International Journal of Biological Macromolecules 263 (2024) 130339

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International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Review

Seed gum-based polysaccharides hydrogels for sustainable agriculture:

A review
Sujata Mandal a, *, Hyemein Chi b, Rhiannon E Moss a, Prabin Dhital a, Eunice O. Babatunde a,
Ranjit Gurav a, Sangchul Hwang a, *
a
Ingram School of Engineering, Texas State University, San Marcos, TX 78666, USA
b
Department of Civil and Environmental Engineering, Yonsei University, Seoul, South Korea

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

Keywords: Globally, water scarcity in arid and semiarid regions has become one of the critical issues that hinder sustainable
Hydrogel agriculture. Agriculture, being a major water consumer, presents several challenges that affect water availability.
Sustainable agriculture Hydrogels derived from polysaccharides seed gums are hydrophilic polymers capable of retaining substantial
Seed gum
moisture in their three-dimensional network and releasing it back into the soil during drought conditions.
Implementation of hydrogels in the agricultural sectors enhances soil health, plant growth, and crop yield.
Furthermore, the soil permeability, density, structure, texture, and rate of evaporation and percolation of water
are modified by hydrogel. In this review, hydrogels based on natural plant seed gum like guar, fenugreek, Tara
and locust beans have been discussed in terms of their occurrence, properties, chemical structure, method of
synthesis, and swelling behavior. The focus extends to recent applications of modified seed gum-based natural
hydrogels in agriculture, serving as soil conditioners and facilitating nutrient delivery to growing plants. The
swelling behavior and inherent structure of these hydrogels can help researchers unravel their maximum pos­
sibilities to promote sustainable agriculture and attenuate the obstacles propounded by our dynamic nature. The
current review also examines market growth, prospects, and challenges of eco-friendly hydrogels in recent times.

1. Introduction agricultural output. Furthermore, a considerable quantity of water loss

via evaporation and increased runoff from the development of imper­
The cumulative impacts of human activities, such as excessive water meable surfaces has lessened the amount of water available for uptake
consumption, deforestation, and pollution, coupled with the increasing by plants [2]. The consequential erosion of topsoil due to increased
challenges posed by a changing climate and global temperature rise, runoff decreases agricultural productivity by the loss of inherent soil
have led to water-stressed conditions in the semi-arid and parched re­ fertility, leading to a decline in crop yield and ultimately, food scarcity
gions of the earth. Water scarcity has become a critical issue and thus [1]. With the increasing global population, the need for increased food
water management is rapidly becoming one of the most serious global supply and non-agricultural development arises. This results in a greater
concerns. Desertification is a process of land degradation and loss of demand for freshwater resources needed to support agricultural and
biodiversity caused by natural and human activities which impact industrial activities. The lack of abundant water supply in drought-prone
nearly 32 % of the global population [1]. Moreover, in the past few areas of the world affects the ability of countries in these regions to
decades, climate change has exacerbated land degradation with irreg­ support their economies and may promote social unrest [3,4]. According
ular rainfall and an escalated rate of drought, thus reducing the to United Nation’s estimation, climate-related water shortage can affect

Abbreviations: 3D, Three dimensional; SGH, Seed gum hydrogel; GMs, Galactomannans; M/G, Mannose/Galactose; GG, Guar gum; FG, Fenugreek gum; TG, Tara
gum; LBG, Locust bean gum; GRAS, Generally Recognized as Safe; XG, Xanthan gum; CS, Chitosan; AA, Acrylic acid; KPS, Potassium per sulphate; PNaA, Partially
neutralized acrylic acid; IPN, Interpenetrating network; APS, Ammonium phosphate; WHC, Water holding capacity; MBA, Methylenebisacrylamide; -OH, hydroxyl;
NaCl, Sodium chloride; MMA, Methacrylate; CNF, Cellulose nanofibrils; SEM, Scanning Electron Microscopy; TEM, Transmission Electron Microscopy; TGA, Thermo-
gravimetric analysis; FTIR, Fourier Transform Infrared Spectroscopy; SR, Swelling ratio; PQ7, Polyquaternium-7; BLSAH, Boron loaded super-absorbent hydrogel; SP,
Soy protein; PC, Pectin; VGI, Volumetric gel index; GA, Gum Arabic; SMF, Slow-release multi-nutrient fertilizer.
* Corresponding authors.
E-mail addresses: [email protected] (S. Mandal), [email protected] (S. Hwang).

https://doi.org/10.1016/j.ijbiomac.2024.130339
Received 27 November 2023; Received in revised form 7 February 2024; Accepted 19 February 2024
Available online 20 February 2024
0141-8130/Published by Elsevier B.V.
S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

more than five billion people around the world by 2050 [5]. Thus, to porosity of the soil, thereby improving plant viability and total crop
introduce judicious management of water and enhance water utility yield [18]. Hydrogels are three-dimensional (3D) polymer networks
competency in agriculture, there is a growing demand for the imple­ with sizeable molecular weights that are hydrophilic, soft, highly
mentation of conservative techniques. Hydrogel, a hydrated polymer, is porous, and adequate for preserving a sizeable volume of water and
a promising material for innovative farming practices. Hydrogels are releasing it slowly in a stressed environment [19].
being studied for their water holding capacity, soil conditioning, and In recent times, through the exploration of plant gums-based
nutrient release in agriculture for their special properties like hydro­ hydrogels and chemically modified plant gums, there has been an in­
philicity, high swelling ratios, and biocompatibility [6–8]. Hydrogels in crease in application pathways for these materials not only in agricul­
agriculture and forestry can effectively utilize water resources and ture but also in pharmaceuticals, food production, cosmetics, and
promote seed germination and growth. Hydrogels play the role of small environmental remedial treatment, as these biopolymers are economi­
reservoirs, and their remarkable water absorption and water control cally viable, eco-friendly, and biodegradable [20,21]. Gum-based
capability can lessen the water facility’s excess requirement during polysaccharides can undergo easy modifications because of their
irrigation and drought conditions. Moreover, hydrogels in agriculture numerous functional groups such as hydroxyl and carboxylic acid [22].
are also utilized as seed coating agents to aid in germination and seed­ Seed polysaccharides are one of the major categories of plant-
ling establishment and can function as plant growth regulators by the originated gums and the chemical compositions, structures, and phys­
controlled release of nutrients [9–11]. Currently, most of the hydrogels ical properties of these polysaccharides can alter the growing environ­
presently available on the market are derivatives of synthetic polymers ments of plants, and production techniques [23,24]. Seed gum-based
[12]. Synthetic hydrogels derived from acrylic acid, malic acid, based on hydrogels (SGHs) have substantial applications in the agricultural
crosslinked polyacrylamide, and acrylate polymers are widely used due sector, they are used for the delivery of fertilizers and nutrient providers
to their ease of synthesis, significant water absorption capacity, and to plants in a controlled manner which can contribute to cross-linking
moderate cost [13]. However, these synthetic polymers are resistant to reactions thereby improving plant viability and hence favorable for
the invasions of microorganisms and are non-biodegradable and non- soil health and plant growth [25,26]. The word “gum” describes a group
ecofriendly. Commercial polymers are disposed of and thus exhibit a of natural, non-toxic polysaccharides that can simultaneously take the
certain degree of toxicity and are regarded as soil contaminants and form of a ‘gel’ and/or a ‘viscous solution’ [27]. Natural gums are clas­
result in increased pollution [14]. sified into diverse groups depending on their source, structure, and
Carbohydrates are one of the most abundant organic compounds functional characteristics. Natural gums are usually categorized into
consisting of complex structures and can undergo a multitude of microbial gums, plant exudate gums, seed gums, seaweed gums, etc.
chemical and biochemical reactions. Monosaccharides, oligosaccha­ depending upon the source or origin [28]. Microbial gums such as
rides, and polysaccharides are three major classifications of carbohy­ xanthan gum (XG) and dextran gum are produced through fermentation
drates [15,16]. Thus, biocompatible and biodegradable hydrogels based by specific microorganisms [29,30]. Exudate gums like Arabic gum,
on natural polymers, like polysaccharides, are more appealing in recent tragacanth gum, karaya gum, and salai gum are synthesized by the
years. Considerable progress has been achieved in utilizing biomass process known as gummosis, the disintegration of plant cellulose
resources to produce engineered hydrogels for sustainable agriculture [31,32]. Guar gum (GG), fenugreek gum (FG), Tara gum (TG), and lo­
(Fig. 1). The development and potential application of hydrogels from cust bean gum (LBG) are some of the vital seed gums that are procured
polysaccharide natural gum is attracting a lot of attention. Natural from the endosperm of Leguminosae seeds [33,34]. The endosperm is a
polysaccharides are a group of abundant complex polymers composed of rich reserve of plant polysaccharides which can perform a dual role by
large units of monosaccharides displaying intrinsic functional groups on retaining water and preventing the drying of seeds during germination
their repeating units serving as covalent and noncovalent crosslinkers [35]. Natural seed gums epitomize one of the most bountiful biode­
for the fabrication of hydrogels [17]. Polysaccharide hydrogel creates a gradable raw materials for the synthesis of hydrogel where they function
conducive ecosystem and amplifies the water-retention capacity and as reserve materials utilized during germination. Due to their

Fig. 1. Applications of natural hydrogel for sustainable agriculture.

