers (Dm et al., 2015;
Habitante et al., 2008; Liu et al., 2011; Smits et al., 2003; van Soest et al., 1996). Neal
(Neale, 1924) studied The effect of glycerol on starch. He found that glycerol has
favorable effect on softening of film made from starch but makes loss in strength if
glycerol concentration exceeded 5%. Deme et al. (Dm et al., 2015) investigated the
loss of crystalline structure and swelling kinetics of various maize flours and starch in
excess of glycerol. Smits et al (Smits et al., 2003) showed that upon heating glycerol
with starch, an interaction takes place between glycerol and amylose as well as with
amylopectin, and that it is independent of the presence of crystallinity of the
polysaccharide. They stated that the interaction is likely to be caused by H-bond
formation. They further added that similar interaction takes place during storage at
room temperature for several days and that the interaction process is kinetically
controlled. This interaction affects the molecular mobility and may influence the flow
properties and resistance to shear when premixing ingredients prior to processing
starch. At room temperature, the glycerol mainly interacts with the amorphous regions
of dry amylopectin or amylase as stated by Smits et al (Smits et al., 2003).

3
 To the knowledge of the authoress and according to the literature survey, the
combination between sodium hydroxide and glycerol in the synthesis process together
with the homogenization during precipitation of StNPs at ambient conditions were not
studied.
Whilst previous research work presented severe mechanical, physical and/or
chemical conditions for too long time to produced little yield of uncontrolled large
size of StNPs, as mentioned earlier (Angellier-Coussy et al., 2009; Chin et al., 2011;
Giezen et al., 2000; Liu et al., 2009; Shi et al., 2011; Wildi et al., 2011), the current
work presents a new technique for the synthesis of StNPs based on the combination
between sodium hydroxide and glycerol in aqueous medium during the synthesis
process or the combination between glycerol and cooking of starch while the
precipitation of StNPs is performed under homogenization at ambient conditions.
This work aimed at the synthesis of StNPs based on three assumptions: 1) the
dual impact of sodium hydroxide and glycerol on the swelling and gelatinization of
starch as a pre-stage of the formation of StNPs (StNPs1), 2) the dual impact of
glycerol and cooking of starch on the swelling and gelatinization of starch as a pre-
stage of the formation of StNPs (StNPs2), and 3) the advantage of precipitation under
homogenization and its effect on breaking the H- bonds of the starch molecule in both
StNPs1 and StNPs2. Tween 80 is used as a capping agent in both cases and NS is
used for comparison. To what extent these three assumptions will come true and a
StNPs with small particle size and uniform distribution will be obtained? To test these
assumptions, the StNPs so obtained are confirmed by FTIR, the crystalinilty profile is
obtained by XRD, thermal behavior is performed by TGA and morphology and
particle size are measured by TEM. The importance of this new technique arises from
the ease of the process, the eco-friendly chemicals used and the combination between
the mechanical and chemical processes to reach StNPs.

2. Experimental

2.1. Materials
Native maize starch (NS) was kindly supplied by the Egyptian Company for
Starch and Glucose Manufacture, Cairo, Egypt.
Glycerin was purchased from El-Gomhouria Pharmaceutical Company, Egypt.
Tween 80 surfactant was purchased from Sigma Chemical Company, USA.
Absolute ethanol and sodium hydroxide were of analytical grade.

4
2.2. Methods

2.2.1. Synthesis of StNPs

Two procedures were used to synthesize StNPs, the first one (StNPs1)
depending on gelatinization of NS by sodium hydroxide and glycerol and the second
one (StNPs2) depending on gelatinization of NS by cooking at 90oC in presence of
glycerol.
StNPs1 were prepared according to a previous work (Hebeish et al., 2014b)
with some modifications such as additives type, reaction time, precipitation technique
and nanoparticles collection method. In the current process, 1.5 g of NaOH and 2.7 g
of glycerin were dissolved in 100 ml H2O followed by portion-wise addition of 5 g of
NS under mechanical stirring. The obtained transparent slurry of the homogeneous
gelatinized starch was left under mechanical stirring at 25oC for 15 min. After that,
the whole contents were subjected to precipitation under homogenization for 15 min.
at ambient conditions. To do so, 100 ml of absolute ethanol was added drop-wise to
the gelatinized starch followed by addition of 10 drops of Tween80 and left under
homogenization (Digital Homoginizer, Model 500, Scilogex, USA) for 15 min. A
white precipitate was easily formed and left for some time then filtered through a
whatman 50 filter papers. The filtrate was washed many times using 80:20
ethanol:water ratio till free from excess sodium hydroxide followed by a final wash
using absolute ethanol and dried at 25oC.
StNPs2 were prepared as follows: 2.7 g of glycerin were dissolved in 100 ml
H2O followed by portion-wise addition of 5 g of NS under mechanical stirring and
regular rise in heating, through a thermostatic water bath, till the temperature reached
90oC and left for 15 min at this temperature under mechanical stirring. While still hot,
the cooked starch was precipitated using ethanol under the same precipitation
conditions as in StNPs1. Filtration, washing and drying conditions are same as in
StNPs1.

