Science of the Total Environment 875 (2023) 162660

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Science of the Total Environment

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In situ forming dialdehyde xanthan gum-gelatin Schiff-base hydrogels as

potent controlled release fertilizers
⁎
Subhraseema Das a, , Ganeswar Dalei b
a
Department of Chemistry, Ravenshaw University, Cuttack 753003, Odisha, India
b
Department of Chemistry, Odisha University of Technology and Research, Bhubaneswar 751029, Odisha, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• In situ forming gelatin-dialdehyde xanthan

gum Schiff-base hydrogel is potent CRF.
• Good water-retention behaviour in soil,
biodegradability and reusability
• Urea release mechanism indicated crucial
role of macromolecular relaxation.
• Phytotoxicity assay indicated nontoxicity
of hydrogel.
• Growth assay on Okra plants suggested
the hydrogel as good soil conditioner.

A R T I C L E I N F O A B S T R A C T

Editor: Baoliang Chen Controlled release fertilizer (CRF) hydrogels have blossomed into promising materials in agriculture owing to the sus-
tained release of the fertilizer and also as soil conditioner. Apart from the traditional CRF hydrogels; Schiff-base
Keywords: hydrogels have garnered significant thrust that release nitrogen slowly in addition to reducing the environmental pol-
Dialdehyde xanthan gum lution. Herein, we have fabricated Schiff-base CRF hydrogels composed of dialdehyde xanthan gum (DAXG) and gel-
Schiff-base hydrogel
atin. The formation of the hydrogels was accomplished via the simplistic in situ crosslinking reaction between the
Controlled release fertilizer
aldehyde groups of DAXG and the amino groups of gelatin. The hydrogels acquired a compact network upon increasing
the DAXG content in the matrix. The phytotoxic assay on different plants indicated the hydrogels to be nontoxic. The
hydrogels demonstrated good water-retention behaviour in soil, along with reusability even after 5 cycles. A controlled
release profile for urea was evident from the hydrogels wherein macromolecular relaxation played a crucial role in the
release mechanism. Growth assays on Abelmoschus esculentus (Okra) plant presented an intuitive evaluation on the
growth and water-holding capacity of the CRF hydrogel. The present work demonstrated a facile preparation of CRF
hydrogels to enhance the utilization of urea and retain soil humidity as fertilizer carriers.

1. Introduction
Owing to rapid increase in population, industrialization, urbanization,
desertification and land degradation; the area of arable land per capita is
plummeting at an alarming rate (Azeem et al., 2014; Klimczyk et al.,
2021). Besides, climate change has brought in major alterations in the
⁎ Corresponding author.
E-mail address: subhraseema@ravenshawuniversity.ac.in (S. Das).
temperature and water resources which has invariably impacted the crop
yield (Fenu and Malloci, 2020). Thus, utilization of fertilizers for higher
crop yield has become an inevitable practice. Current data assesses that
2.50 × 106 tons of fertilizer per year will be required to cater to the global
food demand (Chen et al., 2021). Among the lot; nitrogen-based fertilizers
and urea, to be precise, is the most effective and basic nutrient for plant
growth and need for protein production (Arafa et al., 2022). About
73.4 % of all nitrogen-based fertilizers used for agricultural purposes uni-
versally is in the form of urea (Roberts, 2009; Sutton et al., 2011; Gao

