Proceeding of The 3rd International Seminar on Chemistry, 18-19 July 2018

Preparation of Semi-IPN Hydrogel From Starch

Nanoparticles of Magrove Fruit and Monomer Acrylic
Acid Using Crosslinker N,N’ Methylene Bisacrylamide

Gimelliya Saragih1,2, Tamrin3, Marpongahtun3, Darwin Yunus Nasution3

and Abdillah2
1
Postgraduate School, Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of
Sumatera Utara, Medan, 20155, Indonesia
2
Department of Chemical Engineering, Politeknik Teknologi Kimia Industri,, Jl. Medan Tenggara
VII, Medan 20228, Indonesia
3
Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Sumatera Utara, Jl.
Bioteknologi No. 1, Medan 20155, Indonesia

*Corresponding author: gimelliya.s@gmail.com

Abstract

Starch is a natural biopolymer having many applications as industrial raw material. Nanoparticle technology can improve
characteristic of starch, so its has lower suspension viscosity at high concentration with higher binding strength due to larger
surface area. Starch nanoparticles obtained from the mangrove fruit has been dissolved in PEG / NaOH system and the
polymerized in the presence of monomer acrylic acid and N,N’ Methylene Bisacrylamide crosslinker through radical
polymerization. The semi – IPN hydrogel were characterized by using FTIR, XRD, DSC and SEM. The addition of mangrove
fruit starch nanoparticles has a different impact on the water absorption ratio.
Key words: Hydrogel, Semi – IPN, Starch Nanoparticles, Mangrove fruit, Crosslinker

INTRODUCTION
Hydrogels are polymer tissues that can absorb some water without dissolving or eliminating the
integrity of the polymer structure [1]. Hydrogels contain a high amount of water, similar to the natural tissue of
living things. Hydrogels are therefore, applied as biomaterials, used in the medical, agricultural, food
preparation, and cosmetic industries [2].
Starch is a natural biopolymer have properties used in food, chemical, pharmaceutical / biomedical,
paper, textile and other industry. Starch is renewable, non-toxic, edible and is offerdable and evailable. Natural
starch has several weaknesses that need to be modified to have the appropriate characteristics as industrial
materials. The modification of several types (eq. starch tapioca, sago) can produce starch nanoparticles that
serve as matrix binding active ingredients herbal and lactic acid bacteria [3]. However, there are still many
sources of starch that have not been developed; one of them is starch of mangrove fruit.
Hydrogels can be generated through Interpenetrating Polymer Network (IPN) techniques which are a
combination technique of two or more polymer networks or semi-IPN network and linear polymers in the
absence of covalent or intercellular bonds. IPN is the newest mixing base for polymer composites and is the
blend polymer blend with the fastest development in polymer blends over the past two decades [4].
The formation of crosslinks on starch can improve the characteristics of starch, such as water solubility
or organic solvent. Starch can absorb enzyme, anionic polysaccharide, and metal ion, so it can be applied for
biomedical purposes. Research application of semi-IPN hydrogel manufacture with the utilization of starch and
other polysaccharide for biomedic. The preparation of transdermal hydrogel membranes is made from sodium
alginate and polyvinyl alcohol (PVA) for the transport of trandermal from prazosin hydrochloride compounds as
antihypertensive drugs through the skin [5], Hemicellulose and chitosan based semi – IPN use glutaraldehyde as
a crosslinking agent [6]. IPN mucoadhesive microspheres from gum ghatti and polyvinyl alcohol (PVA) as
ranitidine drug carriers [7]. The culture of cell and the characterization of the poly vinyl alcohol -g-star
crosslinking bonds were use for tissue restructuring [8]. The preparation of semi-IPN as a film (coating) of
curcumin-based bioactive compounds based on chitosan, hypromellose and citric acid with genipine crosslinkers
has been done [9]. The developed semi-IPN based carboxymethyl crosslinking and Clay is potential for in vitro
theophylline release [10]. Modification using another polymer (semi-IPN hydrogel manufacture of cellulose)
has been performed [11]. Hydrogels are prepared by using grafting microcrystalline cellulose from pulp
cellulose with acrylic acid monomer and potassium persulfate (KSP) initiator and N, N'-methylenbicacrylamide

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Proceeding of The 3rd International Seminar on Chemistry, 18-19 July 2018

(MBA) as a crosslinking agent. Another recent research is the Applications of modified Starch as an Enzyme
Matrix of Bioactive Compounds [3].
Based on this background, the authors are interested in doing research on the preparation of Semi - IPN
Hydrogel Nanoparticles Starch Fruit Of Mangrove And Acid Monomer Acrylate Using Cross-Methylene
Bisakralamida binder.

