Green Chemistry Approaches to Develop Antimicrobial Textiles Based

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Green Chemistry Approaches to Develop Antimicrobial Textiles Based on Sustainable BiopolymersA Review Shahid-ul-Islam, Mohammad Shahid, and Faqeer Mohammad* Department of Chemistry, Jamia Millia Islamia (A Central University), New Delhi-110025, India ABSTRACT: In recent years, the population explosion and environmental pollution have increased the interest of researchers in the discovery of new health and hygiene-related products for the well being of mankind. Among the possible approaches initiated by the textile industry, the use of low-environmental impact technologies- based on sustainable biopolymers- presents a novel possible avenue for large scale development of bioactive textiles. The purpose of this article is to review the information on the role of different biopolymers in the development of antimicrobial textiles. Increased sustainability, environment friendliness, reduced pollution, green chemistry, renewability and intrinsic biological activity are some of the attributes which make chitosan, cyclodextrin, sericin protein, and alginate suitable alternative agents for the functional finishing of textile materials. The application of biopolymers, along with the recent impact of various “green chemistry” strategies, on the antimicrobial properties of textile fibers is reviewed. It also includes a brief review on different green pretreatment technologies used for the surface modification of textiles with a special reference to their influence on antimicrobial properties. Finally, the advantages and future studies regarding the use of nanotechnology in the antimicrobial finishing of textiles is also outlined.

1. INTRODUCTION Textile substrates, especially of natural origin, can easily be colonized by high numbers of microbes, because these provide the ideal conditions such as moisture, temperature, oxygen, and nutrients required for their growth.1,2 Microbial pathogens have lethal effects on all forms of life. These may result in offensive odors, color degradation, cross-infection, or transmission of diseases, allergic responses and deterioration of textiles.3 To combat these adversities it is highly desirable to impart antimicrobial properties to the textile materials. In recent years, antimicrobial textiles are rapidly advancing for use in various industries such as textile, pharmaceutical, medical, engineering, agricultural, and food.4−6 As a consequence of their importance, a number of chemicals have been employed to impart antimicrobial activity to textile materials. These chemicals include inorganic salts, organometallics, iodophors (substances that release iodine slowly), phenols and thiophenols, onium salts, antibiotics, heterocyclic compounds with anionic groups, nitro compounds, urea and related compounds, formaldehyde derivatives, amines and synthetic dyes.2,7 However, with the public’s enhanced awareness of ecosafety, there has been considerable debate about their use, because majority of such agents are toxic to humans and are not environmental friendly.3,8,9 The possible toxic effects produced by some of these agents on human beings are listed in Table 1. In addition, another big concern is that some of these agents are being increasingly resisted by microbial pathogens.2 Therefore the role of textile finishers has now become increasingly demanding and has strengthened the interest in alternative ecofriendly and biodegradable finishing agents. In view of these ecological and environmental concerns, natural biopolymers are the only suitable and renewable products that have the potential to become a key resource in the development of sustainable bioactive textiles.10 Recently, the use of natural biopolymers has been preferred for textile modifications. A brief list of the sources and important © XXXX American Chemical Society

Table 1. Possible Toxic Effects of Some Commercially Available Synthetic Antimicrobial Agents on Human Being synthetic agent quaternary ammonium compounds silver zinc pyrithione synthetic azo dyes triclosan

toxic effect respiratory irritation, nausea, skin and eye irritation argyria, contact dermatitis, mucous membrane irritation developmental and neurotoxicity carcinogenic endocrine disrupter, skin and eye irritation

reference 141 142 143 8 144,145

characteristics of some natural biopolymers explored on the textile substrates are summarized in Table 2. Generally, the natural polysaccharides used for the functional finishing of textiles are abundantly available as waste products, and are of an eco-friendly nature. Consequently, a variety of environmentally benign technologies are rapidly expanding for their versatile applications in the textile industry. Hence, the major objective of this review is to explore the role of sustainable biopolymers in antimicrobial finishing of textiles. This is followed by a focus on some recent developmental works pertaining to antimicrobial finishing of textiles using various “green chemistry” approaches in order to provide safe and novel antimicrobial textiles for aesthetic, hygienic, and medical applications in the near future. Received: December 29, 2012 Revised: March 11, 2013 Accepted: March 17, 2013

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dx.doi.org/10.1021/ie303627x | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

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Table 2. Characteristics of Some Biopolymers Used in Antimicrobial Finishing of Textiles biopolymer

source

chitosan

crustaceans and fungi

cyclodextrin

starch

sericin

silk worm (Bombyx mori) brown sea weeds

alginate

characteristics biocompatible, biodegradable, antimicrobial activity, antistatic activity, non toxic, chelating property, deodorizing property, film forming ability, chemical reactivity, polyelectrolyte nature, dyeing improvement ability, cost-effectiveness, thickening property, wound healing activity ecofriendly nature, inclusion complex forming ability, insecticidal delivery, slow release of fragrances, solubilizing ability, ease of production, cost- effectiveness, chelating activity, drug carrier ability biocompatible, biodegradable, uv resistant, oxidative resistant, moisture retention capacity, antibacterial, gelling property, adhesion ability high moisture absorbing capacity, biocompatibility, wound healing ability, antibacterial activity

