biomolecules

Article
Development of Biodegradable
Agar-Agar/Gelatin-Based Superabsorbent Hydrogel
as an Efficient Moisture-Retaining Agent
Jyoti Chaudhary 1 , Sourbh Thakur 1,2, *, Minaxi Sharma 3 , Vijai Kumar Gupta 4, *
and Vijay Kumar Thakur 5,6, *
1 School of Chemistry, Faculty of Sciences, Shoolini University, Solan, Himachal Pradesh 173229, India;
[email protected]
2 Center for Computational Materials Science, Institute of Physics, Slovak Academy of Sciences,
84511 Bratislava, Slovakia
3 Department of Food Technology, Akal College of Agriculture, Eternal University, Baru Sahib,
Himachal Pradesh 173101, India; [email protected]
4 AgroBioSciences (AgBS) and Chemical & Biochemical Sciences (CBS) Department, University Mohammed
VI Polytechnic (UM6P), Lot 660, Hay Moulay Rachid, Benguerir 43150, Morocco
5 Biorefining and Advanced Materials Research Center, Scotland’s Rural College (SRUC), Kings Buildings,
West Mains Road, Edinburgh EH9 3JG, UK
6 Department of Mechanical Engineering, School of Engineering, Shiv Nadar University,
Uttar Pradesh 201314, India
* Correspondence: [email protected] or [email protected] (S.T.); [email protected] (V.K.G.);
[email protected] (V.K.T.)




Received: 1 May 2020; Accepted: 18 June 2020; Published: 22 June 2020


Abstract: Downgrading in the yield of crop is due to the inadequate availability of water. The way
out for this trouble is to construct synthetic resources dependent on natural polymers with great water
absorption and preservation limits. The present study investigated the design of agar-agar (Agr) and
gelatin (GE) copolymerized methyl acrylate (MA) and acrylic acid (AA) hydrogel (Agr/GE-co-MA/AA)
as a soil conditioner for moisture maintenance in agriculture. Agr/GE-co-MA/AA hydrogel was
prepared by utilizing microwave-assisted green synthesis following the most suitable reaction
conditions to obtain a remarkable water swelling percentage. The fabricated Agr/GE-co-MA/AA
hydrogel was investigated through field emission scanning electron microscopy (FESEM), fourier
transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The water holding capacity
of the soil and sand was examined by mixing Agr/GE-co-MA/AA hydrogel with soil and sand.
The result demonstrates that the water holding time extended from 10 to 30 days for soil and 6 to
10 days for sand by using Agr/GE-co-MA/AA hydrogel. This synthesized biodegradable, low-cost
and non-toxic Agr/GE-co-MA/AA hydrogel shows novelty as soil water maintaining material for
irrigation in agriculture.

Keywords: gelatin; agar-agar; green synthesis; hydrogel; biodegradable; swelling; soil; agriculture

1. Introduction
Sustainable development and growth in agriculture management of water is essential [1].
The inadequate supply of water is an exceedingly severe concern for agricultural activities [2].
Substitutes for the irrigation technique will become crucial in regions where the available water is
decreasing with time [3]. Recently, absorbent material, like hydrophilic polymers, considers much
concern for plant growth by maintaining the water and manure [4]. Hydrogels are characterized

Biomolecules 2020, 10, 939; doi:10.3390/biom10060939 www.mdpi.com/journal/biomolecules

Biomolecules 2020, 10, 939 2 of 13
Biomolecules 2020, 10, x FOR PEER REVIEW 2 of 14

cross-linked
as cross-linkedthree-dimensional
three-dimensional hydrophilic
hydrophilicpolymers,
polymers,andandhave
havebecome
becomeoneone of
of the recent
the most recent
interestingresearch
interesting researchtopics
topicsduedue to their
to their highhigh swelling
swelling and hydrophilic
and hydrophilic nature nature [5]. Hydrogels
[5]. Hydrogels are
are broadly
broadly recommended
recommended for agro purposes
for agro purposes to remoldto remold
water water accessibility
accessibility and swollenand swollenstock
hydrogel hydrogel
waterstock
can
water
be usedcan
forbe used
the for the
function offunction of plant
plant water water assimilation
assimilation [6] as demonstrated
[6] as demonstrated in Scheme 1.in Scheme 1.

Scheme 1. Demonstrates hydrogel used in the agriculture field for the function of plant
Scheme 1. Demonstrates hydrogel used in the agriculture field for the function of plant water
water assimilation.
assimilation.