2.3. Characterizations and analyses

FTIR spectra of NS, StNPs1 and StNPs2 were performed using Jasco FTIR-
4700 with ATR Pro One, Japan. The data were recorded from 400 to 4000 cm-1.
Thermal behavior of StNPs1 and StNPs2 was obtained by Thermogravimetric
analysis (TGA) using SDT Q600 V20.9 Build 20, Universal V4.7A TA Instruments.
Temperature range from 0 to 800oC at a heating rate of 5oC/min under nitrogen flow.

5
 X-ray diffraction (XRD) patterns of fine powdered NS, StNPs1 and StNPs2
were obtained using Empyrean, pixcel3D, Amedipixz collaboration, PANALYTICAL,
Netherlands with Cu-K radiation ( = 0.15406 nm) in the 2 range from 10o to 40o
and 30 mA, 45 kV.
The size and shape of StNPs1 and StNPs2 were determined by means of a
JEOLJEM- 1200 Transmission Electron Microscope (TEM). The samples were
prepared by placing a drop of the colloidal solution on a 400-mesh copper grid coated
by an amorphous carbon film and evaporating the solvent in air at room temperature.
The average diameter of the silver nanoparticles was determined from the diameter of
nanoparticles found in several chosen areas in enlarged microphotographs.

3. Results and discussion

3.1. FTIR Spectra of NS, SNPs1 and StNPs2

Figure 1 shows the FTIR spectra of NS, SNPs1 and StNPs2. For the three
samples, one can easily recognize that the main characteristic bands of NS and that of
StNPs1 and StNPs2 are almost identical in the position of the peaks with slight
increase/decrease in the intensity of the peaks of StNPs1 and StNPs2 compared with
NS. This could mean that no real change in the chemical structure of the starch
molecule took place either for StNPs1 or StNPs2. Table 1 presents the groups
frequency and the intensity of the main peaks of the three samples based on the tables
of IR spectra of carbohydrates and their discussions presented by Nicely and
Spedding (Nicely, 1957; Spedding, 1964). Table 1 reveals that the position of the

band 3405 cm-1 for NS and StNPs2 (OH- stretching) are identical, whereas it is shifted

to 3416 cm-1 for StNPs1. Compared with NS, the intensity of the OH- stretching band

of StNPs1 is lower. This could be due to the blocking of some of the hydroxyl groups
as a result of the formation of sodium starchate during the treatment with sodium
hydroxide (Hebeish et al., 2014b; Hebeish et al., 2016). On the other hand, the

intensity of the OH- stretching band of StNPs2 is higher than that of NS. This could

be due to the effect of the gelatinization took place during the cooking process in
presence of glycerol and to the effect of the homogenization during the precipitation
process on the loss of the crystalline structure of the starch molecule (Chun et al.,
2015; Mondragn et al., 2004; ZOBEL et al., 1988). Hence, more abundant hydroxyl

6
groups that could have been shield due to the crystalline structure before the thermal
and mechanical treatment.