http://dx.doi.org/10.1016/j.scitotenv.2023.162660
Received 9 December 2022; Received in revised form 6 February 2023; Accepted 2 March 2023
Available online 7 March 2023
0048-9697/© 2023 Elsevier B.V. All rights reserved.
S. Das, G. Dalei
et al., 2021). However, approximately 20–70 % of the nitrogen applied to
the agricultural field in the conventional form of urea discharges to the at-
mosphere either by nitrogen leaching or NH3 volatilization (Naz and
Sulaiman, 2016; Jia et al., 2020). Also, the oxidation of NH3 produces
NO2 and NO3 (Krajewska, 2009; Ghobashy et al., 2021a) and these forms
of N have deleterious effects on soil, groundwater, and atmosphere through
leaching, runoff, and volatilization processes (Drecht et al., 2003; Galloway
et al., 2008; Gao et al., 2021). It has also been reported that N2O emissions
from such processes contribute to a greater extent in global warming than
CO2 emissions (Ghobashy et al., 2021a) Moreover, the ammonium in soil
is replaced by cations like Ca2+, Mg2+, K+ and Na+ which may be received
by plants resulting in the discharge of hydrogen ions, thereby enhancing
soil acidification (Huang and Xu, 2010; Taiz and Zeiger, 2010; Gao et al.,
2021). Therefore, it is of utmost importance to regulate soil pollution by
controlled release of N (Ghobashy, 2020; Ghobashy et al., 2021a).
Now-a-days, it is a great challenge for the utilization of high efficiency
fertilizers to curb environmental pollution due to overuse of fertilizers for
attaining high crop yields. In this regard, controlled release fertilizers
(CRFs) have evolved as prominent candidates in agriculture as they are
bestowed with noble attributes such as reducing the fertilizer dose, improv-
ing nitrogen consumption, saving irrigational water usage and maintaining
a valid supply period (Babar et al., 2014; Pang et al., 2019). Also, the CRFs
are believed to promote crop yields, in addition to reducing the environ-
mental pollution inherently accompanied by the nitrogenous emissions
from conventional fertilizers (Azeem et al., 2014). These CRFs set a physical
blockade around the urea molecule which reduces the dissolution rate of
urea and modulates its slow release to the crop fields (Guo et al., 2005).
A panoply of methods have been developed for the construction of CRFs
which includes deposition on organic/inorganic functional materials,
coating with polymers, encapsulation in matrices, copolymerization etc.
(Naz and Sulaiman, 2016; Yang et al., 2017; Zhao et al., 2010; Iftime
et al., 2019).
Polymeric materials, and mainly hydrogels, have been profoundly used
as soil conditioners in agriculture (Ghobashy et al., 2018; Song et al., 2020;
Di Martino et al., 2021; Ghobashy et al., 2021b) The most commonly used
hydrogels for CRFs are polyacrylamide (PAAm) and acrylate derivatives
which, however are not completely biodegradable and thus, contaminate
the soil (Aviv et al., 2013; Wang et al., 2015; Di Martino et al., 2021). Al-
though, PAAm is not toxic, its formulations may have little amounts of
Scheme 1. Schematic representation of synthesis of gelatin (GT)-dialdehyde xanthan gum (DAXG) Schiff-base hydrogels (GD) as urea controlled release fertilizers (CRFs) in
agriculture.
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Science of the Total Environment 875 (2023) 162660
acrylamide which is neurotoxic and carcinogenic and pollutes the soil and
food. Hence, natural polymers based hydrogels have blossomed into viable
alternatives; being environmentally benevolent, biodegradable and non-
toxic in nature (McClements, 2017; Mishra et al., 2018; Ramli, 2019; Di
Martino et al., 2021). Of late, such hydrogel systems have gained promi-
nence as CRF hydrogels since they can regulate the plant nutrients and
water as a single material (Liang et al., 2009). Their high water and nutrient
holding ability have aptly rendered them the title of “mini reservoirs”
(Raafat et al., 2012; Saruchi et al., 2014). A clear analysis on different
types and generation of CRF hydrogels has been thoroughly reviewed by
Fu and co-workers (Fu et al., 2018). The authors have pointed that fourth
type/generation of “Schiff-base hydrogels/complexes” are budding mate-
rials that could pave the path forward towards design and optimization of
effectual CRFs (Fu et al., 2018). Schiff-base hydrogels accomplished by
dialdehyde crosslinking with amine-group containing polymers have ren-
dered to be a facile and economical strategy by polymer researchers. A
handful of literature are available for the controlled release of urea from
such Schiff-base hydrogels (Iftime et al., 2019; Kiran et al., 2019).
In this context, xanthan gum (XG), a microbial polysaccharide, has gar-
nered substantial interest. XG finds immense utilities in health, energy and
environmental applications owing to its biocompatibility, stability in high
pH and nontoxicity (Jena et al., 2022). Lately, dialdehyde xanthan gum
(DAXG), accomplished by periodate oxidation of XG, has validated its can-
didature in food packaging (Ge et al., 2017), pharmaceutical packaging (Ge
et al., 2018a), adhesive (Paiva et al., 2016) and wound dressing (Ge et al.,
2018b) material. As verified from different reports; DAXG has overwhelm-
ing attributes such as enhanced water resistance, reduced hydrophilicity,
thermal, light barrier mechanical and good crosslinking properties (Ge
et al., 2015; Paiva et al., 2016; Ngwabebhoh et al., 2021). However, till
date, no work has been conducted on DAXG based Schiff-base hydrogels
as CRFs.
Keeping this in mind, we have developed a Schiff-base hydrogel com-
posed of DAXG and gelatin (GT) for controlled release of urea for agricul-
tural purposes (Scheme 1). GT is a biocompatible, biodegradable polymer
present in the skin of pigs, cattle, and fish (Rigueto et al., 2021). The poly-
morphic structure of a GT molecule contains an amino, hydroxyl and
carboxyl group; thus rendering it prominent in food industries, biomedicine
and environmental applications as an efficient adsorbent (Rigueto et al.,
2021). The Schiff-base hydrogels composed of GT and DAXG were
S. Das, G. Dalei
