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J. Chem Soc. Nigeria, Vol. 44, No.

3, pp 433 -452 [2019]

Synthesis of biodegradable superabsorbent hydrogel from carboxymetylated cassava


starch for use in sanitary pads

T. A. Afolabi

Department of Chemistry, Federal University of Agriculture, P.M.B. 2240, Abeokuta, Nigeria.

E-mail: niyiafo@yahoo.com Telephone: +234 803 5718 657


Received 07 February 2019; accepted 26 April 2019, published online 12 May 2019

Abstract

The synthesis of biodegradable superabsorbent hydrogel from native and carboxymethylated cassava
starch was carried out. The native starch isolated from cassava was chemically modified by
carboxymethylation, and used in the production of the superabsorbent hydrogel. The FTIR spectra
confirmed the presence of the carboxymethylated group on the modified cassava starch granule, while the
X-ray diffractogram revealed the loss of crystallinity after the carboxymethylation of the starch. The DSC
study showed that the gelatinisation temperatures and enthalpy of gelatinization (∆Hgel) of the starch was
reduced after carboxymethylation. The superabsorbent hydrogel produced from the native and
carboxymetylated cassava starch absorbed water and saline more than 100 times their dry weight, with the
carboxymethylated starch – hydrogel having higher water absorbing power. The hydrogels also have good
biodegradability, since about 70% of it was biologically degraded within 14 days. The physicochemical
properties of the superabsorbent hydrogel produced from native and carboxymetylated cassava starch was
at par with that of the commercial ‘synthetic’ hydrogel, while its biodegradability was better than the
commercial hydrogel.

Keywords: biodegradable, carboxymethylation, cassava, starch, superabsorbent hydrogel

Introduction applications [7]. The food and agricultural


industry used hydrogels for delivery and
Hydrogels are hydrophilic, three dimensional packaging [8 – 11]. Hydrogels also find wide
polymer with cross-linked networks, capable of applications in hygiene products such as sanitary
absorbing large amounts of water or saline napkins, disposable diapers, etc [7]. The bulk of
solution. Hydrogels produced by simple reaction the superabsorbent hydrogel of commercial
of one or more monomers, are able to swell importance are used in disposable materials [10].
rapidly and retains large volumes of water in its Hydrogels can be classified based on source as
swollen three-dimensional structure without natural or synthetic polymers [1]. Most of the
dissolution. It can absorb water, more than ‘traditional’ superabsorbent hydrogel
thousand times its original weight and the synthesized from synthetic polymers
swelled composite can retain the liquid even (polyacrylamide, polysodium acrylate, etc)
under some pressure [1]. Hydrogels can be exhibit poor biodegradability which limit their
formulated in a variety of physical forms such as applications, as a result of the environmental
films, gels, slabs, coatings, microparticles, hazards associated with its disposals [7].
nanoparticles, etc [2]. Consequently, the developments of eco-friendly
Due to their unique characteristics compared ‘green’ superabsorbent hydrogels with
with traditional water absorbing materials, biodegradability properties are gradually gaining
hydrogels, found wide applications in medicine - wide acceptance. Natural biopolymers, such as
for diagnostic, barrier materials, or cellular starch [12], chitin [13], cellulose [14], chitosan
immobilization [3,4] drug delivery [5,6], and a [15], chitosan and alginate [16, 17], gum [18],
wide range of commercial biomedical gelatin [19], etc., have shown good potential as
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