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biocompatible, and non-toxic, nature, gums have widespread industrial 3. Occurrence, properties, and chemical structure of seed gums
applications like pharmaceuticals, paper, textiles, petroleum-drilling,
food, cosmetics, and explosives [36–39]. Seed gum-based poly­ 3.1. Guar gum
saccharides, especially GG and LBG are of considerable importance as
they are the most commercially available inexpensive gums while FG 3.1.1. Occurrence
and Tara are gradually gaining significance. The seed gum-based Guar gum (GG) is obtained from the seeds of drought-resilient plant
hydrogel has the potential to surmount several plant growth and guar (Cyampopis tetragonolobus) which is associated with Leguminosae
development challenges, like toxicity due to phytopathogenic attacks, family and is one of the cheapest sources of GMs [59]. Guar plants are
leaching of nutrients, excessive transpiration rates, sparse water reten­ principally grown in north-western India and Pakistan and raised in the
tion, and insufficient supply of nutrients as well as minimize environ­ southern hemisphere in semi-arid zones in Brazil, Australia, South Af­
mental stress [40]. In this review, we selected four natural seed gums: rica, and some regions in the USA like Texas and Arizona [60,61]. About
guar, fenugreek, locust bean, and Tara, according to the factors of 90 % of the world’s GG is cultivated in the Indian subcontinent and
application, overlooked energy capacity, price, and commercial values Pakistan since rain patterns during monsoon season in the northern
in the last few decades. We summarized the occurrence, physicochem­ parts of these two countries delivers optimal conditions for the culti­
ical properties, and structure of the selected plant-based seed gums for vation of GG and the total yield of guar seed in these countries is
their agricultural applications. We also investigated methods of syn­ approximated ~15,000 MT per year [62,63].
thesis as well as some recent advances of SGHs related to water reten­
tion, transportation of nutrients, fertilizer encapsulation, seed coatings, 3.1.2. Properties
and crop protection, leading to higher agricultural yield. Guar, the annual agricultural crop can grow up to 3–6 ft and often
resembles soybean plants (Fig. 2a). Temperature is one of the main
2. Galactomannans-seed polysaccharide factors affecting its germination and early crop growth [64]. Guar plants
can produce 5–12.5 cm long bean-like pods in clusters with 6–9 small
The most popular gums utilized in different fields are extracted from seeds per pod (Fig. 2b). The GG powder is odorless and off-white to
plant seeds and these polysaccharides share basic structural groups yellowish in color (Fig. 2c) [65,66]. Guar gum is a polysaccharide with
known as galactomannans (GMs). Most GMs originate from the Legu­ non-ionic characteristics, and it consists of 0.7 % fat, 2.0 % acidic
minosae family and nearly seventy species of the Leguminosae have been insoluble ash, 5.0 % protein, 12.0 % water, and 80.0 % galactomannan.
recognized as accommodating GMs [41,42]. Galactomannans, the The unique structure of the GM chain is composed of numerous hydroxyl
neutral polysaccharides are composed of a β-(1–4)-D-mannopyranose (–OH) functional groups that hydrate readily in aqueous media even in
which serves as the main framework and is linked with the unit of α- chilly water to produce a viscous pseudo-plastic behavior (decreasing
(1–6) of single D-galactopyranose [43]. The distribution of the galactose viscosity with an increase in shear properties) which exhibits a lower
units along the main chain strongly affects the functionalities of GMs shear viscosity than most of the available hydrocolloids [67,68]. The
[44]. Galactomannans possess considerable hydroxyl groups, exhibit galactose side chains connected to the mannose backbone combine
unique surface properties, and diminish the boundary tension between easily with the adjoining water molecules resulting in the formation of
various structures (gas-liquid/liquid-liquid/solid-liquid) that signifi­ an inter-molecular chain network which improves the viscosity of GG
cantly improves stability via steric forces and thus augments water and thereby induces gelling. In the case of superior quality of GG, 1 %
solubility [45,46]. Galactomannans have huge water binding capability aqueous dispersion may possess a viscosity as high as 10,000 cP [69].
at low concentrations and can easily form very viscous and colloidal Several researchers have also reported that with increasing shear rate, a
solutions. As a result, these polysaccharides find huge applications in decrease in the viscosity is observed and the solution starts exhibiting
food and pharmaceuticals as high-water effective thickeners and stabi­ shear-thinning behavior or pseudoplastic flow [70]. On the other hand,
lizers, as well as in textile, paper, petroleum, mining, and explosives with the increase in temperature, the viscosity decreases as the water
[47–49]. The viscosity of GMs inclines to remain invariable over a wide molecules attached to the gum framework start gradually losing their
pH range (1–10.5), as the molecules are neutral in nature. However, ordered configuration [71]. Guar is insoluble in organic solvents except
GMs exhibit degradation at elevated temperatures in the presence of for formamide, a physiological product of n, n -dimethyl formamide and
acidic or alkaline solutions [50]. The four vital sources of seed GMs it exhibits stable characteristics and offers consistent viscosity over an
discussed are locust bean (Ceratonia siliqua), guar (Cyamopsis tetrago­ extensive pH range. The maximum viscosity is acquired in the pH range
noloba), Tara (Caesalpinia spinosa Kuntze), and fenugreek (Trigonella of 6–9 while the lowest is attained at pH 3.5 [72]. However, strong acids
foenum-graecum L.) [51]. and alkalis at high concentrations often reduce the GG’s viscosity. Guar
The physicochemical properties of GMs like molecular weight dis­ gum is resistant to oil, chemicals, and greases and exhibits a high ability
tributions, galactose distributions, intrinsic viscosity, and evaluation of for chemical modifications which makes it suitable for utilization in
rheological behavior can be carried out using different characterization various fields [73].
methods like gas chromatography, high-pressure anion exchange chro­
matography, size exclusion chromatography, 13C Nuclear Magnetic 3.1.3. Structure
Resonance spectroscopy, capillary viscometry, shear, and extensional Structurally, GG (Fig. 2d) polysaccharides have molecular weights
rheology, respectively [52–56]. ranging (from 50,000–8,000,000 (g/mol) [74]. Guar gum is comprised
Several properties of GMs are heavily reliant upon the mannose: of a mannose linear chain of (1 → 4)-linked β-D-mannopyranosyl, which
galactose ratio (Man/Gal). The molar ratio (Man/Gal) differs from gum served as the principal unit, with a galactose side chain of (1 → 6)-linked
to gum, and this ratio is the primary feature influencing gal­ α-D-galactopyranosyl unit [75,76]. The ratio of mannose to galactose
actomannan’s solubility- the higher the Man/Gal (M/G) ratio, the lower units in GG is approximately 2:1, and the gum can be extricated by
the solubility. In addition, the galactose side chains can obstruct the multistage operations viz. roasting, grinding, sieving, and polishing
mannan backbone from building several hydrogen bonds and thereby [77]. The guar kernel is constituted of several layers, the outer
reduce the conglomeration of hydrogen-bonded molecules [57]. More­ layer–husk or hull (16–18 %), the middle layer–germ portion of the seed
over, the M/G ratio alters the structure of seed GMs, which, in turn, (43–46 %), and the outer layer– galactomannan endosperm (34–40 %)
governs the various industrial applications [58]. The four major GMs [78].
that exhibit profitable significance in food and non-food industries are
GG, FG, TG, and LBG.

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Fig. 2. (a) Guar plant; (b) Guar seeds; (c) Guar splits and powder; (d) Guar Gum structure.