synthesized via the in situ crosslinking reaction between amino groups of GT
and aldehyde groups of DAXG. The hydrogels were characterized by differ-
ent spectroscopic techniques and their urea release behaviour has been in-
vestigated in soil. The mechanism of urea release from the hydrogels was
addressed from kinetic fitting parameters. To assess the phytotoxicity of
the hydrogels, visual assessment was conducted to detect any damage to
garlic, beans and okra plants at the seedlings stage. The efficacy of the
hydrogels towards controlled release of urea was further evaluated from
the plant growth experiment by comparing the growth with our designed
hydrogels and commercially available urea. Finally, the reusability and bio-
degradability of the hydrogels were estimated. Thus, this research work
represents a simplistic method for the synthesis of eco-friendly systems
for CRFs.
2. Experimental
2.1. Materials
Xanthan gum (XG), gelatin (from fish skin) and Ehrlich reagent were
procured from Sigma-Aldrich, India and used as received. Sodium
periodate was obtained from Merck India Ltd. and used as such. Urea was
obtained from HiMedia India. All other reagents were of highest grade pu-
rity and obtained from Merck India Ltd. and HiMedia (India).
2.2. Synthesis of DAXG
Dialdehyde xanthan gum (DAXG) was synthesized by microwave irradi-
ation method. Briefly, the mixture of XG powder (1 g) and 10 mL of
periodate solution (0.075 g/mL) was subjected to microwave irradiation
(UWave-1000 Sineo Microwave) at a power of 300 W for 4 min at 90 °C.
The product (DAXG) was washed with water and dried for further studies.
The aldehyde content of DAXG was assessed as reported by Guo and co-
workers (Guo et al., 2014).
2.3. Synthesis of Schiff-base hydrogel
1 g gelatin (GT) powder was dissolved in 15 mL of water. Then, DAXG
solution was added to the GT solution and mechanically agitated to ensure
homogenization. The obtained mixture solution was evenly poured in petri
dish. The solutions were frozen at −50 °C for 8 h and subsequently lyoph-
ilized for 48 h in a Biobase Freeze Dryer. Different grades of hydrogels were
synthesized by varying the content of GT to DAXG in the ratio (wt%) 1:1,
1:2 1:3, 1:4, 1:5 and designated as GD1, GD2, GD3, GD4, GD5 respectively.
The yield (%) of the reaction was estimated by the gravimetric method as
reported (Ozay et al., 2021) and found to be 89.91, 90.12, 89.9, 89.77,
90.04 % for the formation of GD1, GD2, GD3, GD4, GD5 hydrogels respec-
tively. The incorporation of urea onto the hydrogels was carried out in situ.
Prior to casting, urea (1 g) was added to the solution and stirred briefly. The
urea-loaded GD gel solutions were lyophilized in similar manner as de-
scribed above.
2.4. Characterization
The gelation times of the hydrogels were noted as per previous literature
(Zhou et al., 2008). The FTIR spectra of the hydrogels were recorded in
Thermo Nicolet iS5 spectrophotometer in the range of 4000–400 cm−1 by
the solid KBr pellet method. Carl Zeiss-Gemini FESEM 300 was used for
morphological examination of the hydrogels. The average pore size of the
hydrogels was estimated by random selection of several pores from the
FESEM images using ImageJ software. TGA of the specimens was studied
in NETZSCH STA 449F3 from ambient to 900 °C in nitrogen atmosphere.
2.5. Swelling behaviour
The swelling capacity of the hydrogels was evaluated by the weighing
method (Shen et al., 2020). Dried and pre-weighed GD hydrogels were
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Science of the Total Environment 875 (2023) 162660
immersed in water at 25 °C until equilibrium and the swollen weight was
then measured. The average data has been presented from three readings.
2.6. Water-retention studies in soil
The water-retention behaviour of the designed hydrogels was appraised
from the reported procedure (Shen et al., 2020). 2 g hydrogel was thor-
oughly mixed with the 100 g dried soil taken in a container and 50 mL
water was added to the blend. A container having the same soil and no
hydrogel served as the control. The hydrogels were weighed every alternate
days until equilibrium. The final data have been averaged from five
readings.
2.7. Biodegradation test
For the biodegradation assay, appropriately weighed GD hydrogels
(2 cm × 2 cm) were buried 15 cm under the top soil (garden soil collected
from Ravenshaw University, Cuttack, India) and watered alternate days. At
specified intervals, the samples were taken out, washed with distilled water
and dried to constant weight. The biodegradability was inferred by measur-
ing the weight loss of each sample. The reported data have been averaged
from five readings.
2.8. Urea release behaviour and kinetics
Urea release property of the designed Schiff-base hydrogels was simul-
taneously investigated in water and soil. The amount of released urea was
determined in a UV–Vis spectrophotometer (Cary UV-100, Agilent) based
on the well-known Ehrlich reaction (Wen et al., 2016; Leon et al., 2018).
For the release studies in distilled water, the urea-loaded GD hydrogels
were immersed in water and 3 mL aliquot of solution was withdrawn
every 1 h and assessed by the spectrophotometric method. To the 3 mL
aliquot, Ehrlich reagent (3 mL) was added, the solution was appropri-
ately diluted and shook gently. The dimethylaminobenzaldehyde
gradually reacted with the urea and produced a bright yellow color com-
plex that was proportional to urea concentration. The absorbance values
were compared with the standard calibration curve spectrophotometri-
cally at λ ₌ 430 nm. Each test was performed in triplicate and the mean
data presented.
For release studies in soil; the hydrogels (∼1 g) were enclosed in a
nylon screen (10 mesh screen cloth) and embedded 15 cm away from top
soil wrapped in a vessel (polypropylene pots of 30 cm internal diameter
and 20 cm height) with 500 g soil. The pots were equipped with filter
paper No. 5 at the bottom. The moisture content of the soil was regulated
at 30 % and the container was stored at room temperature. Water