Figure 1. Extraction of chitin and chitosan from different sources.

important polysaccharide biopolymer.18 It is mainly obtained by alkaline deacetylation of chitin (Figure 1); chemically it is composed of glucosamine and N-acetylglucosamine units linked by 1−4 glucosidic bonds.19 Being nontoxic, biodegradable, biocompatible, and microbe resistant has given it huge potential in a broad range of scientific areas such as biomedical,20 food,21 agricultural, cosmetics,19 textiles,17 pharmaceutical,22 and other industries. 2.1.1. Antimicrobial Activity of Chitosan and Its Mode of Action. There are many factors for chitosan biopolymer that can affect its antimicrobial activity and mechanism of activity such as the type of chitosan, the degree of deacetylation, molecular weight, type of microorganism, and other physical and chemical factors including pH, ionic strength, and addition of nonaqueous solvents.10,17,23 The antimicrobial activity of chitosan is generally well documented; however, its mode of action is yet not fully

2. BIOPOLYMERSAN EMERGING ALTERNATIVE SOLUTION Over the past few years, there has been enormous attention on the use of biopolymers in different application fields. Biopolymers derived from agricultural feed stock or marine food resources have several advantages such as abundant availability, biocompatibility, and biodegradability, and therefore ecological safety.11 In textile finishing, incorporation of natural polysaccharides is a new concept, which has been introduced in recent years. This was brought about by the recognition that their unique properties can be applied to different areas of applications such as deodorant,12 aroma,13 insect repellent,14 fire retardant,15 UV block,16 and water resistant and antimicrobial finishes17 which have recently become popular. 2.1. Chitosana Million Dollar Natural Polymer. Chitosan, discovered by Rouget in 1859, is a technologically B



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inhibited growth and permeabilized the membranes of all the tested strains in comparison to the other chitosans. They concluded that chitosan preparation details are critically important in identifying the antibacterial features that target different test organisms. Several studies have shown that the mechanisms of the antibacterial activity of chitosan differ for gram-positive and gram-negative bacteria or the test organism. It is well-known that the outer membrane (OM) of gram-negative bacteria consists essentially of lipopolysaccharides (LPS) containing phosphate and pyrophosphate groups which render to the bacterial surface a density of negative charges superior to that observed for gram-positive ones (membrane composed by peptidoglycan associated to polysaccharides and teichoic acids (Figure 2).24 Owing to this, Chung et al.39 found more chitosan

understood. The most accepted mechanism is the electrostatic interaction of the positively charged amine groups (−NH3+) at C-2 positions in glucosamine monomers at pH lower than its pKa (∼6.3), and the negatively charged residues at the cell surface of many fungi and bacteria. These interactions consequently result in extensive cell surface alteration and cell permeability, leading to the leakage of intracellular substances, such as electrolytes, UV-absorbing material, proteins, amino acids, glucose, and lactate dehydrogenase.24−27 This in turn causes the interruption of all essential functions of microorganisms and finally leads to the death of these cells. Since the mechanism is based on electrostatic interaction, it is worth noting that when the positive charge density of chitosan strengthens, the antimicrobial activity will increase consequently, as is the case with quaternized chitosan28,29 and chitosan metal complexes.30−32 For chitosan and its derivatives, it is quite reasonable that the antimicrobial activity is dependent on the alkyl chain length due to the change in both conformation and charge density of the polymer, which consequently affect the mode of interaction with the cytoplasmic membrane.24 Several studies have confirmed that the degree of deacetylation (DD) and pH determine the charge density of chitosan and thereby the level of antimicrobial activity. The increase in DD means an increased number of amino groups on chitosan, and lowering the pH increases the antimicrobial effect of chitosan due to a higher proportion of charged amino groups.27,33 In addition, the strength and range of electrostatic interactions between the positively charged amine group in chitosan and negatively charged bacteria is also dependent upon ionic strength of the solution.17 Molecular weight plays an important role in determining the antimicrobial efficiency of chitosan. Therefore, many research groups have studied the molecular weight dependence. Conflicting data have been reported on the effect of molecular weight and on the susceptibility among different bacterial species to chitosan. No et al.34 examined antibacterial activity of chitosan and chitosan oligomers with different molecular weights. Tokura et al.35 investigated the molecular weight dependence of chitosan against E. coli and discovered that the chitosan of average molecular weight 9.3 kDa was stacked on the cell wall and inhibited the growth of E. coli. However, the chitosan of molecular weight 2.2 kDa, which permeated into the cell wall, accelerated the growth of E. coli. Gerasimenko and co-workers36 examined the antimicrobial activity of lowmolecular-weight chitosan with a viscosity-average molecular weight of 5−27 kDa and an equal degree of deacetylation (DD, 85%). It was observed that the increase in chitosan molecular weight leads to a decrease in chitosan activity against E. coli. Zheng and Zhu37 found similar results against E. coli. They suggested that antimicrobial action is related to the suppression of the metabolic activity of the bacteria as lower molecular weight chitosan enters the microbial cell more easily than higher molecular weight chitosan. To address the variation in published studies on the antibacterial activity of chitosans, Mellegard et al.38 studied the antibacterial activity of watersoluble hydrochloride salts of chitosans with weight average molecular weights (Mw) of 2−224 kDa and degree of acetylation of 0.16 and 0.48 against Bacillus cereus, Escherichia coli, Salmonella Typhimurium and three lipopolysaccharide mutants of E. coli and S. Typhimurium. They found that the chitosans with a lower degree of acetylation (FA = 0.16) were more active than the more acetylated chitosans (FA = 0.48), and observed that chitosans of Mw 28.4 kDa, (FA = 0.16)