possible substitutes for the traditional fossil–fuel sulfate was also carried out [22]. El-Rehim [23]
based superabsorbent hydrogels. The application also synthesized eco-friendly starch based
of these low cost, renewable and biodegradable hydrogel for use in the cement industry. Graft
polysaccharides for superabsorbent hydrogels copolymerisation of starch [24] was also used to
production offered a cheaper and produce hydrogels with special characteristic.
environmentally friendly product. Starch, a non- Witono and co-worker [25] prepared
toxic, biodegradable, biocompatible and superabsorbent hydrogel with promising water
abundant polysaccharide is one of the potentially absorption capacity using cassava starch grafted
viable alternatives to synthetic polymeric with polyacrylic acid, while another group of
materials in the superabsorbent hydrogels researchers [26] synthesised hydrogel using
production. carbocabxymethylated cassava starch
Starch is next to cellulose in abundance as a crosslinked with di – or polyfunctional
naturally occurring polysaccharide. Starch found carboxylic acids with high swelling properties.
wide applications in the food, pharmaceutical, However, most hydrogels prepared from starch
textile, adhesive, biodegradable, and cosmetic are on corn, wheat, potato, rice starch, few
industries. The main disadvantage of starch is its reports are available on the use of cassava
easy solubility in water and low thermal starch.
degradation which limits its ability to form a The objective of this research is to synthesized
stable hydrogel. To overcome these limitations, superabsorbent hydrogel using cassava starch.
native starch can be modified chemically or Cassava was used because it’s renewable,
physically to enhanced its liquid absorbing readily available and relatively cheap in Nigeria,
power when used in hydrogel production. the largest producer of cassava in the world [27].
The native cassava starch was chemically
Research has shown that chemical and physical modified by carboxymethylation to enhance its
modifications have considerable effect on the physicochemical properties. The
physicochemical properties of the starches most physicochemical properties of the starch and
especially its swelling and solubility power [20]. hydrogels were determined. The
Liu and co-workers [12] synthesised biodegradability of the hydrogels and its water
thermoresponsive poly (2-(2-methoxyethoxy) and saline retention capacity (for use in sanitary
ethylmethacrylate) hydrogels with starch-based pads) was studied and compared with that of the
nanospheres as cross-linkers, with excellent commercial hydrogel made from synthetic
properties. Another group of researchers [21] polymers. It is hoped that the development of a
prepared hydrogels with hydroxyethyl starch viable industrial product from cassava will
using freeze–thawing method. The synthesis of increase its economic potentials.
superabsorbent hydrogel based on sodium starch
Materials and Methods native cassava starch, the determination of its
degree of substitution and reaction efficiency,
Materials was carried out following the procedure of
Afolabi [20]. (The starch yield of the native
Fresh cassava tuber was harvested from an cassava starch from its tubers was 71.50% (on
experimental plot at the Federal University of dry basis). The degree of substitution of the
Agriculture, Abeokuta, Nigeria. carboxymethyl cassava starch was 0.71 with
Dimethylsulphoxide, dimethylaminopyridine, reaction efficiency of 65.70%).
succinic anhydride, and sodium hydroxide were
purchased from Aldrich, USA. All reagents used Synthesis of the superabsorbent hydrogels
were of analytical grade. from starch
Isolation and carboxymethlation of cassava 1g of the starch was dissolved in 99g of
starch. dimethylsulphoxide, and 2.38g of 4-
dimethylaminopyridine was added to the
The cassava starch was isolated from its tuber as mixture in an Erlenmeyer flask, with constant
shown in Fig 1. The carboxymethylation of the
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

