Advertisement

Novel Superabsorbent Cellulose-Based Hydrogels: Present Status, Synthesis, Characterization, and Application Prospects

  • You Wei Chen
  • Siti Hajjar Binti Hassan
  • Mazlita Yahya
  • Hwei Voon LeeEmail author
Living reference work entry
Part of the Polymers and Polymeric Composites: A Reference Series book series (POPOC)

Abstract

Over the past century, hydrogels have emerged as an effective material for an immense variety of applications. This contribution provides a brief overview of recent progress in cellulose-based superabsorbent hydrogels, fabrication approaches, materials, and promising applications. Firstly, hydrogels fabricated directly from various polymerization processes are presented. Secondly, we review on the stimuli-responsive hydrogels such as the role of temperature, electric potential, pH, and ionic strength to control the role of hydrogel in different applications. Also, the synthesis route and its formation mechanism for the production of smart superabsorbent, macro- and nano-hydrogels are addressed. In addition, several applications and future research in cellulose-based superabsorbent hydrogels are also discussed in this chapter.

Keywords

Hydrogel Polymerization reaction Superabsorbent Stimuli-responsive Biopolymer 

1 Introduction

Hydrogels are known as the water-absorbing polymeric materials that are able to form a flexible three-dimensional structure with about 90% of water in the gel base and 10% of polymer chains. The presence of cross-linking interaction between water and hydrophilic characteristic of polymer chains facilitates the water-insoluble product with significant mechanical strength and physical integrity [1, 2]. Since hydrogels can absorb up to 1000 times of dry weight in water, thus this water-absorbing polymers are favorable for a variety of applications, especially for human usage. There is rising demand for hydrogels to be used for personal care and hygiene (baby diapers, sanitary pads, adult incontinence pads, and soft contact lenses), pharmaceuticals (drug carrier system), food (gelatin dessert), agriculture (plant water crystals), and health-care products (scaffolds in tissue engineering, wound care dressings) [3]. In addition to the existing market demand toward the hydrogel, continuous R&D activities have created a new opportunity in the development of intelligent materials for the biomedical areas, such as therapeutics, sensors, microfluidic systems, nanoreactors, and interactive surfaces [4].

Among the various types of biomaterials (e.g., polymers, composites, ceramics, and metals), hydrogels have shown high biocompatibility, tunable biodegradability, improved water retention ability, controlled release (especially for medicine or nutrients), preservation of stored components, easy to modify due to the presence of polar hydrophilic surface, and so on [5]. However, the feasibility of applying hydrogels is still limited due to poor mechanical strength and the fragile nature of hydrogel. In addition, majority of the hydrogels are produced from synthetic polymers (e.g., polyethylene glycol, polyamides, poly(acrylic acid), poly(methacrylamide), poly(N-isopropylacrylamide), poly(hydroxyethyl methacrylate)), which is limited particularly in the food industry, due to the likelihood of impurities in the final product that may cause toxicity and potential environmental hazards [6, 7]. Therefore, novel or natural hydrogels with improved characteristics are still needed and will continue to remain an important direction for research.

Natural hydrogels are mainly derived from natural resources, such as alginate, chitosan, carrageenan, collagen, protein/peptides, matrigel, fibrin, gelatin, hyaluronic acid, and cellulose fibers. These materials render long service life, high capacity of water absorption, biodegradable, high biocompatibility, and high gel strength, which are the green alternative for synthetic polymers [8]. Cellulose fibers are nontoxic and low-cost organic polymers in the form of polysaccharide, which consists of hundreds to thousands of glucose units (C6H10O5)n. It is an abundant lignocellulosic biomass which is found mostly in forestry wood, agricultural residues, industrial wastes, and municipal solid waste [9]. Cellulose consisted of active hydroxyl functional groups (–OH), which can easily develop desirable hydrogels with tailored properties and product structure by chemically modifying the functional groups or using various types of synthesis technologies. Thus, the utilization of green cellulose materials for hydrogels can overcome the limitation of synthetic hydrogels, with enhanced properties that satisfy the requirement particularly in food and biomedical industry [10].

In this chapter, different hydrogel preparation technologies for synthetic and natural hydrogels will be discussed. In addition, focus toward the cellulose-based superabsorbent hydrogel was highlighted with a closer discussion on different kinds of stimuli-responsive cellulose-based hydrogels. The relationship between cellulose structure with hydrogel characteristics (mechanical strength, viscoelasticity, stress-strain, and swelling ability) was covered in this study. Last but not least, application of cellulose-based hydrogels and cross-linking mechanism was also discussed herein.

2 Synthesis and Properties of Hydrogel by Various Polymerization Reaction System

Based on the classification, hydrogels are divided into three groups: synthetic, natural, and hybrid (a combination of synthetic and natural) [2]. The raw materials used to synthesize these three groups of hydrogels are either hydrophilic monomers or hydrophobic monomers. Basically, synthetic polymers possess hydrophobic features in nature with a stronger chemical interaction as compared to natural polymers. Thus, the stronger bonding of synthetic polymers always shows a poorer degradation as compared to natural polymers, with a higher durability [2, 8]. Thus, the challenges to develop hydrogels with both biodegradability and durability are the key requirements for various market demands. Various types of hydrogel preparation techniques are reported to cater to the desirable property range of hydrogels, which includes (i) chemical cross-linking, (ii) physical cross-linking, and (iii) other newly emerging technologies [6]. These processes involve the cross-linking of natural/synthetic polymer chains by different interaction such as electrostatic forces, hydrogen bonds, covalent bonds, hydrophobic interactions, or chain entanglements. The cross-linking is a stabilization process of liquid polymers, where the freely flowing chains were turned into multidimensional polymeric network in the form of a gel. In general, hydrogel preparation usually involved the use of material, such as monomers/polymers, initiator, and cross-linker (Table 1). The presence of water or other aqueous solutions acts as diluents, in order to control the heat generated during polymerization and tuning the final properties of hydrogels. Additional purification step is required to remove impurities (e.g., unreacted monomers/polymers, initiators, cross-linkers, by-products) especially for chemical synthesis process [11].
Table 1

Examples of polymers, initiator, and cross-linkers for hydrogel production

Synthetic [12]

Natural [13, 14]

Poly(hydroxyethyl methacrylate) (PHEMA)

Poly(vinyl alcohol) (PVA)

Poly(ethylene glycol) (PEG)

Poly(acrylic acid) (PAA)

Poly(methacrylic acid) (PMAA)

Polyacrylamide (PAM)

Alginate, fibrin, agarose, chitosan, gelatin, silk, carrageenan, hyaluronic acid, collagen, cellulose, protein/peptides, dextran, matrigel, starch

Initiator [15, 16, 17, 18, 19]

Ammonium persulfate

Benzoyl peroxide

Ammonium persulfate-tetramethylethylenediamine (APS-TMEDA)

Ammonium persulfate-sodium sulfite-Mohr’s salt

1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (Irgacure D-2959)

Cross-linker [11, 20, 21]

N,N′-methylenebisacrylamide (MBAm or MBAA)

Pentaerythritol tetraacrylate (PETRA)

Ethylene glycol dimethylacrylate (EGDMA)

Ethylene glycol diacrylate (EGDA)

Poly(ethylene glycol) diacrylate (PEGDA)

Ethylene glycol dimethacrylate (EGDMA)

2.1 Chemical Synthesis Methods

Chemically cross-linked hydrogels are known as permanent or chemical gels, where the polymeric network is formed via the covalently cross-linked of monomers precursors/polymer chains. The chemical gels reached an equilibrium swelling state under optimized polymer-water interaction parameter and the cross-link density. Thus, chemical gels are considered as ‘strong gels’ with good mechanical strength and durability [6].

In general, the formation of chemical cross-linkage in chemical gel involves grafting of monomers on the backbone of the polymers or usage of a cross-linking agent to interact between polymer chains. The interaction process occurred either by (i) reaction between activated functional groups of natural/synthetic polymers (e.g., –OH, –COOH, and –NH2), (ii) using small molecular weight of cross-linker (e.g., formaldehyde, epoxy compounds, dialdehyde), (iii) using photosensitive agents (e.g., gamma and electron beam polymerization), and (iv) initiation with an enzyme [5, 22]. All the mentioned chemical polymerization approaches are categorized into three groups, which included aqueous solution polymerization, inverse-phase suspension polymerization, and irradiation polymerization (Table 2). The differences among the above polymerization approaches are listed in Table 3.
Table 2

Methods for different chemical cross-link hydrogels

 

Methods

Roles

Examples

Reference

1.

Aqueous solution polymerization

Reaction between ionic and neutral monomers with multifunctional cross-linking agent

Polymerization is initiated thermally by UV irradiation or redox initiator system

Aqueous solvent serves as heat sink for polymerization process (e.g., water, ethanol, water-ethanol mixtures, and benzyl alcohol)

  

(a)

Radical polymerization

Known as chain-growth polymerization or anionic or cationic polymerization

The process involves initiation, propagation, and termination steps

Generation of free-radical activities induces the addition of monomers in polymer chains

Poly(N-isopropylacrylamide)

Poly(sorbitan methacrylate)

Poly(N-vinyl-2-pyrrolidone)

[23]

[24]

[25]

(b)

Chemical reaction of functional groups

The cross-linking involves functional group (–OH, –COOH, –NH2) of hydrophilic polymers with polyfunctional cross-linking agents

  

(i) Aldehydes

Hydrophilic polymers having –OH groups form cross-link through cross-linking agents – aldehydes (e.g., glutaraldehyde)

Polyvinyl alcohol (PVA) cross-linked with glutaraldehyde hydrogels

[26]

(ii) Addition reaction

Bis or higher-functional cross-linkers may be used to react with functional groups of hydrophilic polymers through addition reactions

Cross-linking glycidyl methacrylate derivatized dextran (Dex-GMA) and dithiothreitol (DTT)

[27]

(iii) Condensation reaction

Reaction occurs between the functional group of –OH and –NH2 with carboxylic acids or derivatives to form polyesters and polyamides

Zinc phthalocyanine-PEG-alginate copolymer

[27]

(c)

Enzyme-induced cross-linking

Enzymes act as a catalyst in cross-linking by cleave or form a chemical bond with polymer chains without interference with other chemical functional groups in polymer molecules

For example, horseradish peroxidase, transglutaminase, tyrosinase, phosphopantetheinyl transferase, and lysyl oxidase

Enzymatic cross-linking of a nanofibrous multidomain peptide hydrogel

[28]

2.

Inverse-phase suspension polymerization

Monomers and initiator are dispersed in the nonpolar solvent (e.g., n-hexane, toluene) as a homogeneous mixture (water in oil system)

Continuous stirring and utilization of low hydrophilic-lipophilic-balance (HLB) suspending agent/surfactant to maintain the dispersion of mixture

The final hydrogel products present in the form of powder or microspheres (beads) with desirable sizes

Polymerization of highly hydrophilic monomers, such as salts of acrylic and methacrylic acids, as well as acrylamide

For example, poly(methacrylic acid-co-partially neutralized acrylic acid) hydrogels prepared using SPAN 80 as the dispersant, heptane as the organic phase

[29]

3.

Irradiation polymerization

High-energy electromagnetic irradiations (e.g., gamma, x-ray, and electron beams) are applied as an initiator/cross-linker to induce the formation of radicals from hydrophilic polymer chains for the cross-linking process

The process is initiator-free and render high purity of hydrogels

Gamma-radiation water-soluble polymer blends based on poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG)

[30]

Table 3

Comparison between three polymerization approaches

Polymerization type

Characterization

Microwave irradiation polymerization

High efficiency, fast heat, and clean (mass shape products)

Inverse-phase suspension polymerization

Higher costs, complex, and unstable (particle products)

Aqueous solution polymerization

Lower cost, easy control, and stable (mass shape products)

2.2 Physical Synthesis Methods

Physically cross-linked hydrogels are known as reversible or physical gels. It is present in three-dimensional network via polymeric molecular entanglements and/or secondary interaction including ionic, hydrogen force or hydrophobic interactions. Physical gels are divided into two groups, which are strong physical gels and weak gels. The strong gels provide permanent physical interaction between polymer chains under certain experimental conditions. It shows similar characteristics as chemically cross-linked gels. Examples of strong physical bonds are lamellar microcrystals, glassy nodules, or double and triple helices. In contrast, physical gels with temporary connections between polymeric chains can lead to a reversible process. This cross-linkage leads to finite lifetimes of products and continuously restructuring ability. Examples of weak physical bonds are hydrogen bond, block copolymer micelles, and ionic associations [2, 6].

Generally, the dissolution of physical gel is inhibited by physical interaction between polymer chains without the presence of cross-linking agents. Some of the cross-linking agents contain toxicity which affect the purity of substances (e.g., drugs, cell, proteins, etc.) to be entrapped in gels, as well as the need for further removal before application, particularly in the food and personal care industries. However, these physical interactions are reversible, which are easily decomposed under the physiological environment (such as temperature, pH, or electric field) or application of stress. Thus, the physical gels are considered biodegradable and biocompatible [5]. There are several methods for the preparation of physically cross-linked hydrogels, which include crystallization, amphiphilic graft and block copolymers, ionic interaction, complex coacervation, hydrogen bonding, and protein interaction. The roles and examples of physical hydrogels are summarized in Table 4.
Table 4

Methods for different physically cross-linking hydrogels

 

Methods

Roles

Examples

Reference

1.

Crystallization

The gelation process involves the formation of microcrystals in the polymer structure due to the cycle of freeze-thawing

By homopolymer systems: Polyvinyl alcohol and calcium alginate gel rendered touch and elastic behavior after repeated freeze-thaw process

By stereocomplex: The presence of stereoisomers with opposite chirality (e.g., l-lactic acid and d-lactic acid) with high molecular weight

[31]

[32]

2.

Ionic reaction

Polymers with ionic groups formed cross-linking with the presence of di- or trivalent counterions (metallic ions)

Cross-linking occur under mild condition: physiological pH and room temperature

Polyelectrolyte solution (e.g., Na+ alginate) with a multivalent ion of opposite charges (e.g., Ca2+ and 2Cl)

[33]

3.