Figure 2. Gram-positive bacteria cell wall. Adapted with permission from ref 24. Copyright 2010 Elsevier.

adsorption on the cell surface of the tested gram-negative bacteria and hence a higher inhibitory effect than that on the tested gram-positive bacteria. The anionic groups like phosphate and carboxyl, of LPS and proteins in the gramnegative bacteria OM are held together by electrostatic interactions with divalent cations that are required to stabilize the OM. Polycationic antimicrobial agents like chitosan and its derivatives at low pH may also compete with divalent metals for binding with polyanions (Figure 3).24 Chitosan also possesses excellent metal-binding capacity, acts as a water binding agent, and inhibits various enzymes.27 It selectively binds with Mg2+ and Ca2+ ions present in the cell wall, and hence disrupts the integrity of the cell wall or influence the activity of degradative enzymes. The disruption of cell wall integrity has been testified by several methods. Chelation mechanism is generally more efficient at high pH in where the amine groups are unprotonated and the electron pair on the amine nitrogen is available for donation to metal ions. This model was investigated in a recent work by Kong et al.40 who observed that the chelation of divalent cations (which mainly contribute to the stability of gram-negative outer membrane) resulted in destabilization of the outer membrane of E. coli. It was possible to observe and identify under fluoresce spectroscopy the changes in amino acid namely phenylalanine which was located at the surface and inside of the proteins present in the membrane of E. coli. On the other hand; it is also claimed that the positively charged chitosan interacts with cellular DNA of some fungi and bacteria, which consequently inhibits the mRNA and protein synthesis.24,27,41 2.1.2. Chitosan in Antimicrobial Finishing. Due to its antimicrobial property, chitosan provides increasing interest to researchers working on adding functionalities to the textile surfaces; it has been used in wool, cotton, cellulose, and polyester finishing.17 Unfortunately, the weak binding of C



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Figure 3. Schematic representation of gram negative cell wall. Adapted with permission from ref 140. Copyright 1997 Elsevier.

Figure 4. The mechanism of the cross-linking of butantetracarboxylic acid (BTCA) in the presence of chitosan, based on the data reported by Eltahlawy et al.46

chitosan with the textile fibers constitutes the main problems in its application. To address this issue, various cross-linking agents have been used such as glutaric dialdehyde or other formaldehyde reactant-based cross-linkers.42−44 However, the release of toxic and irritant formaldehyde vapors from these substances, besides several other constraints like the reduction of mechanical properties and fiber degradation, have increased the desirability of finding new cross-linking agents, which do not release formaldehyde. Recently, in some studies, polycarboxylic acids, particularly 1,2,3,4- butantetracarboxylic acid (BTCA) and citric acid have been used as safer cross-linking agents between chitosan and cellulose fibers. The hydroxyl functional group interactions with the carboxyl groups of the polycarboxylic acids greatly improve the antimicrobial durability and other fiber properties.43,45−47 The cross-linking mechanism of BTCA with cellulose in the presence of chitosan is shown in Figure 4.46 Likewise, the surface modification of wool fabrics using anhydrides, succinic anhydride (SA), and phthalic anhydride (PA), to graft the chitosan have delivered better antimicrobial results, in an environmentally friendly manner.48 Citric acid and low toxic oxidizing agents, such as potassium permanganate and sodium hypophosphite, have been shown to promote an effective cross-linking between chitosan and textile substrates such as cotton cellulose45 and woolen fabrics49 in an esterification reaction. This greatly improves antimicrobial and antiseptic effects of the treated fabrics. The antimicrobial effect was attributed to the formation of quaternary ammonium salt by the amino groups of chitosan in the treatment which can bind to the negatively charged bacterial surface thereby inhibiting their vital functions.

Nowadays, a safe, healthy and comfortable living environment becomes more important; as a result, special focus on various “green chemistry” approaches by researchers is strongly created. In this sense, UV irradiation has been proposed as a suitable nontoxic procedure for producing durable antimicrobial finished textiles. Alonso et al.50 studied the application of chitosan to previously UV-irradiated cellulose fibers for the preparation of antimicrobial textiles (Figure 5). They utilized citric acid as a cross-linking agent, and sodium phosphate (NaH2PO4) as reaction catalyst and found that treated fiber significantly decreases the spore germination percentage of Penicillium chrysogenum and colony forming units per milliliter for E. coli in comparison to raw cellulose fiber. Recently, chitosan has been applied on cotton and synthetic fabrics by radical UV-curing, and high values of antimicrobial activity were reported by Ferrero and Periolatto.51 Likewise, Periolatto et al.52 developed antimicrobial chitosan finish based on radical UV-curing with 2-hydroxy-2-methylphenylpropane-1-one on cotton and silk fabrics. They found that chitosan UV-curing yields strong antimicrobial properties against E. coli on cotton and silk fabrics at low polymer add-on, with a high wash durability of antimicrobial activity conferred by such treatment. In 2009, chitosan was studied to explore its antimicrobial effect on wool fabrics, in presence of henna (Lawsonia inermis), a natural dye. It was observed that chitosan treatment had a drastic change on the antimicrobial properties of the fabrics. In addition, it resulted in high dye uptake of the fabric.53 The studies performed using chitosan-coated fabrics have demonstrated better inhibition against gram-negative bacteria than gram-positive. This variation could be attributed to their D