Hydrogels can absorb and retain any biological fluid or aqueous media 100 times while correlating
Hydrogels can absorb and retain any biological fluid or aqueous media 100 times while
with the density [7]. The water absorption property depends upon the cross-linked arrangement
correlating with the density [7]. The water absorption property depends upon the cross-linked
and accessibility of hydrophilic units, like –OH, –SO3 H, and –CONH2 [8]. The fascinating extremely
arrangement and accessibility of hydrophilic units, like -OH, -SO3H, and -CONH2 [8]. The
large characteristic of water makes it a remarkable material that can be used in attractive goods, such
fascinating extremely large characteristic of water makes it a remarkable material that can be used in
as female hygiene sanitary, diapers, soil strengthener, drug delivery systems, and hydro blockade
attractive goods, such as female hygiene sanitary, diapers, soil strengthener, drug delivery systems,
tapes [9–12]. Because of the superb water-absorbing tendency, absorbent materials are widely exposed
and hydro blockade tapes [9–12]. Because of the superb water-absorbing tendency, absorbent
to soil conditioning in the field. The utilization of water-sparing materials in farming for the recovery
materials are widely exposed to soil conditioning in the field. The utilization of water-sparing
of infertile, barren, and aired fields requires splendid attempts and potential outcomes are initiated as
materials in farming for the recovery of infertile, barren, and aired fields requires splendid attempts
they decrease the irrigation water utilization and the downfall of plants, increases the soil- grip for the
and potential outcomes are initiated as they decrease the irrigation water utilization and the
fertilizer, and overhaul the plant upgrade standard [5].
downfall of plants, increases the soil- grip for the fertilizer, and overhaul the plant upgrade standard
The absorbent material probably affects the physical characteristics of the soil, i.e., upgrading the
[5].
permeability rate of the soil, and diminishing soil corrosion and runoff. The integrated dry and wet
The absorbent material probably affects the physical characteristics of the soil, i.e., upgrading
techniques applied in soil decide the efficiency of hydrogel materials [13]. The absorbent materials are
the permeability rate of the soil, and diminishing soil corrosion and runoff. The integrated dry and
layered under the soil for reasonable execution. In cultivation, they are extensively used as moisture
wet techniques applied in soil decide the efficiency of hydrogel materials [13]. The absorbent
maintenance materials and bio-remediation purposes in soil. The manufacturing of advanced goods
materials are layered under the soil for reasonable execution. In cultivation, they are extensively
for spraying water strategies is significant for attaining lifelong beneficial evolution, generally in the
used as moisture maintenance materials and bio-remediation purposes in soil. The manufacturing of
regions where the accessibility of water is less [14].
advanced goods for spraying water strategies is significant for attaining lifelong beneficial evolution,
Hydrogel materials from natural polymers build up an acceptable idea, being an abundant
generally in the regions where the accessibility of water is less [14].
property, low-cost production, and biodegradable in nature [5]. Agar-agar (Agr) is a gelling agent,
Hydrogel materials from natural polymers build up an acceptable idea, being an abundant
which acts as a remarkable soil water moisture-maintaining material and improves the harvest yield.
property, low-cost production, and biodegradable in nature [5]. Agar-agar (Agr) is a gelling agent,
Gelatin (GE) is acquired from animal bones and is soluble in lukewarm water, having low thickness
which acts as a remarkable soil water moisture-maintaining material and improves the harvest yield.
properties in comparison with agar-agar [15]. Gelatin and agar-agar based materials have been
Gelatin (GE) is acquired from animal bones and is soluble in lukewarm water, having low thickness
exploited in various biomedical- and environmental-related applications; however, their utilization as
properties in comparison with agar-agar [15]. Gelatin and agar-agar based materials have been
a substitute for a water-retaining agent in the farming field still needs to be explored.
exploited in various biomedical- and environmental-related applications; however, their utilization
as a substitute for a water-retaining agent in the farming field still needs to be explored.
Biomolecules 2020, 10, 939 3 of 13

Agricultural synthetic polymers are common but not biodegradable and their by-products are
not eco-friendly [16]. Hydrogels made from Agr/GE can be utilized as an alternative material to
synthetic polymers due to their biodegradability, non-toxicity, varying solubility, controlled release
characteristics, and responsiveness to microbial degradation in the environmental atmosphere [17–19].
Table 1 provides a comparative chart of synthesized agar-agar (Agr) and gelatin (GE) copolymerized
methyl acrylate (MA) and acrylic acid (AA) hydrogel (Agr/GE-co-MA/AA) absorbent material to
that of other reported absorbents in the literature. The Agr/GE-co-MA/AA absorbent material is
efficient compared to other reported materials from the water retention ability point of view. The easy
fabrication, high absorption capacity, stability, and biodegradable nature make Agr/GE-co-MA/AA
hydrogel an attractive alternative for irrigation treatment in the agriculture field. The present work
concentrated on microwave-facilitated synthesis of Agr/GE-co-MA/AA hydrogel for the first time as
a high moisture-retaining agent.

Table 1. Comparison between water retention ratios of synthesized agar-agar/gelatin copolymerized

methyl acrylate/acrylic acid (Agr/GE-co-MA/AA) hydrogel and reported absorbents.

Water Evaporation
S.N.* Analysis of Media Absorbent Material Reference
Ratio (Days)
1. Soil Alginate nanoparticles 11 [20]
2. Sandy soil Fenugreek galactomannan-borax hydrogel 11.5 [14]
3. Alluvial soil Nano clay polymer composite 13 [5]
Double-coated, slow-release and
4. Soil 17.3 [4]
water-retention urea fertilizer
5. Clay soil IPN hydrogel 27 [21]
6. Soil Agar/Ga-Cl-poly(AA) 28 [15]
7. Sand Agr/GE-co-MA/AA 10 Present work
8. Soil Agr/GE-co-MA/AA 30 Present work
* Serial number.

The Agr/GE-co-MA/AA hydrogel swelling and water preservation properties were studied.
The fabricated Agr/GE-co-MA/AA hydrogel was examined using fourier transform infrared
spectroscopy (FTIR), X-ray diffraction (XRD), and field emission scanning electron microscopy (FESEM).
The results of the water preservation studies demonstrate the excellent ability of Agr/GE-co-MA/AA
hydrogel to maintain moisture in soil and sand for a long period.

2. Materials and Methods

2.1. Materials
Gelatin (GE) (cattle bone), agar-agar (Agr), methyl acrylate (MA) (C4 H6 O2 , 99%), acrylic acid
(AA) (C3 H4 O2 , 98%), N,N0 -methylenebisacrylamide (NMBA) (C7 H10 N2 O2 , 99%), and ammonium
persulfate (APS) ((NH4 )2 S2 O8 , 98%) were acquired from Loba Chemie, Central Drug House (Solan,
India). Soil and sand were collected from the Himalayan region of North India (Shoolini University,
Solan, Himachal Pradesh, India). Every single chemical was of analytical grade and utilized without
future refinement. All reactions were completed utilizing deionized water.