EXPERIMENTAL
Material
The materials used in this study were mangrove fruit, aquadest, sodium hydroxide (NaOH) 2% (E.Merck),
acrylic acid monomer (AAc), crosslinker N, n'methylene bisacrylamide (MB), potassium per sulfate Initiator
(KPS) or ammonium persulfate (APS) retrieved From Merck Chemical Industry, Poly Ethylene Glycol (PEG)
1000 Ph-Euro.
Preparation of Semi-IPN Hydrogel
Nanoparticles of mangrove fruit starch were made by acid hydrolysis method using H2SO4 solution
(3.16 M) by following the modified procedure, which was described by Angellier, Choisnard, Molina-Boisseau,
Ozil, and Dufresne [12].
As many as 0.2 grams of mangrove fruit starch nanoparticles were mixed into 100 mL of aqueous
solution, which contained PEG (6% w/v) and NaOH (8% w/v). The dispersion of the solution was introduced
into the freezer at a temperature of -5°C for 24 hours to obtain a solid mass of the solids. Frozen solid mass was
melted and homogenized using a magnetic stirrer with strong stirring speed at room temperature for 2 hours.
The resulted transparent solution was filtered with ordinary filter paper and used to prepare the hydrogels.
The solution obtained in the above step was used to prepare the ternary hydrogel system. Briefly, the
preparation of representative samples can be described as follows: a 6 ml of monomer AAc was added into 50
mL of ternary hydrogels solution. Then, 0.5 gram of initiator KPS and 0.4 gram of crosslinker MB were added
into previous solution. After that, the mixture was stirred so that all components were homogeneous. The
reaction solution was then transferred to the tube and stored in an electric oven at 60 0C for 2 hours. After the
polymerization is over, the resulted semitransparent hydrogel was brought out of the tube, cut into pieces (2.6
mm), and then placed in distilled water for 4 hours to remove the salt reacting in the polymer. Finally, the
hydrogels were extracted and dried in the desiccator until the weight was constant following the existing
methods [11]. The same thing was done on the variation of 0.4 grams, 0.6 grams, 0.8 grams and 1 gram of
mangrove nanoparticles.
Characterization
The FTIR spectrum of the sample was recorded using a Bruker OPUS 7.5.18 infrared spectrometer (Bruker,
Germany) at wavelengths from 400 cm-1 to 4000 cm-1 at a speed of 20 cm-1. s1. Analysis of crystallinity of
mangrove fruit starch nanoparticles using X-Ray Diffraction (XRD) was operated at 40 kV and current of 30
mA of electricity using Cu Kα radiation at 1.5418 A wavelength and scanned from 0.0050 (2 Ɵ / s). The surface
morphology of a hydrogel matrix was characterized using SEM (Carl Zeiss, Germany). Thermal analysis using
differential scanning calorimeter (DSC) (Shimadzu). This analysis was performed to measure the energy
absorbed or emitted by the analyzed sample. DSC provides the measurement of calorimetry and of transition
energy at a certain temperature.
Swelling of sample analysis
Swelling test was conducted based on the gravimetric method on water. It was employed to discover
the amount of substances or materials that can be absorbed by the membrane.
The membrane was dried in a vacuum oven at 60 0C for 48 hours, then weighed. The obtained
membrane was appointed as a dry weight of membrane (Wdry). Then, the membrane was immersed in water for
24 hours at room temperature. After that, the water was separated from the sample. This membrane was named
as a wet weight of the membrane (Wwet). The swelling percentage was given by the following formula.

Wwet− Wdry
% Swelling = × 100%
Wdry
Crosslinking degree analysis
The degree of crosslinking is determined by means of extraction. Hydrogels were immersed into chloroform for
24 hours. After submersion, the hydrogel was dried using oven at 600C. Then, the dry weight prior to soaking
and dry weight after immersion were determined by gravimetric. Percentage of the degree of crosslinking can be
determined by using the below formula.
Wa
% Crosslinking = × 100%
Wb
Where Wa is the dry hydrogel weight after immersion and Wb is the dry hydrogel weight before immersion.