(100 mL) was added slowly at pre-determined intervals and the leachate
was then centrifuged to separate sandy soil particles from water (Vudjung
and Saengsuwan, 2018). The urea release was evaluated by UV–Vis method
described above.
The kinetics of urea release in water and soil was addressed by fitting
the release data to four basic mathematical models namely Higuchi,
Ritger-Peppas, Peppas-Sahlin and Zero-order (Serra et al., 2006).
2.9. Plant growth assessment
The phytotoxicity of the hydrogels was performed in accordance with
OECD 208 method, using 1 g of dry hydrogel per kg of soil. The OECD
208 method is generally used to confirm that biodegraded materials do
not induce any toxic components into the soil (Chen and Chen, 2019).
Three different plants, namely garlic, beans and okra, were used for the as-
sessment of toxicity. The plant growth testing and harvesting was estimated
as per reported method (Chen and Chen, 2019).
To assess the impact of controlled release of urea from the GD
hydrogels, pot culture experiments were carried out. Three plant chambers
containing 1 kg of soil in each and 5 g of urea-loaded hydrogel and commer-
cially available urea were placed at 25 ± 2 °C in well lighting and
S. Das, G. Dalei
ventilation conditions. Abelmoschus esculentus (Okra) plants having approx-
imately same size were planted 5 cm from the soil surface and watered
every two/three days interval to maintain the water availability. After the
plants yielded the fruits, they were stopped watering and the plant growth
index was observed in the drought condition to gauge the role of the CRF as
soil conditioner.
2.10. Chlorophyll content
Since photosynthetic pigments such as chlorophyll a and chlorophyll b
are vital parameters for plant growth; we have estimated the aforemen-
tioned content from different leaves of the plant of our study by UV–Vis
spectrophotometry (Lichtenthaler and Wellburn, 1983; Kumaraswamy
et al., 2021). Briefly, 0.2 g leaf samples were hand homogenized in 20 mL
of 100 % acetone and then filtered. The absorbance was read at 663 nm
and 646 nm implying the quantification of chlorophyll a and b respectively.
Data have been presented as mean of five replicates ±SD.
2.11. Reusability test
The reusability tests of the hydrogels were carried out in distilled water
as per the procedure in Section 2.5. After the first test, the hydrogel was
dried in an oven at 50 °C and reused. This process was performed for five
runs (Mohammadbagheri et al., 2021).
3. Results and discussion
3.1. Synthesis of DAXG
The periodate oxidation of polysaccharides introduces selective
cleavage of C\\C bond between vicinal hydroxyl group of the anhydro-D-
glucopyranose residues, resulting in the formation of ring opening
dialdehyde products. In our study, XG was oxidized by periodate to pro-
duce corresponding dialdehyde xanthan gum (DAXG) (Fig. 1A). The for-
mation of DAXG was affirmed from FTIR data. The yield % and the
degree of oxidation was evaluated and found to be 96 % and 46 %
respectively.
The FTIR spectra of XG and DAXG were presented in Fig. 1B. The peaks
at 1000–1240 cm−1 indicates (CO and C\\O\\C stretching), 1410 cm−1
(OH bending), 2925 cm−1 (CH vibrations) and 3000–3600 cm−1 (OH
stretching) was witnessed in both the spectra of XG and DAXG. However,
Fig. 1. The periodate oxidation of xanthan gum (XG) to dialdehyde xanthan gum (DAXG). (A) Schematic reaction and (B) FTIR spectral depiction.
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Science of the Total Environment 875 (2023) 162660
the appearance of new peak at 1735 cm−1 ascribed to the C_O stretching
vibration represents the dialdehyde groups of DAXG. Such an observation
has been reported earlier in the study by Ngwabebhoh and team
(Ngwabebhoh et al., 2021). Also, we could observe the appearance of an in-
tense band in the region 750 cm−1. This was attributed to the C\\H out of
plane bending arising from the formation of hemiacetal and/or hydrated
bonds between aldehyde and hydroxyl groups (Kim et al., 2000). In addi-
tion, sharper peak around 1038 cm−1 owing to C\\O\\C stretching was
witnessed in DAXG as a result of hydration of aldehydes (Ragothaman
et al., 2014). Thus, the FTIR analyses indicated the successful accomplish-
ment of DAXG by periodate oxidation of XG.
3.2. Formation of Schiff-base GD hydrogel
The plausible scheme of hydrogel formation between DAXG and GT is
shown in Fig. 2A. The formation of GD hydrogel occurred via the Schiff-
base reaction between the amino group of GT and aldehyde group of
DAXG, which was confirmed from FTIR spectroscopy (Fig. 2B). The FTIR
spectrum of pure GT showed peaks at 3440 cm−1 ascribed to N\\H
stretching of secondary amide, C_O stretching at 1670 cm−1, N\\H bend-
ing between 1550 and 1500 cm−1, and C\\H stretching at 2963 cm−1. The
Schiff-base formation was ascertained from the spectra of the GD hydrogels
that revealed a peak at 1635 cm−1, which is attributed to the imine bond
formed due to C_N linkages between GT and DAXG (Iftime et al., 2017).
Moreover, modification of the broad band from 3500 to 3000 cm−1 attrib-
uted to the overlapped stretching bands of the O\\H and N\\H bonds and
the intra- and inter-molecular H-bonds are also suggestive of the imine link-
ages in the GD hydrogels (Iftime et al., 2017; Iftime et al., 2019). It could
further be observed that with increasing dialdehyde content in the
hydrogels, the bands in this particular domain gradually shift to higher
wavenumbers (3417 in GD1; 3435 in GD2; 3438 in GD3; 3440 in GD4;
3442 cm−1 in GD5). Such an observation could be ascribed to the forma-
tion of imine units inducing a tighter packing in the hydrogel matrix
(Iftime et al., 2017). Thus, the FTIR spectral data recommended the
Schiff-base formation of GD hydrogels and formation of a rigid matrix
with an increased crosslinking efficiency of GD5 hydrogel.
3.3. Gelation of GD hydrogels
The gelation time is a significant factor which is defined as the time re-
quired for the in situ crosslinking of the hydrogel. Fig. 3A displays the digital
S. Das, G. Dalei Science of the Total Environment 875 (2023) 162660