3.2. XRD of NS, SNPs1 and StNPs2

Figure 2 shows the XRD patterns of NS, SNPs1 and StNPs2. Humps at 2 of
15.1, 17.1, 17.8, 18.1, 22.7, 23 and 23.6 characteristic to crystalline structure of starch
(Avval et al., 2013; El-Sheikh, 1999; Ma et al., 2006; Singh et al., 2006) are clearly
shown in NS pattern. On the other hand, StNPs1 pattern shows the disappearance of
all the humps found at the XRD pattern of NS, which indicates the melt of the
crystalline structure of NS and the formation of the amorphous structure instead. This
is mainly due to the effect of sodium hydroxide and glycerol on the swelling of starch,
the formation of sodium starchate (Hebeish et al., 2014b; Hebeish et al., 2016), and to
the breakdown of the hydrogen bonds between the chains due to the swelling effect
and the precipitation under homogenization. StNPs2 pattern shows an intermediate
state between the crystalline structure (NS) and the amorphous structure (StNPs1).
StNPs2 pattern is characteristic by the appearance of humps at 2 of 12.6 and 19.8
while many of the humps found in the NS pattern have disappeared. This means that
the cooking of NS in presence of glycerol and the precipitation under homogenization
are not enough to bring about complete amorphous structure to the treated NS but
only sufficient to decrease the crystalline structure. These findings are in agreement
with the FTIR spectra. The crystallinity of the NS, StNPs1, StNPs2 follows the
descending order: NS > StNPs2 > StNPs1.

3.3. TGA of SNPs1 and StNPs2

Figure 3 shows the TGA of StNPs1 and StNPs2.
Results obtained from the TGA curve of StNPs2 shows: An initial weight loss
of 4.6% of the original weight. The weight loss represents the loss of water (moisture
content). A single stage of decomposition represents a weight loss of 81.5% of the
original weight. The weight loss in this stage is due to the decomposition of the starch
molecule. This stage is well-defined with higher level of decomposition (similar to
that of NS obtained from a previous work (El-Sheikh, 1999; Hebeish et al., 2014c).
The cooking in presence of glycerol and precipitation under homogenization did not
bring about massive change to NS.

7
 Results obtained from the TGA curve of StNPs1shows: An initial weight loss
of 5.4% of the original weight. The weight loss represents the loss of water. The
increase in the percent of weight loss (compared with StNPs2) is mainly due to the
increase in the water content which in this case is due to the moisture content and
bound water arising from the introduction of the hydrophilic O-Na group. This is,
again, in agreement with the FTIR and XRD analyses. A main single stage of
decomposition represents a weight loss of 56% is shown. The weight loss in this stage
is due to the decomposition of the starch as well as the sodium starchate molecules.
The single weight loss profile suggests a uniform substitution reaction (O-Na). This is
a good achievement meaning that the dual effect of sodium hydroxide and glycerol in
addition to the precipitation under homogenization brought about a positive impact to
NS. The residual solids stage represents a weight loss of 11.9% of the original
weight. The residual solid is mainly due to the sodium salt of sodium starchate formed
as a result of the reaction between NS and sodium hydroxide.

8
3.4. TEM of SNPs1 and StNPs2
Figure 4 represents the morphology and particle size of StNPs1 and StNPs2 as
seen by TEM. As seen in Figure 3, StNPs1 shows well-defined round particles
uniformly distributed with size of about 62.5 nm. This is, again, a good achievement.
The dual effect of sodium hydroxide and glycerol on the swelling of starch and the
effect of precipitation under homogenization on the breakdown of the hydrogen bonds
helped in the synthesis of a uniformly distributed and small sized StNPs. On the other
hand, StNPs2 showed a non-specific shape and unsizable starch particles. To this end,
StNPs2, regretfully, is not assumed to be a starch nanoparticle candidate and would
not be utilized for further nano-applications although it showed improved crystalline
structure, compared to NS, as seen by XRD pattern. Successfully, StNPs1 is supposed
to be a promising StNPs candidate and would be further utilized in Ulcers healing.

4. Conclusions
To overcome the severe conditions used for the preparation of StNPs, the little
yield and the uncontrolled large size of StNPs, the current work presents a new
technique for the synthesis of StNPs The new technique is based on 1) the dual
impact of sodium hydroxide and glycerol (StNPs1), 2) the dual impact of glycerol and
cooking of starch (StNPs2) and 3) the homogenization at ambient conditions during
precipitation of both StNPs1 and StNPs2. Tween 80 is used as a capping agent of
StNPs in both cases and NS is used for comparison. FTIR results revealed that the
main characteristic bands of NS, StNPs1 and StNPs2 are almost identical in the
position of the peaks with slight increase/decrease in the intensity of the peaks of
StNPs1 and StNPs2 compared with NS. XRD patterns showed that the crystallinity of
NS, StNPs1 and StNPs2 follows the descending order NS > StNPs2 > StNPs1.
Revealing that the dual impact of sodium hydroxide and glycerol is more favorable
than the that of glycerol and cooking. TGA curves of both StNPs1 and StNPs2
showed an initial weight loss due to the loss of water (moisture content). TGA curve
of StNPs2 also showed a single stage of decomposition represents the decomposition
of the starch molecule. While TGA curve of StNPs1 showed, a main single stage of
decomposition represents the decomposition of starch molecule and a residual solids
stage represents the decomposition of sodium starchate molecule. TEM of StNPs1