2.2. Synthesis of Agar-Agar/Gelatin Copolymerized Methyl Acrylate/Acrylic Acid Hydrogel

The microwave-assisted method was used to synthesize Agr/GE-co-MA/AA. For a particular
reaction, homogeneous solution of agar-agar/gelatin (1:1) was prepared in lukewarm water (temperature:
39 ◦ C). In this solution, ammonium persulfate (0.24 mol L−1 ), methyl acrylate (1.10 × 10−2 mol L−1 ),
acrylic acid (0.72 × 10−2 mol L−1 ), and N,N0 -methylenebisacrylamide (0.16 mol L−1 ) were added.
The mixture formed was stirred for 20 min at room temperature to ensure homogeneity of the reaction.
After the formation of the homogeneous mixture, the mixture was placed in a microwave reactor
(IFB Model-20PG3S microwave oven, 1000 W) operated at 20% microwave power for 90 s to complete
Biomolecules 2020, 10, 939 4 of 13

the polymerization reaction. The successful polymerization reaction was confirmed by the appearance
of gel-like material (Agr/GE-co-MA/AA). The formed Agr/GE-co-MA/AA hydrogel was washed with
acetone to remove homopolymers and dried under a hot air oven at 50 ◦ C for 24 h. Optimization
of different reaction factors, like the initiator, monomer, solvent, cross-linker, time, and microwave
power (Table 2) was carried out to obtain Agr/GE-co-MA/AA hydrogel with an excellent water
absorption ability.

Table 2. Various reaction conditions for the synthesis of Agr/GE-co-MA/AA hydrogel.

Initiator Reaction Microwave Monomer Crosslinker Monomer

Solvent %
S. N. (APS) Time power (MA) (NMBA) (AA)
(mL) Swelling
(mol L−1 ) (s) (%) (mol L−1 ) (mol L−1 ) (mol L−1 )
1. 0.15 70 5.0 20 1.10 × 10−2 0.16 – 329.6
2. 0.19 70 5.0 20 1.10 × 10−2 0.16 – 370.5
3. 0.24 70 5.0 20 1.10 × 10−2 0.16 – 470.7
4. 0.28 70 5.0 20 1.10 × 10−2 0.16 – 265.3
5. 0.32 70 5.0 20 1.10 × 10−2 0.16 – 244.9
6. 0.24 50 5.0 20 1.10 × 10−2 0.16 – 431.8
7. 0.24 70 5.0 20 1.10 × 10−2 0.16 – 470.7
8. 0.24 90 5.0 20 1.10 × 10−2 0.16 – 498.3
9. 0.24 110 5.0 20 1.10 × 10−2 0.16 – 402.9
10. 0.24 130 5.0 20 1.10 × 10−2 0.16 – 363.7
11. 0.24 90 3.0 20 1.10 × 10−2 0.16 – 422.2
12. 0.24 90 3.5 20 1.10 × 10−2 0.16 – 452.2
13. 0.24 90 4.0 20 1.10 × 10−2 0.16 – 478.5
14. 0.24 90 4.5 20 1.10 × 10−2 0.16 – 518.7
15. 0.24 90 5.0 20 1.10 × 10−2 0.16 – 498.3
16. 0.24 90 4.5 20 1.10 × 10−2 0.16 – 518.7
17. 0.24 90 4.5 40 1.10 × 10−2 0.16 – 478.1
18. 0.24 90 4.5 60 1.10 × 10−2 0.16 – 468.8
19. 0.24 90 4.5 80 1.10 × 10−2 0.16 – 458.1
20. 0.24 90 4.5 100 1.10 × 10−2 0.16 – 311.1
21. 0.24 90 4.5 20 0.55 × 10−2 0.16 – 306.8
22. 0.24 90 4.5 20 1.10 × 10−2 0.16 – 518.7
23. 0.24 90 4.5 20 1.65 × 10−2 0.16 – 299.6
24. 0.24 90 4.5 20 2.20 × 10−2 0.16 – 157.6
25. 0.24 90 4.5 20 2.75 × 10−2 0.16 – 132.2
26. 0.24 90 4.5 20 1.10 × 10−2 0.09 – 252.4
27. 0.24 90 4.5 20 1.10 × 10−2 0.16 – 518.7
28. 0.24 90 4.5 20 1.10 × 10−2 0.22 – 353.9
29. 0.24 90 4.5 20 1.10 × 10−2 0.29 – 196.4
30. 0.24 90 4.5 20 1.10 × 10−2 0.35 – 141.5
31. 0.24 90 4.5 20 1.10 × 10−2 0.16 0.72 × 10−2 636.1
32. 0.24 90 4.5 20 1.10 × 10−2 0.16 1.45 × 10−2 560.7
33. 0.24 90 4.5 20 1.10 × 10−2 0.16 2.17 × 10−2 525.0
34. 0.24 90 4.5 20 1.10 × 10−2 0.16 2.91 × 10−2 492.7
35. 0.24 90 4.5 20 1.10 × 10−2 0.16 3.63 × 10−2 430.2

2.3. Characterization
Fourier transform infrared spectroscopy (FTIR) interpretations were conducted using the KBr
pellet method in the scale of 400–4000 cm−1 using a Nicolet 5700 FTIR spectrophotometer (Agilent
Technologies, L1600312; CA, USA). The morphology of Agr/GE-co-MA/AA hydrogel was measured by
a field emission scanning electron microscope (FESEM) (JSM-6100). The X-ray diffraction (XRD) was
assessed by a SmartLab 9kW rotating anode x-ray (Rigaku Corporation, Tokyo, Japan).