stirring for 24 h at room temperature. After amount of remaining excess NaOH was
complete dissolution, 1.86g of succinic determined by titration with HCl [28].
anhydride was added to the solution with
continuous stirring for another 24 h. The mixture Fourier Transform Infra-red spectroscopy
was dialysed by the use of seamless cellulose (FTIR)
tube against deionized water at room
temperature for 7 days. During the dialysis, the
reaction product gradually separated as a gel, FTIR spectroscopic analysis of the native and
followed by neutralization with aqueous NaOH modified starch sample was carried out as
solution. The product was precipitated in 500ml follows: the sample was ground using a Mikro-
of methanol, and filtered. The solid product was Dismembrator (2000 rpm for 3 min; Satorius
dried under reduced pressure, blended and Biotech Inc., Bohemia, NY, USA). The fine
finally screened through a 16-mesh sieve. powder sample was then mixed with dry KBr in
a sample to KBr ratio of 1:100, and mixing was
Degree of substitution of the hydrogel performed in a vibratory ball mill capsule for 5
min. The ground mixture was transferred to a
The degree of substitution (DS) of the hydrogel Specadie to produce an 8.5 mm diameter film
was determined by titration method. All the ester that was analysed in the beam of the FT-IR
linkage was saponified by NaOH, and the spectrophotometer (Horiba FT-IR).
the area between the thermogram and a base line
under the peak and was expressed in terms of
Differential Scanning Calorimetry (DSC) Joules per gram of dry starch.
The thermal properties of the starch were studied Wide angle X-ray Diffraction
with the aid of a differential scanning
calorimeter (DSC – Mettler TA 4000, X-ray diffractograms of starch powders were
Switzerland). 12μl of distilled water was added obtained with a Rigaku D-Max- 2200 X-ray
to 3.00mg of starch in the DSC pans. The pan diffractometer (Rigaku Denki Co. Tokyo,
was sealed, reweighed, and allowed to stand for Japan). The scanning region of the diffraction
3h at room temperature before the DSC analysis. angle was from 3 to 40o, with target voltage 40
This is to allow the sample to have an even kV, target current, 100mA, aging time 5 min,
distribution of water. The scanning temperature and radiation wavelength of 0.1542nm. The
range was 30 – 140oC, while the heating rates degree of crystallinity was quantitatively
was 10oC/min, an empty aluminum pan was determined as using the methods of Nara &
used as the reference. The transition Komiya [29].
temperatures reported are the onset (To), peak
(Tp), and conclusion (Tc). The enthalpy of
gelatinisation (ΔH) was estimated by integrating
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

Cassava (fresh roots)

PEELS (‘waste’)
Peeling

Water

Washing

Water

Mechanical grating

Water
‘WASTE’
Sieving Pulp ( 5 – 7 %)
HCN (< 0.0001%)

Water

‘WASTE’
Sedimentation Solids (0.2%)
HCN (0.03 – 0.05%)

Starch residue

Drying

STARCH

Fig 1: Schematic diagram for isolation of cassava starch


J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

Granule Morphology Statistical analysis

Granule morphology of the starch was studied All determinations were done in triplicate, and
by scanning electron microscopy (SEM). the results were then averaged. Data were
Samples were sputter-coated with Au/Pd using a assessed by General Linearized Model (GLM)
vacuum evaporator (Edwards, Milano, Italy) and of Statistical Analysis System (SAS) to generate
examined using a scanning electron microscope analysis of variance (ANOVA), means, standard
(model 500, Philips, Eindhoven, The error, and range. Correlation and regression
Netherlands) at 10 KV accelerating voltage analysis were also performed using procedure
using the secondary electron technique. for correlation (Proc Corr) and procedure for
regression (Proc Reg), procedures of SAS [30,
Absorbency 31]
The water absorbency of the hydrogels was Results and Discussion
carried out using the teabag method (Japanese Fourier transforms infrared spectroscopy
Industrial Standard, JIS K 7223) as follows: A (FTIR)
200 X 100 mm nylon teabag was prepared by
heat sealing, the blank tea bag was dipped in The infra-red spectra of the native and
liquid, drained, and then weighed (Wb). 0.2g carboxymethylated cassava starch are presented
(Wh) of the hydrogel sample was placed into a in Fig 2. In the native cassava starch (NCS), the
teabag, and the bag was dipped in an excess absorbencies at 2934.16cm-1 was attributed to
amount of water or saline solution (0.9% and the methylene C-H asymmetrical stretch, while
3.5% NaCl solution) for specified time. The that of 1456.96cm-1 was attributed to the methyl
excess solution was removed by hanging the bag C-H asymmetrical bend. Also the band at
for 5 min (until no liquid is dropped off) before 996.05cm-1 is indicative of the vinyl C-H out of
the teabag was weighed (Wt). The water plane bend. Since the major structure of a starch
absorbency was calculated using equation 1. is the hydrogen bonded hydroxyl groups, most
This procedure was also repeated for saline of the frequencies observed in the NCS are
solution (0.9% NaCl and 3.5% NaCl). indicative of the hydrogen-bonded hydroxyl
group of the starch.
Absorbency = (Wt – Wb – Wh)/Wh
[Equation 1] After carboxymethylation of the starch, the new
peaks observed at 1094.4 cm-1 was attributed to
Biodegradability the C-O-C alkyl substituted ether, while the
The biodegradability of the superabsorbent 858.17 cm-1 is attributed to the carbonate ions
hydrogel was measured at 25oC for 14 days present in the modified starch. Also the peaks at
(Japanese Industrial Standard, JIS K 6960) by 1601.59 and 1425.14 cm-1 were indicative of the
placing it in an activated sludge. The presence of carboxylate (carboxylic acid salt) in
biodegradability was evaluated by monitoring the carboxymethyl cassava starch (CCS) starch.
the biological oxygen demand (BOD) with the This confirms the presence of the
aid of an OM3001 coulometer (Ohkura Electric carboxylmethyl group on the starch structures.
Co., Ltd., Japan) which detected the oxygen gas The carboxymethyl cassava starch synthesized
consumption. by the reaction between the starch and
(sodium)monochloroacetic acid in the presence
of NaOH product will be:
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