Fig. 2. (A) In situ crosslinking reaction of gelatin (GT) and dialdehyde xanthan gum (DAXG) forming GD hydrogel via Schiff-base reaction and (B) FTIR spectra of GT, DAXG
and the GD hydrogels.

photographs of gelation for the GD hydrogels respectively. As depicted in could be explained by the differences in the DAXG content in the hydrogels,
Fig. 3B, the gelation time of the hydrogels has significantly decreased which greatly influenced the crosslinking reaction rate and subsequently
with an increase in the DAXG content. This difference in gelation times reduced the gelation time.

Fig. 3. The gelation of GD hydrogels. (A) Photographs and (B) time plots of GD hydrogels (***p < 0.001).

5
S. Das, G. Dalei
3.4. TGA of GD hydrogels
Fig. 4 elucidates the TG curves of gelatin (GT), dialdehyde xanthan gum
(DAXG), neat urea, urea-loaded GD5 hydrogel and GD1, GD5 hydrogels
from ambient temperature to 950 °C. As witnessed for GT, DAXG, GD1,
GD5 and GD5-urea hydrogels, the TGA curves displayed three mass loss re-
gions. The first stage of weight loss in the region 25 °C–150 °C indicates the
loss of free water. The second stage of weight loss was observed in the range
of 250 °C–300 °C which is likely associated with the decomposition of the
polymer composite. The weight loss region around T > 400 °C could be
accredited to the carbonaceous residues originating due to polymer degra-
dation (Mishra et al., 2011). As seen, the TG curve of GD1 showed a slight
improvement in thermal stability in comparison to individual GT and
DAXG likely due to formation of Schiff-base hydrogel. More so, the pres-
ence of enhanced crosslinking in GD5 hydrogel rendered an enhanced ther-
mal stability with respect to GD1 hydrogel. Similar improvement in thermal
stability has been reported for Schiff-base hydrogels wherein the Schiff-
base bonds were attributed for the same (Nezhad-Mokhtari et al., 2021;
Dalei et al., 2023). The TGA curve of neat urea is consistent with literature
report (Jones and Rollinson, 2013). For the urea-loaded GD5 hydrogel, an
enhancement in thermal stability is clearly evident in comparison to GD1
and GD5 hydrogels. The findings suggested that GD5-urea hydrogel was
thermally stable and could be a good candidate for CRF in agriculture.
3.5. Morphology of hydrogels
In this study, the influence of different content of DAXG on the hydrogel
microstructure was morphologically studied by FESEM. Fig. 5A illustrates
the FESEM images of GD hydrogels. Although an inter-connected porous
network structure was revealed by all the prepared samples; the pore
sizes varied. Quantification of the pore sizes for the hydrogels (Fig. 5B)
projected that an increase in DAXG content in the hydrogel led to a reduc-
tion in the hydrogel porosity. As the DAXG content was increased in the
hydrogels, a rather compact network structure with smaller pores was rec-
ognized. The average pore size for GD1 hydrogel was found to be 58.658 ±
19.17 μm while that for GD5 revealed a 1.4 times diminution to 42.602 ±
16.03 μm. Basically, the presence crosslinking influenced the porosity of
the hydrogel by forming higher network entanglements. In our case;
Fig. 4. TGA curves of gelatin (GT), dialdehyde xanthan gum (DAXG), urea, GD1 hydrogel, GD5 hydrogel and urea-loaded GD5 hydrogel.
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Science of the Total Environment 875 (2023) 162660
DAXG, being a macromolecule, creates more crosslinks rendering a denser
matrix in GD5 hydrogel.
3.6. Swelling behaviour of hydrogels
Swelling is one of the most important parameters that impacts the per-
formance of CRFs. The swelling of the GD hydrogels was evaluated in dis-
tilled water at 25 °C and the profiles are illustrated in Fig. 6A. It could be
clearly witnessed that the GD5 hydrogel displayed the lowest swelling
ratio among all the synthesized hydrogels. While the equilibrium swelling
percent of GD1 hydrogel reached 2500 after 24 h, there was almost a 2.5
times reduction for GD5 hydrogel. This observation puts forth that as
DAXG content was increased, the swelling ratio of the hydrogels was
lowered substantially. Such an observation could be justified considering
the tighter packing and compact matrix in GD5 hydrogel. The swelling
data further corroborates with our FTIR spectral data, the lower gelation
times and denser morphology of GD5 hydrogel as studied earlier.
3.7. Water-retention property of hydrogels
One of the crucial features of a material designed as CRF is its water-
retention ability in soil. In parched areas, this property could be exploited
for the slow release of the trapped water to aid crop growth. As evident
from Fig. 6B, the water-retention rate of the soil devoid of GD5 hydrogel
presented a total water loss by the 8th day. In contrast, the water-
retention rate of the soil endowed with GD5 hydrogel was prolonged to
the 14th day. This study proved that the synthesized GD5 hydrogel was ef-
fective in retention of soil-moisture and could be used as soil conditioner for
agriculture purposes in arid/ semi-arid areas.
3.8. Urea release and kinetics
3.8.1. Urea release behaviour in water and soil
The cumulative release rates of neat urea and urea-loaded GD hydrogels
in distilled water and soil have been projected in Fig. 7A and B respectively.
From Fig. 7A, it was evident that the cumulative release of urea was faster
than the urea-loaded GD hydrogels. The release rates of urea from the GD
hydrogels obviously decreased, with GD5 hydrogel displaying the slowest
S. Das, G. Dalei Science of the Total Environment 875 (2023) 162660