3.2. Fenugreek gum cultivated in India and grown in northern Africa, the Mediterranean,
Egypt, Spain, Turkey, China, Morocco, and Canada [80]. Australia also
3.2.1. Occurrence has displayed a keen interest in gum cultivation and is gradually
Fenugreek (Trigonella Foenum – grecum L) a leguminous plant, be­ becoming a significant FG producer [81].
longs to the category of Fabaceae family and is marked as one of the most
promising plants in terms of nutritional and medicinal value owing to its 3.2.2. Properties
hypoglycemic and hypercholesteremic properties [79]. It is widely The plants are medium-sized bushy annual legumes (Fig. 3a) and can

Fig. 3. (a) Fenugreek plant, (b) Fenugreek seeds (c) Fenugreek seed powder (d) Fenugreek seed structure.

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grow up to 3–6 (60 cm) feet and usually take 90–150 days to mature 3.2.3. Structure
depending on the cultivated varieties. It can produce long bean-like pods Fenugreek seed has the bioactive compound galactomannan which is
of dimensions 5–12.5 cm with 10–20 small seeds per pod which are comprised of a linear chain of mannose backbone and single galactose
generally golden to pale yellow color. The seeds emanate a strong odor side chains (Fig. 3d) and the ratio of mannose to galactose is nearly 1:1,
and are bitter in taste (Fig. 3b), and the FG powder is light brown in color so it is comparatively close to GG (1.62). On average, the linear mannan
(Fig. 3c) [76,82]. The linear mannan polymer in FG is insoluble in water backbone of FG polysaccharide is comprised of the same number of
and prevents polymer chains from drying but the presence and galactose mannopyranosyl units [95], β, 1 → 4) and α 1 → 6 linked galactopyr­
substitution in FG makes it the most soluble of seed gums. Fenugreek anosyl group [96].
exhibits remarkable stability in freeze-thaw cycles as it gets dissolved in
cold water [83]. On account of the similarity in the G/M ratio of FG and
GG, FG is often used as a pertinent substitute for GG [84]. Fenugreek 3.3. Tara gum
gum is a pulverized endosperm of FG seeds holding an identical sugar
concentration as GG. The chemical composition of FG (such as seeds, 3.3.1. Occurrence
husk, and cotyledons) showed that endosperm has elevated saponin Tara gum (TG) is procured from the endosperm of the seed of Cae­
(4.63 g/100 g) and protein (43.8 g/100 g) content [85]. The major salpinia spinosa tree. The gum is primarily cultivated in the Andes of Peru
bioactive constituents in FG seeds are carbohydrates (45–60 %), most of (85 % of the world supply) and has been abundantly farmed in some
which is a mucilaginous fiber with 30 % soluble fiber (GMs) and 20 % parts of China like Yunnan, and Sichuan regions, Southern and Northern
insoluble fiber. Protein (20–30 %) rich in lysine and tryptophan, 3–4 % America, Chile, and Ecuador [97]. Peruvian carob, Huarango, and
ash, and 7.5 % lipids are also important chemical constituents [86,87]. guaranga are some of the common names of TG as known in different
The average molecular weight of non-extruded FG is 561,900 (g/mol) countries [98].
and extruded FG had a dissimilar molecular weight value than non-
extruded gum. According to Salarbash and Bazeli, this effect was 3.3.2. Properties
explained due to the complete decomposition of the macromolecular The gum is flavorless, stable, and nontoxic and recorded as ‘Gener­
structure of FG during the extrusion of the gum [88]. It is also reported ally Recognized as Safe’ (GRAS) gum [99]. This evergreen shrub is
by many researchers that the viscosity of FG increases with the increase widely cultivated (Fig. 4a) and can grow to a height of 3–10 m at a fast
in temperature thereby FG seed gum exhibits “non-Newtonian behavior rate and its pods are loaded with pyrogallol tannin and contain several
or sheer thinning” characteristics [89,90]. The shear rate increases, with seeds of size 8–12 mm (Fig. 4b) [99]. Pure TG powder is white or beige
the decrease in the viscosity, exhibiting a shear thinning behavior in FG in color (Fig. 4c) like GG. The plant is not wind tolerant and prefers
gum solutions [91,92]. The purified powder of FG has incredibly good moist soil. It is a neutral reserved polysaccharide with an approximate
interfacial activity compared to other GMs [93]. Fenugreek is used to molecular weight of 1519 ± 30 × 103 gmol− 1 [100]. In general, when
make many products: its leaves can be used dried or fresh, dried as an dissolved in water at ambient temperatures, TG can attain about 75 % of
herb, or fresh as a vegetable, while its seeds are employed as a spice or in its viscosity potential within a few minutes. Therefore, TG demonstrates
the production of artificial maple syrup flavoring, steroids, and hor­ superb water-holding ability, and effective protective colloidal charac­
mones [94]. Additionally, the seeds contain diosgenin, a key ingredient teristics [101]. In addition, TG has high acid and salt resistance, can
in oral contraceptives. Fenugreek also contains the bioactive compounds significantly reduce surface tension, and has superior interfacial tension
saponins and sapogenins which have been proven effective in treating activity compared to other GMs [102]. Tara gum is consistent over a
diabetes [95]. broad scope of pH scale and at any given shear rate the viscosity of TG
solutions diminishes with the rise in temperature suggesting the non-

Fig. 4. (a) Tara plant, (b)Tara seeds (c) Tara seed powder (d) Tara Gum seed structure.

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S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

Newtonian behavior with shear thinning feature of the TG [103,104]. polymer, it also noted that pH alteration has negligible impact on the
viscosity and solubility [116]. Locust beans are dispersible both in hot
3.3.3. Structure and cold water, and they readily form a sol between the pH range of 5–4
Tara gum (galactomannan) comprise of a linear main chain of (1–4)- and 7.0 and transform to a gel by the addition of sodium borate
β-D-mannopyranose units linked by glycosidic bonds of 1–4, attached to [117,118]. The resulting solution is pseudoplastic (decreasing viscosity
(1–6) linkage of α-D-galactopyranose units and the ratio of mannose to with increasing shear) and pseudoplastic behavior becomes stronger
galactose (M/G) ratio in TG is approximately 3:1 (Fig. 4d) [105]. with increasing LBG concentration and molecular weight.

3.4. Locust bean gum 3.4.3. Chemical structure

Like other GMs, LBG is a non-ionic, high molecular weight hydro­
3.4.1. Occurrence colloid polysaccharide comprised of binary units i.e., galactose and
The Locust bean (Ceratonia Siliqua) is a leguminous plant from mannose. The gum is comprised of an enormous molecular weight
Fabaceae family, and seeds of the plant are used for GMs gum extraction. polysaccharide composed of a linear chain of (1 → 4)-linked-d-man­
The plants are grown in the Mediterranean region, Asia, the Middle East, nopyranosyl units with (1 → 6)-linked-d-galactopyranosyl residues as
and to a smaller extent in California [106]. Locust bean gum (LBG), the side chains combined through glycosidic linkages (Fig. 5) and the M/G
non-starch polysaccharide is also known as carob bean gum, locust bean ratio is approximately 4:1 for LBG [119,120]. Sources, chemical
tree gum, carob seed gum, carob tree gum, carob flour, and Ceratonia composition, properties, and Man/Gal ratio of four seed gums are
[107]. summarized in Table 1.

3.4.2. Properties 4. Application of seed gum hydrogels in sustainable agriculture

The locust bean (Fig. 5) is a drought-resistant and slow-growing
plant. The LBG tree yields pods, and each pod comprises 10–12 uni­ Water management is a crucial input for attaining higher agricultural
form seeds which are hard and brown in color (Fig. 5). Locust bean gum productivity. In the last decades, several types of natural gum-based
is partly soluble in chilly water and does not form a gel. In cold water, polysaccharides have been considered for farming due to their
LBG is less soluble as compared to GG, however, its solubility increases swelling capacity, high swelling rate, biocompatibility, and biodegrad­
with the increase in temperature and reaches full hydration at 80 ◦ C ability [125–128]. Due to reduced price, and stable characteristics,
[108]. Higher temperature results in complete hydration of the gum. hydrogels obtained from abundant natural polysaccharides were
Locust bean kernel is made of three primary sections, outer husk (30–33 considered as a substitute for petroleum-based non-biodegradable
%), germ section (23–25 %), and endosperm section (42–46 %) by seed hydrogels [129]. The increasing impact of climate change, as well as the
weight [109]. The primary portion of locust bean endosperm is GMs limited availability of water will make soil improvement techniques
which comprise 85 % of the weight of the endosperm and the remaining increasingly important in the future. Hydrogels within their three-
15 % comprised of (~8 %) water, (~5 %) proteins, and (~1 %) ash fi­ dimensional polymeric network can bind substantial volumes of water
bers, and fat respectively [110]. The study has reported the molecular and make it accessible to the plants for extended intervals, hence
weight of LBG lies between 50 and 1000 kDa [111]. The gum exhibits functioning as ‘mini water tanks.’ The swelling properties of hydrogels
pseudoplastic behavior and the concentration of GMs and its micro­ count on the nature and density of the monomer in the polymer chain
structure are two crucial parameters to influence the dynamic viscosity [130] and can operate in the capacity of nutrient and other agrochem­
of LBG [112–114]. The gum’s viscosity is within a range of 2500–3500 icals carriers, which can lead to superior crop yields, seed coating agent
cps at higher temperatures ~95 ◦ C and at high-temperature hydration, to facilitate the process of germination, especially in arid regions
LBG usually results in a viscous solution [115]. Since LBG is a neutral [131,132]. Due to their non-toxic nature and easy modification, SGHs

Fig. 5. Locust Bean plant; seeds; powder; Locust Bean Gum structure.