2.4. Swelling Studies of Agar-Agar/Gelatin Copolymerized Methyl Acrylate/Acrylic Acid Hydrogel

The pre-weighted Agr/GE-co-MA/AA hydrogel was taken in 40 mL of deionized water and kept
for 18 h at room temperature. The swollen Agr/GE-co-MA/AA hydrogel was weighed on an analytical
 Biomolecules 2020, 10, x FOR PEER REVIEW 5 of 14

26. 0.24 90 4.5 20 1.10 × 10-2 0.09 -- 252.4

27. 0.24 90 4.5 20 1.10 × 10-2 0.16 -- 518.7
28. 0.24
Biomolecules 90939
2020, 10, 4.5 20 1.10 × 10-2 0.22 -- 5 of 13 353.9
29. 0.24 90 4.5 20 1.10 × 10-2 0.29 -- 196.4
30. 0.24 90 4.5 20 1.10 × 10-2 0.35 -- 141.5
31. balance
0.24 (accuracy: 90 ± 0.00001
4.5 g). The swelling
20 percentage
1.10 × 10-2was evaluated
0.16 through0.72
the× 10
following
-2 636.1
32. 0.24
equation [22]: 90 4.5 20 1.10 × 10 -2 0.16 1.45 × 10-2 560.7
33. 0.24 90 4.5 20 Ws −1.10
Wd× 10 -2 0.16 2.17 × 10-2 525.0
% Swelling = × 100, (1)
34. 0.24 90 4.5 20 W1.10
d × 10
-2 0.16 2.91 × 10-2 492.7
35. 0.24 90 4.5 20 1.10 × 10 -2 0.16 3.63 × 10 -2 430.2
where Ws is the weight of swollen Agr/GE-co-MA/AA hydrogel and Wd is the weight of dry
Agr/GE-co-MA/AA hydrogel.
2.5. Water
2.5. Water Retention
Retention Study
Study
Twodifferent
Two differentsoilsoil and
and sand
sand media
media werewere
usedused to perform
to perform the water
the water retention
retention experiments
experiments by
by using
using Agr/GE-co-MA/AA hydrogel. In a particular experiment, 2 g of Agr/GE-co-MA/AA
Agr/GE-co-MA/AA hydrogel. In a particular experiment, 2 g of Agr/GE-co-MA/AA hydrogel was hydrogel
was mixed
mixed with
with 20 g of20 g taken
soil of soilintaken in thecontainer.
the plastic plastic container. Then,
Then, 40 mL 40 mL
of tap of was
water tap slowly
water was slowly
added into
added into the plastic container and measured (W 1) with an analytical balance (accuracy: ± 0.00001
the plastic container and measured (W1 ) with an analytical balance (accuracy: ±0.00001 g). The control
g). The
(soil control
without (soil without Agr/GE-co-MA/AA)
Agr/GE-co-MA/AA) experiment was alsoexperiment
performed wasin also performed
a similar way (Win a similar way
2 ). The analysis
(W2). The were
containers analysis containers
placed at room were placed and
temperature at room
were temperature
weighed through and were weighedbalance
an analytical through an
daily
analytical balance daily until no clear decrease in weight was noted. The reduction
until no clear decrease in weight was noted. The reduction in weight was measured daily with the in weight was
measured
help daily withbalance
of an analytical the help of an analytical
(accuracy: ±0.00001balance
g). The(accuracy: ± 0.00001 ratio
water evaporation g). The
(Wwater
%) of evaporation
the soil was
ratio (W %) of the soil was calculated
calculated through Equation (2) [15]: through Equation (2) [23]:

W1 − W2 (2)
W% = × 100 , (2)
40
where W
where W11 and W22 are the weights of the
the plastic
plastic container
container with
with Agr/GE-co-MA/AA
Agr/GE-co-MA/AA hydrogelhydrogel and
and
without Agr/GE-co-MA/AA
without Agr/GE-co-MA/AA hydrogel,
hydrogel, respectively;
respectively; and
and 40
40 is
is the
the volume
volume of of water
water (mL).
(mL). The
The same
same
experiments for
experiments for sand
sand were
were repeated
repeated by
by using
using sand
sand ininplace
placeof ofsoil.
soil. The
The FTIR
FTIR was
was performed
performed for
for
Agr/GE-co-MA/AA hydrogel fragments after the final result of moisture retention to
Agr/GE-co-MA/AA hydrogel fragments after the final result of moisture retention to confirm theirconfirm their
degradablenature.
degradable nature.

3.
3. Results
Results and
and Discussions
Discussions
The
TheAgr/GE-co-MA/AA
Agr/GE-co-MA/AA hydrogel was was
hydrogel prepared by a microwave-assisted
prepared green method
by a microwave-assisted greeninvolving
method
the polymerization
involving reaction as reaction
the polymerization presentedas in Scheme 2.
presented in Scheme 2.

Scheme 2. Representation of the synthesis of Agr/GE-co-MA/AA hydrogel.

Scheme 2. Representation of the synthesis of Agr/GE-co-MA/AA hydrogel.