Fig. 5. The morphology of GD hydrogels. (A) FESEM images (Scale bar 100 μm) and (B) average pore size distribution histograms of GD1, GD2, GD3, GD4 and GD5 hydrogels.

release among all. Similar pattern of urea release was also witnessed in the than that in distilled water medium. Such an observation could be largely
soil study (Fig. 7B). However, there was pronounced difference in the re- attributed to the reduction in the dynamic exchange rate of water and
lease rates of urea in soil and in water. It could be clearly witnessed that CRF (urea-loaded hydrogels) because of the decreased amount of urea dif-
the cumulative rates of urea release in soil was significantly prolonged fusion in the soil environment. The urea release from GD5 hydrogel in soil

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S. Das, G. Dalei Science of the Total Environment 875 (2023) 162660

Fig. 6. (A) Swelling behaviour of GD hydrogels and (B) Water-retention behaviour of soil with and without GD5 hydrogel.

was stabilized upto a period extending for >30 days which suggested its
high potency as a CRF. From the observations in Sections 3.5 and 3.6; the
GD5 hydrogel displayed the lowest water absorbency and endowed with
a compact matrix; the diffusion of urea molecules from this hydrogel to
the soil was greatly lowered in comparison to other specimens.
3.8.2. Urea release mechanism analysis
Four basic release kinetic models namely the Higuchi model, the Ritger-
Peppas model, the Peppas-Sahlin model and Zero-order model were
adopted to address the preliminary kinetics of urea release in water and
soil. The results of the fittings of the release data have been presented in

Fig. 7. Urea release and the kinetics of its release from GD hydrogels. The release profiles of urea in (A) distilled water and (B) soil. (C) Plot of ratio of polymer relaxation to
Fickian diffusion (R/F) contribution to the mechanism of urea release from GD5 hydrogel in water and in soil by fitting to Peppas-Sahlin equation.

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S. Das, G. Dalei Science of the Total Environment 875 (2023) 162660

Table 1
Kinetic and fitting parameters for urea release from GD hydrogels in water and soil.
Models Higuchi Ritger Peppas Peppas-Sahlin Zero-Order
Samples kH R2 n kRP R2 k1 k2 R2 k0 R2
GD1 (water) 0.283 0.772 0.89 0.234 0.996 0.005 0.242 0.996 0.237 0.996
GD1 (soil) 0.202 0.804 1.01 0.103 0.993 0.000 0.104 0.993 0.105 0.993
GD2 (water) 0.259 0.867 0.73 0.199 0.949 0.074 0.124 0.941 0.137 0.883
GD2 (soil) 0.169 0.718 1.28 0.059 0.988 0.060 0.119 0.982 0.089 0.964
GD3 (water) 0.184 0.865 0.83 0.125 0.999 0.052 0.072 0.999 0.099 0.981
GD3 (soil) 0.144 0.777 1.10 0.045 0.995 0.020 0.063 0.994 0.056 0.991
GD4 (water) 0.167 0.863 0.90 0.086 0.996 0.028 0.061 0.997 0.072 0.982
GD4 (soil) 0.118 0.752 1.18 0.032 0.994 0.028 0.056 0.990 0.046 0.982
GD5 (water) 0.147 0.888 0.88 0.070 0.999 0.027 0.045 0.999 0.055 0.983
GD5 (soil) 0.104 0.750 1.18 0.019 0.996 0.029 0.039 0.994 0.031 0.984

kH: Higuchi rate constant; n: diffusion exponent; kRP: Ritger-Peppas rate constant; k1: Fickian diffusion
rate constant; k2: Relaxation rate constant; k0: Zero-order rate constant; R2: fitting parameter.