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Table 1
Sources, chemical composition, properties, and Man/Gal(M/G) ratio.
Plant seed Botanical Name Composition Properties References
gum
MW pH Viscosity (1 % Swelling Man/
(g/mol) solution) index Gal
(mL) in
water

Guar gum Cyamopsis Galactomannan, D-mannose units joined by 1, 4- 535.12 1.0–10.5 1000 cP 8.1 2:1 [121]
tetragonolobus β-glycosidic linkages
Tara Gum Caesalpinia Galactomannan, 1,519,000 3.5 5500 cP 3:1 [122]
spinosa (1 → 4)-linked β-D-mannopyranosyl units, one-third of
which possess side groups of single (1 → 6)-linked α-D-
galactopyranosyl units
Fenugreek Trigonella foenum- Galactomannan, 561,900 6–7 72.40 4.5 1:1 [123]
Gum graecum a linear chain of mannose connected by β-(1 → 4)
glycosidic interactions, with galactose substitution at
the position of C-6
Locust Bean Ceratonia Siliqua Galactomannan, composed of galactose and mannose 226.66 5.4–7.0 3000-3500 20 4:1 [124]
Gum units combined through glycosidic linkages.

are commonly used as soil conditioners which support plant growth by added to the soil can boost the above parameters. Hydrogel fabricated
supplying them with nutrients and water at regular intervals. using natural materials can be physically or chemically cross-linked to
individual polymeric chains. In a recent study, chitosan–gelatin–guar
4.1. Guar gum gum /oxidized guar gum hydrogels were fabricated by physical and self-
crosslinking mechanisms in the presence of acetic acid and using sodium
In agriculture, synthetic non-biodegradable polymers are prevalent, meta periodate, as an oxidizing agent. Acetic acid gets dissociated into
however, these are unsafe for the environment and human health. Guar water leading to the formation of acetate ions (CH3COO− ) and hydro­
gum-based polysaccharides can be used as substitutes for synthetic nium ions (H3O+) which protonated the chitosan (Fig. 6a). Gelatin also
polymers due to their biodegradability, benignity, varying dissolv­ gets dissolved in acetic acid and its amino acid gets protonated (Fig. 6b).
ability, film-forming ability, controlled release quality, and suscepti­ Sodium bicarbonate (NaHCO3) and β-glycerophosphate were used as
bility to bacterial degradation [133,134]. Recently, the use of crosslinkers to enhance the mechanical strength of the hydrogel. It was
inexpensive polysaccharides hydrogel substitutes for non-biodegradable found that β-glycerophosphate was responsible for physical crosslinking
petroleum-based polymers has demonstrated commercial and environ­ and sodium bicarbonate decreased the charge density by deprotonation.
mental benefits. Plant growth depends on two major parameters – soil The reaction of sodium bicarbonate with water released bicarbonate
moisture content and soil nutrient holding capability. The hydrogels (HCO−3 ) which further interacted with protonated gelatin and chitosan

Fig. 6. Molecular mechanism of the formation of hydrogel before and after addition of crosslinkers
Reproduced with permission from ref. [135].

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and facilitated the formation of hydrogen bonding thereby decreasing the effects of different types of electrolytes on the swelling behaviors of
the charge density. The interaction of chitosan and gelatin was possible the SM hydrogel were extensively analyzed. The effect of three different
due to C–O bond formation, β-glycerophosphate was responsible for electrolytes viz. NaCl, CaCl2, and AlCl3 was investigated, and it
binding the chitosan units (hydroxyl and amino groups) together by demonstrated the equilibrium swelling values increased with an in­
ionic bond, gelatin (amino groups) interacted with guar by C–N bond crease of the cationic concentration up to 15 mmol L− 1, and then
formation and with oxidized GG (carboxylic groups) by amide bond decreased rapidly till it reached a uniform constant swelling capacity
formation. Moreover, the presence of hydroxyl groups in GG assisted in value [139].
the crosslinking mechanism due to the presence of many intramolecular Chandrika et al. synthesized crosslinked guar gum-g-polyacrylate (cl-
hydrogen bonds, and the entire mechanism is represented in Fig. 6. GG-g-PA) superabsorbent hydrogel (SAP) to explore its potential as soil
Swelling index studies were carried out to assess the water absorption conditioning material and carriers [140]. The hydrogel was prepared by
capacity of the five different kinds of hydrogel prepared. Chitosan graft polymerization reaction using acrylamide as a crosslinker followed
gelatin guar gum (CGgg) exhibited maximum swelling capacity (932.2 by hydrolysis. The cross-linked GG–SAP presented remarkable swelling
± 562.5 %) after 24 h [135]. in diverse environmental conditions. The impact of GG–SAP on moisture
By opting for varied development technologies and chemical cross- absorption and retention characteristics was explored using sandy loam
linkers, hydrogels can be customized to address precise applications. soil and soil-less medium designed both for temperature and moisture
Superabsorbent hydrogels which promote plant growth are synthesized content. The addition of GG–SAP dramatically boosted the moisture
by graft polymerizations/copolymerization of hydrophilic monomers retention attributes of plant growth media simultaneously both for soil
onto the backbone of long-chain polymers [136]. Grafting is an appro­ and soil-less conditions. Additionally, moisture retention and release
priate technique for the derivatization of natural polymers and has characteristics were investigated in the presence of NaCl, fertilizers, and
gained a great deal of attention in the current age. Wang & Wang under acidic to alkaline media. The superabsorbent biocompatible
developed an environmental-friendly GG-based hydrogel by graft GG–SAP hydrogel exhibited tremendous potential like water holding
polymerization technique where partially neutralized acrylic acid abilities and wide pH resistant characteristics for diverse applications in
(PNaA), was grafted on natural GG and sodium humate (SH) using N, N′- agriculture. Factors like water content, cross-linker concentration, and
methylenebisacrylamide (MBA) as a crosslinking agent. The outcomes of monomer-backbone ratio influenced the swelling efficacy of the devel­
the content and concentration of GG-based hydrogel on the water oped hydrogel which rendered superb moisture preservation and release
holding capability were explored and the results indicated that the use of characteristics and could serve as a remarkable candidate for boosting
the gum as a raw material, improved the swelling rate, water absorption crop production in the agricultural sector [140]. Hydrogels regulate soil
rate, and wide range of pH stability. The water absorbency study permeability, density, structure, and texture, as well as evaporation and
revealed that absorption of the GG hydrogel reached 532 g/g in water water infiltration rates through the soils. Kaith and co-workers studied
and 62 g/g in 0.9 wt% of saline solution. The reusability study is also an the biodegradability of various hydrogels including guar gum, guar
important factor in exploring the effectivity of the hydrogel and the gum-crosslinked-poly (acrylic acid), and guar gum-crosslinked-poly
developed SGH maintained 50.1 with 10 wt% SH, 52.9 with 15 wt% SH, (acrylic acid-ipn-aniline) using soil burial and composting methods
and 48.4 with 25 wt% SH of the original water absorptivity despite [141]. Grafting is an appropriate technique for the derivatization of
reswelling for six times [137]. natural polymers and has gained significant attention in recent years.
In 2010, the same group of researchers reported the synthesis and Guar gum was first modified by graft co-polymerization interpenetrating
efficacy of novel GG-based superabsorbent in terms of swelling as well as network (IPN) using AA as a monomer, APS as an initiator, and hex­
water-retention properties in sandy soil. Sandy soil is light and is usually amine as a cross linker. The resulting mixture was added to aniline.
characterized by low water and nutrient holding capacity. Guar gum Results obtained by the soil bur method revealed the complete degra­
hydrogel was treated with partially neutralized acrylic acid (AA) in the dation of GG hydrogel within 7 days and 14 days by the compositing
presence of an initiator ammonium persulphate (APS) as well as N, N′- method. The other two hydrogels took around 50–70 days for their
methylene-bisacrylamide (MBA), a crosslinker. Results indicated that complete degradation. The study further reported that mixing synthe­
graft polymerization reaction occurred between biopolymer GG and sized products with various categories of soil like silt and clay increased
initiator APS and increasing the concentration of APS enhanced the the water retention period by 43 to 59 days. After mixing with soil,
water absorption property of the hydrogel. The concentration of GG and synthesized SAP could efficiently increase water holding capacity of the
cross-linkers also had a considerable effect on the swelling. Moreover, soil and encourage optimal plant growth through the controlled release
GG hydrogel displayed remarkable pH stability in a broad array from 4 of water especially in water-stressed regions [141]. In a study by Deh­
to 11 due to the presence of hydrophilic functional groups like -COOH ghan and his co-workers (2018), it was found that the interaction of
and COO-. The sandy soil when mixed with hydrogel exhibited a slower collapsible soil with the mixture of GG and XG had a significant impact
water evaporation rate compared with other water-retention capabil­ on soil morphology. Concentration and curing time of biopolymers were
ities of sandy soils devoid of hydrogel. Thus, fabricated hydrogel not investigated and stabilization of the soil with seed gums aided in mini­
only exhibits favorable water withholding capacity but also can serve as mizing dry density and permeability of soil thereby enhancing the
a superior, eco-friendly, water-saving material for agricultural purposes strength of soil particles [142]. Biopolymers are promising candidates
[138]. for increasing the mechanical stability of soil, soil health, and mini­
In another study, GG hydrogel was developed by using a radical graft mizing wind erosion [143,144]. The loss of soil through wind erosion is
co-polymerization reaction mechanism. This GG hydrogel was produced one of the greatest concerns globally, especially for arid and semi-arid
by the process of cross-linking polymerization reaction in presence of regions that deal with water scarcity. Wind erosion not only robs the
neutralized AA, styrene (St) and attapulgite (APT) clay powder, and fertility of the topsoil but also eroded soil particles can sandblast foliage
MBA as a cross-linking agent with APS as an initiator. The hydrophobic and other neighboring crops leading to defoliation and depletion of
styrene functioned as a co-monomer which altered the physical prop­ plant tissue [145]. Guar not only exhibits a remarkable impact on the
erties of the polymeric network of the fabricated novel SGH which improvement of soil strength and can be used for sand stabilization, but
resulted in a modified surface morphology. The network structure of the it also aids in the reduction of soil compressibility.
GG-g-P(NaA-co-St)/clay hydrogel was further improved by adding three Collapsible soil is one of the universally problematic soils found in
different surfactants anionic surfactant sodium n-dodecyl sulfate (SDS), arid and semi-arid regions. In a recent study, Ayeldeen and co-
cationic surfactant dodecyltrimethyl ammonium bromide (DTAB), and researchers used two biopolymers GG and XG to study three vital
non-ionic surfactant p-octyl poly (ethylene glycol) phenyl ether (OP). components of soil properties i.e. compaction characterizations,
The swelling kinetics, environment sensitivity, salt, pH sensitivity, and collapsible potential, and shear parameters. Compaction is a crucial