Block and amphiphilic graft copolymers

Self-assemble characteristic for amphiphilic (both hydrophilic and hydrophobic) graft and block polymers

The copolymers may consist of hydrophobic chains with hydrophilic grafts (or water-soluble polymer backbone)

Poly(lactide-co-glycolide) (PLGA) and polyethylene glycol (PEG) copolymers favor for drug delivery system

PEG and polybutylene terephthalate (PBT) copolymers

Hydrophobized polysaccharides (e.g., dextran, chitosan, carboxymethyl-curdlan, and pullulan)

[34]

[35]

[36]

4.

Hydrogen bonding

Formation of hydrogen bonding occurs between polymers carrying carboxyl groups (–COOH)

Protonation favorable in low-pH condition

Hydrogen-bounded carboxymethyl cellulose (CMC)

Carboxymethylated chitosan (CMC) hydrogels

Xanthan-alginate

Poly(acrylic acid)- and poly(ethylene oxide)-based hydrogel

Poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) with polyethylene glycol (PEG)-based hydrogel

[36]

5.

Complex coacervation

The presence of the mixture of polyanion-polycation will form complex coacervate gels

Polymers with opposite charges will tend to attract each other to form soluble and insoluble complexes under different concentrations and pH of respective polymer solutions

Polyanionic xanthan with polycationic chitosan

Proteins below its isoelectric point are positively charged and likely to associate with anionic hydrocolloids and form polyion complex hydrogel

[37]

[38]

6.

Protein interaction

Protein interaction involves block copolymers of Prolastin (consisted repetition of silk-like and elastin-like blocks)

Prolastin is fluid solutions in water and form the gel under physiological conditions as the crystallization of the silk-like domains occurs

Genetically engineered proteins interaction

Antigen-antibody interaction

[39]

[40]

2.3 Newly Emerging Approaches

The existing technology for hydrogel production, such as cross-linking copolymerization, cross-linking of reactive polymer precursors, and cross-linking via polymer-polymer reaction, is still rendering limited criteria during the process and features of hydrogels. Several studies have reported difficulty in controlling the detailed structure (chain length, sequence, and three-dimensional structure) due to the presence of side reaction, and unreacted pendant groups and entanglements occur. In addition, the produced hydrogels are of poor mechanical properties and slow or delay in response times to external stimuli [1]. Thus, process modification is necessary in order to control the polymerization and improve the characteristic of hydrogels (better mechanical properties, viscoelasticity). Several novel technologies for the hydrogel production were presented in Table 5.
Table 5

Methods for different novel technologies

Methods

Roles

Examples

Reference

Solid-liquid interface technology

Polymerization occurs by immersed agarose gel rod loaded with acetic acid in the cellulose solution, to form onion-like and multilayered tubular cellulose-based hydrogels

Controllable size, layer thickness, and interlayer space of the multilayered hydrogels

Hydrogels render good architectural stability, solvent resistance, high compressive strength, and excellent biocompatibility

Multilayered tubular cellulose hydrogels

[41]

Electrospinning technique

Well-aligned, highly ordered, and covalently cross-linked polyacrylamide (PAM) hydrogel microfiber produced by using electrospinning techniques

This technique is able to generate ordered structures from nanoscale to microscale fibers for biological muscle application

Highly aligned and covalently cross-linked polyacrylamide hydrogel microfibers

[42]

Microwave technology

Cross-linking approach assisted by microwave led to strong irradiation penetrating ability, faster heating, and a cleaner process

Poly(vinyl alcohol) with either poly(acrylic acid) or poly(methyl vinyl ether-alt-maleic anhydride) forms cross-linking without the use of monomers, thus avoiding the purification step of unreacted species

Combination between poly(vinyl alcohol) with either poly(acrylic acid) or poly(methyl vinyl ether-alt-maleic anhydride)

[43]

3 Cellulose-Based Superabsorbent Hydrogels

Owing to the hydrophilic characteristic performance, superabsorbent hydrogels have a high capacity for water uptake, which can absorb, swell, and retain aqueous solutions up to hundreds of times from their own weight (dry sample). Since most of the superabsorbent hydrogels are produced from synthetic polymers (acrylics), the tendency for replacing these synthetics with greener alternatives is more than overwhelming due to the poor degradability and biocompatibility of synthetic superabsorbent [10]. Thus, as an alternative to a greener route, cellulose-based superabsorbent hydrogel was invented. Cellulose (abundant biomass, biocompatibility, biodegradable, nontoxic, low cost and renewable, abundant hydroxyl groups) can be used to produce superabsorbent hydrogels easily with fascinating structures and properties which will be discussed in detail in this section.

3.1 Cellulose Structure and Biodegradability

The biodegradability characteristic for cellulose has been broadly investigated because of its capacity of molecular weight reduction, lower mechanical strength, and high solubility aspect. The great biocompatibility of cellulose, cellulosic, and cellulose disintegration has provoked the extensive utilization of cellulose-derived materials in biomedical utilizations. Moreover, the chemical alteration and cross-linking of water-solvable cellulosic material with bioresorbable component are able to produce degradable, absorbable, and resorbable cellulose-derived materials. In addition, cellulose and its subordinates are ecologically well disposed, as they are degradable by a few microscopic and macroscopic organisms that are present in our surrounding [44], which can disintegrate cellulose into cellulose-specific enzyme (i.e., cellulase) [45].

3.2 Water-Soluble Cellulose Derivatives

Most of the water-soluble cellulose derivatives are obtained via the surface modification of cellulose with the etherification process (reaction between hydroxyl groups of cellulose with the organic compounds, e.g., methyl and ethyl units). Subsequently, cellulose-based hydrogels are either reversible or stable, which can be formed by cross-linking between aqueous solutions of cellulose ethers, such as methylcellulose (MC), hydroxypropyl methylcellulose (HPMC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), and sodium carboxymethylcellulose (CMCNa), which are among the most widely used cellulose derivatives. The chemical structure of such derivatives is shown in Table 6. It is worth highlighting that all these polymers have shown a wide application as thickeners and/or emulsifying agents in the food, pharmaceutical, and cosmetic industries, due to their non-toxicity and low cost. Water-soluble cellulose derivatives are mostly biocompatible which can be used as thickener, binding agents, emulsifiers, film formers, suspension aids, surfactants, and more. They have been used to fabricate cellulose-based hydrogels through physical cross-linking, chemical cross-linking, and irradiation cross-linking which have been discussed above.
Table 6

Chemical structure of soluble cellulose derivatives

3.3 Cellulose-Based Hydrogels and Cross-Linking Strategies

Hydrogels can be divided into those formed from natural polymers and those formed from synthetic polymers. On the basis of the cross-linking method, the hydrogels can be divided into chemical gels (covalent bond), physical gels (molecular self-assembly through ionic or hydrogen bonds), and irradiative cross-linking (formation of covalent bonding between polymer chains).

3.3.1 Physical Cross-Linking of Cellulose Derivatives

In the family of thermos-reversible gelling polymers for hydrogels, hydrophobically modified cellulose is one of the largest members. When hydroxyl groups are substituted partly by methyl groups or hydroxypropyl groups, some hydrogen bonds are prevented, and the resultant derivatives become water soluble [46]. Methylcellulose (MC) aqueous solutions possess the unusual properties in forming reversible physical gels, due to hydrophobic interactions when heated above a particular temperature [47]. On the other hand, hydroxypropyl methylcellulose (HPMC) has a higher gelation temperature than MC, which forms firmer gels with equivalent substitution and molecular weight. Evidence have indicated that the gelation of HPMC cellulose derivatives resulted from the removing of water molecules from methoxylated regions of the polymer [48]. Sammon’s group [48] successfully modified hydroxypropyl methylcellulose with 9.1% hydroxypropyl and 29.3% methoxyl at 4 °C for 24 h. In addition, Sekiguchi et al. [49] discussed the hydrophobic interactions and hydrogen bonds contributed to thermally reversible gelation of methylcellulose aqueous solution. They were successfully modified cellulose acetate with dimethyl sulfoxide (DMSO) under a reaction condition of 60 °C and 1-h process. Subsequently, the sample underwent the methylation process (methylene chloride) and was further washed with deionized water.

As reported by Joshi et al. (2008), methylcellulose (MC) in cold deionized water shows a higher gelation rate at higher concentrations by using heating-cooling cycles. Initially, dried methylcellulose mixed with deionized water and heated till the temperature at 95 °C. The sample was allowed to cool down to 22 °C for at least 24 h, and finally the sample was maintained at a temperature of 4 °C. As a result, the gelation rate during the second heating-cooling cycle is higher than that in the first cycle [50].

Hydroxypropyl methylcellulose (HPMC) is a methylcellulose modified with a small amount of propylene glycol ether group attached to the anhydroglucose of the cellulose. Weiss’ group [51] has developed a series of biomaterials based on HPMC. The first generation of injectable calcium phosphate ceramic suspensions is composed of a mixture of HPMC solution and biphasic calcium phosphate granules. The aggregation and gelation behavior of HPMC (19–24% methoxyl and 7–12% hydroxypropyl) aqueous solutions is concluded as follows: (i) polymer reputation increases due to thermal motion, which led to a weaker network; and (ii) above 55 °C, the polymer chains become more hydrophobic, and polymer clusters start to form [52].

The second generation of hydrogel products that can suppress the long-term flow by easily controlling the cross-linking of silated HPMC (Si-HPMC) has been developed by Vinatier’s group [53] in 2009. Basically, Si-HPMC powder was solubilized in NaOH for 2 days. The solution was then sterilized by steam (121 °C, 30 min). To allow the formation of a reticulated hydrogel, the solution was finally mixed with N-(2-hydroxyethyl)piperazine-N′-(2-ethanesulfonic acid) (HEPES) buffer. The resulted Si-HPMC is nontoxic and biocompatible so that it can be widely used in biomedical areas, such as scaffolding for cell culture and cartilage model, and implanted in bone defects [54]. In addition, Si-HMPC-based hydrogels are developed as a scaffold for the 3D culture of osteogenic cells, which would be suitable for both in vitro culture and in vivo injection. The results from the mineralization assay and gene expression analysis of osteoblastic markers and cytokines indicate that all of the cells cultured in 3D into this hydrogel exhibit a more mature differentiation status from cells cultured as a monolayer on plastic. This Si-HPMC hydrogel is well suited to support osteoblastic survival, proliferation, and differentiation as it is used as a new scaffold and represents a potential basis for an innovative bone repair material [55].

3.3.2 Chemical Cross-Linking of Cellulose Derivatives

The stable structure and effective swelling of cellulose-based hydrogels often require a chemically cross-linked network. Some difunctional molecules are employed as the cross-linker for cellulose or its derivatives to covalently bind different polymer molecules in a three-dimensional hydrophilic network [46].

Sannino et al. [45] exploited the superabsorbent hydrogels based on cellulose through cross-linking carboxymethyl cellulose (CMC) and hydroxyethyl cellulose (HEC) with a cross-linking agent such as divinyl sulfone (DVS). Then sodium hydroxide (NaOH) and poly(ethylene glycol) (PEG) which acted as spacers between cross-links were added into the solution. These polyelectrolyte hydrogels display a high sensitivity in sorption capacity with variations of the ionic strength and pH of the external solution. Besides, the superabsorbent hydrogels are also developed to treat edemas for body water elimination. If hydroxypropyl cellulose (HPC) hydrogels are synthesized at certain temperatures in the single-phase regime, they remain nonporous, whereas when cross-linked in the biphasic regime, it will turn to microporous structure. Additionally, Hirsch and Spontak [56] reported the dynamic mechanical properties and swelling capacities of these hydrogels as a function of cross-linking temperature. The results showed that the HPC hydrogels when cross-linked with ammonia (NH3) and epichlorohydrin (ECH) had excellent ability to absorb anionic dye with maximum adsorption capacity of 2478 (g/kg) which can be achieved at pH 3.96.

In 2008, Demitri et al. [57] reported the preparation of HEC and CMCNa hydrogels with citric acid as a cross-linker, which can overcome toxicity and material costs, as compared to divinylsulphone or with a carbodiimide cross-linking agent. Briefly, CMCNa and HEC (3:1) were mixed with citric acid which acts as a cross-linking agent. Results indicated that the swelling ratio of hydrogels depends on the reaction time and citric acid concentration, when the swelling degree reaches 900 with 3.75% of acid.

3.3.3 Irradiative Cross-Linking of Cellulose Derivatives

Irradiation is a useful method for the formation of covalent bonding between polymer chains. This method is advantageous because of the high purity of the hydrogel product without the use of toxic cross-linkers, thus enlarging the applications in food and pharmaceutical industries. However, only a small fraction (17–30%) of gel aggregates (lumps) can be obtained by γ-ray irradiation at a dose of 20 kGy from 20 wt% of biopolymer solutions (such as cellulose/ionic liquid/water, CMC, and carboxymethyl chitosan (CMCT) aqueous solutions), with the assistance of generated hydroxyl radicals [58, 59].

The electron beam (EB) irradiation in the vacuum seems to be able to increase the gel yield (the gel fraction reached up to 55% at 20 kGy and increased with the irradiation dose). Petrov group [60] successfully obtained an opaque spongy material via UV irradiation from 3 wt% of aqueous cellulose polymers (HPMC, HEC, and MC) with (4-benzoylbenzyl) trimethylammonium chloride (BBTMAC) as a photo initiator. At high energy doses and low polymer concentration (10 wt%), the degradation of the polymer chains competes with cross-linking, thus resulting in the destruction of network structure and a decrease in tensile strength. The occurrence of degradation was due to EB irradiation (higher radical number created in the system) or irradiation in an oxygen-free atmosphere to avoid the generation of oxides and peroxides.

4 Stimuli-Responsive Cellulose-Based Hydrogels

The smart hydrogel can be categorized as physical or chemical stimuli-responsive hydrogels. Physical stimuli (temperature, electric or magnetic fields, and mechanical stress) will affect various energy sources and alter molecular interaction at a critical onset point. However, the chemical stimuli (pH, ionic factors, and chemical agents) will change the interaction between polymer chains and solvent at the molecular level. Thus, the responsive cellulose-based hydrogels found a new generation of smart materials to be used in numerous fields (biomedical devices, scaffolds for engineered tissues, biosensors, and actuators).