OH OR
OH
O + O
Cl
HO RO
O
HO O RO O

ONa
R = H or O
O
Carboxylmethyl starch
(starch glycolate)

[Equation 2]

There is a possibility of a side reaction taken glycolate (at the expense of starch

place from the reaction of NaOH with the glycolate).

monocholoroacetic acid producing sodium


J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

1425.14cm-1
858.17cm-1

CCS

NCS

1601.59cm-1

1094.40cm-1 1456.96 cm-1 2934.16 cm-1

996.05cm-1

0 500 1000 1500 2000 2500 3000 3500 4000 4500

Wavenumber (cm-1)

Fig 2: The Fourier transform infrared spectroscopy spectra of native (NCS) and
carboxymethlated (CCS) cassava starch.

Thermal properties chains after the carboxymethylation of the starch


[32]. Incorporation of the carboxylmethyl group
The thermal property of the native and into the starch structure probably leads to the
carboxymethylated cassava starch was studied breakdown of the α-1,6- glycosidic bond of the
with the aid of Differential Scanning amylopectin, with concomitant effect on the
Calorimeter – DSC (Table 1). There was amylose to amylopectin ratio. The increase in
significant reduction in the onset and peak the amylose content of the starch after
temperatures after carboxymethylation of the carboxymethylation of the cassava starch, leads
native cassava starch. The decreased in the to loss of crystallinity in the carboxymethyl
melting temperatures (To, Tp, Tc) after starch as evidenced in the X-ray diffractogram
carboxymethylation of the starch, maybe an of the starch.
indication of the presence of short amylopectin
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

Table 1: The thermal properties of the native (NCS) and carboxymethylated (CCS)
cassava starch measured with DSC.
1 2
SAMPLE TEMPERATURES ∆Tgel ∆Hgel

ONSET PEAK CONCLUSION (oC) (J/g)

To (oC) Tp (oC) Tc (oC)

NCS 59.15±0.04b 95.16±0.06b 150.65 ± 0.35b 91.50±0.04b 27.95±0.02b

CCS 49.22±0.01a 93.38±0.02a 132.59± 0.47a 83.37±0.07a 27.63±0.01a

Mean values of triplicate determinations ± standard error. Values in the same column with same
superscript are not significantly different (P < 0.05).

1
∆Tgel = Change in gelatinization temperature (Tp – To).
2
∆Hgel = Enthalpy of gelatinization.

Starch crystallinity crystallinity of the carboxymethylated starch.


Loss of crystallinity as a result of
The X-ray diffractogram of the native and carboxymethylation of starch has been reported
carboxymethylated cassava starch is presented in for bambara groundnut [20], jack fruit starch
Fig 3. The native cassava starch exhibits Type [33], kudzu root [34], cocoyam and water yam
‘C’ crystallinity pattern with strong peaks at [35], and mung bean [36]. The loss in
3.86Å and 5.10A; medium peak at 5.89 Å and crystallinity of the starch after
weak peaks at 7.97 Å. The degree of carboxymetylation is an indication of the
crystallinity of the native cassava starch was concomitant increase in the amorphous region of
34.45%, with pronounced reduction in the the starch relative to the amylopectin.
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

5.10Å

5.89Å 3.86Å

3.43Å
7.97Å

NCS
CCS

0 5 10 15 20 25 30 35 40 45 50

Diffraction angle (2θ)

Fig 3: X-ray diffractogram of native (NCS) and carboxymethyl (CCS) cassava starch.