In general, sulfate anion radicals are produced by disintegration of APS. Subsequently, the reaction
of sulphate anion radicals with MA and AA initiates the reaction with the formation of monomer
Biomolecules 2020, 10, 939 6 of 13

radicals. Meanwhile, the extraction of hydrogen from Agr/GE through SO4 •− (sulphate anion radicals)
gives • O-R (alkoxy radicals). Thus, Agr/GE is converted to Agr/GE macro radicals followed by
propagation steps. After the expansion of polymer chains, the monomer radicals that are closer to the
reaction sites turn into acceptors of Agr/GE macroradicals. Accordingly, the cross-linked structure
is formed during chain growth reactions by the concurrent reaction between polymer chains and
vinyl groups of NMBA. Hydroxyl and other hydrophilic functional groups on Agr/GE contribute
to the hydrogen bonding between Agr, GE, MA, AA, and NMBA, resulting in the formation of
Agr/GE-co-MA/AA hydrogel.

3.1. Optimization of Various Reaction Factors for the Swelling of Agar-Agar/Gelatin Copolymerized Methyl
Acrylate/Acrylic Acid Hydrogel
The outcome of the initiator concentration (APS) on the swelling percentage of Agr/GE-co-MA/AA
hydrogel is shown in Figure 1a as the APS concentration varies in the range of 0.15–0.32 mol L−1 .
The % swelling rises with the increasing initiator concentration up to 0.24 mol L−1 ; subsequently,
it begins to reduce. Initially, APS creates additional active sites on Agr/GE and MA/AA, resulting in
the copolymerization process taking place rapidly, and leading to a rise in the percentage swelling.
The higher initiator concentration support side chains and homo-polymerization processes, which are
accountable for the reduction in the swelling percentage.
The effect of the reaction time on the swelling ability of Agr/GE-co-MA/AA hydrogel was analyzed
in the range of 50–130 s and the outputs are presented in Figure 1b. The % swelling increases with an
increase in the reaction time from 50 to 90 s, where it attains the maximum value. For the reaction
time below 90 s, Agr/GE-co-MA/AA hydrogel shows lower % swelling, which can be ascribed to
insufficient cross-linking, resulting in poor water uptake. However, when the reaction time is longer
than 90 s, excessive cross-linking occurred, which results in a more rigid structure. This ultimately
leads to a poor water uptake capability [23]. The solvent volumes utilized for the formation of
Agr/GE-co-MA/AA hydrogel varied from 3 to 5 mL. The optimized value of the solvent is interpreted
as 4.5 mL (Figure 1c). Approximately, the swelling percentage achieved at 4.5 mL of solvent was
518.7%. Further increments in the solvent volume led to a reduction in the swelling percentage
because of a reasonable decrease in the concentration of the initiator (APS), monomer, and cross-linker
(NMBA), which resulted in the poor polymerization rate [24]. The impact of the microwave power on
the % swelling of Agr/GE-co-MA/AA hydrogel is presented in Figure 1d. The results demonstrated
that the maximum % swelling was obtained at 20%, and thereafter, it decreased. With the increase
in the microwave power, the dissociation rate of APS increased, which led to the formation of a
large number of radicals, which further enhanced the homo-polymerization and termination reaction;
hence, the swelling percentage decreased [25]. On increasing the monomer (MA) concentration from
0.55 × 10−2 mol L−1 to 1.10 × 10−2 mol L−1 (Figure 1e), the rate of copolymerization increased as more
MA molecules were available for chain propagation sites and thus the swelling percent was enhanced.
The decrease in the swelling percentage at a higher MA concentration (beyond 1.10 × 10−2 mol L−1 ) was
due to the rise in the viscosity of the reaction, which prevented the movement of radicals and favored
homo-polymerization over copolymerization [26]. The Agr/GE-co-MA/AA copolymer displayed
the highest percentage swelling at a cross-linker (NMBA) concentration of 0.16 mol L−1 (Figure 1f).
The decrease in percentage swelling with a further increase in the cross-linker concentration was due
to the formation of a dense and inflexible Agr/GE-co-MA/AA hydrogel, which was not able to absorb a
large amount of water [23]. The copolymer Agr/GE-co-MA/AA hydrogel shows a maximum swelling
of 636.1% at the AA concentration of 0.72 × 10−2 mol L−1 (Figure 1g).
Biomolecules 2020, 10, 939 7 of 13
Biomolecules 2020, 10, x FOR PEER REVIEW 7 of 14

Figure 1. Swelling optimization of Agr/GE-co-MA/AA hydrogel as a function of (a) ammonium

Figure 1. Swelling optimization of Agr/GE-co-MA/AA hydrogel as a function of (a) ammonium
persulfate initiator, (b) reaction time, (c) solvent volume, (d) microwave power, (e) methyl acrylate
persulfate initiator, (b) reaction time, (c) solvent volume, (d) microwave power, (e) methyl
concentration, (f) N, N0 -methylenebisacrylamide concentration, and (g) acrylic acid concentration.
acrylate concentration, (f) N, N′-methylenebisacrylamide concentration, and (g) acrylic acid
3.2. Characterization
concentration.