Table 1. The Higuchi model is associated with the Fickian diffusion of the
molecule from the hydrogel matrix. From the Ritger-Peppas equation, the
term ‘n’ is referred to as the diffusional exponent which describes the trans-
port mechanism. n = 0.5 implies Fickian diffusion occurring due to molecu-
lar diffusion. When n = 1, case II transport occurs. When n lies between 0.5
and 1, anomalous transport is observed, where both Fickian and polymer re-
laxation phenomena contribute to the release. n > 1 implies super case II
transport mechanism, which is due to a large increase in osmotic pressure
driving forces, followed by the relaxation and swelling of polymers. From
the results depicted in Table 1; we could witness that the n values for urea re-
lease from GD hydrogels in water lied between 0.73 and 0.90. This data sug-
gested that urea release in water followed the mechanism of anomalous
transport wherein both diffusion and polymer relaxation processes impact
the release. On the other hand, the respective n values for urea release from
GD hydrogels in soil revealed to be >1.00. This indicated that the release
mechanism was super case II transport which reflected the crucial role of
the macromolecular relaxation on the molecular movement of urea inside
the matrix in soil. For urea release in soil, the water molecules penetrated
into the hydrogel matrix owing to the osmotic pressure gradient, followed
by relaxation and swelling of matrix. To further impound the influence of dif-
fusion and relaxation on the release mechanism; the data was fit to Peppas-
Sahlin equation which accounts for the coupled effects of Fickian diffusion
and case II transport whence k1 denotes the diffusion kinetic constant and
k2 is the relaxation rate constant. From Table 1, we discovered that k2 domi-
nated over the diffusional constant k1 for all the hydrogels. However, it is not
possible to exactly estimate the contribution of Fickian mechanism or case II
mechanism, just from the depicted values. Thus, the ratio of relaxation vs.
Fickian diffusion (R/F) was plotted against the fraction of urea released
from the GD5 hydrogel in water and in soil and presented in Fig. 7C. It was
evident that urea release mechanism is predominantly governed by matrix re-
laxations in both water and soil media. However, the magnitude of R/ F value
was higher for urea release from GD5 hydrogel in soil in comparison to that in
water. Thus, we could infer that matrix relaxations played a vital role in
penetration of water molecules and regulation of urea release in soil. Taken
altogether, a diagrammatic representation of the mechanism of urea release
from GD5 hydrogel in soil is proposed in Scheme 2. When implanted in

Scheme 2. Schematic representation of proposed mechanism of controlled release of urea from GD5 hydrogel in soil.

9
S. Das, G. Dalei Science of the Total Environment 875 (2023) 162660

Fig. 8. (A) Reusability of GD5 hydrogel in water as a function of reswelling for 5 cycles and (B) biodegradability of GD5 hydrogel as a function of time in soil.

agricultural soil, the water first penetrates through the walls of GD5 hydrogel
and then dissolves the fertilizer nutrients (urea, in this case) present inside
the matrix. As the urea starts to get dissolved, an osmotic pressure is built
within the matrix resulting in a swelled matrix. Thereafter, the pressure gra-
dient acts as the driving force for the controlled urea release via diffusion.
Such a multi-stage diffusion release mechanism for CRFs has also been ac-
cepted previously (Li and Chen, 2020).
3.9. Reusability of GD hydrogel
The water absorbency of GD5 hydrogel in distilled water as a function of
reswelling times for 5 number of cycles is depicted in Fig. 8A. It was seen that
the water absorbency amounted to ∼823 % after 5 cycles; which was about
20 % of the initial swelling capacity of GD5 hydrogel. Thus, we could see that
GD5 hydrogel still had the ability to absorb high amounts of water, even
after 5 cycles. This could be likely attributed to its denser and tough network
structures owing to in situ crosslinking. However, the decrease in the water
absorbing capacity of the GD5 hydrogel after 5 cycles could likely be as-
cribed to the breakdown of the physical crosslinking points inside the matrix
during the swelling-deswelling process (Salimi et al., 2020). Subsequently,
the network entanglements weaken and a reduced swelling is witnessed.
3.10. Biodegradation
To access the biodegradability of GD5 hydrogel, it was buried in soil and
its weight loss was estimated subsequently as a function of time. As

Fig. 9. The phytotoxicity assay. Digital photographs of (A) garlic, (B) beans and (C) okra plants on the 15th day of incubation with soil and GD hydrogels. (D) The average
fresh weight of the plants exposed to soil and GD hydrogels after 15 days.