9
showed well-defined round particles uniformly distributed with size of about 62.5 nm.
On the other hand, StNPs2 showed a non-specific shape and unsizable starch
particles. Regretfully, StNPs2 are not assumed a starch nanoparticle candidate and
would not be utilized for further nano-applications although it showed improved
crystalline structure compared to NS. Successfully, StNPs1 is supposed to be a
promising StNPs candidate and would be further utilized in Ulcers healing.

5. Acknowledgements
The authoress acknowledges the National Research Center, Egypt for facilities
provided.

10
References

Angellier-Coussy, H., Putaux, J. L., Molina-Boisseau, S., Dufresne, A., Bertoft, E., &
Perez, S. (2009). The molecular structure of waxy maize starch nanocrystals.
Carbohydrate Research, 344(12), 1558-1566.

Avval, M. E., Moghaddam, P. N., & Fareghi, A. R. (2013). Modification of starch by

graft copolymerization: A drug delivery system tested for cephalexin antibiotic.
Starch/Staerke, 65(7-8), 572-583.

Chin, S. F., Pang, S. C., & Tay, S. H. (2011). Size controlled synthesis of starch
nanoparticles by a simple nanoprecipitation method. Carbohydrate Polymers,
86(4), 1817-1819.

Chun, A., Lee, H.-J., Hamaker, B. R., & Janaswamy, S. (2015). Effects of ripening
temperature on starch structure and gelatinization, pasting, and cooking
properties in rice (Oryza sativa). Journal of Agricultural and Food Chemistry,
63(12), 3085-3093.

Dm, F., Peuvrel-Disdier, E., & Vergnes, B. (2015). Loss of crystalline structure and
swelling kinetics of maize starch and flour granules in glycerol excess: The role
of the envelope structure. Industrial Crops and Products, 70, 149-157.

El-Feky, G. S., El-Rafie, M., El-Sheikh, M., El-Naggar, M. E., & Hebeish, A. (2015).
Utilization of Crosslinked Starch Nanoparticles as a Carrier for Indomethacin
and Acyclovir Drugs. Journal of Nanomedicine & Nanotechnology, 6(1), 1-8.

El-Naggar, M. E.-S. (2015). Synthesis, Characterization and Medical Applications of

Nano-Starch. In M. E.-S. El-Naggar (Ed.) (p. 388): Scholars' Press.

El-Naggar, M. E., El-Rafie, M. H., El-Sheikh, M. A., El-Feky, G. S., & Hebeish, A.
(2015). Synthesis, characterization, release kinetics and toxicity profile of drug-
loaded starch nanoparticles. International Journal of Biological
Macromolecules, 81, 718-729.

El-Sheikh, M. A. (1999). Preparation and Characterisation of Carboxymethyl Starch.

In "Synthesis of New Polymeric Materials Based on Water-Soluble Starch
Composites", pp 62-114, PhD Thesis, Cairo University, Faculty of Science,
Department of Chemistry, Egypt.

11
El-Sheikh, M. A. (2013). Synthesis of poly acrylamide-g-carboxymethyl starch silver
nanoparticles composite and its corresponding hydrogel. 7th Aachen-Dresden
International Textile Conference (pp. 1-43). Aachen, Germany: DWI an der
RWTH Aachen e.V.

El-Sheikh, M. A. (2014). A Novel Photosynthesis of Carboxymethyl Starch-

Stabilized Silver Nanoparticles. The Scientific World Journal, 2014, 1-11.

El-Sheikh, M. A. (2015). Synthesis of conductive elastic film and conductive fabric

based on crosslinked carboxymethyl starch-AgNPs composite. 2015
TechConnect World Innovation Conference, Expo and National Innovation
Summit (pp. 55-59). Maryland, U.S.A.: Techconnect.

El-Sheikh, M. A., El-Gabry, L. K., & Ibrahim, H. M. (2013). Photosynthesis of

Carboxymethyl Starch-Stabilized Silver Nanoparticles and Utilization to Impart
Antibacterial Finishing for Wool and Acrylic Fabrics. Journal of Polymers,
2013, 1-9.