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S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

technique for improving surface layers of soil. A compaction test was

performed using collapsible soil to determine the maximum dry density
and the result concluded that the unit weight reduced from 19 kN/m3 to
17.0 kN/m3 after mixing with stabilizing material prepared from GG and
XG. To investigate the collapsible behavior of the soil, two mixing
conditions (wet and dry) using different concentrations of gums were
used. In the wet method, the biopolymer solution was first synthesized
with specific concentrations and then mixed with the air-dried soil to
reach an average water content of 8 % ± 0.1 %. The study revealed that
collapsible potential was reduced to 1 % from 9 % after mixing the soil
with 2 % biopolymer concentration in the wet case. After one week of
curing, the cohesion increased from 8.5 kPa to 105 kPa by increasing the
concentration of XG from zero to 2 %, leading to an overall improvement
in soil shear strength. The study also proved that the GG mixtures with
XG rendered maximum cohesion strength than only XG-treated soil Fig. 7. Water sorption studies of hydrogels from Guar Gum with acrylic acid
samples. The shear strength of soil also increased by about 30 % when and further cross-linking with ethylene glycol di methacrylic acid. (a)
using the GG in comparison with the XG at the same experimental Appearance of dry, and (b) swollen hydrogel
conditions [146]. Reproduced with permission from ref. [150].
In another study, by the same group of researchers, the efficacy of
four polysaccharides (XG, GG, carrageenan, and modified starch- Star­ weight loss was recorded from 100 to 180 days. The SEM images for the
pol 136) with different concentrations (0.25 %, 0.50 %, and 0.75 %) in degradation study of the hydrogel further confirmed the eroded surface
reducing wind erosion was investigated. The effectiveness of the and a completely broken and brittle network of the biopolymer (Fig. 8b
different biopolymers in reducing soil erosion was measured from the and c). Moreover, the addition of powdered hydrogel not only improved
mass loss of different samples. They found GG had a minimum quantity the moisture bearing capacity of soil to 1.5 times, but the tested soil
of mass loss due to wind erosion at a 0.75 wt% (in dry condition) ad­ could also preserve higher water content even at considerably larger
ditive to the soil and exhibited maximum shear strength (75 kPa -wet matric suction (~15 bar). Thus, GG-AA-EGDMA hydrogel proved to be a
soil; 260 kPa -dry soil) of the amended soil. The presence of numerous promising material for soil conditioning and water-conserving agents in
hydroxyl or carboxyl groups in GG accelerated the chemical reaction for the agriculture sector [150].
the formation of adhesive forces that hold the soil particles together by, Behera et al. reported the formulation of superabsorbent hydrogel by
building a robust matrix thus increasing the shear strength remarkably grafting acrylic acid (AA) on the GG backbone using microwave irra­
[147]. diation. This novel technique is known as free-emulsion graft polymer­
Agricultural sprayers are commonly used to protect soil from wind ization. Guar gum grafted poly (GG-g-PAA) superabsorbent, thermally
erosion during fallow seasons or between disking and seeding when the stable, and biodegradable hydrogel exhibited high water absorption
soil is most vulnerable to wind erosion. The application of the poly­ capacity. The maximum swelling capacity was observed at a pH of
saccharide spray strengthens the soil crust by binding soil particles 5.0–7.4 [151]. Over the past few years, hydrogels have been added to
together and protecting topsoil from wind erosion. Alginate and GG the soil to reduce water intake for irrigation and revamp the physical
prepared spray was applied to improve soil aggregation and soil crust properties of soil. Songara et al. obtained an SGH by grafting GG with
integrity. It was found at the higher concentrations of the biopolymer methyl methacrylate (MMA) and crosslinking with polyethylene glycol
solution (e.g., guar gum at 2 g/L and alginate at 5 g/L), there was a (PEG) [152]. The developed GG–based hydrogel was characterized by
significant increase (1.5 times) in the mean size or aggregate diameter of various analytical techniques and SEM demonstrated a pore size of 50
soils thus there was a remarkable reduction in their susceptibility to μm–10 μm while TEM analysis exhibited spherical shapes of hydrogel
wind erosion [148]. with particle sizes in the range of 141.1 nm–182.2 nm. The hydrogel was
Rathore et al. reported the fabrication of cross-linked superabsorbent added to the field of sugarcane crop and the moisture content of the soil
composite hydrogel using natural polymer GG and methyl methacrylate was examined after 20 days of treatment. An excellent result was ob­
by graft co-polymerization reaction using (KPS) as an initiator, and boric tained in terms of moisture content (28 %) compared to the area devoid
acid as a cross-linking agent in an aqueous solution. The synthesized of fabricated hydrogel. The superior absorption capacity of 110 mL of
composite hydrogel showed superior swelling behavior in the presence water per gram of developed hydrogel could be attributed to high
of KPS and a maximum percentage swelling of 3650 % was observed in porosity. Additionally, the efficacy of the synthesized SGH was
distilled water and 2890 % in saline solution (NaCl). The developed compared with hydrogels prepared from other sources. In all cases, the
product exhibited remarkable water absorption efficacy in the pH range synthesized hydrogel outperformed, and the developed hydrogel
of 4–9 and thus finds its use in agricultural areas [149]. In another study, exhibited high water retention capacity thus acting as a water tank
Thombare and his group synthesized novel hydrogel in an inert atmo­ discharging water in a regulated manner. According to the authors,
sphere of nitrogen by grafting GG with acrylic acid and further cross- some crucial advantages of the formulated hydrogels were that con­
linking with ethylene glycol di methacrylic acid (EGDMA). The effi­ trolling the release of stored water may maintain the soil humidity as the
cacy of the developed hydrophilic hydrogel treatment to soil was eval­ soil dries up over a relatively long period and it can act as soil condi­
uated by exploring physico-chemical properties of soil like porosity, tioning material which can improve perennial crop productivity and
moisture uptake, and retention competencies. As shown in Fig. 7, GG- combating moisture stress condition and thereby exhibiting tremendous
AA-EGDMA swelled enormously in size by absorbing water into its potential in agriculture [152].
porous network and the fabricated hydrogel could absorb up to 800 mL Pesticides play a vital role in the prevention and management of crop
water per gram. The biodegradability studies showed that the GG–based diseases and thus facilitate crop health. Chlorpyrifos is an organophos­
hydrogels are biodegradable, having a half-life of about 77 days. Fig. 8a phorus insecticide commonly used to control pests, insects, and worms.
depicts the weight loss pattern of GG-AA-EGDMA hydrogel under the In a recent study, chlorpyrifos was encapsulated inside the biopolymeric
soil at ambient temperature. The degradation curve of synthesized matrix of chitosan and GG using glyoxal crosslinker, a dialdehyde
hydrogel showed three sequential phases and it was observed that the compound that can easily crosslink the chitosan and the biopolymer.
weight loss rates were about 40 %, (highest in the first 56 days), while The encapsulation efficiency of the nano-formulation, release behavior
only 11 % weight loss was noted from 56 to 100 days and about 30 % with altered experimental conditions, biocompatibility, and mobility in