4.1 pH-Responsive Hydrogels

pH-responsive hydrogels are produced of polymeric backbones with the ionic pendant groups that can accept or donate protons in response to an external pH change [46, 61]. The acid- or basic-side functional groups in polyelectrolytes undergo dissociation in a similar way as the acidic or basic groups of monoacids or monobases. The ionization on polyelectrolytes, however, is more difficult due to electrostatic effects of other adjacent ionized groups. So, the apparent dissociation constant (Ka) may be different from that of the corresponding monoacid or monobase. When the macromolecules are constituted by a huge amount of ionizable groups, such polymer is called polyelectrolyte. Hydrogels constituted by polyelectrolytes are, often, sensible to pH changes, which makes the hydrogel to swell (if the side functional groups are in an ionized state) or to collapse (if the side functional groups are not ionized). The process of swelling/collapsing of pH-sensitive hydrogel is reversible and may have strong applications in the pharmaceutical field because hydrogels can protect a given encapsulated drug from hostile environments, e.g., the presence of enzymes and low pH in the stomach region. A drug that can suffer degradation at acidic conditions can be transported through the gastric tract and be released in the colon if it is encapsulated in an appropriated pH-sensitive hydrogel. Hydrogels can also control drug release by changing the gel structure in response to environmental stimuli. Hydration under alkaline pH favors enzyme access to the hydrogel and its later enzymatic decomposition with the ensuing delivery of the drug entrapped in the hydrogel [61].

4.2 Temperature-Responsive Hydrogels

Chemically cross-linked thermosensitive hydrogels undergo volume change rather than sol-gel transitions. Certain molecular interactions, such as hydrophobic associations and hydrogen bonds, play a vital role in the abrupt volume change of these hydrogels at the critical solution temperature. In a swollen state, water molecules form hydrogen bonds with polar groups of polymer backbone within the hydrogels and organize around hydrophobic groups as iceberg water. At critical solution temperature, hydrogen bonding between the polymer and water, when compared with polymer-polymer and water-water interactions, becomes unfavorable. This forces the quick dehydration of the system, and water is released out of the hydrogel with a large gain in entropy, resulting in the shrinkage of the polymeric structure. Temperature-sensitive hydrogels will have a small variation in temperature which induces a phase transition, and therefore shrinking or expansion of the material is observed. This is because chemically cross-linked thermosensitive hydrogels undergo a volume change rather than sol-gel transitions. Theoretically, certain molecular interactions (hydrophobic associations and hydrogen bonds) play a vital role in the abrupt volume change of these hydrogels at a critical solution temperature. As a result, an abrupt transition in the 3D matrix occurs: water-solvated macromolecule quickly dehydrates and changes to a more hydrophobic structure.

4.3 Ionic Strength-Responsive Hydrogels

The swelling, loading, and releasing-solute capabilities of hydrogels are, sometimes, dependent on the ionic strength (IS) of the external fluid. Due to the diffusion and convection, an osmotic pressure is produced via the difference in the ionic concentration of the exterior solution and interior hydrogel, thus, causing the swelling and shrinking of the cellulose smart hydrogel [46].

4.4 Solvent-Responsive Hydrogels

The response to solvent is also a very important issue on stimuli hydrogels. Several aspects are exploited in this way. The change from hydrophilic to hydrophobic solvent (or the reverse) is a common strategy to induce the shrinking or expansion of a three-dimensional network [46].

4.5 Other Responsive Hydrogels

Other than stimuli-responsive cellulose-based hydrogel, there are a few different strategies for visible stimuli, for example, ultraviolet-visible, magnetic field, mechanical stress, and others to generate changes in hydrogels. As specified, a few frameworks have been produced to join more stimuli-responsive structure in the polymer systems [62]. As stimuli-responsive cellulose-based hydrogel is actively developing, there is a pattern in growing new smart hydrogel to be responsive not only to stereotype stimuli but also to machine and analytical device that have a more responsive characteristic.

5 Structure Property Relationships in Hydrogels

Generally, hydrogels consist mostly of 60–90% fluid and 10–30% polymer [63]. Due to its characteristic properties such as swell ability in the water, high water content and elastic nature similar to natural tissue, biocompatibility, and lack of toxicity, hydrogels have been utilized in a wide range of biological, medical, pharmaceutical, and environmental applications [64]. Moreover, to achieve a successful network of hydrogels, it must consider its chemical cross-linking, physical entanglement, ionic bond, and hydrogen bond [65]. In a broad sense, it shows that the hydrogels are categorized into chemical gels when the cross-links of hydrogen bonds in the main chains are replaced by the stable covalent bonds [66] and into physical gels when the links are held together by secondary weak bonds such as ionic bonds, hydrogen bonds, van der Waals and electrostatic interactions, or molecular entanglements [65, 67].

A different type of preparation method for hydrogels is another parameter to classify the hydrogels, which includes (i) homopolymer hydrogels, (ii) copolymer hydrogels, (iii) interpenetrating polymeric hydrogels, and (iv) multi-polymer hydrogels [7]. The homopolymer hydrogels referred to as polymer networks are composed only of one type of hydrophilic monomer, while the copolymer hydrogels are composed of two types of monomers, where at least one is hydrophilic monomers [7]. Meanwhile, the interpenetrating polymeric hydrogels are hydrogels that are prepared by swelling a network without any chemical bonds between them, such as a swelling process of polymer 1 in monomer 2, to make an intermeshing network of polymer 1 and polymer 2 [68]. Last but not least, the multi-polymer hydrogels indicate that hydrogels consist of a combination of more than three types of monomers [68]. Different types of hydrogel lead to different characteristic features, which included structure parameters, mechanical properties, and swelling effect.

5.1 Structural Parameters

Theoretically, several parameters of hydrogel structures are intensively discussed in many studies which are (i) polymer volume fraction in the swollen state (Ѵ2, S), (ii) average molecular weight between cross-links (Me), and (iii) correlation length (ξ) also known as the network mesh (or pore) size [68]. The equilibrium polymer volume fraction in the gel (Ѵ2, S) is the ratio of the polymer volume (Vp) to the volume of the swollen (Vgel) and the reciprocal of the volume swelling ratio (Q):
Ѵ 2 , S = V p V gel = Q 1 Open image in new window
(1)
Besides, the polymer volume fraction in the swollen state can also be determined by the equilibrium swelling experiments when the average molecular weight between cross-links (Me) is theoretically related to the degree of cross-linking (X):
$$ \left({\mathrm{M}}_{\mathrm{e}}\right)=\frac{{\mathrm{M}}_0}{2\mathrm{X}} $$
(2)
where M0 is the molecular weight of the repeating unit of a polymer.

The correlation length or the network mesh size (ξ) indicates the distance between the consecutive junctions, cross-links, or tie points. All the network parameters can be measured through a range of experimental techniques or calculated by the application of the network deformation theory [68].

5.2 Mechanical Properties

At present, there are a few methods available for characterizing the mechanical properties of hydrogel constructs. The mechanical properties of hydrogels are very difficult to describe and understand its structure. Besides, its mechanical behavior can be studied by using theories to analyze its polymer structures and to determine the effective molecular weight between cross-links and to provide information about the number of elastically active chains and cyclization versus cross-linking tendency [68].

5.2.1 Dynamical Mechanical Analysis

The dynamical mechanical analysis is characterization method for hydrogels to provide information related to the viscoelastic behavior of hydrogels by measuring the response of a sample when it is deformed under periodic oscillation (stress or strain) [68]. Based on the dynamic experiment, the material is subjected to a sinusoidal shear strain (or stress):
$$ \upgamma ={\upgamma}_0\ \sin \left(\upomega \mathrm{t}\right) $$
(3)
where γ0 is the shear strain amplitude, ω is the oscillation frequency (which can also be expressed as (2λ gƒ) where ƒ is the frequency in Hz), and t is the time. The mechanical response shows that the shear stress (σ) of viscoelastic materials is intermediate between an ideal pure elastic solid (in phase with the deformation) and an ideal pure viscous fluid (90° out of phase with the deformation). Therefore, it is out of phase with respect to the imposed deformation as expressed by:
$$ \sigma ={G}^{\ast}\left(\omega \right)\ {\gamma}_0\sin \left(\omega t+\delta \mathrm{p}\right) $$
(4)
And consequently
$$ \sigma ={G}^{\ast}\left(\omega \right){\gamma}_0\sin \left(\omega t g\right)\cos \left(\delta \right)+{G}^{{\prime\prime}}\left( g\omega \right)\ {\gamma}_0\cos \left(\omega t\right)\sin \left(\delta \right) $$
(5)
and if it is defined
$$ {G}^{\prime }={G}^{\ast}\cos \left(\delta \right) $$
$$ {G}^{{\prime\prime}}\left(\omega \right)={G}^{\ast}\sin \left(\delta \right) $$
(6)
we get:
$$ \sigma ={G}^{\prime}\left(\omega \right){\gamma}_0\sin \left(\omega t\right)+{G}^{{\prime\prime}}\left( g\omega \right)\ {\gamma}_0\cos \left(\omega t\right) $$
(7)
where G′(ω) is the shear storage (or elastic) modulus and G″(ω) is the shear loss (viscous) modulus. G′ is referred to as the elasticity or the energy stored in the material during deformation, whereas G″ gives information about the viscous character or the energy dissipated as heat. The dependence of the elastic and viscous moduli upon frequency is called mechanical spectra. The combined viscous and elastic behavior is given by the absolute value of complex shear modulus G*:
$$ {\mathrm{B}}^{\ast}\left(\upomega \right)=\sqrt{{{\mathrm{G}}^{\prime}}^2{{\mathrm{G}}^{{\prime\prime}}}^2} $$
(8)
or by the absolute value of complex viscosity η* defined as:
$$ {\upeta}^{\ast }\ \left(\upomega \right)=\sqrt{\frac{{{\mathrm{G}}^{\prime}}^2+{{\mathrm{G}}^{{\prime\prime}}}^2}{\omega }} $$
(9)
On the other hand, the ratio between the viscous modulus and the elastic modulus is expressed by the loss tangent:
$$ \tan\ \delta =\frac{G^{\prime }}{G^{{\prime\prime} }} $$
(10)
where J is the phase angle. The loss tangent is a measure of the ratio of energy lost to the energy stored in the cyclic deformation.

Theoretically, the ratio between the stress and strain may depend both on time and stress. The ratio will only depend on time if the deformations are kept small in order to obtain a liner material behavior. To determine the region of linearity, the preliminary strain sweep tests at fixed oscillation frequency are performed. Specifically, the dynamic moduli are monitored while logarithmically varying the strain amplitude, γo.

5.2.2 Viscoelastic Properties

According to Borzacchiello et al. [68], the mechanical spectra analysis can clearly distinguish the concentrated (entangled) polymer solutions and gels based on the concentration and its frequency. For the concentrated solution at low frequency, the solution presents a viscous behavior (G″ > G′), while at high frequency, it shows an elastic behavior (G′ > G″). The transition between viscous and elastic behavior is indicated by the cross point of G′ and Gil curves, as a function of frequency, occur at a given value of the frequency (ƒ*). Besides that, the common behavior of the concentrated solution when at low frequency shows that the solution behaves as a viscous liquid which the polymer chains are able to achieve the equilibrium configuration through the Brownian motion within the time scale of the experiment. Meanwhile, when at high frequency, the chains cannot be detached during the short period of oscillation, and it behaves as a temporary cross-linked network to accommodate stress by network deformation and elastic behavior (G′ > G″). The crossover frequency (ƒ*) depends on the intrinsic rate of disentanglement of polymer chains.

5.2.3 Stress-Strain Behavior

Hydrogels consist of a water-swollen network of cross-linked polymer chain which can be considered in a rubber state. This rubber state condition allows them to respond to external stresses with a rapid rearrangement of polymer segments. The mechanical stress-strain properties of hydrogels in this rubber-like behavior correspond mainly to the architecture of the polymer network. Besides, to generate an equation of rubber elasticity, the relationship of network characteristics, mechanical stress-strain behavior with the classical and statistical thermodynamics, and phenomenological approaches must be used and considered. Based on the classical thermodynamics, the state equation for rubber elasticity is shown below:
$$ \mathrm{f}={\left(\frac{\delta U}{\delta L}\right)}_{T,V}+{\left(\frac{\delta U}{\delta L}\right)}_{L,V} $$
(11)
where ƒ is the retractive force of the elastomer in response to a tensile force, U is the internal energy, L is the length, V is the volume, and T is the temperature.
Other than that, for elastomeric materials, the change in length is not internally driven by retractive forces. Indeed, for those materials, the bonds are not stretched with a change in L, but an increase in length will decrease the entropy due to the changes in the end-to-end distances of the network chains. The entropic model for rubbery elasticity is the most reasonable approximation for hydrogels while the entropy is full with 90% of the stress. The retractive force and entropy are related through the Maxwell equation:
$$ -{\left(\frac{\delta U}{\delta L}\right)}_{T,V}={\left(\frac{\delta U}{\delta L}\right)}_{L,V} $$
(12)
By expressing the retractive force using the statistical thermodynamics, it can be assumed there is no volume change upon deformation. The free energy change on straining the polymer chains is due to the restraints placed on the configurational rearrangements and is considered to be totally entropic in origin [8]. It is, therefore, possible to write the equation of state for rubber elasticity as follows:
$$ \tau ={\left(\frac{\delta A}{\delta \lambda}\right)}_{T,V}=\frac{\rho RT}{\overline{M}C}\frac{{\overline{r}}_0^2}{{\overline{r}}_{\mathrm{f}}^2}\left(\lambda -\frac{1}{\lambda^2}\right) $$
(13)
where τ is the shear stress per unit area, ρ is the density of the polymer, Mc is the average molecular weight between cross-links, and λ is the extension ratio. The quantity, \( {\overline{r}}_0^2 \) / \( {\overline{r}}_{\mathrm{f}}^2 \), is the ratio of the end-to-end distance in a real network versus the end-to-end distance of the isolated chains; it is generally approximated as 1 when it is unknown. From Eq. 13, it can be deduced that the stress is directly proportional to the number of network chains per unit volume (i.e., ρMc). The equation assumes that the network is ideal in that all chains are elastically active and contribute to the elastic stress and network imperfections such as cycles, chain entanglements, and chain ends which are not taken into account [33, 34, 35]. To correct the chain ends:
$$ \tau =\frac{\rho RT}{\overline{M}c}\frac{{\overline{r}}_0^2}{{\overline{r}}_{\mathrm{f}}^2}\ \left(1-\frac{2\overline{M}c}{\overline{M}n}\right)\left(\lambda -\frac{1}{\lambda^2}\right) $$
(13)
where Mn is the average molecular weight of the linear polymer chain before cross-linking. The correction can be neglected when MnMC. From the constitutive equation, the modulus can be expressed as:
$$ G=\frac{\rho RT}{\overline{M}c}\frac{{\overline{r}}_0^2}{{\overline{r}}_{\mathrm{f}}^2}\ \left(1-\frac{2\overline{M}c}{\overline{M}n}\right) $$
(14)
and the force per unit area as:
$$ \tau =G\left(\lambda -\frac{1}{\lambda^2}\right) $$
(15)

The rubber elasticity theory predicts the nonlinear stress-strain behavior. The theory predictions describe the experimental results fairly well at low extension but are less accurate at higher elongations.