El-Sheikh, M. A., & Ibrahim, H. M. (2014). One Step Photopolymerization of N, N-

Methylene Diacrylamide and Photocuring of Carboxymethyl Starch-Silver
Nanoparticles onto Cotton Fabrics for Durable Antibacterial Finishing.
International Journal of Carbohydrate Chemistry, 2014, 1-9.

Giezen, F. E., Jongboom, R. O., Gotlieb, K. F., & Boersma, A. (2000). Biopolymer
Nanoparticles. US Patent (Vol. WO 2000069916 A1). USA: Ato B.V.

Habitante, A. M. B. Q., Sobral, P. J. A., Carvalho, R. A., Solorza-Feria, J., & Bergo,
P. V. A. (2008). Phase transitions of cassava starch dispersions prepared with
glycerol solutions. Journal of Thermal Analysis and Calorimetry, 93(2), 599-
604.

Hebeish, El-Rafie, M. H., El-Sheikh, M. A., Seleem, A. A., & El-Naggar, M. E.

(2014a). Antimicrobial Wound Dressing and Anti-inflammatory Efficacy of
Silver Nanoparticles. International Journal of Biological Macromolecules, 65
509515.

Hebeish, A., El-Rafie, M. H., El-Sheikh, M. A., & El-Naggar, M. E. (2013).

Nanostructural Features of Silver Nanoparticles Powder Synthesized through

12
 Concurrent Formation of the Nanosized Particles of Both Starch and Silver.
Journal of Nanotechnology, 2013, 1-10.

Hebeish, A., El-Rafie, M. H., El-Sheikh, M. A., & El-Naggar, M. E. (2014b). Ultra-
Fine Characteristics of Starch Nanoparticles Prepared Using Native Starch With
and Without Surfactant. Journal of Inorganic and Organometallic Polymers and
Materials, 24(3), 515524.

Hebeish, A., El-Rafie, M. H., Rabie, A. M., El-Sheikh, M. A., & El-Naggar, M. E.
(2014c). Ultra-microstructural features of perborate oxidized starch. Journal of
Applied Polymer Science, 131(8), 1-9.

Hebeish, A., Shaheen, T. I., & El-Naggar, M. E. (2016). Solid state synthesis of
starch-capped silver nanoparticles. International Journal of Biological
Macromolecules, 87, 70-76.

Liu, D., Wu, Q., Chen, H., & Chang, P. R. (2009). Transitional properties of starch
colloid with particle size reduction from micro- to nanometer. Journal of
Colloid and Interface Science, 339(1), 117-124.

Liu, P., Xie, F., Li, M., Liu, X., Yu, L., Halley, P. J., & Chen, L. (2011). Phase
transitions of maize starches with different amylose contents in glycerolwater
systems. Carbohydrate Polymers, 85(1), 180-187.

Ma, X., Yu, J., & He, K. (2006). Thermoplastic starch plasticized by glycerol as solid
polymer electrolytes. Macromolecular Materials and Engineering, 291(11),
1407-1413.

Mondragn, M., Bello-Prez, L. A., Agama-Acevedo, E., Betancur-Ancona, D., &

Pea, J.-L. (2004). Effect of Cooking Time, Steeping and Lime Concentration
on Starch Gelatinization of Corn During Nixtamalization. Starch - Strke, 56(6),
248-253.

Neale, S. M. (1924). The elasticity and tensile strength of starch. Journal of the
Textile Institute Transactions, 15(9), T443-T452.

Nicely, W. B. (1957). Infrared Spectra of Carbohydrates. In L. W. Melville & R. S.

Tipson (Eds.). Advances in Carbohydrate Chemistry (Vol. Volume 12, pp. 13-
33): Academic Press.

13
Qin, Y., Liu, C., Jiang, S., Xiong, L., & Sun, Q. (2016). Characterization of starch
nanoparticles prepared by nanoprecipitation: Influence of amylose content and
starch type. Industrial Crops and Products, 87, 182-190.

Shi, A.-m., Li, D., Wang, L.-j., Li, B.-z., & Adhikari, B. (2011). Preparation of starch-
based nanoparticles through high-pressure homogenization and miniemulsion
cross-linking: Influence of various process parameters on particle size and
stability. Carbohydrate Polymers, 83(4), 1604-1610.