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can be manipulated and standardized by controlling the parameters of fermentation. Several fungi, such as Mucor rouxi, Absidia glauca, Aspergillus niger, Gongronella butleri, Rhizopus oryzae, and different species of Basidiomycetes have been explored to upgrade the possible alternative sources of chitosan for biomedical, textile, and other applications.58 Recently, Moussa et al.60 isolated a chitosan-rich fraction termed the acetic acid soluble material (AcSM) from the cell wall of Mucor rouxii DSM-1191. The predominant component of the fractions have demonstrated excellent antibacterial properties, and such fractions have been applied as finishing agents for cotton fabrics. The treated fabric showed high antimicrobial efficacy against Escherichia coli and Micrococcus leteus, with a significant enhancement in other physical properties. Furthermore, they proposed that Mucor rouxii DSM-1191 has the excellent potential to be used for cell wall AcSM production on an industrial scale. Likewise, isolation of chitosan from Aspergillus niger mycelial waste, subsequent to its production of citric acid, has been proven to develop antimicrobial cotton textiles. It was examined that the high antimicrobial activity of such fabrics against both infection causing bacterial (E. coli) and fungal (Candida albicans) pathogens can be retained up to many launderings.61 These studies reveal that fungal chitosan can be explored on an industrial scale, besides these may initiate new research opportunities in the development of bioactive textiles for various medical and hygienic applications. 2.1.4. Chitosan DerivativesDo They Really Make Sense? The use of chitosan to impart the antimicrobial property to textiles has been the focus of textile antimicrobial finishing over the last few decades. In fact, it has been described that chitosan can be used as a multifunctional textile finishing agent, because its antimicrobial activity can be combined with other functions, such as dyeing improvement, antistatic property, and deodorant activity.17 However, in its native form, the loss of biological activity and low solubility at neutral or alkaline conditions, in addition to its poor durability on textiles due to poor adhesion are the main problems, which hinder its use as an antimicrobial textile finishing agent. To overcome this, a number of chitosan derivatives that are soluble in water over a wide pH range have been synthesized and used as antimicrobial agents on textiles. These include N(2-hydroxy) propyl-3-trimethylammonium chitosan chloride,62 chito-oligosaccharide, N-p-(N-methylpyridinio)methylated chitosan chloride and N-4-[3-(trimethyl-ammonio) propoxy] benzylated chitosan chloride.2 Kim et al.62 applied N-(2hydroxy) propyl-3-trimethylammonium chitosan chloride (HTCC) (Figure 6a) as an antimicrobial agent to cotton fabrics and observed a lower minimum inhibition concentration (MIC) against Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli compared to that of native chitosan; however, the imparted antibacterial activity was lost on laundering. By using BTCA cross-linker, they found that the antibacterial activity of HTCC was maintained over 90% even after being exposed to 20 consecutive laundering cycles. The imparted laundering durability of antimicrobial cotton fabrics was because of the introduced covalent bond formation between the cellulose molecule and HTCC via the esterification of BTCA catalyzed by sodium acetate. Likewise Montazer and Afjeh63 used the very same derivative of chitosan (HTCC) to achieve a multifunctional finishing on the cotton fabric in the presence of three cross-linkers namely glutaraldehyde (GA), citric acid (CA), and butantetracarboxylic acid (BTCA). They

Figure 5. Reaction of chitosan with cellulose using citric acid, NaH2PO4 and UV-irradiation.