5.3 Swelling Properties

Swelling properties of hydrogels are important both dynamically and at equilibrium. The polymer chains in hydrogels can be obtained via either by physical or chemical stabilization of aqueous solutions, and thus, it is considered as one molecule regardless of its size [45]. A small change in environmental condition may trigger fast and reverse changes in the hydrogel. Hydrogels have the ability to sense changes in environmental parameters like pH, temperature, electric signal, and the presence of enzyme and other ionic species which may change the hydrogel physical texture. Apart from that, this swelling behavior of hydrogels can be determined by the several parameters which are the polymer volume fraction in the swollen state (Ѵ2, S), the number average molecular mass between cross-links (Mc), and the mesh size (ξ) [69]. Besides, the equation of hydrogel volume in the dry state (Vd) and hydrogel volume when swollen to equilibrium (Vs) are shown below as (16) and (17), respectively:
$$ {V}_s=\frac{m_{a,s}-{m}_{h,s}}{\rho_h} $$
(16)
$$ {V}_d=\frac{m_a-{m}_h}{\rho_h} $$
(17)
where (ma) is the mass of the initial dry polymer in air (mh) is the mass of the dry polymer in a swelling medium, ma, s is the mass of the swollen hydrogel in the air after reaching equilibrium swelling, mh, s is the mass of swollen hydrogel in a swelling medium after equilibrium swelling, and ρ is the density of swelling medium. The mass of hydrogel in a non-solvent can be measured by placing the sample in a stainless steel mesh basket suspended in swelling medium before swelling measurements are made and after the equilibrium swelling is achieved. The polymer volume fraction of the hydrogel in swollen state (Ѵ2, S) is calculated from the swelling data by using the following relationship:
Ѵ 2 , S , = V d V s Open image in new window
(18)
where (Vd) is the volume of the dry polymer and (Vs) is the volume of the hydrogel after equilibrium swelling. The determination of swollen hydrogel volume (Vs) requires the placement of hydrogel sample in the buffer and allows it to attain equilibrium.

6 Synthesis and Characteristics of Cellulose-Based Smart Superabsorbent

Throughout the years, the “superabsorbent polymer” has been developed and widely used in various areas due to its extraordinary properties [70, 71]. Due to its superior characteristics such as excellent hydrophilic properties, high swelling ratio, and improved biocompatibility, this superabsorbent hydrogel shows a high potential to attribute in many industries such as sanitary, agriculture, biomedical, food packaging, pharmaceuticals, and others [72, 73]. Generally, most of the superabsorbent hydrogels are produced from synthetic polymers (acrylics acid), and for the past several years, researchers have focused its attention to replace synthetic polymers with “greener” alternatives due to poor degradability and biocompatibility of the synthetic superabsorbent [10]. Cellulose is one of the carbohydrate polymers with the most inexhaustible resources on Earth. This type of biopolymer is biocompatible, biodegradable, and nontoxic and is a low-cost material. Besides, cellulose consists of an abundance of hydroxyl groups that will interact between the hydrogen bond, which contributes to the cellulose’s mechanical strength, molecular structures, and its properties [10]. Additionally, the advantages of cellulose-based superabsorbent hydrogels give superior characteristics such as high absorbency, high strength, good salt resistance, excellent biodegradable ability and biocompatibility, and other special functions that promise a wide range of applications in many fields [10, 65].

According to Sannino et al. [45] and Fekete et al. [74], the superabsorbent hydrogels were synthesized by both chemical and physical methods. The chemical method involves the synthesis processing of cellulose-based superabsorbent hydrogels via covalent linkages, and this includes aqueous solution polymerization, inverse-phase suspension polymerization, and even microwave irradiation pathways [3]. Most of the cellulose-based superabsorbent hydrogels are synthesis via aqueous solution polymerization due to lower production cost, better control for heat of polymerization, and more convenience as compared to other methods. Besides, this method is mainly attributed to free-radical-induced polymerization, which monomers are polymerized through the action of initiators in the aqueous medium condition that is safe and harmless [10]. Other than that, the physical synthesis methods refer to the molecular assembly cross-linked by hydrogen bonds or ionic bonds between the polymers or by the interaction between the polymers. These physical cross-link techniques include freeze/thaw cycle technology and hydrogen bond cross-linking, which are also adapted in some cases [75]. Among the methods that are used for the preparation of cellulose hydrogels, physical approach is the best choice of process due to its simple pathway with zero solvent for environmentally friendly purposes [10].

7 Synthesis and Applications of Macro- and Nano-hydrogels

7.1 Synthesis Routes of Macro- and Nano-hydrogels

Recently, the synthesis of hydrogels by using biocompatible/biodegradable polymers in macro- and nanometer range is getting much attention. Among the research conducted are for the application in catalysis, electronics, bio-sensing, drug delivery, and nano-medicine [76]. The incorporation of nanoparticles or macro-particles with various structures and morphologies into the polymeric hydrogel matrix can be considered as a facile and effective way to obtain enhanced characteristics of hydrogels, which is similar to the particle strengthening effect in polymer bulk matrix [77]. For instance, the macro- and nano-sized hydrogels produced a higher area/volume ratio that significantly modifies the mechanical, thermal, and catalytic properties. As reported by Feeney et al. [78], under IUPAC classification, the micro-hydrogel is defined as a particle of hydrogel of any shape with an equivalent diameter of 0.1 to 100 μm. For nano-hydrogel, it is defined as a particle of hydrogel of any shape with an equivalent diameter of 1 to 100 nm. Generally, micro- and nano-hydrogels can be produced by several methods such as self-assembling, suspension, emulsion, precipitation or dispersion polymerization, micro-molding, droplet generation, microfluidics, and others [76].

7.2 Potential Application Fields

According to the Global Industry Analysts, Inc. report, the global superabsorbent hydrogel consumption was around 2.3 million metric tons in 2015, and it is expected that the global demand will continue to rise and reach 3.48 million metric tons in 2020 [79]. The rapid growth and demand for hydrogels were reflected on the developing markets and its different applications. On the other hand, Transparency Market Research reported that the global superabsorbent hydrogel market was valued at US$ 10084.9 million in 2016 and was predicted to reach US$ 17487.6 million by 2024. This large market suggests a strong tendency to develop novel superabsorbent hydrogel materials with higher water absorbency and excellent mechanical properties. This section discusses about the highly potential applications of cellulose-based superabsorbent hydrogels, which range from the conventional use of hydrogels in agriculture and personal health care to the more innovative biomedical applications. In fact, there are a number of hydrogel products that have either been commercially available or are in the progress of development. Cellulose-based superabsorbent hydrogels act as promising biomaterials for hydrogel products which show the greatest significance for various fields of application and thus are extensively studied in industrial and academic research.

7.2.1 Agriculture and Horticulture

Hydrogels have been widely proposed over the last 40 years for agricultural and horticulture usage. There is an increasing interest in using superabsorbent hydrogels in agriculture and horticulture due to several reasons, which includes ameliorating the water availability for plants, increasing the water holding properties of growing media (soilless or soils substrates), optimizing the water resources, and reducing the water consumption. Due to its unique properties, several possible agricultural applications of hydrogels have been defined.

During the swelling of hydrogel, it turns the glassy material to a rubber-like state, which is able to store water even under compression. However, the swollen hydrogel can slowly release its absorbed water via a diffusion-driven mechanism when there is a humidity gradient between the outside environment and the inner part of the material. Generally, the water molecules loaded in the polymer network can be released in a sustained and controlled manner through diffusion. In order to make the cultivation possible in the arid, desert, and drought-prone areas (especially in South America, Africa, and west of Asia), where there is always a lack of sufficient available water resources, the dry hydrogel (i.e., xerogel) which is in the form of granules or powder is envisaged to be mixed with the soil in proximity of the plant root area. In addition, the hydrogel is possibly charged with the plants, pharmaceuticals, or nutrients [45]. When the cultivation is watered (by either rain or irrigation), the water is absorbed and retained by the water, which can avoid the rapid water loss after watering due to drainage and evaporation. When the soil is in dried condition, the hydrogel will release the stored water and loaded nutrients in a continuous manner via diffusion mechanism as needed, keeping the soil or the substrate in the humid state over long periods of time [57]. On the other hand, this process allows a high saving of water as well as the redistribution of the water resources that is available for cultivation in other applications. A further advantage of using this novel material in the agricultural application is related to its swelling effect in the soil. Basically, the dry form of hydrogel granules which is almost similar in size with the substrate granules is able to increase in size after swelling, thus increasing the soil porosity and providing a better oxygenation to the plant roots.

Unfortunately, most of the acrylate-based superabsorbent products available in the market are non-biodegradable, and some concern about toxicity was raised for agriculture application [57]. This is harmful to cultivation and human consumption; thus, it should be avoided. As a result, the concern of the public and researchers toward the biological system and environment issues has led to an increase in demand for cellulose hydrogel-based products. Several studies have been conducted toward the manufacturing of biodegradable nature hydrogel-based superabsorbent. So far, the development of environmentally friendly cellulose-based hydrogels fits perfectly in the current trend as an alternative to replace the conventional acrylate-based superabsorbent hydrogels. Such studies have been conducted and patented by Sannino and coworkers [80, 81], in which degradable cellulose-based superabsorbent hydrogels have been successfully invented. It is worth mentioning that the obtained hydrogels exist in the form of powder or a well-defined-shaped bulky material with the strong memory of its shape after swelling. Such hydrogels are capable of absorbing up to 1 l of water per gram without releasing it under compression and are able to charge with nutrients and to be released under a controlled kinetic [82]. Researches on the development of novel and green superabsorbent hydrogels for agriculture and horticulture have been further extended to recent years. In 2014, Li et al. [83] studied the effects of superabsorbent polymers on a soil-wheat (Triticum aestivum L.) system as a soil additive to increase crop yield and reduce the loss of soil water. The authors investigated the changes of crop yield, soil microbial activity, and water content between the modified soil and original soil; the results showed that the addition of superabsorbent hydrogels into the soil is able to improve the soil conditions with better crop yield and reduced detectable adverse effects on the soil microbial community. Besides that, Demitri et al. [57] proposed that the use of large-scale hydrogel might have an innovatory impact on the optimization of water resource management, especially in the agriculture field. The preliminary results revealed that the produced polyelectrolyte cellulose-based hydrogel could significantly increase the water retention capability of the soil and allow for the continuous release of water for a prolonged time effectively; thus, no additional watering is needed for the plants and soil. In fact, the proposed hydrogel potentially acts as an efficient storage and water reservoir in agriculture. A similar finding has been supported by Salmawi et al. [84], in which the superabsorbent hydrogel produced from acrylic acid and carboxymethyl cellulose with clay montmorillonite by gamma irradiation showed a higher percentage of swelling in distilled water and could act as a water-managing material in dried and drought-prone areas.

Pesticides are the most cost-effective way to control the growth of pest and weed. It is known that the cellulose-based superabsorbent hydrogels are used as pesticide carriers for special interest in terms of both sustainable and economic development. Hydrogels can be impregnated with fertilizer components such as nitrogen compounds, potassium ions, and soluble phosphate. Encapsulating the pesticides or herbicides into the cellulose-based superabsorbent hydrogels could be used to reduce the release rate of these herbicides [85]. This is because the chemical trapped in a polymer network is normally unable to wash out immediately by water but is gradually released into the root zone before being absorbed by plants. Compared to those of conventional polymers such as poly(acrylic acid), polyacrylamide, polymethacrylic, cross-linked poly(vinyl alcohol), pectin, chitosan, and carboxymethyl cellulose, which normally have severe limitation such as rapid biodegradability in soil, cellulose-based superabsorbent hydrogel is able to increase the water capacity of soil, at the same time minimizing the water loss through evaporation and seepage [86]. In the mixture with other active substances, it can be used as the polymer matrix to transfer bioinsecticides or herbicides, which is mainly designed to control, for example, proliferation of insect larvae into the soil. In general, the superabsorbent and fertilizers are combined via two methods, which have been well described in the literature [87, 88]. In the first approach, fertilizers are blended with cellulose superabsorbent hydrogels. In the second methodology, fertilizers are added to the reaction mixture and polymerized in situ in order to be entrapped in the superabsorbent. Results verified that these two procedures always result to a higher release rate.

Furthermore, the role of hydrogels as horticultural substrates enhances the soil water capacity. During rainfall or irrigation, the hydrogels bind the water in the soil to prevent it from seeping into deeper layers [89]. Up to date, researchers have proposed the combination of inorganic clays, such as bentonite, kaolin, montmorillonite, etc., into pure cellulose superabsorbent hydrogels with the intention of improving the hydrogel strengths and swelling property and reduced production costs. In recent years, a study conducted by Bortolin et al. [90] has proven that polyacrylamide/methyl cellulose/montmorillonite nanocomposite superabsorbent hydrogels have presented a synergistic effect by rendering high fertilizer loading and the slow release of fertilizers. The results revealed that the produced cellulose-based hydrogels effectively reduced the loss of nitrogen by volatilization of ammonia.