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RESULT AND DISCUSSION

Preparation of Semi-IPN hydrogels
Preparation of semi-IPN Hydrogels was done by dissolving mangrove starch nanoparticles on PEG /
NaOH solvents and adding the acrylic acid monomers, PPP initiators, and MBA crosslinkers. After those
preparations, the stirring process was applied to produce a strong, dense structure and a good mechanical
properties, especially its elastic properties.
The above preparation can be employed by free radical polymerization of sodium acrylate monomer
(NA) in the presence of MBA crosslinking and the dissolved starch polymer. The polymerization formed the
covalent crosslinking between the macromolecular portion of PEG and starch, which is physically entangled so
that the hydrogels can be generated. The obtained hydrogel can be seen in Fig. 1.

FIGURE 1. Semi- IPN Hydrogel

Fourier transform infrared spectroscopy analysis (FTIR) Analysis

FTIR spectrum of mangrove starch nanoparticles and hydrogel with variation of addition of mangrove
starch nanoparticles can be seen in Fig. 2

Hydrogel 1
5 Hydrogel 2
Hydrogel 3
Hydrogel 4
4
Hydrogel 5
Transmittance (%)

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500
-1
Wavenumber (cm )

FIGURE 2. FTIR spectrum of (a) starch nanoparticle of mangrove fruit (NPM), (b) hydrogel 1,
(c) hydrogel 2, (d) hydrogel 3, (e) hydrogel 4 and (f) hydrogel 5
The widespread peak shape is visible in the absorption area of 3000 - 3600 cm-1. This range shows the
vibration of the hydrogen holding area with the O-H bond from carboxylic acid, alcohol, starch and PEG and.
Besides, The amide NH amide group from the MBA exists in that range. The vibration peak in the region
2850-2960 cm-1 was assigned to the stretching of the C-H aliphatic bond. The wavenumbers 1403 cm-1 and 1560
cm-1 indicate the presence of stretching symmetry and asymmetry of the carboxylic anions. The absorption
region with wavenumbers of 1636 cm-1, 2110 cm-1 and 685 cm-1 shows the presence of C = C, CH2 and O-C-N
groups derived from crosslinking. The absorption area of 860 - 944 cm-1 points out the presence of an alkene
bond.

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Proceeding of The 3rd International Seminar on Chemistry, 18-19 July 2018

X-Ray Diffraction (XRD) analysis

The crystal and amorphous structures of the material can be seen using XRD tools [13]. Fig. 3 showed
mangrove fruit starch nanoparticles showing the crystal peak at 15 0 and 230, while the hydrogel showed the
crystal peaks at 170 and 230 structure of starch nanoparticle crystal was changed when AA and MBA were
grafted into the starch skeleton.

1400
Starch nanoparticle
1200 Hydrogel 1
Hydrogel3
Hydrogel 5
1000
Intensity (counts)

800

600

400

200

0
5 10 15 20 25 30 35 40
Two theta

FIGURE 3. The XRD of (a) starch nanoparticles, (b) hydrogel 1, (c) hydrogel 2 and (d) (b) hydrogel 3

Scanning Electron Microscopy (SEM) analysis

The surface morphology of the hydrogel 1, hydrogel 2, hydrogel 3, hydrogel 4 and hydrogel 5 matrix is shown
in Fig 4. SEM analysis shows the increased concentration of mangrove starch nanoparticles causing the surface
structure to be more rough and interspersed with the number of cracks, due to the presence of two phases the
starch dispersion is trapped in a continuous phase copolymerization [14]. Absorbtion can occur because the
irregular shape of the hydrogel provides a porous space so that absorption can occur.

FIGURE 4. The SEM Hydrogel

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Proceeding of The 3rd International Seminar on Chemistry, 18-19 July 2018

Differential scanning calorimeter (DSC) analysis

The formation of physical interactions between two materials can be estimated using thermal analysis. If there is
a change in the shape of the crystal, then there is a change in thermodynamic aspects of a solid. The DSC of the
semi-IPN hydrogel is shown in Fig 5. The hydrogel undergoes early decomposition at a temperature of 340.57 °
C and a perfect decomposition at 470.38 ° C. The endothermic peak is about 129.23 ° C in hydrogel addition of
a 1 gram mangrove starchy nanoparticle starch (hydrogel 5) which may be due to loose water loose molecules
loosened from the tissue

50

Hydrogel 1
40 Hydrogel 2
Hydrogel 3
Hydrogel 4
Hydrogel 5
30
DSC mW

20

10

0 100 200 300 400 500 600

o
Temperature C

FIGURE 5. The DSC Hydrogel

Swelling of sample analysis

The swelling ratio is the ratio of the hydrogel weight ratio in the swelling to the dry weight which is
one of the main parameters of the hydrogel especially for the testing of a superabsorbent [15]. Hydrogels can
experience swelling, with a transparent appearance and have a smooth, rather hard but flexible surface. The
value of the nanoparticles of mangrove starch can be seen in Fig 6.