differences in cell wall structure and outer membrane permeability. The effectiveness of antimicrobial functionalization on textiles has been shown to be dependent upon the pretreatment way and chitosan application methods.54 In a recent study, Ibrahim et al.55 claimed that a new environmental friendly treatment using the incorporation of chitosan and other bioactive ingredients into pigment pastes results in the development of antibacterial cellulose fabrics. They reported that the antibacterial activity by the modified pigment prints against S. aureus and E. coli was maintained for more than 20 washings. The printability and antibacterial activity was also found to be affected by the type of bioactive ingredient, binder, pigment, and substrate. 2.1.3. Role of Chitosan from Different Sources. Chitosan is obtained by the deacetylation of chitin from the exoskeleton of marine crustaceans, such as crabs, shrimps, prawns, lobsters, and the cell walls of some fungi (Figure 1). Currently, it is most often produced by deacetylation of chitin from exoskeleton of shellfish, because these are abundantly available, and have been abandoned as waste products by the worldwide seafood companies. Teli and Sheikh56 has reported the extraction of chitosan from shrimp shells waste and its use in the development of antibacterial rayon. The antibacterial rayon fabric portrayed promising results against gram positive and gram negative bacteria with a high wash durability. The high durability in antibacterial activity by the lignocellulosic rayon fiber was maintained by the use of acrylic acid as a grafting agent. It was demonstrated that acrylic acid has high ability to react with amine groups of chitosan. Nowadays, the commercial production of chitosan by the deacetylation of chitin from crustaceans appears to have limited potential for industrial acceptance. This fact is due to their seasonal and limited supply, requirement of harsh chemicals, such as concentrated NaOH, either in alcohol or aqueous solution for deacetylation, and their inconsistent physicochemical properties.57 On the other hand, the recent advances in fermentation technology suggest that the cultivation of fungi can provide an alternatives to produce chitosan because of many advantages,58,59 such as abundant availability, no need of any aggressive treatment, and physiochemical properties that E



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Figure 6. Structures of chitosan derivatives used in antimicbial finishing: (a) N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride; (b) Oacrylamidomethyl-N-[(2-hydroxy-3-trimethylammoniu) propyl] chitosan chloride; (c) N- carboxymethyl derivatives of chitosan; (d) O-quaternizedN,N-biethyl-N-benzylammonium chitosan chloride; (e) O-quaternized-N-chitosan Schiff bases; (f) O-quaternized-N-benzyl-chitosan; (g) Cationic hyperbranced PAMAM-chitosan.

found that BTCA can provide a more efficient finish durability than CA and same as that of GA, but without yellowing and unpleasant odor. The HTCC derivative was also used by Bu and co-workers to modify cotton fabrics for improving aqueous pigment-based inkjet printing and antibacterial properties. The results indicated that at the concentration of 0.8%, the

inhibitory rate of HTCC against Staphylococcus aureus and Escherichia coli was more than 95%.64 Interestingly, the reactivity of the HTCC has been improved by the introduction of functional acrylamidomethyl groups to the primary alcohol groups by Lim and Hudson.65 They reported that such a reactive chitosan derivative can be covalently bonded to textile F



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fibers having nucleophilic groups, especially to cellulose. In a subsequent publication, the same group studied the application of their synthesized fiber reactive chitosan derivative Oacrylamidomethyl-N-[(2-hydroxy-3-trimethylammonium)propyl] chitosan chloride (NMA-HTCC) (Figure 6b), as an antimicrobial textile finish for cotton fabrics and discovered that the antimicrobial activity against Staphylococcus aureus was maintained over 99% even after being exposed to 50 consecutive home laundering cycles.7 On the other hand, the cotton treated with native chitosan in the same study showed relatively low antibacterial activity (about 70%) only after 10 home launderings. They also reported that the antimicrobial function of NMA-HTCC treated fabric arises from attractive interactions between the quaternary ammonium groups on the fabric and the negatively charged cell membrane of the microbe. The slight decrease in the antibacterial activity after laundering was attributed to the fact that anionic groups of the surfactant present in the detergent interact ionically with the cationic groups of NMA-HTCC and reduce the chance of NMA-HTCC to interact with negatively charged bacterial membranes. The results from their both studies also showed that antibacterial activity against Staphylococcus aureus increases after one laundering than before laundering. It could be due to the high amount of protonated chitosan on the fabric before laundering, which may coat the bacterial cell surface and thus prevent the leakage of intracellular components. More recently, Gupta and Haile66 synthesized carboxymethyl derivatives of chitosan by carboxymethylation (Figure 6c), with a view to develop a multifunctional finish on cotton. They observed very high inhibitory activity of such cotton fabrics against bacterial pathogens with improved wash durability. ElShafei and co-workers67 also reported synthesis of carboxymethyl chitosan by chemical reaction of chitosan with monochloroacetic acid under alkaline conditions, followed by its treatment on precationized cotton using a cold-batchmethod (Figure 7). It was interesting to observe that the