10
S. Das, G. Dalei
witnessed in Fig. 8B, the GD5 hydrogel degrades gradually with time. By
the end of second month, almost 70 % of the hydrogel has degraded. This
observation could be explained by the fact that the hydrogel is invaded
by different kinds of microorganisms present in the soil which aid in the
degradation process. This result demonstrated that GD5 hydrogel is a po-
tent candidate as a CRF in agriculture.
3.11. Phytotoxicity of GD hydrogels
To assess the phytotoxicity induced by the prepared hydrogels, visual
assessment was conducted to detect any damage to the saplings of our
study. Fig. 9A, B and C project the digital photographs of various plants,
namely garlic, beans and Okra, subjected to GD hydrogels respectively. Ev-
idently, there was no damage to the plants after 15th day of incubation with
GD1, GD3 and GD5 hydrogels. Fig. 8D depicts the average weights of the
plants exposed to soil (control) and GD hydrogels. Negligible differences
(p < 0.05) were observed in the average fresh weights of the plants.
These findings were highly suggestive of nontoxicity perspective of the
GD hydrogels.
3.12. Evaluation of urea-loaded GD5 hydrogel on the growth of Okra plants
The influence of urea-loaded GD5 hydrogel on the growth of Okra
plants was investigated. Along with our chosen sample, okra plants in
neat soil and urea-based soil devoid of GD hydrogel, were also examined
for a comparative analysis. Of the various assessment of plant growth
such as measurements of dry mass of plant or that of seeds or fruit; the mea-
surement of plant height and the number of leaves is an easy method and
have been employed in our case. The plant growth test was measured in
soil upto 8 weeks and presented in Fig. 10A and B. The plants without
any fertilizer (represented as Control) showed mediocre growth both in
terms of stalk height and number of budding leaves, even after weeks 8.
However, the prominence in the growth of the plants furnished with pure
urea or GD5-urea hydrogel is clearly evident. While the pure urea supple-
mented plant reached a height of 30 cm after week 6; the GD5-urea hydro-
gel facilitated the height to 41 cm. This enhancement in plant height
promoted by the GD5-urea hydrogel suggested its greater efficacy than
the plant supplemented with pure urea only. Apparently, the nitrogen re-
leased quickly from the neat urea resulting more in loss than utility. On
the contrary, the controlled release of nitrogen from GD5-urea hydrogel
Fig. 10. The plant growth assay. The histograms of (A) number of leaves and (B) stalk height of the Okra plant in different soil conditions in week 1 and week 6. (C) Images of
plants growth in week 1 and week 8. (D) Images of plant growth in drought conditions after yielding fruits for week 2.
11
Science of the Total Environment 875 (2023) 162660
Table 2
Chlorophyll content (mg/g fresh leaves) in okra plants.
Sample Chlorophyll a Chlorophyll b Chlorophyll a + b
Control 20.78 ± 0.88 15.78 ± 0.13 36.57 ± 1.23
GD5-Urea 21.45 ± 1.01 19.35 ± 0.55 40.81 ± 1.21
facilitated the growth of a healthier plant. This is also witnessed from the
photographs depicted in Fig. 10C. The Okra plant that is furnished with
the designed GD5-urea hydrogel yielded higher fruits among the rest.
After the period of week 8, the plants were subjected to drought condi-
tions and were stopped watering. Fig. 10D illustrates the selected digital
photographs of the plants under different fertilizer conditions. We could ob-
serve that the Okra plant promoted by GD5-urea hydrogel could maintain
for week 2 while the control could hardly be kept alive. This surprising
drought resistance feature of GD5-urea hydrogel indicated that it is condu-
cive for plant growth and apt in retaining soil moisture.
Photosynthetic pigments, chlorophyll to be precise, are specialized in
light-energy absorbing used for carbon fixation. Their content have a direct
impact on the photosynthetic capacity and subsequently, the plant growth.
Hence, both the content and proportion of chlorophyll a and chlorophyll b
impact the selective absorption of light and its use by the plant. The respec-
tive data for chlorophyll content have been tabulated in Table 2. The GD5-
urea promoted plant displayed enhanced chlorophyll content, thus suggest-
ing better photosynthesis and better plant growth.
4. Conclusion
The focus of this work was to explore the synthesis of an eco-friendly
bio-inspired Schiff-base hydrogel composed of gelatin and dialdehyde
xanthan gum with controlled release feature of urea for agricultural pur-
poses. The hydrogel fabrication was accomplished via the facile strategy
of in situ crosslinking reaction between the aldehyde groups of DAXG and
the amino groups of gelatin. Various grades of hydrogels were constructed
by varying the DAXG content. The hydrogels possessed an interconnected
porous network structure and an increasing DAXG content lowered the
swelling and rendered a more compact matrix. The water-retention prop-
erty in soil was prolonged to the 14th day in presence of GD5 hydrogel.
From the urea release data, it could be witnessed that the cumulative
rates of urea release in soil was significantly extended than that in distilled
S. Das, G. Dalei
water medium. Furthermore, the urea release from GD5 hydrogel in soil
was stabilized upto a period of >30 days which suggested its high potency
as a CRF. The kinetics of urea release recommended a multi-stage diffusion
release mechanism driven by the osmotic pressure that is built within the
hydrogel matrix upon implantation in soil. The reusability experiments re-
vealed that the GD5 hydrogel could retain its swellability even after 5 cy-
cles. From the biodegradation study, it was found almost 70 % of the GD5
hydrogel had degraded by the end of second month, thereby suggesting
its environmental benevolence. The phytotoxic assay on garlic, beans and
Okra plants indicated the hydrogels did not induce any toxic components
into the soil. Moreover, the presence of GD5-urea hydrogel in the soil af-
fected the plant-growth process remarkably. An evaluation on the promi-
nent soil water holding and plant growth promotion role of GD5-urea
hydrogel revealed good results in Okra plants. In conclusion, our work
has provided a facile and simplistic in situ crosslinking strategy for prepar-
ing eco-friendly CRF hydrogels to facilitate the plant growth and simulta-
neously maintain soil humidity. The results indicate that our designed
Schiff-base GD5 hydrogel not only ensures a controlled release activity
but also enables as a soil moisturizer for agricultural applications in arid
and semi-arid regions.
Funding
This research did not receive any specific grant from funding agencies in
the public, commercial, or not-for-profit sectors.
CRediT authorship contribution statement
GD: conceptualization, writing original draft, summarizing.
SD: conceptualization, supervision, writing - review and editing.
Data availability
Data will be made available on request.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgements
SD expresses her gratitude to Department of Chemistry, Ravenshaw
University, Cuttack, Odisha and GD acknowledges Department of Chemis-
try, Odisha University of Technology and Research Bhubaneswar, Odisha
for providing the essential amenities to carry out this study.
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