3.2.1.The
Fourier
effectTransform Infraredtime
of the reaction Analysis
on the swelling ability of Agr/GE-co-MA/AA hydrogel was
analyzed in the
The FTIR range of 50–130
interpretations of GE, s Agr,
and the
and outputs are presented
Agr/GE-co-MA/AA in Figure
hydrogel were1b. The %
carried outswelling
to gain
increases with an increase in the reaction time from 50 to
insight into the various interactions and functional groups (Figure 2). 90 s, where it attains the maximum value.
For the reaction time below 90 s, Agr/GE-co-MA/AA hydrogel shows lower
The FTIR interpretation of GE presented peaks around 3215.2, 3361.2, and 3443.2 cm % swelling, which can
−1
be ascribed to insufficient
corresponding cross-linking,
to N–H stretching resulting
of 2◦ amide, C=Oinstretching
poor water at uptake.
1651.6 cmHowever,
−1 , N–H when
bendingthebetween
reaction
time is longer
−1 than 90 s, excessive
−1 cross-linking occurred, which results
1556.6 cm and 1404.6 cm , N–H out of plane wagging at 608.8 cm , and C–H stretching at in
−1 a more rigid structure.
This ultimately
928.2 and 2846.3leads cm−1to a poor
[27] water
(Figure 2a).uptake
The Agr capability
showed[24]. The solvent
an intense volumes
and sharp peakutilized
at 1047.7 forand
the
formation −1 of Agr/GE-co-MA/AA hydrogel varied from 3 to 5 mL. The optimized
890.8 cm related to 3,6-anhydro galactose networks and CH3 rocking, respectively [28] (Figure 2b). value of the solvent
is interpreted
The characteristicas 4.5 mL (Figure
adsorption band1c).atApproximately, the swelling
1643.6 cm−1 is ascribed to thepercentage
>C=O stretchingachievedunitatof4.5
AA mL of
[15]
solvent2c).
(Figure wasThe518.7 %. of
peaks Further
MA atincrements in the cm
2950.3 and 1526.6 solvent
−1 werevolume
due toled
C-Htostretching
a reduction in theand
vibration swelling
C=O
percentage because of a reasonable decrease in the concentration of the initiator (APS), monomer,
and cross-linker (NMBA), which resulted in the poor polymerization rate [25]. The impact of the
 The Agr/GE-co-MA/AA copolymer displayed the highest percentage swelling at a cross-linker
(NMBA) concentration of 0.16 mol L-1 (Figure 1f). The decrease in percentage swelling with a further
increase in the cross-linker concentration was due to the formation of a dense and inflexible
Agr/GE-co-MA/AA hydrogel, which was not able to absorb a large amount of water [24]. The
copolymer Agr/GE-co-MA/AA hydrogel shows a maximum swelling of 636.1% at the AA
Biomolecules 2020, 10, 939 8 of 13
concentration of 0.72 × 10-2 mol L-1 (Figure 1g).

3.2. Characterization
bonding correspondingly. Besides, the C-O-C stretching and deformation vibration were found at
1253.7 and 1123.7 cm−1 , respectively, while peaks at 993.7, 772.8, 694.8, and 525.8 cm−1 were due to
3.2.1.
the C-HFourier
bending Transform Infrared
vibrations Analysis
of polymer networks [29]. Some additional peaks (3380.2, 3215.2, 2950.3,
2280.4,The
2176.5, and 2020.5 cm −1 ) and variation in Agr/GE-co-MA/AA
intensity of peaks confirmed
FTIR interpretations of GE, Agr, and hydrogelthe copolymerization
were of
carried out to gain
MA, AA, Agr, and GE (Figure 2c).
insight into the various interactions and functional groups (Figure 2).

Biomolecules 2020, 10, x FOR PEER REVIEW 9 of 14

2280.4, 2176.5, and 2020.5 cm-1) and variation in intensity of peaks confirmed the copolymerization of
Figure
MA, AA, 2.FTIR
Agr,2.and
Figure GEinterpretations
FTIR 2c). ofof(a)
interpretations
(Figure (a)GE,
GE,(b)
(b)Agr,
Agr,and
and(c)(c)Agr/GE-co-MA/AA
Agr/GE-co-MA/AAabsorbent.
absorbent.

3.2.2. X-ray Diffraction

The X-Ray
3.2.2. FTIR Diffraction
interpretation of GE presented peaks around 3215.2, 3361.2, and 3443.2 cm−1
corresponding
Gelatin
Gelatin
to
shows N–H
shows
stretching
a broad
a broad
of 2° amide,
humpatat2θ2θ∼∼22.5
hump C=O
22.5(Figure
stretching
(Figure 3a). TheXRD
3a). The
at 1651.6
XRD cm−1of, N–H
spectrum
spectrum of Agr
Agr
bending
shows
shows
between
a peak
a peak
−1◦ and 1404.6 cm−1, N–H out of plane wagging at 608.8 cm−1, and C–H stretching at 928.2
at1556.6 cm
2θ at∼2θ
19.1∼ 19.1° with the intensity of 1624 (a.u), which demonstrates the semi-crystalline nature of Agr of
with the intensity of 1624 (a.u), which demonstrates the semi-crystalline nature
and(Figure
Agr 2846.3 3b).
(Figure cm −1 [28] (Figure 2a). The Agr showed an intense and sharp peak at 1047.7 and 890.8 cm−1
The intensity
3b). The intensityofofthe
themain
maindiffraction
diffraction peak
peak decreased
decreased (relative
(relative intensity
intensity ∼1543)
∼1543) and and
related
shifted toto
shiftedthe 3,6-anhydro
to higher range
the higher galactose
(concerning
range networks
(concerning Agr)
Agr)(2θ and
(2θ CH◦3) in
∼∼ 20.1
20.1°) rocking,
inthe
thecase
caserespectively
ofof [29] (Figure
Agr/GE-co-MA/AA
Agr/GE-co-MA/AA 2b). The
hydrogel
hydrogel
characteristic
(Figure 3c).adsorption
The band
broadening ofat 1643.6
the cm
spectra −1 is ascribed
proposed a changeto the >C=O
towards a
(Figure 3c). The broadening of the spectra proposed a change towards a disordered arrangement stretching
disordered unit of
arrangementAA [15]
after after
(Figure copolymerization.
2c). The peaks of MA at 2950.3 and 1526.6 cm were due to C-H stretching vibration and C=O
copolymerization. -1

bonding correspondingly. Besides, the C-O-C stretching and deformation vibration were found at
1253.7 and 1123.7 cm-1, respectively, while peaks at 993.7, 772.8, 694.8, and 525.8 cm-1 were due to the
C-H bending vibrations of polymer networks [30]. Some additional peaks (3380.2, 3215.2, 2950.3,

Figure
Figure 3. The
3. The XRDXRD patternsofof(a)
patterns (a)GE,
GE, (b)
(b) Agr,
Agr, and
and(c)
(c)Agr/GE-co-MA/AA
Agr/GE-co-MA/AAhydrogel.
hydrogel.