In summary, the main advantages of cellulose superabsorbent hydrogels are controlled by the release of water, increase of soil porosity, long time maintaining soil humidity, and better oxygenation of plant roots. On the other hand, this type of hydrogels is biodegradable and low cost, has high holding capacity, and is an eco-friendly resource. Its application helps to reduce irrigation water demand, minimizes the plants death rate, increases the growth rate of plant and improves fertilizer retention in soil [91, 92].

7.2.2 Personal Health Care

Superabsorbent polymers have been introduced for various hygienic applications such as disposable diaper and feminine napkin industry for about 30 years ago due to their excellent water retention and the ability to retain the secreted liquids under pressure. In 1978, the commercial production of superabsorbent polymers began in Japan for the production of feminine napkins. This is considered to be the first generation of commercial superabsorbent hydrogels that has been successfully marketed [3]. Previously, the commercial superabsorbent hydrogels were made through alkaline hydrolysis of starch-graft-polyacrylonitrile in the 1970s. However, the high expenses and inherent structural weakness (lack of sufficient gel strength) had contributed to the major factors of its market defeat [93]. Further development of superabsorbent materials is being employed in baby diapers in France and Germany in the 1980s. In 1983, the low-fluff diapers which contained about 5 g superabsorbent polymers were launched. This was followed by the introduction of superabsorbent diapers with a thinner layer in several Asian countries, Europe, and the United States. The thinner layer of diapers and nappies was mainly due to the replacement of bulkier cellulose fluff with superabsorbent polymers that can retain much liquid more effectively [94].

Continuous development of superabsorbent materials has led to a new generation of high-performance diapers. It was worth noting that the diapers not only become thinner but have also improved the retention performance significantly which has proven to be beneficial in reducing diaper rash and leakage [45]. The results showed that premium diapers have the leakage values below 2%, while the average weight of a typical medium-size diaper was further decreased by 50%. This was advantageous in terms of economic sense and environmental issues due to the reduced packaging cost. Compared to superabsorbent polymers, traditional absorbent materials (such as polyurethane sponge and tissue papers) will not be able to hold most of the absorbed water when these materials are squeezed. As a result, superabsorbent polymers caused a huge revolution in the personal health-care industries over these years. Table 7 shows the water absorptiveness of some common absorbent materials using the commercially available superabsorbent polymers.
Table 7

Water absorbency of different types of common absorbent materials [93]

Absorbent material

Water absorbency (wt%)

Superab A-200

20,200

Cotton ball

1890

Wood pulp fluff

1200

Soft polyurethane sponge

1050

Facial tissue paper

400

Whatman No. 3 filter paper

180

Making recyclable and disposable products such as napkins, diapers, hospital bedsheets, and sanitary towels is one of the important targets for the modern industry due to environmental awareness of society. Therefore, an innovative idea to this issue has recently been proposed, which involves the production of cellulose-based hydrogels with fully biodegradable properties. At present, the superabsorbent hydrogels contained in sanitary napkins are mostly derived from polymerized acrylamide or acrylic acid, which is a costly process, and the final product is environmentally unfriendly and poorly degradable [10]. Due to these reasons, some novel types of hydrogels composed of a mixture of hydroxyethyl cellulose and sodium carboxymethyl cellulose cross-linked with divinyl sulfone have been innovated. This hydrogel material is able to swell like conventional superabsorbent polymer, which exhibits higher water retention under centrifugal loads and swelling kinetics due to the capillary effects and the resulted introduction of microporous structures into hydrogel [45].

In order to establish more innovative methods for developing novel and new hydrogel products, many attempts have been made, which possess better swelling capabilities and are able to retain more fluids absorbed under the existence of external pressure or applied restraining force. Liu et al. reported a novel tactics for the production of eco-friendly superabsorbent hydrogels incorporated with flax yarn waste for sanitary napkin applications [95]. Their study proved that the product obtained exhibits from several outstanding properties such as excellent biodegradability, superabsorbent, and good in retention of artificial blood solution as compared to the currently commercialized, marketed sanitary napkin products. A similar study has been reported by Zhang et al., in which a flax cellulose-based superabsorbent composite was synthesized by the free-radical graft copolymerization of acrylic acid and acrylamide [96]. The results revealed that the yielded composite material attained the best water absorbency of urea. Most importantly, they found that 46.6% of the remaining residue after buried in soil after 90 days presented an excellent biodegradability. In modern times, a lot of convenient and comfortable disposable health-care products made up of hydrogels have been reported in literature; however, biodegradable health-care products have either not been commercially available or been industrialized [10]. In reality, more than 90% of superabsorbent composites are landfilled or incinerated after usage. This will cause serious environmental problems, undesirable water-keeping capacity, and higher cost that limit its practical applications [97]. Hence, continuous effort needs to be done in order to convert the cellulose-based superabsorbent hydrogels into the core layer of health-care products.

Further developments in the personal health-care area are expected with the formulation of the superabsorbent hydrogel materials containing enzymes and other additives in order to prevent unpleasant smells or infections. Furthermore, considering the scale of production of these materials is prerequisite as there is a clear need for environmentally friendly hygiene products that undergo biodegradation. Thus, it has a high value in the development of novel, green superabsorbent hydrogels by minimizing the consumption of chemicals or improving the degradability of disposed hydrogels. In this context, recent innovations about the cellulose-based hydrogels have move toward the implementation of an environmentally sustainable production process [98] as well as utilization of the nontoxic cross-linking agents during the process [72].

7.2.3 Water Treatments

Rapid industry developments had caused a series of severe problems to the surroundings and the environment, such as water contamination. The release of wastewater that consists of heavy metal ions into the local waterway or environment can be harmful to plants, humans, and animals. Pollution resulted from heavy metals has been accorded more attention due to the increase in awareness regarding the hazardous effects of heavy metal ions in the environment. A number of technologies have been established for water treatments, which mainly include chemical oxidation, adsorption, pressurized membrane-based separation, etc. However, several disadvantages such as high energy consumption and the pollution caused by traditional materials have been reported. Therefore, research-scholars have shifted their attention to the cellulose-based superabsorbent hydrogels.

Zhou and coworkers [99] prepared a novel magnetic hydrogel bead in order to remove Pb2+ from the polluted streams. The authors blended the chitosan with carboxylated cellulose nanofibrils, amine-functionalized magnetite nanoparticles, and poly(vinyl alcohol) by using instantaneous gelation method. This novel magnetic hydrogel beads can be used to absorb Pb2+ metal ion in sewage effectively, which are mainly attributed to the various carboxylate groups on the carboxylated cellulose nanofibrils as well as the abundant amino and hydroxyl groups on the chitosan [69]. Tripathy et al. [100] examined the metal ion sorption behavior of cellulose-based superabsorbent hydrogels (sodium carboxymethylcellulose-g-N-vinylformamide) to the selected metal ions including Hg2+, Pb2+, Zn2+, Ni2+, and Cu2+. They found that the values of the percent ion uptake were 8.7, 9.0, 9.8, 11.5, and 13.8 at the maximum values, respectively. On the other hand, a study reported by Kamel et al. [101] proved that the cyanoethyl cellulose-based superabsorbent hydrogels were capable of the adsorption of copper (II) ions from aqueous solution effectively. The authors reckoned that metal ion removal mainly depends on the protonation and deprotonation properties of its acidic and basic groups, specifically pH value. A similar finding has been reported by Abdel-Aal’s group [102] in which the metal ion absorption capacities increased with the increase of pH values. They prepared the maize starch-acrylic acid hydrogels by radiation grafting technique, and the obtained hydrogels were used to remove the heavy metal ions (Fe3+, Cr3+, Pb2+, and Cd2+) from wastewater. Hashem et al. [103] reported three types of hydrogels which were prepared via graft polymerization of acrylonitrile into maize starch and ceric ammonium nitrate which were used as the initiator. The study has proven that the prepared hydrogels could be used for the removal of Hg(II) ions from aqueous solutions with the maximum adsorption capacity of 1250 mg/g. The adsorption data agreed with the Freundlich and Langmuir isotherms.

Apart from the metal ion pollution, increasing oil contamination and oil spills from the industrial wastewater have become a new source of water pollution. In order to be cost-effective and an energy-efficient oil separation, Rohrbach’s group [104] has fabricated the nanofibrillated cellulose-based superabsorbent hydrogel as the filter for water/oil separation. The fabricated filter possesses oleophobic and hydrophilic properties, resulting in an increase in filter life and reduced negative impact toward the environment while showing the efficiency of more than 99% under gravitational force. Basically, cellulose nanofibril-based aerogels have been of great interest as absorbent materials owing to their biodegradability, high absorption capacity, large surface area, and low density. In addition, the hydrophobic aerogels have been designed to contribute excellent absorption tendency for various oil from water [105].

7.2.4 Biomedical (Controlled Drug Delivery, Scaffolds for Regenerative Medicine, Wound Dressings)

In 1960, poly-2-hydroxyethylmethacrylate was used as a synthetic biocompatible hydrogel for the application of contact lens. Wichterle and Lim reported the cross-linked poly-2-hydroxy-ethylmethacrylate hydrogel using ethylene glycol dimethacrylate as a starting material [106]. The hard contact lenses are primarily made up of hydrophobic materials such as poly(hexa-fluoroisopropyl methacrylate) or poly(methyl methacrylate), while soft lenses are based on hydrogels [107]. Usually, contact lenses are classified as soft or hard, according to their elasticity. Albeit the hard lenses are longer lasting compared with soft lenses, they tend to be poorly accepted by the users and require a lengthier adaptation period. Many efforts are made to obtain lenses with good oxygen permeability. For this purpose, several hydrophilic monomers are proposed including methacryloylamino-4-t-butyl-2-hydroxycyclohexane, 4-t-butyl,2-hydroxycyclohexyl methacrylate, and 4-t-butyl,2-hydroxycyclopentyl methacrylate with hydroxyethyl methacrylate and N-vinyl-2-pyrrolidone. After that, a significant progress has been accomplished, and a diverse range of polymers have been used for the fabrication and synthesis of hydrogels for various applications.

The cellulose superabsorbent hydrogels have gained noticeable interests in the application of controlled drug delivery system. This is due to their remarkable characteristics such as versatility and flexibility in fabrication; high tunability in the chemical, physical, and biological properties; variety in composition; excellent biocompatibility; and high moldability in shape [108]. One of the most notable characteristics of hydrogels is the highly porous structure, which permits a depot maintaining a high local concentration of an active pharmaceutical ingredient or drug at the targeted tissues over a long period, ranging from hours to weeks [109]. The transportation capability of high porosity of hydrophilic/hydrophobic molecules is important for a hydrogel-based drug delivery system. The drug diffusion and release behavior via the polymer network can easily be adjusted by manipulating the cross-linking density in the gel matrix and monitoring the porosity (i.e., mesh size) of hydrogels [109]. Also, the porous structure allows the drugs to be loaded and then released continuously. So far, the drug can be loaded into a hydrogel followed by releasing to the targeted place through several mechanisms: swelling controlled, chemically controlled, diffusion controlled, and environmentally responsive release. He et al. [41] fabricated the multilayered tubular and onion-like cellulose-based superabsorbent hydrogels for the first time. Their results indicated that the multilayered superabsorbent hydrogels are important and have a great potential application in the biomedical field due to its non-cytotoxicity, good architectural stability, good biocompatibility, and solvent resistance against acetone, ethanol, dimethylacetamide (DMAc), and sodium hydroxide aqueous solution.

It is known that the drug release rate is highly dependent on the network parameters (i.e., mesh size and degree of cross-linking) as well as the water content of the swollen hydrogel [110]. In the typical matrix systems, the drug is dissolved or dispersed uniformly throughout the 3D structure of the hydrogel. The drug is released through the macromolecular pores or mesh, and the initial release rate of drug is proportional to the square root of time. Depending on the structure of the hydrogels used, the chain dissolution takes place along with the swelling process due to the physical nature of the hydrogel network; thus, the release of drug results from the complex combination of diffusion, swelling, and erosion mechanisms. When using hydrogels to modulate the bioactive molecules and drug release, the loading of the drug is performed either during network formation or after cross-linking [111]. Moreover, the bioactive molecule can be physically or covalently linked to the polymer network and further tune the release rate. It is important to note that the cross-linking reaction has to be conducted under mild conditions in order to prevent the denaturate of loaded bioactive molecule. Although hydrogel formulations for transdermal and oral delivery can be non-degradable, the direct delivery of drugs to different body interest sites requires the hydrogel biodegradation. This is to avoid foreign body reaction, and further surgical removal is necessary [45]. At present, injectable hydrogel formulations are mostly appealing and still under investigation. Recently, a new and novel injectable cellulose nanocrystal-reinforced superabsorbent hydrogel has been developed by Yang’s group [112] which could maintain their original shape for more than 60 days when immersed in 10 mM phosphate buffered saline or purified water and exhibits the excellent storage modulus. These properties make nanocellulose-reinforced injectable hydrogels a high potential interest for various biomedical applications such as tissue engineering matrices or drug delivery vehicles.

In the last decade, the use of excellent biocompatibility cellulose hydrogel and its derivatives as biomaterials for the design of tissue engineering scaffolds has received increasing attention. Regenerative medicine is an interdisciplinary research which deals with the induced regeneration of organs and tissues in vivo, by means of a scaffolding template or material that support and guide the cells during the synthesis of new tissues. In other words, it involves the replacement or improvement of specific organs or tissues using engineered materials and synthetic strategies. Basically, the superabsorbent hydrogels can be altered by using linker molecules that enable covalent or non-covalent molecular interactions between the hydrogel matrix and its surroundings in order to enhance the mechanical performance and tissue-/cell-adhesive properties [3].

For an ideal tissue regeneration, the generated scaffold has to be biodegradable with a reasonable biodegradation rate that matches with the biological process of the body. Practically, a slow degradation process is often favored to minimize the risk of premature resorption of the scaffold. Due to the bio-durability of cellulose, it is a suitable candidate for the design of tissue engineering scaffolds. However, it is known that a too slow degradation or a bio-durable material may cause the undesired biological responses in the long term, such as foreign body reaction, which limits the applications of cellulose in regenerative medicine. In fact, several studies [113, 114] have been conducted to prove the potential application of cellulose-based hydrogels for inducing the regeneration neural tissues, cartilage, and bone. A final remark about the development of regenerative medicine concerns the important role played by the scaffold porosity, which enhances the infiltration, attachment, and survival of cells within the scaffold. Owing to its nano-dimensional mesh structure [110], the superabsorbent hydrogels are usually employed to the small tissue defects while failing in larger implants. Several novel techniques for producing porous hydrogels had been summarized in several review papers [3, 45] and might be of great value in improving the regenerative potential of cellulose-based superabsorbent hydrogels.