groups with 2,3-epoxypropyltrimethylammonium chloride and benzaldehyde as modifiers through formation of Schiff base, reduction, N-methylation and O-quaternization for producing durable antimicrobial finished cotton fabric. They found that synthesized derivatives O-quaternized-N,N-biethyl-N-benzylammonium chitosan chloride (O-QCTS-DEBn) (Figure 6d), O-quaternized-N-chitosan Schiff bases (O-QCTSS) (Figure 6e) and O-quaternized-N-benzyl-chitosan (O-QCTS-Bn) (Figure 6f) in the presence of citric acid as a cross-linking agent display strong antibacterial activities and fairly good durability. Following the application of the derivatives on the cotton fabric, the O-QCTS-DEBn derivative exhibited particularly high activity due to its high cationic charge density (two cationic charges of ammonium salt), which is known to act on the bacterial cell membrane, making the cell membrane lose it barrier function and finally the death of bacteria. It was also found that the O-QCTSS derivative at a concentration of 3% made the antibacterial rate reach nearly 100% against both gram-positive and gram-negative bacteria. Its antibacterial activity arises because of the presence of two different antimicrobial groups such as a quaternary ammonium group and a Schiffs base group in its structure. Furthermore, the OQCTS derivative made the finished fabric durable for 20 times of home laundering due to its lower water solubility than that of the other two derivatives. Klaykruayat et al.69 grafted cationic hyperbranched dendritic polyamidoamine (PAMAM), a dendrimer analogue to the reactive amino group of chitosan (Figure 6g). The modified chitosan with PAMAM after application onto cotton fabrics was highly active against microbes, in particular bacterial species, even at a near neutral pH. However, there was no antibacterial mechanism suggested for PAMAM-modified chitosan-fiber, but it is possible that it was due to the cationic character. In general, since the application of chitosan derivatives on the textile surfaces, a new area has developed in the realm of textile finishing. In addition to overcoming the limitations of native chitosan, further research may be focused on the use of more efficient and novel agents that can impart multifunctional properties to the finished fabrics before such technologies can be adopted on a large practical scale. 2.1.5. ChitosanMetal Complexes in Antimicrobial Textiles. Chitosan can form coordinate or chelate complexes with metal ions like copper, zinc, iron, and cobalt, etc. Some of these complexes are reported to have potent antimicrobial activity.70 This complex forming ability of chitosan with transition and other heavy metal ions have portrayed manifolds advantages, in textile applications. Chitosan-metal complexes have successfully been used in the development of antimicrobial fibers. Gouda and Keshk71 studied the feasibility of using metal such as zirconium, titanium, and chitosan films on cotton fabrics to impart multifunctional properties. The resultant fabric showed antibacterial activity in addition to the UV protection properties. Furthermore, it was shown that inhibitory activity of treated cotton fabrics depends upon the nature of metal oxide. Nowadays, with the consumer’s enhanced awareness about the contaminations associated with food products, there has been a growing need for alternative safe food packaging substrates. In this context, antimicrobial jute fibers for packaging applications based on chitosan and chitosan−metal complexes have delivered promising results.31 Therefore, a search for more innovative ways, and further research on the chitosan-metal complexes, may result in high value utilization of these antimicrobial fibers for food preservation applications.

Figure 7. Ionic cross-linking of cationized cotton with carboxymethyl chitosan. Data is based on El-Shafei et al.67

carboxymethyl chitosan was more effective in the presence of cationized cotton against Escherichia coli DSMZ 498 and Micrococcus luteus ATCC 9341 strains. The possible mode of action was attributed to the polycationic nature of carboxymethyl chitosan in addition to the permanent positive charge raised from the cationized cotton, both interact with the negative charged residues present at the cell wall of bacteria leading to alteration of the cell wall permeability and consequently, interfere with the bacterial metabolism and result in the death of cells. In 2011, Fu and his co-workers68 synthesized three watersoluble chitosan derivatives bearing dual-antibacterial functional G



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2.2. Cyclodextrins (CD). Cyclodextrins (CDs) are a family of cyclic oligosaccharides; they are produced during enzymatic degradation of starch by the enzyme, namely cyclodextrin glycosyltransferase. CDs are composed of alpha-1,4-linked glucopyronase sub units, the most commonly available types are α-CD, β-CD, and γ-CD having 6, 7, and 8 glucopyronase moieties, respectively. These substances, and in particular β-CD (Figure 8) have shown huge potential in textiles, because of

ation strength and longevity of host−guest complexes mainly depends upon the size of incoming guest molecule and the type of interaction such as hydrogen bonding, van der Waals interaction, charge transfer and hydrophobic. 2.2.1. Inclusion with Antimicrobial Agents. Cyclodextrin inclusion complexes can be formed in solutions, in a solid state as well as when cyclodextrins are linked to various surfaces. They can act as permanent or temporary hosts for small molecules. Inclusion in cyclodextrins exerts a profound effect on the physicochemical properties of guest molecules which are not achievable otherwise.74 The principal advantages of natural cyclodextrins as carriers for biologically active guests, such as drugs, insect repellents, and antimicrobial agents, etc., are as follows:75 • well- defined chemical structure, yielding many potential sites for chemical modification or conjugation • availability of cyclodextrins of different cavity size • low toxicity and low pharmacological activity • certain water solubility • protection of included/conjugated drugs from biodegradation • controlled release of drugs and flavours. The release of enthalpy-rich water molecules from the cavity of CDs is the main driving force of complex formation. It has been proposed that water molecules are displaced by more hydrophobic guest molecules present in the solution to attain an apolar−apolar association and decrease of cyclodextrin ring

Figure 8. β-Cyclodextrin.

their ability to selectively form inclusion complexes with other substances72,73 through host−guest interactions. The complex-

Table 3. Some Antimicrobial Cyclodextrin Guest Molecules Used in Antimicrobial Textile Modifications