Granule morphology granules appears dishevelled, with flat


wrinkled surfaces. Some granules had been
The starch’s granule size and shape was ruptured as a result of the
studied with the aid of Scanning Electron carboxymethylation of the cassava starch.
Micrograph (SEM), the result is presented in Incorporation of the carboxylmethyl group
Fig 4. The native cassava starch (NCS) into the starch structures leads to the
have smooth, round, irregularly shaped ball- granules disorganisation and rupture of the
like granules with axes of 7 - 10μm. The starch granular structures [20, 26, 35].
carboxylmethylated cassava starches (CCS)
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

NCS (500X)
CCS (500X)

NCS (1000X) CCS (1000X)

Fig 4: The scanning electron micrograph of native (NCS) and carboxylmethylated (CCS) cassava starch
at 500X and 1000X magnifications.
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

Absorbency ability of the solvent (water, saline, etc) to


continuously overcome the osmotic pressure
The superabsorbent hydrogel produced from inside the absorbent [10]. The reaction
the native and carboxymethylated cassava between the starch and succinic anhydride in
starch, along with a commercial the hydrogel preparation (Equation 4) leads
superabsorbent hydrogel – AQUA® to the introduction of hydrophilic groups
(Sumitomo Seika Company Ltd, Japan) (COO-, CHO, OH, etc) on the hydrogel.
were subjected to absorbency test in water This strengthen the osmotic difference of the
and saline solutions (0.9% and 3.5%), the hydrogel (due to electrostatic repulsion
results are presented in Fig 5 – 7. The enhancement), with consequential increase
swelling of hydrogel is dependent on the in the absorbent powers of the hydrogels
.

OH OR
O O
O
O + O
HO RO

HO O Succinic RO O
anhydride
O

O-H(Na)
R = H or O

O
Starch succinate
(starch-ester carboxylate)

[Equation 4]

After 1 hour in distilled water solution, AQUA 48 hour, with concomitant increase in its
had the highest water absorbency power (312.6 absorption power.
g/g), however, the absorbency power of AQUA
significantly reduced by more than half (Fig 5) The absorbency power of the hydrogels was
in the second hour, with pronounced drop in the significantly different in 0.9% saline solution
retention power after 3 hour, and couldn’t retain (Fig 6). The absorbing power of the
the water by the end of 48 hour test. The native carboxymethyl cassava starch-based hydrogel
and carboxymethylated cassava starch based was slightly lower than that of its native starch
hydrogel have higher absorbing and retention between 0 – 3 hour, however, the value was at
power than the commercial hydrogel (AQUA). par after 24 hour. The commercial hydrogel
Unlike the commercial hydrogel –AQUA, the (AQUA) absorbing power in 0.9% was about
native and carboxymetyl cassava starch-based 80% lower than that observed in water, but with
hydrogel can retain the water absorbed for over higher retention power since it could retain
about 90% of the solvent after 48 hr. This is an
indication that the carboxylmethyl cassava
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

starch-based hydrogel have high water absorbing hydrogel was higher than that of the
power and high retention power over a carboxymethyl cassava starch. AQUA
prolonged period of time in the 0.9% saline absorption was almost constant in the first 3 hr
solution. of the test, and it retained more than 80% of
solvent for 48hrs.
In 3.5% saline solutions (Fig 7), the absorbing
power of the native cassava starch based
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

400
Solvent: Water

350

300
Absorbency (g/g)

250
h-NCS

200

150
h-CCS
100

50

AQUA
0
1hr 2hr 3hr 24hr 48hr
Absorption time (hour)