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S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

Fig. 8. Biodegradation studies of GG-AA-EGDMA hydrogel using soil burial method. (a) Decay curve; (b) SEM morphology after three months and (c) SEM
morphology after six months. Reproduced with permission from ref. [150].

the soil were investigated. The study revealed that the formulated concentrations and curing periods. Additionally, plain soil and
chlorpyrifos exhibited nearly 25 % slower release as compared to the biopolymer-treated specimens were exposed to real atmospheric con­
conventional formulation [153]. ditions to gain insight into the susceptibility to natural elements. The
Boron-loaded super-absorbent hydrogel (BLSAH) was fabricated by extensive experimental results revealed that the strength of the soil
integration of boric acid, the source of boron (B), with GG, acrylic acid, increased with the increase of biopolymer concentration and with the
crosslinker ethylene-glycol-di-methacrylate, and benzoyl peroxide curing time [155].
initiator in presence of nitrogen atmosphere. The hydrogel was fully A sustainable GG hydrogel was fabricated in the presence of gamma
characterized by FTIR, TGA, and SEM. A maximum absorption of 356 g/ irradiations. For this purpose, GG, polyacrylamide, pectin, and zinc
g was observed at pH 9 and 20.7 g/g was observed at pH 4. The increase oxide (ZnO) were cross-linked via gamma irradiation. The results indi­
in the swelling index at an alkaline medium could be explained due to cated superior biodegradability and water-holding capacity of hydrogel
the increase in hydrogen bonding and expansion in the crosslinked improved considerably by raising ZnO concentrations. This composite
network. The release pattern of boron (Fig. 9) from the fabricated hydrogel could be exploited as a powerful soil conditioner and help in
hydrogel and its kinetics was examined in both water as well as in soil. reducing the consumption of water in the agriculture sector [156]. In a
The boron release pattern of the boron-loaded hydrogel was also recent study, Tariq et al. reported the synthesis of GG polyacrylic acid-
matched with the commercial fertilizers, and it was reported that about polyaniline-based electrically conducting biodegradable hydrogel via a
60 % of the boron was discharged in 5 days and the developed hydrogel two-step polymerization reaction where hexamine and APS were used as
exhibited a promising matrix for nutrient delivery ensuring a sustained crosslinking agents for the AA chains on GG backbone. Formulated
supply of boron and other essential micronutrient, over the conventional hydrogel not only exhibited superior water retention ability and
fertilizers [154]. biodegradability but also exhibited antibacterial properties [157].
Sustainable biopolymers show substantial environmental and tech­
nological contributions to the improvement of sustainable engineering. 4.2. Fenugreek gum
Guar gum along with other four biopolymers- Xanthan Gum, Beta 1,3/
1,6 Glucan, Chitosan, and Alginate were investigated. Their effect on the Sustainable polymer materials have exhibited excellent emerging
soil strength improvement was experimentally investigated by per­ scope in improving structural stability, diminishing runoff erosion, and
forming unconfined compression, splitting tensile, triaxial, and direct fostering plant growth. Fenugreek gum is a non-toxic, natural polymer
shear tests. All tests were performed with different biopolymer rich in hydroxyl group which can easily form hydrogen bonding and

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S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

Fig. 9. Illustration of synthesis of boron-loaded guar gum hydrogel and boron release mechanism. Reproduced with permission from ref. [154].

exhibits immense potential as a water-retaining agent. Liu and his co­ radiolysis products of water, especially hydroxyl free radicals, are highly
workers reported the formulation of borax crosslinked FG hydrogel potent in producing free radicals on both AAc monomer and TG, and the
(FGB). To develop FG–based hydrogel 0.1, 0.3, 0.5 wt% of FG powder latter can easily establish the grafting of AAc onto gum chains and thus
was crosslinked with 10 mL of 15 wt% of borax solution. Moisture plays developed hydrogel focused on water retention and plant development
a significant role in seed germination and the water absorption study of [160]. Shen and coworkers have reported the one-pot synthesis of TG-
FGB with different FG concentrations was explored by swelling index as based hydrogel by graft copolymerization of AA onto TG poly­
shown in Fig. 10. The study reported that FGB–0.5 exhibited the saccharide and blended with 2 N-Hydroxypropyl-3-trimethylammonium
maximum swelling ratio (115 g/g) at pH ~ 9 while FGB–1.5 demon­ chloride chitosan, and MBA which served as a pivotal crosslinker with
strated the lowest swelling index in 0.9 % NaCl solution. Additionally, KPS as the initiator. The blended hydrogel exhibited super absorption,
FGB increased the soil water holding time from 2 to 11.5 days. Thus, the antibacterial, and biodegradable properties. The resulting hydrogel was
FG-based hydrogel not only improves the water retention capability of subjected to a swelling study and the biopolymer swelled to a larger
soil but also controls soil erosion and thus can serve as an emerging extent (650 g/g) in distilled water and 0.9 wt% (65 g/g) of NaCl [161].
biodegradable polysaccharide polymer that exhibits great promise in In a different study, Shen et al. [162] reported the synthesis of
sustainable cultivation [158]. Polyquaternium-7 (PQ7) incorporated hydrogels by grafting TG with
polyacrylic acid. Polyquaternium is a class of cationic polymeric qua­
ternary ammonium salts that not only capture bacteria but also inhibit
4.3. Tara gum bacterial growth thus demonstrating antibacterial qualities. The super­
absorbent hydrogel was interpreted by TGA, FTIR, XRD, and SEM
Tara gum (TG), a low-cost stable galactomannan polysaccharide analysis. The results confirmed the grafting of polyacrylic acid onto TG
partially soluble in cold water and fully in hot water, exhibits excellent resulted in the formation of three-dimensional networks with PQ7
water retention and gelling properties. It is a suitable candidate for the chains. The hydrogels exhibited remarkable swelling ratios in neutral
synthesis of superabsorbent polymers and has outstanding synergy with water and saline solution at ambient temperature. The bactericidal
other gums as well [159]. Safaa et al. reported the fast formulation of analysis of the synthesized hydrogels was conducted using E. coli and
TG-based novel superabsorbent hydrogel by copolymerization method S. aureus [162]. In the same manner, interpenetrating network (IPN)
using gamma radiation to illuminate a mixture of TG and partially structures of TG–grafted–poly methyl methacrylate-co-acetonitrile‑cal­
neutralized acrylic acid (NaA), in the presence of MBA crosslinker and cium oxide were prepared using microwave radiation. The prepared
APS, an initiator [160]. When an aqueous solution of TG/AAc mixtures TG–based hydrogel displayed antibacterial and superior superabsorbent
is exposed to gamma irradiation, free radicals are generated on the properties. The physicochemical, rheological, and tensile strength
chains of both species. The sterilization technique by radiation not only properties of the prepared polymers were explored, and the results
enhanced the secondary reaction involving the creation of free radicals indicated that the developed hydrogel showed excellent absorbent
but also led to the fabrication of non-contaminated products. Also, the