H



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strain resulting in a more stable lower energy state.76 Some of the antimicrobial agents used for inclusion compounds on textiles are given in Table 3. 2.2.2. CyclodextrinRole in Functional Finishing of Textiles. The toxicological studies have shown that CDs do not give rise to skin irritation, skin sensation, or mutagenicicity.77 In the USA α-, β-, and γ-CDs have obtained the GRAS list (FDA list of food additives that are “generally recognized as safe”) status,78 and since 2000, Germany has also approved the use β-CD as a food additive.79 Owing to these facts they are increasing being researched all around the globe as new auxiliaries for textile finishing. Several studies have reported that textiles containing CDs fixed on their surfaces can be used for fragrance release (odoring in laundry cycles),80 odor adsorption (sheets and personal clothing), controlled release (antibacterial, fungicide, or insect repellent finishing),14,72,81 UV protection,82 and stabilization of active ingredients. It is evident from the architecture of CDs that they cannot form direct covalent bonds with textile fibers; however, this problem has been solved by the grafting of CDs using polycarboxylic acid (nonformaldehyde cross-linking agents) and other binding agents.83−85 These properties enable them to be used in a wide variety of medical, technical, and geotextiles products. Bajpai et al.86 have described antibacterial properties of fabrics obtained by a novel method, based on the grafting of CD loaded with silver(I) ions onto cellulose backbone of cotton fabrics using citric acid as a cross-linker. It was observed that incorporating silver(I) ions into the cavity of CDs depicts excellent antibacterial action with slow release mechanism after application onto the fabric. The results showed that silver(I) ions can be conveniently loaded into CD cavities for their use as slow release devices for antimicrobial applications. In the year 1996, the first reactive cyclodextrin derivative, namely monochlorotriazinyl-β-cyclodextrin (MCT-β-CD) having a monochlorotriazinyl group as a reactive anchor was introduced for permanent surface modification of textiles.73 Recently, cellulase enzyme treatment has been done to raise the grafting yield of MCT-β-CD on organic cotton. The inclusion of antibacterial agent thymol on biopolished MCT-β-CD grafted fabric has shown high efficiency against Staphylococcus aureus and Escherichia coli. Durability to the antibacterial property was maintained up to several repeated washing cycles by the treatment.87 Wang and Cai.88 reported incorporation of miconazole nitrate (antibacterial agents) into the β-CD cavities permanently bound to cellulose fabrics. The optimal reaction conditions for grafting of β-cyclodextrin to cellulose fabrics were found to be MCT-β-CD 60−100 g/L, catalyst Na2CO3 50−60 g/L, the reaction temperature of 150−160 °C and the reaction time 5−8 min. According to their findings, the MCTβ-CD grafted cellulose retained the antibacterial abilities more than 70% even after washing 10 cycles, while the antibacterial activity of the unmodified textile was almost lost. Likewise, Cabrales et al.89 investigated the grafting of monochlorotriazinyl-β-cyclodextrin (MCT-β-CD) onto cotton fabrics followed by their inclusion formation with triclosan (a powerful antibacterial agent). They observed excellent antibacterial results. Abdel-Halim et al.90 used linear electron beam radiation to graft glycidyl methacrylate/monochlorotriazinyl-β-CD mixture onto cotton fabrics. They loaded the grafted fabrics with a commercially available antimicrobial agent (chlorohexidin diacetate). Grafted cotton loaded with an antimicrobial agent was found to show very good antimicrobial activity in contrary

to control and grafted fabrics not loaded with antimicrobial agent. The results reported in this study demonstrate also that the GMA/MCT-CD grafted fabrics loaded with antimicrobial agent retain good durability toward antimicrobial activity after five washings. This is due to the cavities present in cyclodextrin moieties which are used as a host for the antimicrobial agent, resulting in long lasting antimicrobial efficiency. Nowadays, other CDs derivative have also been designed, such as with bifunctional moieties and have been introduced into textile applications.91 CDs have the potential to act as reducing and stabilizing agents for green nanoparticles synthesis; nanoparticles hold the current increasing interest of textile researchers.92 Furthermore, CDs have the unique ability to reversibly complex with a range of nanoinorganic materials, and hence can carry and stabilize them on the fabric surfaces.93 On the basis of these facts, CDs represent a great potential to be used in novel applications, particularly in the area of medical and hygienic textiles. Therefore, these may provide immediate opportunities for developing novel functional textiles in the near future. 2.3. Sericin Protein. Sericin is a natural macromolecular protein derived from silk worm, Bombyx mori. It generally constitutes between 20 and 30% of silk protein and ranges in size from 65 to 400 kDa. Sericin envelopes the fibroin fiber which forms the main silk filament content with successive sticky layers that help in the formation of a cocoon. Being an amorphous glue-like substance, it helps in the cohesion of the cocoon by gluing silk threads together.94,95 Because of its several inherent properties, such as biocompatibility, biodegradability, antibacterial, UV resistance, oxidative resistance, and moisture absorption ability, sericin has become an appealing product for its versatile applications in different fields, including pharmaceuticals, cosmetics, and textiles.96 Generally, the sericin protein has been studied to increase the functional properties of many synthetic fibers.97,98 Some recent studies have also demonstrated its potential for application on natural fibers. Although, sericin has not really shown any antimicrobial properties on textiles, it has been suggested that silk sericin may act as a functional agent for cotton and wool fabrics.99 Rajendran et al.100 successfully applied silk sericin as an antibacterial finishing agent onto cotton fabrics. It was observed that the resultant fabric displays a reduction rate of 89.4% and 81% against S. aureus and E. coli, respectively. They concluded to increase the durability of the finish in order to retain the antimicrobial property by using cross-linking agents in the near future. More recently, Doakhan and co-workers101 prepared sericin/TiO2 nanocomposite as a new finishing agent for cotton fabrics by extraction of sericin from raw silk using hot water followed by dispersion of nano-TiO2 in its solution. They found that the antibacterial activity of the finishing against Staphylococcus aureus was more effective than Escherichia coli. They claimed laundering durability of the antimicrobial treatment up to 40 cycles by using polycarboxylic acid crosslinking agents. On the basis of their findings, the same authors proposed that the antibacterial activity of sericin could originate from its polycationic nature, conveyed by its positively charged NH3+ groups at acidic pH. The polycationic nature might be a fundamental factor contributing to its interaction with the negatively charged bacterial cell membrane, causing leakage of proteinaceous and other intracellular constituents, ultimately resulting in the death of bacteria. Low molecular weight sericin could also penetrate the cell wall of bacteria, complex with anionic materials in the cells, inhibit the normal physiological I