3.2.3. 3.2.3.
FieldField
Emission Scanning
Emission Electron
Scanning ElectronMicroscope
Microscope
The morphological
The morphological characteristics
characteristics of Agr,
of the the GE,
Agr,and
GE,Agr/GE-co-MA/AA
and Agr/GE-co-MA/AA hydrogel
hydrogel are
are displayed
displayed in Figure 4 through different magnification scales. The GE demonstrated a regular and
in Figure 4 through different magnification scales. The GE demonstrated a regular and uniform surface
uniform surface (Figure 4a,b). The Agr showed (Figure 4c,b) a smooth and compact surface
morphology. The surface morphology of Agr/GE-co-MA/AA hydrogel changed into a distorted
pattern with a rough and porous surface (Figure 4e,f). Hence, the Agr/GE-co-MA/AA hydrogel
surface favored high water absorption.
 Figure 3. The XRD patterns of (a) GE, (b) Agr, and (c) Agr/GE-co-MA/AA hydrogel.

3.2.3. Field Emission Scanning Electron Microscope

The 2020,
Biomolecules morphological
10, 939 characteristics of the Agr, GE, and Agr/GE-co-MA/AA hydrogel9 ofare 13
displayed in Figure 4 through different magnification scales. The GE demonstrated a regular and
uniform surface (Figure 4a,b). The Agr showed (Figure 4c,b) a smooth and compact surface
(Figure 4a,b). The Agr
morphology. showed
surface (Figure 4c,b)
morphology a smooth and compact
of Agr/GE-co-MA/AA surfacechanged
hydrogel morphology.
into The surface
a distorted
morphology of Agr/GE-co-MA/AA hydrogel changed into a distorted pattern with a rough
pattern with a rough and porous surface (Figure 4e,f). Hence, the Agr/GE-co-MA/AA hydrogel and porous
surface (Figure
favored4e,f).
high Hence, the Agr/GE-co-MA/AA hydrogel surface favored high water absorption.
water absorption.

Biomolecules 2020, 10, x FOR PEER REVIEW 10 of 14

Figure 4. The FESEM morphology of (a,b) GE, (c,d) Agr, and (e,f) Agr/GE-co-MA/AA hydrogel at
different magnifications.
Figure 4. The FESEM morphology of (a,b) GE, (c,d) Agr, and (e,f) Agr/GE-co-MA/AA hydrogel at
3.3. Water Retention
different Properties of Agar-Agar/Gelatin Copolymerized Methyl Acrylate/Acrylic Acid Hydrogel
magnifications.
in Soil and Sand
3.3. Water Retention Properties of Agar-Agar/Gelatin Copolymerized Methyl Acrylate/Acrylic Acid Hydrogel in
SoilNowadays,
and Sand improvement in the water-holding ability of soil in cultivation is gaining
extraordinary
Nowadays,attention [31]. The
improvement in thepre-weighed
water-holdingAgr/GE-co-MA/AA hydrogel
ability of soil in cultivation was extraordinary
is gaining used in soil to
increase the[16].
attention water retention
The capacity.
pre-weighed The water evaporation
Agr/GE-co-MA/AA hydrogelrate
wasof soilin
used and
soilsand is shown
to increase thein Figure
water
5. retention capacity. The water evaporation rate of soil and sand is shown in Figure 5.

Figure5. 5.
Figure Water
Water retention
retention ratioratio of soil,
of (a) (a) soil, (b) Agr/GE-co-MA/AA
(b) Agr/GE-co-MA/AA hydrogel
hydrogel in (c)
in soil, soil,sand,
(c) sand,
and (d)
and (d) Agr/GE-co-MA/AA hydrogel
Agr/GE-co-MA/AA hydrogel in sand. in sand.

The evaporation rate percentage in soil and sand containing Agr/GE-co-MA/AA hydrogel was
less than that of the control (soil and sand without Agr/GE-co-MA/AA hydrogel). The rate of water
loss was different for soil and sand, with variation in the number of days. The water evaporation
 Biomolecules 2020, 10, 939 10 of 13

The evaporation rate percentage in soil and sand containing Agr/GE-co-MA/AA hydrogel was
less than that of the control (soil and sand without Agr/GE-co-MA/AA hydrogel). The rate of water
loss was different for soil and sand, with variation in the number of days. The water evaporation levels
in the soil and Agr/GE-co-MA/AA hydrogel in the soil are shown in Figure 5a,b. The water-retaining
tendency for soil was increased three times when used with Agr/GE-co-MA/AA hydrogel. The sand
with Agr/GE-co-MA/AA hydrogel was capable of holding the water as long as 10 days and water
evaporated within 6 days in the case of sand only as presented in Figure 5c,d. The sandy loam soil can
reduce moisture effortlessly in the atmosphere [30]. Thus, when Agr/GE-co-MA/AA hydrogel was
sited with soil and sand, it upgraded the water-saving tendency (Scheme 3) up to 20 (soil) and 4 days
(sand) extra because of the existence of a hydrophilic group, like –OH, –CONH, and –NH2 , in the
polymeric
Biomolecules 2020,structure of Agr/GE-co-MA/AA
10, x FOR PEER REVIEW hydrogel [15]. 11 of 14