In addition, there has been considerable interest in using cross-linked carboxymethyl cellulose (CMC) as tablet disintegrants. In order to achieve this, the cellulose superabsorbent hydrogels in powder form is mixed well with other excipients and thus is compressed to a tablet. Sadly, the cellulose-based superabsorbent hydrogel tablets may get soften at high-humidity condition, and thus, it may have an instability concern to the moisture-sensitive drugs [115]. Tissue engineering is the latest application of hydrogels which is mainly served for three purposes including as delivery vehicles for bioactive substances (for encapsulation of secretory cells and promotion of angiogenesis), as space-filling agents (to prevent adhesion, employed for bulking and as biological glue), and as three-dimensional structures that organize cells and present stimuli in order to ensure the development of a required tissue in the body (i.e., smooth muscle, bone, and cartilage) [111].

Superabsorbent hydrogels are widely applied in the wound treatment. During the wound healing, several processes including inflammation, autolytic debridement, granulation tissue formation, and reepithelialization are normally involved. Large wounds result in high risk of infection as well as loss of large amounts of fluids. Therefore, suitable wound dressings are designed to promote healing while protecting the wound from further infection. For an ideal wound management product, it should have numerous properties such as being able to absorb excess toxins and exudate, preserve the wound from external infection, prevent excess heat at the wound, maintain good moisture between the dressing and wound, have good permeability to gases, be easy to remove without further trauma to the original wound, and be supplied completely sterile [116]. It is known that a moist environment encourages rapid healing; therefore, the hydrogels in the form of sheets or amorphous state are optimal candidates for the development of wound dressings [117]. Basically, amorphous hydrogels are physically cross-linked, and their viscosity will be decreased when absorbing the physiological fluids. Amorphous-state hydrogels are generally reapplied daily, while the sheet structure hydrogels are usually changed 2–3 times weekly [3]. The hydrogels may be packaged in foil packets or in tubes and can reinforce with a polymeric mesh or gauze for the ease of removal and to prevent gel liquefaction. The advanced dressings are aimed to keep the moist environment at the applied site, allowing the fluids to remain close to the wound rather than spread to the healthy, unaffected skin areas [118]. The significance of the moist condition around the wound as a factor accelerating the healing process was first observed in 1962 by Winter [119] but only has received much attention recently.

Besides that, hydrogels are used as moist dressings, debriding agents, and components of pastes for wound care. Yet, they do not prerequisite wound fluids to convert into gels and, thus, are suitable for dry wounds [120]. It is worth mentioning that the superabsorbent hydrogels are able to provide non-adherent dressings which can be easily detached from the wound bed without further hurt. A further advantage of hydrogel is the transparency properties as the user can easily monitor the condition of wound healing. In recent year, the antimicrobial agents, such as silver ions, have been included in the formulation of hydrogel dressing production, as shown in Table 8. Bacterial cellulose has been extensively investigated for wound healing due to its high purity and excellent water retention capacity, and a series of bacterial cellulose-based wound dressing are currently marketed [121].
Table 8

Commercially available hydrogel for application of wound dressings [45]

Hydrogel wound dressing

Producer

Composition

IntraSiteTM Gel

Smith & Nephew

Propylene glycol, water, NaCMC

Aquacel AgTM

ConvaTec

NaCMC, silver ions (1.2%)

GranuGelTM

ConvaTec

Water, NaCMC, propylene glycol, pectin

Purilon GelTM

ColoPlast

Water, calcium alginate, CMC

SilvercelTM

Johnson & Johnson

Calcium alginate, silver ions (8%), CMC

8 Formation Mechanism of Cellulose-Based Hydrogels

In general, there are three main types of hydrogel-forming mechanisms: chemical cross-linking, ionotropic cross-linking, and complex coacervate formation. The mechanism for the formation of hydrogels (gelation behavior) has a direct and significant impact on the methods used to fabricate the hydrogel component for tissue engineering. Certain gel-forming processes resulted in the rapid prototyping fabrication process, while the slower fabrication techniques (i.e., porogen leaching) are suitable for robust hydrogels, which normally require more time to develop [122]. All hydrogels possess physical attraction between macromers due to the presence of hydrogen bonding and entanglements among one another [20]. Unfortunately, these physical interactions are strong enough only for the formation of a weak gel but not strong enough for tissue engineering applications or layer-upon-layer fabrication. Therefore, a hydrogel is usually intended for tissue engineering applications which must be strengthened through additional chemical cross-linking or electrostatic interactions.

In the current era, chemical cross-linking is the highly resourceful method for the formation of hydrogels having an excellent mechanical strength. Cross-linking is responsible for the three-dimensional network structures of hydrogels and their physical properties (i.e., swelling and elasticity) that are attributed to the presence of chemical or physical cross-links within polymer chains. The cross-linking level of the hydrogels is also vital because the physical states of the hydrogels can be altered by changing the cross-linking level [123]. In this process, a cross-linking agent is added to a diluted hydrophilic polymer solution, and the polymer must have a suitable functionality to react with the cross-linking agent. This process is applicable for preparation of hydrogels from synthetic and natural hydrophilic polymers [124].

Ionotropic hydrogels are formed from the electrostatic interactions between polycations and anions or polyanions and cations. For instance, chitosan is a polycationic polymer comprised of glucosamine residues, which form a firm ionotropic hydrogel upon addition of phosphate ions and which are positively charged above its isoelectric point [11]. Another example is alginate, a polyanionic polymer containing glucuronic and mannuronic residues, which will form a firm ionotropic hydrogel with calcium ions [125]. Usually, these hydrogels are able to form a firm hydrogel upon cooling; therefore, it is particularly useful for use in rapid prototyping fabrication techniques or for in situ tissue engineering [126]. Normally, ionic cross-links are beneficial for biomedical applications due to its self-repair properties. Thus, it is proposed to be used as cartilage tissue scaffolds which consist of epoxy amine polymers and gellan gum (a water-soluble anionic polysaccharide) [127].

Complex coacervate hydrogels (as referred to polyelectrolyte complexes or polyion complexes) are formed upon mixing of a polycation and a polyanion with one another (i.e., poly(l-lysine) and alginate) or with an amphoteric polymer (i.e., gelatin and chondroitin sulfate) [20, 128]. This approach is based on the principle that the opposite charges of the polymers stick together to form either soluble or insoluble complexes, depending on the pH and concentration of the solutions [38]. Hydrogels can be produced by a variety of cross-linking methods as well as agents. However, most of the cross-linking agents are toxic and must be eliminated from the hydrogel before contact with the body or cells.

9 Conclusion

Considering the desirable features of hydrogels in terms of biocompatibility, biodegradability, high water content, controllable swelling behavior, low cost, hydrophilicity, and non-toxicity characteristics, cellulose-based superabsorbent hydrogels that are made from natural biomass resources are drawing attention to both industrialist and academicians. These types of novel hydrogels are potentially used for a variety of industrial applications such as drug delivery system, agriculture, tissue engineering, water engineering, hygiene products, wound dressing, and more. In this chapter, we had summarized several polymerization reaction systems that were widely used for the superabsorbent hydrogel production. In addition, stimulate-responsive cellulose-based hydrogels established a new generation of green materials to be applied in several fields, such as pharmaceutical and medical systems. According to different applications, these materials are able to respond to various internal and external stimuli and are sensitive to the changes of temperature, pH, ionic strength, and solvent system. Undoubtedly, superabsorbent hydrogels derived from cellulose and cellulose derivatives offer abundance of promising opportunities in various industries’ usage.

10 Outlook/Future Scope

This chapter discusses the current progress of cellulose-based superabsorbent hydrogels from different aspects. Generally, cellulose-based superabsorbent hydrogels possess several favorable properties such as biocompatibility, biodegradability, hydrophilicity, transparency, low cost, and non-toxicity. Therefore, these bio-based materials offer a wide variety and diverse range of applications for agriculture and horticulture, water treatments, personal health care, and biomedical industries. Nevertheless, some of the novel applications need to be explored, such as electronics, catalysis, capacitors, dye-sensitized solar cells, plugging agent, biosensor, and fire control. Up to date, the established conventional hydrogel-based product could not meet the requirements of the present day and thus the future development on superabsorbent hydrogels by emerging natural biomass resources (cellulose or cellulose derivatives) with the intention of achieving the demands for different product requirements. From the economic and application point of view, the performance of superabsorbent hydrogels (e.g., distinctive mechanical strength, anti-mildew properties, swelling capability, and electrochemical properties) can be further improved in order to expand to more industrial field. As a result, intense research on the production of cellulose-based superabsorbent hydrogels has to be conducted continuously. It is worth mentioning that cellulose fibers are low cost and is an environmentally friendly material, which is the suitable alternative of petroleum-based materials. Up to date, many hydrogel-based drug delivery devices and scaffolds have been designed, studied, and patented; however, not much of the products are able to reach commercialization stage. On the other hand, commercial hydrogel products for tissue engineering and drug delivery are still limited. It is believed that the limited commercial products with hydrogels in these areas are due to high production costs. Furthermore, advanced technologies need to be further developed in order to produce superabsorbent hydrogels with intrinsic and unique properties. Most important is an in-depth study on the reaction mechanism, and swelling kinetics of superabsorbent hydrogels originated from interdisciplinary angles is needed for deeper investigation.

Notes

Acknowledgments

The authors are grateful for the financial support from the University of Malaya: SATU Joint Research Scheme (ST015-2017) and Postgraduate Research Grant Scheme (PPP) (PG249-2016A, PG253-2016A).