1800
1600
1400
Ratio Swelling (%)

1200
1000
800
600
400
200
0
0.2 0.4 0.6 0.8 1
Starch Nanoparticle of Mangrove fruit (g)

FIGURE 6. swelling ratio of hydrogel

With variations in the addition of mangrove starch nanoparticles have an effect on the change of
swelling ratio of various hydrogels, the first ratio increases then decreases and rises again. The addition of a
sufficient number of starch nanoparticles not only increases the water absorption but also is resistant to salt.
Starch nanoparticles have a large number of hydrophilic (OH) groups, triggering a synergistic effect with other

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Proceeding of The 3rd International Seminar on Chemistry, 18-19 July 2018

polymer groups forming hydrogen bonds between molecular chains and accelerating penetration of water
molecules into the hydrogel matrix [16]. The addition of excessive mangrove starch nanoparticles will increase
crosslinking, so that the hydrogel structure is rigid and can not accommodate large amounts of water volume,
and water absorption will weaken [17]. The optimum swelling ratio of 1584.18% in the concentration of
nanoparticle starch addition of 1 gram mangrove fruit. There is a difference in the resulting swelling ratio of
Pati-gP (acrylic acid-co-acrylamide) / PVA semi-IPN Hydrogel [18] water absorption capacity of 245.9% and
acrylate starch-graft-sodium copolymer [19] using cross-linked poly (vinyl alcohol) -g-starch [8] water
absorption capacity up to 1100% and 800%.
Crosslinking Degree analysis
Data from the determination of degree of crosslinking can be seen in Fig 7.

106
105
Crosslingking degree (%)

104
103
102
101
100
99
0.2 0.4 0.6 0.8 1
Starch Nanoparticle of Mangrove fruit (g)

FIGURE 7. Crosslinking degree of hydrogel

The percentage of crosslinking increases with increasing number of Starch Nanoparticles used. This is
because the more number of Starch Nanoparticles used, the hydrogel will be more solid but still elastic. The
crosslinks play a major role in determining elasticity. The crosslinks serve as shape binders which allow for very
large elastic deformations. The expected network is the formation of a chain as long as possible and crosslinked
only in some places. In addition of 0.6 gram of Starch Nanoparticles 0.6 gram percentage of crosslinked degrees
decreased. This is due to physical interactions or the formation of hydrogen bonds between the hydrogen groups
of the starch nanoparticles with hydrogen bonds of acrylic acid, these bonds are like hydrogen bridges or
vanderwalls thereby increasing the limited elasticity properties. In this case the physical bonds that occur are
optimum and so on there is a decrease in mechanical properties (addition of 0.6 g of starch nanoparticles). This
decrease is due to the occurrence of equilibrium so that the addition of Nanoparticles Starch can reduce
mechanical properties due to chain chains of irregular polymer.

CONCLUSION
The mangrove fruit starch nanoparticles are easily dissolved in the PEG / NaOH solvent system. semi-IPN
hydrogel has been successfully synthesized with copolymerization of Acrylic acid monomer addition, PPP
initiator, MBA crosslinker and mangrove fruit starch nanoparticles as a hydrogel matrix. Hydrogels are
characterized using FTIR, SEM, XRD and DSC. The percent parameter of swelling and cross bundle is
evaluated. Hydrogels were synthesized with the addition of variation of mangrove starch nanoparticles. The
analysis of hydrogel properties revealed that the addition of mangrove starch nanoparticles had different effects
on the water absorption ratio. highest swelling was found in the concentration of mangrove fruit starch
nanoparticles 1 gram (Hydrogel 5).

ACKNOWLEDGMENT
The authors are grateful to the Pusdiklat Industri Kementerian Perindustrian who has supported the funding of
this research, Politeknik Teknologi Kimia Industri medan, Department of Chemistry, University of Sumatera
Utara, Medan for its support in the use of laboratories, and not forgetting my promoters who have provide useful
guidance and advice in conducting this research.

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