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S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

Fig. 10. Swelling index of FGB at different fenugreek galactomannan concentrations. (a)The maximum swelling index at three solutions; (b) Swelling index in water
at pH 9; (c) Swelling index in 0.9 % NaCl solution; (d) Swelling index in tap-water. Reproduced with permission from ref. [158].

properties, which could be successfully applied in arid regions [163]. polymers with explicit functions have been widely pursued. In a recent
In a recent study, a sustainable nontoxic hydrogel was prepared by study, Matar et al. [165] published the synthesis of LBG-based hydrogel
graft copolymerization reaction. AA and methacrylate (MMA) were with polyvinyl alcohol (LBG/PVA) by the gel casting method. Polyvinyl
grafted onto the backbone of long-chained TG. The water retention, alcohol is a polar, water-soluble polymer that offers superior strength
erosion resistance, and compressive strength of TG hydrogel-treated and elasticity to LBG. The swelling behavior of crosslinked LBG/PVA
loess and laterite soils were investigated under laboratory conditions. hydrogels was explored under different pH conditions and the equilib­
The prepared hydrogel (TG-g-P(AA-co-MMA)) exhibited superior vis­ rium swelling ratio of fabricated LBG hydrogel was found to increase
cosity, wettability enhanced thermal stability, and high compressive from 260 g/g to 407 g/g with an increase in pH from 4.0 to 10.0 at room
strength. A soil water erosion resistance test of TG-g-P (AA-co-MMA) temperature and thus can serve as an excellent candidate for soil
was conducted in the presence of simulated rainfall. The erosion resis­ remediation applications [165].
tance time of all TG hydrogel-treated soils increased with increasing The oxidation of carboxylated locust bean gum (CLBG) by a tech­
polymer content. The fabricated hydrogel TG-g-P (AA-co-MMA)-loess nique known as TEMPO mediated oxidation in the presence of acetylene.
showed the highest erosion resistance and adding a minimum quantity The synthesized CLBG was further irradiated with gamma rays, using a
60
(0.25 %) of TG-g-P (AA-co-MMA) could resist continuous precipitation Co gamma-ray source at the dose rates of 30 Gy/h and 300 Gy/h up to
for >20 h, which was within the period of highest long-term rainstorms 10 kGy in highly concentrated solutions. The water uptake capability of
and floods. Additionally, the compressive strength test of the laterite soil the fabricated hydrogel was investigated, and the test result revealed
treated with 0.4 % TG-g-P (AA-co-MMA) was conducted and the result of that the swelling capacity of the hydrogel increased from 19,000 % to
the test was 3.7 MPa, which was about three times that of the untreated 34,000 % [166].
soil. Application of TG-g-P (AA-co-MMA) polymer on soil can improve The water holding capacity (WHC), and the swelling ratio of
soil degradation and moisture holding capability and provide the hydrogels are often enhanced by the coexistence of protein and carbo­
requirement for the growth of sustainable agriculture [164]. hydrates. Recently, LBG, the natural hydrocolloid with high gelling
properties was reacted with soy protein (SP) to design a novel hydrogel.
4.4. Locust bean gum The mixture was heated for 5 h in ambient conditions at a low mixing
rate and then stored overnight at 4 ◦ C to provide complete hydration.
Over the years, locust bean gum (LBG) either individually or in its The water holding capacity of locust bean gum -soy protein hydrogel
altered forms has been employed as superabsorbent polymers and its (LBG–H) was compared with various natural polymers like gum Arabic-
hydrogel-derived formulations have become more popular in pharma­ soy protein (GA–H), maltodextrin-soy protein (MD–H), soy protein
ceutical, biomedical, cosmetic, food, and agriculture. Due to the flexible (SP–H), and Pectin–Soy protein (PC–H) hydrogels. A notable increment
physicochemical properties of the LBG, swelling, viscoelastic behavior, in the swelling ratio (9.37 %) was detected in the LBG-H hydrogel in
and slow delivery abilities have been upgraded by grafting technique or comparison to the swelling ratio for SP–H (2.39 %), PC–H (4.41 %),
synergy with other complementary polymers retaining its eco-friendly, GA–H (5.36 %) MD–H (6.76 %). Moreover, the SEM study (Fig. 11) also
biocompatible, benign, or non-mutagenic properties unaltered. The exhibited a denser and more compact structure of LBG-H in comparison
latest methods for the chemical modifications of LBG with other to other biopolymer–based synthesized hydrogels. Volumetric gel index

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S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

Fig. 11. Fabricated hydrogels with soy protein alone (SP–H), locust bean gum and soy protein mixture (LBG–H), gum Arabic and soy protein mixture (GA–H),
maltodextrin and soy protein mixture (MD–H), and pectin and soy protein mixture (PC–H). Reproduced with permission from ref. [167].

(VGI) is another parameter to define the efficacy of the synthesized intensified research interest in providing innovative technology to
hydrogel in terms of its gelation property. The LBG–H exhibited a su­ achieve the optimal level of crop protection which can ensure food se­
perior VGI value of 98 % followed by MD–H (77 %), GA–H (75 %), PC–H curity with marginal environmental damage. The practice of coating
(66 %), and SP–H (58 %). Thus, the fabricated LBG-based hydrogel was seeds has evolved to be one of the most extensively used remedies in
not only natural, non-toxic, biodegradable, and plant-based, but it also accomplishing superior crop returns [168]. There have been few reports
exhibited resistance to various environmental stresses and thus could be of patents on the use of GG in seed coating [169]. Duke (1998) disclosed
used as a good soil conditioning material [167]. Table 2 summarizes the the use of hydroxy propyl guar solution as a seed coating for fuzzy cotton
polysaccharide seed gum-based hydrogel (SGHs), their method of syn­ seeds to achieve superior flowability through planting equipment. In
thesis, and their applications for sustainable agriculture. recent research, a group of researchers also disclosed the use of cationic
GG along with starch for coating corn seeds. The study demonstrated no
5. Advanced hydrogels disastrous impact on seeds and the dust experiment exhibited emission
limitations from the coated seeds compared to the uncoated cotton seeds
The last decade has witnessed rising demand to accomplish food [170]. Ni et al. reported the development of a slow-release multi-
security for a steadily growing world population. Consequently, there is nutrient fertilizer (SMF) fabricated from urea, potassium dihydrogen

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S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

Table 2 Table 2 (continued )