Fig 5: The absorbency power (g/g) of the AQUA, native (h-NCS) and carboxymethylated
(h-CCS) cassava starch based hydrogels in water solution (bar represents standard error).
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

Solvent: Saline solution (0.9% NaCl)


90.00

80.00
CCS

70.00 NCS
Absorbency (g/g)

60.00

50.00

AQUA
40.00

30.00

20.00

10.00

0.00
1hr 2hr 3hr 24hr 48hr

Absorption time (hour)

Fig 6: The absorbency power (g/g) of the AQUA, native (h-NCS) and
carboxymethylated (h-CCS) cassava starch based hydrogels in 0.9% saline
solution (bar represents standard error).
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

SOLVENT: Saline solution [3.5% NaCl ]


120.00

100.00

NCS
80.00
Absorbency (g/g)

60.00
CCS

40.00

AQUA

20.00

0.00
1hr 2hr 3hr 24hr 48hr
Absorption time (hour)

Fig 7: The absorbency power (g/g) of the AQUA, native (h-NCS) and carboxymethylated (h-
CCS) cassava starch based hydrogels in 3.5% saline solution (bar represents standard
error).
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

Biodegradability rate of biodegradation is comparable with


that of cellulose. AQUA on the other hand
Biodegradability test which is a measure of did not biodegrade within the 14 days test
the biological oxygen demand (BOD) is period. This observation is understandable
done to ascertain the samples potential to since AQUA was developed from synthetic
biodegrade in the environments. The fossil-fuel based chemicals that are non-
biodegradability test of the starch-based biodegradable. The high biodegradability of
superabsorbent hydrogel, AQUA, and the carboxymethylated cassava starch was
cellulose is presented in Fig 8. Cellulose was probably due to the incorporation of the
used as a standard since it would completely carboxylmethyl group into the starch
biodegrade and its rate of biodegradtion was structure which leads to rupture of some of
used to compare the rate of biodegradation the starch granules as shown in the Scanning
of other hydrogels. Carboxymetylated electron micrograph of the starch.
cassava starch-based hydrogel had better
biodegradation than its native starch, and its
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

100.000

90.000 Cellulose

80.000

70.000

60.000 h-CCS
Biodegradability (%)

50.000

h-NCS
40.000

30.000

20.000

10.000
AQUA
0.000
0 2 4 6 8 10 12 14
(10.000)
Time (days)

Fig 8: The biodegradability of the cellulose, AQUA, native (h-NCC) and carboxylmethlated
cassava starch (h-CCS) based superabsorbent hydrogels.

Conclusion biodegradable superabsorbent from native and


carboxylmethlated cassava starch becomes
The development of superabsorbent hydrogel expedient. This will militate against the
from native and carboxylmethylated cassava environmental hazards associated with the non-
starch, revealed the potential of the starch based biodegradable fossil-fuel based superabsorbent
superabsorbent hydrogel as a possible hydrogels currently available in the markets.
replacement for the synthetic non-biodegradable
hydrogels. The carboxylmethylated cassava Acknowledgement
starch based hydrogel had good biodegradability
properties and high water and saline absorbing The author acknowledge the support of Prof
power and can retain the solvent for about 48 Toshio Yoshimura (Faculty of Human
hours, making it a suitable choice material in Environmental Science, Fukuoka Women’s
production of sanitary napkins and disposable University, Fukuoka 813-8529, Japan) for the
diapers. Since the bulk of the superabsorbent provision of laboratory space. This research was
hydrogels are applied in ‘one-use’ disposable sponsored by the Matsumae International
articles, the production of eco-friendly, cheaper, Foundation, Tokyo, Japan.
J. Chem Soc. Nigeria, Vol. 44, No. 3, pp 433 -452 [2019]

Conflict of interest [8] S. Mun, Y. Kim, M. Shin, D.J. McClements.


Control of lipid digestion and
There is no known conflict of interest or nutraceutical bioaccessibility using
whatsoever in this research or with any of the starch-based filled hydrogels: Influence
researchers. of starch and surfactant type. Food
Hydrocol. 2015, 44, 380 – 389.
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