Scheme
Scheme 3. 3. Schematic presentation
Schematic presentation of of
water retention
water in the soil
retention in through
the soilAgr/GE-co-MA/AA hydrogel.
through Agr/GE-co-MA/AA
hydrogel.
These outcomes show that the Agr/GE-co-MA/AA absorbent material can absorb and retain an
immense amount of water [31]. The prepared Agr/GE-co-MA/AA hydrogel can be employed as a
These outcomes show that the Agr/GE-co-MA/AA absorbent material can absorb and retain an
significant water-holding material in horticultural/agricultural applications.
immense amount of water [33]. The prepared Agr/GE-co-MA/AA hydrogel can be employed as a
significant water-holding
3.4. Confirmation material in horticultural/agricultural
of Agar-Agar/Gelatin applications.
Copolymerized Methyl Acrylate/Acrylic Acid Hydrogel
Biodegradability via Fourier Transform Infrared Study
3.4. Confirmation
The FTIRofresults
Agar-Agar/Gelatin
demonstrate thatCopolymerized Methyl Acrylate/Acrylic
Agr/GE-co-MA/AA Acid Hydrogel
hydrogel begins degrading in the soil as
Biodegradability via because
well as in sand Fourier of
Transform
bacterial Infrared Study
indigestion and bond breaking, mainly liable for H2 O discharge
(Figure 6).
The FTIR results demonstrate that Agr/GE-co-MA/AA hydrogel begins degrading in the soil as
The characteristic peaks at 3633.1, 3339.2, 2969.3, 2334.4, 1614.6, 1414.6, 2988.3, 2884.3, 2343.4,
well and
as in sand because of bacterial indigestion and bond breaking, mainly liable for H2O discharge
1414.6 cm−1 almost vanished and the transmittance values of the bands decreased. The cross-linked
(Figure 6).
network of Agr/GE-co-MA/AA hydrogel with soil and sand led to the shifting of peaks and breaking of
covalent bonds [32]. The degradation of Agr/GE-co-MA/AA hydrogel in soil and sand is a direct result
of the activity of microbes and microorganisms. The degradation of fabricated Agr/GE-co-MA/AA
hydrogel through bacterial indigestion demonstrates that it has no harmful impacts on sand and soil
fertility and enhances the organic matter in the agricultural field.
3.4. Confirmation of Agar-Agar/Gelatin Copolymerized Methyl Acrylate/Acrylic Acid Hydrogel
Biodegradability via Fourier Transform Infrared Study
The FTIR results demonstrate that Agr/GE-co-MA/AA hydrogel begins degrading in the soil as
well as in sand
Biomolecules because
2020, 10, 939 of bacterial indigestion and bond breaking, mainly liable for H2O discharge
11 of 13
(Figure 6).

Figure 6.
Figure FTIR interpretation
6. FTIR interpretation of
of Agr/GE-co-MA/AA
Agr/GE-co-MA/AAhydrogel
hydrogelinin
(a)(a)
soilsoil
after 30 days
after andand
30 days (b) sand after
(b) sand
10 days.
after 10 days.

4. Conclusions
The characteristic peaks at 3633.1, 3339.2, 2969.3, 2334.4, 1614.6, 1414.6, 2988.3, 2884.3, 2343.4,
and 1414.6
A novel cmbiodegradable
-1 almost vanished and the transmittance values of the bands decreased. The
Agr/GE-co-MA/AA superabsorbent was developed as an effective
cross-linked
water-holding network of Agr/GE-co-MA/AA
agent through hydrogel
microwave-supported with soil
synthesis. and sand led to the
Agr/GE-co-MA/AA shiftingexhibited
hydrogel of peaksa
swelling capacity of 636.1% at optimized conditions (APS = 0.24 mol L , time = 90 s, solvent =
and breaking of covalent bonds [34]. The degradation of −1
Agr/GE-co-MA/AA hydrogel in soil
4.5and
mL,
sand is a direct
microwave power = 20%,
result of the
MA = 1.10 of
activity −2
microbes
× 10 −1
mol Land = 0.16 mol The
microorganisms.
, NMBA −1 AA = 0.72 × 10
L , degradation −2 mol L−1 ).
of fabricated
The porous and rough surface of Agr/GE-co-MA/AA hydrogel favored the water retention ability of
soil and sand. Agr/GE-co-MA/AA hydrogel was executed for water absorption in combination with
sand and soil. Agr/GE-co-MA/AA was found to enhance the water absorption and retention ability
of sand and soil effectively at a low dose of 2 g. The water-retaining capacity of soil and sand was
improved up to three times and 1.6 times, respectively. Importantly, it is useful in an economic way,
and is biodegradable and non-toxic. This biodegradable Agr/GE-co-MA/AA hydrogel can be applied as
a promising absorbent as a water-holding agent in agricultural applications.

Author Contributions: Experiments and original draft writing, J.C.; data analysis, J.C., S.T. and M.S.; writing,
review and editing, M.S., S.T., V.K.G. and V.K.T.; supervision, S.T., V.K.G. and V.K.T. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: School of Chemistry, Faculty of Sciences, Shoolini University, Solan for financial support in
characterization part.
Conflicts of Interest: The authors declare no conflict of interest.

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