Polysaccharide seed gum-based hydrogel, method of synthesis, and their Polymers Synthesis method and cross- Applications References
application for sustainable agriculture. linker used
Polymers Synthesis method and cross- Applications References water)
linker used -62 g/g (0.9%NaCl)
Guar gum Graft co-polymerization Soil amendment- [127] Locust TEMPO mediated oxidation Soil amendment – [166]
(N, N′- enhances water bean using acetylene and in significant
methylenebisacrylamide- holding capacity gum presence of Gamma radiation improvement in
cross linker) both in distilled WHC and SR
water and saline increased from
water 88 g/g in 19,000 % to 34,000
saline solution %
Guar gum Facile Synthesis of hydrogel Soil amendment- [142] Locust Graft polymerization (soy Soil amendment [167]
using XG and GG remarkable impact bean protein- crosslinker) -improves soil
on collapsible soil by gum stability, reduce soil
reducing dry density free pore space due
and permeability superior (WHC 925
and the mechanical ± 0.70 %)
strength of the High moisture
collapsible soil retention improves
Guar gum Facile Synthesis of GG and Soil amendment [148] survivability during
alginate hydrogel using XG -improves drought conditions.
and GG flowability, spray
characteristics,
compressive phosphate, natural attapulgite clay, and guar gum-poly/ humic acid as a
strength, and superabsorbent polymer coating. The coated composite of size 2–3 mm
integrity of soil exhibited low moisture content with superior mechanical strength. The
Guar gum free-emulsion graft Soil amendment- [151]
polymerization (polyacrylic enhances water-
impact of SMF and water retention capacity of the soil was analyzed, and
acid co acrylic acid polymer) holding capacity, four application rates were further applied at 0, 0.5 %, 1.0 %, and 2.0 %
microwave radiation moisture retention of SMF to the soil. The water withholding competency of the soil was
Guar gum Graft polymerization Soil amendment and [154] 45.2 %, 47.1 %, 49.4 %, and 52.5 % for 0 %, 0.5 %, 1.0 %, and 2.0 %
(ethylene glycol di- fertilizer
respectively. Not only did the water retention capacity of soil increase
methacrylic acid) benzoyl encapsulation-
peroxide -cross linker) acrylic exhibited higher with increasing SMF content in the soil, but SMFs can also effectively
acid swelling index, minimize the depletion of nutrients leaching, ameliorate the moisture
effectively content of the soil, and modulate the soil acidity and alkalinity level
controlled soil pH, [171]. A novel biosensor using FG, agarose, and gold nanoparticles for
and reduced nutrient
delivery
detecting pesticides was developed by Kestwal and the group. This
Guar gum XG Soil amendment [155] composite significantly enhanced enzyme stability by immobilizing
Beta 1,3/1,6 Glucan -enhances water- acetylcholinesterase, leading to improved biosensor performance [172].
Guar gum holding capacity, Another advancement in the preparation of hydrogels involves the use of
Chitosan and soil strength
carbon dots; these materials have been proven to have great fluores­
Alginate
Fenugreek Graft polymerization (borax- Soil amendment- [158] cence stability, sensing, self-healing properties, antimicrobial, and su­
gum crosslinker) water holding perior adsorption capacities. Carbon dot hydrogels can be functionalized
capability improved to improve their unique properties. Carbon dot-based hydrogels are used
the swelling rate, in the agricultural industry for food safety and packaging. These can be
water absorption
rate, and wide range
used to promptly monitor food safety using fluorescence responses and
of pH stability quenching. Together with smartphone applications, carbon dot hydro­
Tara gum Gamma radiation; N, N′- Soil amendment- [160] gels can enable quantitative detection in food safety [173].
methylenebisacrylamide significant increase
(MBAAm) –crosslinker in viscosity,
6. Market growth-seed gums
wettability and
enhanced thermal
stability. The development of hydrogels, especially from natural gums, is
Compressive receiving attention since it is accepted as raw material that would be
strength value rose easily accessible in the foreseeable future. Globally, it is expected North
significantly to 3.7
MPa which was
America, Europe, and Asia Pacific to be the dominant regional markets
about three times and become major consumers of GG with the development of strategies
that of the untreated by leading players [174]. In the next five to six years, the global market
soil for GG is predicted to register a Compound Annual Growth Rate (CAGR)
Tara gum Graft polymerization (acrylic Soil amendment [162]
of 4.4 % [175]. Developing countries with a strong infrastructure and
acid-crosslinker) -improved tensile
(0.5 g PQ7 per gram of tara strength, drought favorable climatic conditions are likely to offer more opportunities for
gum) resistance, superior exports of GG. The growth of the Global GG market is driven by the
antibacterial increasing usage of advanced technology. However, the market is facing
efficacy, greater challenges due to erratic production and substitutes. This soluble dietary
swelling ratio
Tara gum Graft polymerization Soil amendment [164]
fiber is used as a natural emulsifier, water barrier, stabilizer, lubricating
(Polyacrylic acid) MBA- -excellent water agent, and thickener in a variety of liquid-solid systems. Due to the high
crosslinker absorbency and viscosity of GG, it is widely used in oil and gas, and oil well fracturing
moisture retention processes. It is also anticipated to observe a growing demand for
(473 g/g (distilled
pharmaceutical-grade GG. Guar gum powder has wide applications in
many end-use industries such as food and beverages, water drilling, and

14
S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

paper manufacturing [176]. destination of their products, while processors/exporters have no in­
The market for Tara gum is expanding significantly because it is a formation about fenugreek’s origin. India is the largest producer and
cost-effective alternative to GG. The use of TG in the cosmetics industry exporter of fenugreek, and in the 2023 fiscal year, it contributed around
is also on the rise. As an immensely absorbent polymer, the grafted gum 226 thousand metric tons [182]. The primary importers include the
has proven to be extremely effective. Additionally, this gum is a po­ United Arab Emirates (UAE), Yemen Arab Republic (YAE), Japan, South
tential candidate for developing edible films which are utilized widely in Africa, United Kingdom, United States, Egypt, Bangladesh, Saudi Arabia,
the food packaging sector [177]. Though TG has become a highly France, Germany, Malaysia, Netherlands, and Nepal [183]. Locust bean
desirable biopolymer in the culinary and medical industries, way more gum is an appropriate natural gum for several applications, and it is
specific information about TG remains to be uncovered. The global TG synergetic with other gums like xanthan gum. The estimated global
market size is projected to reach USD 28 million by 2028, expanding at a production of the LBG is about 315,000 tons annually, generated from
CAGR of 2.6 % over the forecast period. In 2022, the TG market was two lakh hectares. Morocco (38 %), Spain (28 %), Italy (8 %), Portugal
estimated to be worth USD 24 million [178]. Exandal, Molinos Asocia­ (8 %), Greece (6 %), Turkey (6 %) and Cyprus (2 %) are the primary
dos, Silvateam, and Polygal are some promising global leaders in the producers [184]. Locust bean gum is in high demand globally, and its
production of TG [160]. Globally, the top three companies possess a import trade spans across multiple countries. The top import countries
market share of over 40 %. Europe is the greatest market with a 45 % for LBG are the United States, Germany, France, the United Kingdom,
share, followed by North America and Asia-Pacific, each with a 20 % China, and Paris. The gum is mainly utilized in the food processing,
share. pharmaceutical, and cosmetic industries [109,185,186]. Fig. 12 shows
India is the largest provider and exporter of fenugreek, and it con­ the market trend of the four seed gums between 2021 and 29.
tributes around 63 % of the estimated 35,000 MT fenugreek trade
worldwide [179]. Fenugreek gum has historical significance as a forage 7. Conclusion
crop, known as an old-world crop, traditionally grown in South Asia, the
Middle East, North Africa, and Mediterranean Europe [180]. Fenu­ Seed gum-based superabsorbent hydrogels occupy a dominant po­
greek’s resilience in drylands makes it suitable for low-input agriculture, sition in agriculture. This review aims to fill in some fundamental areas
benefiting developing nations. Its unique traits, including nitrogen fix­ of synthesis, characterization, and usage of SGH hydrogels targeting
ation and its water conservation properties, enable growth in semiarid their wide implementations in agriculture. Various methods of seed
climates, supporting sustainable agriculture practices in a water-scarce gum-based biopolymers and crosslinking agents, and different formu­
future [181]. The fenugreek market structure operates in a typical lation techniques are also discussed. Natural gums have attained
farm-to-market pattern. Farmers sell to collectors/aggregators, who extensive focus and spotlight due to their accessibility, affordability,
then supply to local markets. From there, the product moves to pro­ heterogeneity, and as a biogenic inexhaustible resource. The develop­
cessors and exporters. The main problem arises from casual handling in ment of superabsorbent polysaccharide seed gum-based hydrogel is one
the lower stages of the marketing process, leading to quality concerns. of the most effective and fast solutions for agricultural water scarcity
The absence of a direct link between processors/exporters and the farms issues. Soil water serves a critical role in vegetation and soil health and is
where fenugreek is grown means that farmers are unaware of the thus significant for plant growth. The presence of hydrogel enhances the

Fig. 12. Market trend of the four seed gums between 2021 and 2029 [176,178–180,186].

15
S. Mandal et al. International Journal of Biological Macromolecules 263 (2024) 130339

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hydrogels: in biomedical, environment, agriculture, and food industry, Crit. Rev.
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Sujata Mandal: Writing – review & editing, Visualization, Supervi­ [22] S. Mohamadi Sodkouieh, M. Kalantari, Synthesis of a new hydrogel based on
ethylene glycol crosslinked Tragacanth gum with emphasis on its agricultural
sion, Conceptualization. Hyemein Chi: Writing – original draft, Inves­
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Declaration of competing interest 110042.
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interests or personal relationships that could have appeared to influence Advances in gum-based hydrogels and their environmental applications,
the work reported in this paper. Carbohydr. Polym. 121102 (2023).
[28] S. Barak, D. Mudgil, S. Taneja, Exudate gums: chemistry, properties and food
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