References

  1. 1.
    Kopeček J (2007) Hydrogel biomaterials: a smart future? Biomaterials 28(34):5185–5192PubMedPubMedCentralCrossRefGoogle Scholar
  2. 2.
    Ahmed EM (2015) Hydrogel: preparation, characterization, and applications: a review. J Adv Res 6(2):105–121PubMedCrossRefPubMedCentralGoogle Scholar
  3. 3.
    Caló E, Khutoryanskiy VV (2015) Biomedical applications of hydrogels: a review of patents and commercial products. Eur Polym J 65:252–267CrossRefGoogle Scholar
  4. 4.
    Kopeček J, Yang J (2012) Smart self-assembled hybrid hydrogel biomaterials. Angew Chem Int Ed 51(30):7396–7417CrossRefGoogle Scholar
  5. 5.
    Khan S, Ullah A, Ullah K, Rehman NU (2016) Insight into hydrogels. Des Monomers Polym 19(5):456–478CrossRefGoogle Scholar
  6. 6.
    Gulrez SK, Al-Assaf S, Phillips GO (2011) Hydrogels: methods of preparation, characterisation and applications. In: Progress in molecular and environmental bioengineering-from analysis and modeling to technology applications. InTech, RijekaGoogle Scholar
  7. 7.
    Das N (2013) Preparation methods and properties of hydrogel: a review. Int J Pharm Pharm Sci 5(3):112–117Google Scholar
  8. 8.
    Chai Q, Jiao Y, Yu X (2017) Hydrogels for biomedical applications: their characteristics and the mechanisms behind them. Gels 3(1):6CrossRefGoogle Scholar
  9. 9.
    Kumar P, Barrett DM, Delwiche MJ, Stroeve P (2009) Methods for pretreatment of lignocellulosic biomass for efficient hydrolysis and biofuel production. Ind Eng Chem Res 48(8):3713–3729CrossRefGoogle Scholar
  10. 10.
    Ma J, Li X, Bao Y (2015) Advances in cellulose-based superabsorbent hydrogels. RSC Adv 5(73):59745–59757CrossRefGoogle Scholar
  11. 11.
    Hennink WE, Van Nostrum CF (2012) Novel crosslinking methods to design hydrogels. Adv Drug Deliv Rev 64:223–236CrossRefGoogle Scholar
  12. 12.
    Gibas I, Janik H (2010) Synthetic polymer hydrogels for biomedical applications. Chem Chem Technol 4(4):297–304Google Scholar
  13. 13.
    Laftah WA, Hashim S, Ibrahim AN (2011) Polymer hydrogels: a review. Polym Plast Technol Eng 50(14):1475–1486CrossRefGoogle Scholar
  14. 14.
    Zhao W, Jin X, Cong Y, Liu Y, Fu J (2013) Degradable natural polymer hydrogels for articular cartilage tissue engineering. J Chem Technol Biotechnol 88(3):327–339CrossRefGoogle Scholar
  15. 15.
    Bel’nikevich N, Bobrova N, Elokhovskii VY, Zoolshoev Z, Smirnov M, Elyashevich G (2011) Effect of initiator on the structure of hydrogels of cross-linked polyacrylic acid. Russ J Appl Chem 84(12):2106–2113CrossRefGoogle Scholar
  16. 16.
    Xiao X (2007) Effect of the initiator on thermosensitive rate of poly (N-isopropylacrylamide) hydrogels. Express Polym Lett 1:232–235CrossRefGoogle Scholar
  17. 17.
    Kaihara S, Matsumura S, Fisher JP (2008) Synthesis and characterization of cyclic acetal based degradable hydrogels. Eur J Pharm Biopharm 68(1):67–73PubMedCrossRefPubMedCentralGoogle Scholar
  18. 18.
    Betancourt T, Pardo J, Soo K, Peppas NA (2010) Characterization of pH-responsive hydrogels of poly(itaconic acid-g-ethylene glycol) prepared by UV-initiated free radical polymerization as biomaterials for oral delivery of bioactive agents. J Biomed Mater Res A 93(1):175–188PubMedPubMedCentralGoogle Scholar
  19. 19.
    Wu H, Yu G, Pan L, Liu N, McDowell MT, Bao Z, Cui Y (2013) Stable Li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles. Nat Commun 4:1943PubMedCrossRefPubMedCentralGoogle Scholar
  20. 20.
    Hoffman AS (2012) Hydrogels for biomedical applications. Adv Drug Deliv Rev 64:18–23CrossRefGoogle Scholar
  21. 21.
    Wong RSH, Ashton M, Dodou K (2015) Effect of crosslinking agent concentration on the properties of unmedicated hydrogels. Pharmaceutics 7(3):305–319PubMedPubMedCentralCrossRefGoogle Scholar
  22. 22.
    Ullah F, Othman MBH, Javed F, Ahmad Z, Akil HM (2015) Classification, processing and application of hydrogels: a review. Mater Sci Eng C 57:414–433CrossRefGoogle Scholar
  23. 23.
    Haraguchi K, Xu Y, Li G (2011) Poly (N-isopropylacrylamide) prepared by free-radical polymerization in aqueous solutions and in nanocomposite hydrogels. Macromol Symp 306-307:33. Wiley Online LibraryCrossRefGoogle Scholar
  24. 24.
    Jeong GT, Lee KM, Yang HS, Park SH, Park JH, Sunwoo C, Ryu HW, Kim D, Lee WT, Kim HS (2007) Synthesis of poly(sorbitan methacrylate) hydrogel by free-radical polymerization. Appl Biochem Biotechnol 137–140(1–12):935–946PubMedPubMedCentralGoogle Scholar
  25. 25.
    Thürmer MB, Diehl CE, Brum FJB, Santos LA (2014) Preparation and characterization of hydrogels with potential for use as biomaterials. Mater Res 17:109–113CrossRefGoogle Scholar
  26. 26.
    Reis EF, Campos FS, Lage AP, Leite RC, Heneine LG, Vasconcelos WL, Lobato ZIP, Mansur HS (2006) Synthesis and characterization of poly(vinyl alcohol) hydrogels and hybrids for rMPB70 protein adsorption. Mater Res 9(2):185–191CrossRefGoogle Scholar
  27. 27.
    Liu ZQ, Wei Z, Zhu XL, Huang GY, Xu F, Yang JH, Osada Y, Zrínyi M, Li JH, Chen YM (2015) Dextran-based hydrogel formed by thiol-Michael addition reaction for 3D cell encapsulation. Colloids Surf B Biointerfaces 128:140–148PubMedCrossRefPubMedCentralGoogle Scholar
  28. 28.
    Bakota EL, Aulisa L, Galler KM, Hartgerink JD (2011) Enzymatic cross-linking of a nanofibrous peptide hydrogel. Biomacromolecules 12(1):82–87PubMedCrossRefPubMedCentralGoogle Scholar
  29. 29.
    Bajpai S, Bajpai M, Sharma L (2007) Inverse suspension polymerization of poly(methacrylic acid-co-partially neutralized acrylic acid) superabsorbent hydrogels: synthesis and water uptake behavior. Des Monomers Polym 10(2):181–192CrossRefGoogle Scholar
  30. 30.
    Abd Alla SG, Said HM, El-Naggar AWM (2004) Structural properties of γ-irradiated poly(vinyl alcohol)/poly(ethylene glycol) polymer blends. J Appl Polym Sci 94(1):167–176CrossRefGoogle Scholar
  31. 31.
    Doria-Serrano MC, Ruiz-Treviño FA, Rios-Arciga C, Hernández-Esparza M, Santiago P (2001) Physical characteristics of poly(vinyl alcohol) and calcium alginate hydrogels for the immobilization of activated sludge. Biomacromolecules 2(2):568–574PubMedCrossRefGoogle Scholar
  32. 32.
    de Jong SJ, De Smedt SC, Demeester J, van Nostrum CF, Kettenes-van den Bosch JJ, Hennink WE (2001) Biodegradable hydrogels based on stereocomplex formation between lactic acid oligomers grafted to dextran. J Control Release 72(1):47–56PubMedCrossRefGoogle Scholar
  33. 33.
    Navarra MA, Dal Bosco C, Serra Moreno J, Vitucci FM, Paolone A, Panero S (2015) Synthesis and characterization of cellulose-based hydrogels to be used as gel electrolytes. Membranes 5(4):810–823PubMedPubMedCentralCrossRefGoogle Scholar
  34. 34.
    Penco M, Marcioni S, Ferruti P, D’Antone S, Deghenghi R (1996) Degradation behaviour of block copolymers containing poly(lactic-glycolic acid) and poly(ethylene glycol) segments. Biomaterials 17(16):1583–1590PubMedCrossRefGoogle Scholar
  35. 35.
    Wang Y, Liu C, Fan L, Sheng Y, Mao J, Chao G, Li J, Tu M, Qian Z (2005) Synthesis of biodegradable poly(butylene terephthalate)/poly(ethylene glycol)(PBT/PEG) multiblock copolymers and preparation of indirubin loaded microspheres. Polym Bull 53(3):147–154CrossRefGoogle Scholar
  36. 36.
    Patil S (2008) Crosslinking of polysaccharides: methods and applications. Latest Rev 6(2):1Google Scholar
  37. 37.
    Kulkarni N, Wakte P, Naik J (2015) Development of floating chitosan-xanthan beads for oral controlled release of glipizide. Int J Pharma Investig 5(2):73CrossRefGoogle Scholar
  38. 38.
    Francis R, Kumar DS (2016) Biomedical applications of polymeric materials and composites. Wiley, Weinheim, GermanyGoogle Scholar
  39. 39.
    Zustiak SP, Wei Y, Leach JB (2012) Protein–hydrogel interactions in tissue engineering: mechanisms and applications. Tissue Eng Pt B-Rev 19(2):160–171CrossRefGoogle Scholar
  40. 40.
    Akhtar MF, Hanif M, Ranjha NM (2016) Methods of synthesis of hydrogels…a review. Saudi Pharm J 24(5):554–559PubMedCrossRefPubMedCentralGoogle Scholar
  41. 41.
    He M, Zhao Y, Duan J, Wang Z, Chen Y, Zhang L (2014) Fast contact of solid–liquid interface created high strength multi-layered cellulose hydrogels with controllable size. ACS Appl Mater Interface 6(3):1872–1878CrossRefGoogle Scholar
  42. 42.
    Bassil M, AL Moussawel J, Ibrahim M, Azzi G, El Tahchi M (2014) Electrospinning of highly aligned and covalently cross-linked hydrogel microfibers. J Appl Polym Sci 131(22):41092CrossRefGoogle Scholar
  43. 43.
    Cook JP, Goodall GW, Khutoryanskaya OV, Khutoryanskiy VV (2012) Microwave-assisted hydrogel synthesis: a new method for crosslinking polymers in aqueous solutions. Macromol Rapid Commun 33(4):332–336PubMedCrossRefGoogle Scholar
  44. 44.
    Tomšič B, Simončič B, Orel B, Vilčnik A, Spreizer H (2007) Biodegradability of cellulose fabric modified by imidazolidinone. Carbohydr Polym 69(3):478–488CrossRefGoogle Scholar
  45. 45.
    Sannino A, Demitri C, Madaghiele M (2009) Biodegradable cellulose-based hydrogels: design and applications. Materials 2(2):353PubMedCentralCrossRefPubMedGoogle Scholar
  46. 46.
    Fajardo A, Pereira A, Rubira A, Valente A, Muniz E (2015) Stimuli-responsive polysaccharide-based hydrogels. In: Polysaccharide hydrogels. Pan Stanford, Singapore, pp 325–366CrossRefGoogle Scholar
  47. 47.
    Li L, Thangamathesvaran PM, Yue CY, Tam KC, Hu X, Lam YC (2001) Gel network structure of methylcellulose in water. Langmuir 17(26):8062–8068CrossRefGoogle Scholar
  48. 48.
    Sammon C, Bajwa G, Timmins P, Melia CD (2006) The application of attenuated total reflectance Fourier transform infrared spectroscopy to monitor the concentration and state of water in solutions of a thermally responsive cellulose ether during gelation. Polymer 47(2):577–584CrossRefGoogle Scholar
  49. 49.
    Sekiguchi Y, Sawatari C, Kondo T (2003) A gelation mechanism depending on hydrogen bond formation in regioselectively substituted O-methylcelluloses. Carbohydr Polym 53(2): 145–153CrossRefGoogle Scholar
  50. 50.
    Joshi SC, Liang CM, Lam YC (2008) Effect of solvent state and isothermal conditions on gelation of methylcellulose hydrogels. J Biomater Sci Polym Ed 19(12):1611–1623PubMedCrossRefPubMedCentralGoogle Scholar
  51. 51.
    Weiss P, Gauthier O, Bouler JM, Grimandi G, Daculsi G (1999) Injectable bone substitute using a hydrophilic polymer. Bone 25(2):67S–70SPubMedCrossRefPubMedCentralGoogle Scholar
  52. 52.
    Silva SM, Pinto FV, Antunes FE, Miguel MG, Sousa JJ, Pais AA (2008) Aggregation and gelation in hydroxypropylmethyl cellulose aqueous solutions. J Colloid Interface Sci 327(2): 333–340PubMedCrossRefPubMedCentralGoogle Scholar
  53. 53.
    Vinatier C, Gauthier O, Fatimi A, Merceron C, Masson M, Moreau A, Moreau F, Fellah B, Weiss P, Guicheux J (2009) An injectable cellulose-based hydrogel for the transfer of autologous nasal chondrocytes in articular cartilage defects. Biotechnol Bioeng 102(4):1259–1267PubMedCrossRefPubMedCentralGoogle Scholar
  54. 54.
    Chang C, Zhang L (2011) Cellulose-based hydrogels: present status and application prospects. Carbohydr Polym 84(1):40–53CrossRefGoogle Scholar
  55. 55.
    Trojani C, Weiss P, Michiels JF, Vinatier C, Guicheux J, Daculsi G, Gaudray P, Carle GF, Rochet N (2005) Three-dimensional culture and differentiation of human osteogenic cells in an injectable hydroxypropylmethylcellulose hydrogel. Biomaterials 26(27):5509–5517PubMedCrossRefPubMedCentralGoogle Scholar
  56. 56.
    Hirsch SG, Spontak RJ (2002) Temperature-dependent property development in hydrogels derived from hydroxypropyl cellulose. Polymer 43(1):123–129CrossRefGoogle Scholar
  57. 57.
    Demitri C, Scalera F, Madaghiele M, Sannino A, Maffezzoli A (2013) Potential of cellulose-based superabsorbent hydrogels as water reservoir in agriculture. Int J Polym Sci 2013:Article ID 435073.  https://doi.org/10.1155/2013/435073. 6 pagesCrossRefGoogle Scholar
  58. 58.
    Shen X, Shamshina JL, Berton P, Gurau G, Rogers RD (2016) Hydrogels based on cellulose and chitin: fabrication, properties, and applications. Green Chem 18(1):53–75CrossRefGoogle Scholar
  59. 59.
    Kimura A, Nagasawa N, Taguchi M (2014) Cellulose gels produced in room temperature ionic liquids by ionizing radiation. Radiat Phys Chem 103:216–221CrossRefGoogle Scholar
  60. 60.
    Petrov P, Petrova E, Stamenova R, Tsvetanov CB, Riess G (2006) Cryogels of cellulose derivatives prepared via UV irradiation of moderately frozen systems. Polymer 47(19): 6481–6484CrossRefGoogle Scholar
  61. 61.
    Ebara M, Kotsuchibashi Y, Uto K, Aoyagi T, Kim YJ, Narain R, Idota N, Hoffman JM (2014) Smart hydrogels. In: Smart biomaterials. Springer, Tokyo, pp 9–65Google Scholar
  62. 62.
    Gil ES, Hudson SM (2004) Stimuli-reponsive polymers and their bioconjugates. Prog Polym Sci 29(12):1173–1222CrossRefGoogle Scholar
  63. 63.
    Sharma K, Singh V, Arora A (2011) Natural biodegradable polymers as matrices in transdermal drug delivery. Int J Drug Dev Res 32:85–103Google Scholar
  64. 64.
    Thakur A, Wanchoo R, Singh P (2011) Structural parameters and swelling behavior of pH sensitive poly (acrylamide-co-acrylic acid) hydrogels. Chem Biochem Eng Q 25(2):181–194Google Scholar
  65. 65.
    Onofrei M, Filimon A (2016) Cellulose-based hydrogels: designing concepts, properties, and perspectives for biomedical and environmental applications. In: Polymer science: research advances, practical applications and educational aspects. Formatex, Badajoz, pp 108–120Google Scholar