Simi, C. K., & Emilia Abraham, T. (2007). Hydrophobic grafted and cross-linked
starch nanoparticles for drug delivery. Bioprocess and Biosystems Engineering,
30(3), 173-180.

Singh, V., Tiwari, A., Pandey, S., & Singh, S. K. (2006). Microwave-accelerated
Synthesis and Characterization of Potato Starch-g-poly(acrylamide). Starch -
Strke, 58(10), 536-543.

Smits, A. L. M., Kruiskamp, P. H., van Soest, J. J. G., & Vliegenthart, J. F. G. (2003).
Interaction between dry starch and plasticisers glycerol or ethylene glycol,
measured by differential scanning calorimetry and solid state NMR
spectroscopy. Carbohydrate Polymers, 53(4), 409-416.

Spedding, H. (1964). Infrared Spectroscopy and Carbohydrate Chemistry. In L. W.

Melville (Ed.). Advances in Carbohydrate Chemistry (Vol. Volume 19, pp. 23-
49): Academic Press.

van Soest, J. J. G., Bezemer, R. C., de Wit, D., & Vliegenthart, J. F. G. (1996).
Influence of glycerol on the melting of potato starch. Industrial Crops and
Products, 5(1), 1-9.

Wildi, R. H., Egdom, E. V., & Bloembergen, S. (2011). Process for producing
biopolymer nanoparticles. US Patent (Vol. 9011741). USA: EcoSynthetix Ltd.

Xie, F., Pollet, E., Halley, P. J., & Avrous, L. (2013). Starch-based nano-
biocomposites. Progress in Polymer Science, 38(10-11), 1590-1628.

Yang, J., Huang, Y., Gao, C., Liu, M., & Zhang, X. (2014). Fabrication and
evaluation of the novel reduction-sensitive starch nanoparticles for controlled
drug release. Colloids and Surfaces. B, Biointerfaces, 115, 368-376.

14
ZOBEL, H. F., YOUNG, S. N., & ROCCA, L. A. (1988). Starch Gelatinization: An
X-ray Diffraction Study. Cereal Chemistry, 65(6), 443-446.

15
Figure Caption:

Figure 1: FTIR Curves of NS, StNPs1 and StNPs2

Figure 2: XRD Curves of NS, StNPs1 and StNPs2
Figure 3: TGA Curves of StNPs1 and StNPs2
Figure 4: TEM micrographs of StNPs1 and StNPs2
Table 1: Main group frequencies and intensities of NS, StNPs1 and StNPs2

Figure 1

Figure 2
200
180
160
SNPs2
140
120
100
Counts

80
60
40
20
0
10 20 30 40
Position (2)

16
 200
180
160
SNPs1
140
120
100
Counts

80
60
40
20
0
200 10 20 30 40
180 Position (2)
160
NS
140
120
100
Counts

80
60
40
20
0
10 20 30 40
Position (2)

17
Figure 3

StNPs2

StNPs1

18
Figure 4

StNPs1 StNPs2

19
Table 1: (according to Nicely (Nicely, 1957))

NS StNPs1 StNPs2
Position Intensity Position Intensity Position Intensity
Cm-1 %T Cm-1 %T Cm-1 %T
OH- stretching 3405.67 46.9188 3416.28 55.0499 3405.67 37.024
CH-stretching 2929.34 67.8088 2928.38 70.5308 2927.41 55.3943
Double bond stretching of 1646.91 76.4599 1650.77 76.3167 1646.91 70.0576
carbonyl, carboxyl and
carboxyl salt
Hydrogen bending or 1453.1 62.6155 1455.03 62.683 1452.14 58.0847
deformation of saturated
CH2
Hydrogen bending or 1378.85 67.7335 1248.68 81.5975 1239.04 72.0627
deformation of the methyl
hydrogen
C-O-C stretch and C-OH 1158.04 51.7382 1155.15 66.7266 1155.15 51.5776
grouping
Hydrogen bending or 1078.98 49.8888 1086.69 65.1928 1078.01 49.4886
deformation of O-H
1006.66 38.4767 1021.12 55.5796 1023.05 40.4935
Antisymmetrical Pyranose 929.521 81.8472 926.628 83.8405 926.628 80.6235
ring vibration
- Anomeric C-H 859.132 92.0317 862.025 88.6937 856.239 92.7659
deformation vibration
Symmetrical Pyranose ring 764.637 87.6008 761.744 86.2831 762.709 87.716
breathing vibration

20