  66. 66.
    Sakaguchi T, Nagano S, Hara M, Hyon S-H, Patel M, Matsumura K (2017) Facile preparation of transparent poly (vinyl alcohol) hydrogels with uniform microcrystalline structure by hot-pressing without using organic solvents. Polym J 49(7):535–542CrossRefGoogle Scholar
  67. 67.
    Karoyo AH, Wilson LD (2017) Physicochemical properties and the gelation process of supramolecular hydrogels: a review. Gels 3(1):1CrossRefGoogle Scholar
  68. 68.
    Borzacchiello A, Ambrosio L (2009) Structure-property relationships. In: Hydrogels in hydrogels. Springer, Berlin, pp 9–20CrossRefGoogle Scholar
  69. 69.
    Peppas NA, Hilt JZ, Khademhosseini A, Langer R (2006) Hydrogels in biology and medicine: from molecular principles to bionanotechnology. Adv Mater 18(11):1345–1360CrossRefGoogle Scholar
  70. 70.
    Chang C, Duan B, Cai J, Zhang L (2010) Superabsorbent hydrogels based on cellulose for smart swelling and controllable delivery. Eur Polym J 46(1):92–100CrossRefGoogle Scholar
  71. 71.
    Pourjavadi A, Ayyari M, Amini-Fazl M (2008) Taguchi optimized synthesis of collagen-g-poly(acrylic acid)/kaolin composite superabsorbent hydrogel. Eur Polym J 44(4):1209–1216CrossRefGoogle Scholar
  72. 72.
    Demitri C, Del Sole R, Scalera F, Sannino A, Vasapollo G, Maffezzoli A, Ambrosio L, Nicolais L (2008) Novel superabsorbent cellulose-based hydrogels crosslinked with citric acid. J Appl Polym Sci 110(4):2453–2460CrossRefGoogle Scholar
  73. 73.
    Luo X, Zhang L (2013) New solvents and functional materials prepared from cellulose solutions in alkali/urea aqueous system. Food Res Int 52(1):387–400CrossRefGoogle Scholar
  74. 74.
    Fekete T, Borsa J, Takács E, Wojnárovits L (2016) Synthesis of cellulose-based superabsorbent hydrogels by high-energy irradiation in the presence of crosslinking agent. Radiat Phys Chem 118:114–119CrossRefGoogle Scholar
  75. 75.
    Duan J, Zhang X, Jiang J, Han C, Yang J, Liu L, Lan H, Huang D (2014) The synthesis of a novel cellulose physical gel. J Nanomater 2014:1CrossRefGoogle Scholar
  76. 76.
    D’Arrigo G (2013) Macro and nano shaped polysaccharide hydrogels as drug delivery systems. Northeastern University, BostonGoogle Scholar
  77. 77.
    Li L, Jiang R, Chen J, Wang M, Ge X (2017) In situ synthesis and self-reinforcement of polymeric composite hydrogel based on particulate macro-RAFT agents. RSC Adv 7(3): 1513–1519CrossRefGoogle Scholar
  78. 78.
    Feeney M, Giannuzzo M, Paolicelli P, Casadei MA (2007) Hydrogels of dextran containing nonsteroidal anti-inflammatory drugs as pendant agents. Drug Deliv 14(2):87–93PubMedCrossRefPubMedCentralGoogle Scholar
  79. 79.
    Zhang Y, Liu Y, Liu J, Guo P, Heng L (2017) Super water absorbency OMMT/PAA hydrogel materials with excellent mechanical properties. RSC Adv 7(24):14504–14510CrossRefGoogle Scholar
  80. 80.
    Sannino A, Esposito A, Nicolais L, Del Nobile M, Giovane A, Balestrieri C, Esposito R, Agresti M (2000) Cellulose-based hydrogels as body water retainers. J Mater Sci-Mater M 11(4):247–253CrossRefGoogle Scholar
  81. 81.
    Sannino A, Mensitieri G, Nicolais L (2004) Water and synthetic urine sorption capacity of cellulose-based hydrogels under a compressive stress field. J Appl Polym Sci 91(6): 3791–3796CrossRefGoogle Scholar
  82. 82.
    Sannino A, Esposito A, Rosa AD, Cozzolino A, Ambrosio L, Nicolais L (2003) Biomedical application of a superabsorbent hydrogel for body water elimination in the treatment of edemas. J Biomed Mater Res A 67((3):1016–1024CrossRefGoogle Scholar
  83. 83.
    Li X, He JZ, Hughes JM, Liu YR, Zheng YM (2014) Effects of super-absorbent polymers on a soil–wheat (Triticum aestivum L.) system in the field. Appl Soil Ecol 73:58–63CrossRefGoogle Scholar
  84. 84.
    Salmawi KME, El-Naggar AA, Ibrahim SM (2018) Gamma irradiation synthesis of carboxymethyl cellulose/acrylic acid/clay superabsorbent hydrogel. Adv Polym Technol 37(2), 515–521CrossRefGoogle Scholar
  85. 85.
    Li J, Jiang M, Wu H, Li Y (2009) Addition of modified bentonites in polymer gel formulation of 2, 4-D for its controlled release in water and soil. J Agric Food Chem 57(7):2868–2874PubMedCrossRefPubMedCentralGoogle Scholar
  86. 86.
    Kołodyńska D, Skiba A, Be G, Hubicki Z (2016) Hydrogels from fundaments to application. In: Emerging concepts in analysis and applications of hydrogels. InTech, ViennaGoogle Scholar
  87. 87.
    Coviello T, Matricardi P, Marianecci C, Alhaique F (2007) Polysaccharide hydrogels for modified release formulations. J Control Release 119(1):5–24PubMedCrossRefPubMedCentralGoogle Scholar
  88. 88.
    Xiaoyu N, Yuejin W, Zhengyan W, Lin W, Guannan Q, Lixiang Y (2013) A novel slow-release urea fertiliser: physical and chemical analysis of its structure and study of its release mechanism. Biosyst Eng 115(3):274–282CrossRefGoogle Scholar
  89. 89.
    Kashyap PL, Xiang X, Heiden P (2015) Chitosan nanoparticle based delivery systems for sustainable agriculture. Int J Biol Macromol 77:36–51PubMedCrossRefPubMedCentralGoogle Scholar
  90. 90.
    Bortolin A, Aouada FA, Mattoso LH, Ribeiro C (2013) Nanocomposite PAAm/methyl cellulose/montmorillonite hydrogel: evidence of synergistic effects for the slow release of fertilizers. J Agric Food Chem 61(31):7431–7439PubMedCrossRefPubMedCentralGoogle Scholar
  91. 91.
    Davidson DW, Verma MS, Gu FX (2013) Controlled root targeted delivery of fertilizer using an ionically crosslinked carboxymethyl cellulose hydrogel matrix. Springerplus 2(1):318PubMedPubMedCentralCrossRefGoogle Scholar
  92. 92.
    Davidson DGu FX (2012) Materials for sustained and controlled release of nutrients and molecules to support plant growth. J Agric Food Chem 60(4):870–876CrossRefGoogle Scholar
  93. 93.
    Zohuriaan-Mehr MJ, Kabiri K (2008) Superabsorbent polymer materials: a review. Iran Polym J 17(6):451Google Scholar
  94. 94.
    Spagnol C, Rodrigues FH, Pereira AG, Fajardo AR, Rubira AF, Muniz EC (2012) Superabsorbent hydrogel composite made of cellulose nanofibrils and chitosan-graft-poly(acrylic acid). Carbohydr Polym 87(3):2038–2045CrossRefGoogle Scholar
  95. 95.
    Liu H, Zhang Y, Yao J (2014) Preparation and properties of an eco-friendly superabsorbent based on flax yarn waste for sanitary napkin applications. Fibers Polym 15(1):145CrossRefGoogle Scholar
  96. 96.
    Zhang Y, Wu F, Liu L, Yao J (2013) Synthesis and urea sustained-release behavior of an eco-friendly superabsorbent based on flax yarn wastes. Carbohydr Polym 91(1):277–283PubMedCrossRefPubMedCentralGoogle Scholar
  97. 97.
    Zhang J, Wang Q, Wang A (2007) Synthesis and characterization of chitosan-g-poly (acrylic acid)/attapulgite superabsorbent composites. Carbohydr Polym 68(2):367–374CrossRefGoogle Scholar
  98. 98.
    Marcì G, Mele G, Palmisano L, Pulito P, Sannino A (2006) Environmentally sustainable production of cellulose-based superabsorbent hydrogels. Green Chem 8(5):439–444CrossRefGoogle Scholar
  99. 99.
    Zhou Y, Fu S, Zhang L, Zhan H, Levit MV (2014) Use of carboxylated cellulose nanofibrils-filled magnetic chitosan hydrogel beads as adsorbents for Pb (II). Carbohydr Polym 101:75–82PubMedCrossRefPubMedCentralGoogle Scholar
  100. 100.
    Tripathy J, Mishra DK, Behari K (2009) Graft copolymerization of N-vinylformamide onto sodium carboxymethylcellulose and study of its swelling, metal ion sorption and flocculation behaviour. Carbohydr Polym 75(4):604–611CrossRefGoogle Scholar
  101. 101.
    Kamel S, Hassan E, El-Sakhawy M (2006) Preparation and application of acrylonitrile-grafted cyanoethyl cellulose for the removal of copper (II) ions. J Appl Polym Sci 100(1):329–334CrossRefGoogle Scholar
  102. 102.
    Abdel-Aal S, Gad Y, Dessouki A (2006) The use of wood pulp and radiation-modified starch in wastewater treatment. J Appl Polym Sci 99(5):2460–2469CrossRefGoogle Scholar
  103. 103.
    Hashem A, Ahmad F, Fahad R (2008) Application of some starch hydrogels for the removal of mercury (II) ions from aqueous solutions. Adsorpt Sci Technol 26(8):563–579CrossRefGoogle Scholar
  104. 104.
    Rohrbach K, Li Y, Zhu H, Liu Z, Dai J, Andreasen J, Hu L (2014) A cellulose based hydrophilic, oleophobic hydrated filter for water/oil separation. Chem Commun 50(87): 13296–13299CrossRefGoogle Scholar
  105. 105.
    Mulyadi A, Zhang Z, Deng Y (2016) Fluorine-free oil absorbents made from cellulose nanofibril aerogels. ACS Appl Mater Interfaces 8(4):2732–2740PubMedCrossRefPubMedCentralGoogle Scholar
  106. 106.
    Wichterle O, Lim D (1960) Hydrophilic gels for biological use. Nature 185:117–118CrossRefGoogle Scholar
  107. 107.
    Lloyd AW, Faragher RG, Denyer SP (2001) Ocular biomaterials and implants. Biomaterials 22(8):769–785PubMedCrossRefPubMedCentralGoogle Scholar
  108. 108.
    Zhao F, Yao D, Guo R, Deng L, Dong A, Zhang J (2015) Composites of polymer hydrogels and nanoparticulate systems for biomedical and pharmaceutical applications. Nanomaterials 5(4):2054–2130PubMedPubMedCentralCrossRefGoogle Scholar
  109. 109.
    Hoare TR, Kohane DS (2008) Hydrogels in drug delivery: progress and challenges. Polymer 49(8):1993–2007CrossRefGoogle Scholar
  110. 110.
    Lin C-CMetters AT (2006) Hydrogels in controlled release formulations: network design and mathematical modeling. Adv Drug Deliv Rev 58(12):1379–1408Google Scholar
  111. 111.
    Drury JL, Mooney DJ (2003) Hydrogels for tissue engineering: scaffold design variables and applications. Biomaterials 24(24):4337–4351PubMedCrossRefPubMedCentralGoogle Scholar
  112. 112.
    Yang X, Bakaic E, Hoare T, Cranston ED (2013) Injectable polysaccharide hydrogels reinforced with cellulose nanocrystals: morphology, rheology, degradation, and cytotoxicity. Biomacromolecules 14(12):4447–4455PubMedCrossRefPubMedCentralGoogle Scholar
  113. 113.
    Leone G, Fini M, Torricelli P, Giardino R, Barbucci R (2008) An amidated carboxymethylcellulose hydrogel for cartilage regeneration. J Mater Sci-Mater M 19(8):2873–2880CrossRefGoogle Scholar
  114. 114.
    Vinatier C, Magne D, Moreau A, Gauthier O, Malard O, Vignes-Colombeix C, Daculsi G, Weiss P, Guicheux J (2007) Engineering cartilage with human nasal chondrocytes and a silanized hydroxypropyl methylcellulose hydrogel. J Biomed Mater Res A 80((1):66–74CrossRefGoogle Scholar
  115. 115.
    Zohuriaan-Mehr M, Omidian H, Doroudiani S, Kabiri K (2010) Advances in non-hygienic applications of superabsorbent hydrogel materials. J Mater Sci 45(21):5711–5735CrossRefGoogle Scholar
  116. 116.
    Jones V, Grey JE, Harding KG (2006) ABC of wound healing: wound dressings. BMJ- Brit Med J 332(7544):777PubMedCrossRefPubMedCentralGoogle Scholar
  117. 117.
    Dabiri G, Damstetter E, Phillips T (2016) Choosing a wound dressing based on common wound characteristics. Adv Wound Care 5(1):32–41CrossRefGoogle Scholar
  118. 118.
    Stashak TS, Farstvedt E, Othic A (2004) Update on wound dressings: indications and best use. Clin Tech Equine Pract 3(2):148–163CrossRefGoogle Scholar
  119. 119.
    Winter GD (1962) Formation of the scab and the rate of epithelization of superficial wounds in the skin of the young domestic pig. Nature 193:293–294PubMedCrossRefPubMedCentralGoogle Scholar
  120. 120.
    Murphy PS, Evans GR (2012) Advances in wound healing: a review of current wound healing products. Plast Surg Int 2012:190436PubMedPubMedCentralGoogle Scholar
  121. 121.
    Czaja WK, Young DJ, Kawecki M, Brown RM (2007) The future prospects of microbial cellulose in biomedical applications. Biomacromolecules 8(1):1–12PubMedCrossRefPubMedCentralGoogle Scholar
  122. 122.
    Liu X, Ma PX (2009) Phase separation, pore structure, and properties of nanofibrous gelatin scaffolds. Biomaterials 30(25):4094–4103PubMedPubMedCentralCrossRefGoogle Scholar
  123. 123.
    Bukhari SMH, Khan S, Rehanullah M, Ranjha NM (2015) Synthesis and characterization of chemically cross-linked acrylic acid/gelatin hydrogels: effect of pH and composition on swelling and drug release. Int J Polym Sci 2015:Article ID 187961.  https://doi.org/10.1155/2015/187961. 15 pagesCrossRefGoogle Scholar
  124. 124.
    Saini K (2017) Preparation method, properties and crosslinking of hydrogel: a review. PharmaTutor 5(1):27–36Google Scholar
  125. 125.
    Hatefi A, Amsden B (2002) Biodegradable injectable in situ forming drug delivery systems. J Control Release 80(1):9–28PubMedCrossRefPubMedCentralGoogle Scholar
  126. 126.
    Park SA, Lee SH, Kim W (2011) Fabrication of hydrogel scaffolds using rapid prototyping for soft tissue engineering. Macromol Res 19(7):694–698CrossRefGoogle Scholar
  127. 127.
    Bakarich SE, Pidcock GC, Balding P, Stevens L, Calvert P (2012) Recovery from applied strain in interpenetrating polymer network hydrogels with ionic and covalent cross-links. Soft Matter 8(39):9985–9988CrossRefGoogle Scholar
  128. 128.
    Jin KM, Kim YH (2008) Injectable, thermo-reversible and complex coacervate combination gels for protein drug delivery. J Control Release 127(3):249–256PubMedCrossRefPubMedCentralGoogle Scholar

Copyright information

© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  • You Wei Chen
    • 1
  • Siti Hajjar Binti Hassan
    • 1
  • Mazlita Yahya
    • 1
  • Hwei Voon Lee
    • 1
    Email author
  1. 1.Nanotechnology & Catalysis Research Centre (NANOCAT)Institute of Graduate Studies, University of MalayaKuala LumpurMalaysia

Personalised recommendations