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Figure 9. Alginate consisting of 1,4-linked α-L-guluronic acid and ß-D-mannuronic acid residues.

Figure 10. Hyaluronan.

activities of bacteria, and finally may lead to the death of these cells. Despite the promising use of sericin in value-added products in the biomedical, pharmaceutical, cosmetic, food, and textile industries,95 at present sericin is mostly discarded in silk processing wastewaters. Recovery of silk sericin from degumming liquor or cocoons could provide significant economic and social benefits. Unfortunately, an extensive literature survey revealed that there are only relatively few specific and objective research studies to support the many claims made about sericin and sericin modified materials. In view of its many beneficial effects, particularly the antimicrobial activity, in-depth research needs to be carried out on its antimicrobial mode of action in addition to the stability, biocompatibility, and other functional characteristics of its finished products. Therefore, it can be concluded that use of sericin for antimicrobial modifications are in the phase of basic investigations. Nevertheless, sericin protein also has recently revealed its potential to be used as a capping agent for nanoparticles synthesis. The synthesized silver nanoparticles were further used in the development of antimicrobial silk fabric.102 In this context, sericin protein provides an evidence to satisfy the current consumer’s demand for natural bioactive textiles, which have potential applications in textile industry, hospital sterilization, and environmental cleanup. 2.4. Other Biopolymers. With the recent advancement in fiber technology, a widespread interest has emerged in the development of bioactive textiles using other biopolymers as well, including alginate (Figure 9), collagen,103 and hyaluronan (Figure 10). There have been several reports about their versatile applications in the biomedical field.104 2.4.1. Alginate Fibers in Wound Dressing. Alginate fibers due to their recently discovered ion-exchange and gel-forming abilities have been extensively used in wound dressing

applications.105,106 Moreover, alginate fibers are particularly useful due to their excellent biocompatibility, nontoxicity, and potential bioactivity, and thus may offer many advantages over traditional cotton and viscose gauzes.107 Alginate fibers, typically as insoluble calcium salt, upon contact with wound exudates, may cause an exchange of sodium ions in the wound exudates with calcium ions in the fiber.108 As a result of the ion exchange between the calcium ions in the fiber and the sodium ions in exudates, the fibers are transformed from waterinsoluble calcium alginate into water-soluble sodium alginate, resulting in the absorption of a large amount of water by the fibers. Such gelation provides the wound with a moist environment, which promotes healing and leads to a better cosmetic repair of the wounds.109 Owing to their low antibacterial activity, alginate fibers can be incorporated with broad-spectrum antimicrobial agents to enhance the overall antimicrobial activity, and thus may form highly absorbent alginate wound dressings having antimicrobial properties. Qin.110 observed that the silver-containing alginate fibers can maintain the white physical appearances while providing a sustained release of silver ions when in contact with wound exudates. Fan and co-workers107 prepared antibacterial fibers from a mixture of alginate, carboxymethyl chitosan and silver nitrate. Carboxymethyl chitosan was found to improve the water-retention of the blend fibers and silver nitrateenhanced activity against gram-positive S. aureus. Knill et al.111 studied the modification of alginate with hydrolyzed and unhdrolysed chitosan. Their results showed that the hydrolyzed chitosan could penetrate the alginate fibers and had the ability to provide a slow release/leaching of antibacterial active components (presumably hydrolyzed chitosan fragments). It is interesting that the hydrolyzed chitosan fragmenting into base alginate fibers perhaps via ionic interactions (Figure 11) results in some reinforcement and thus increases the tensile properties of the fibers for their potential applications in wound J



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focus of researchers. The ecological and economic restrictions imposed on the textile industry have led to the development of modern strategies based on environment friendly approaches. Nowadays, surface modification of polymer surfaces is considered one of the most promising treatments. Surface modification increases the functional group accessibility of the fiber without affecting other bulk properties. Some of the important surface modification treatment methods (Table 4) adopted recently are discussed below. 3.1. Plasma Treatment. Plasma treatment is a novel and an ecofriendly strategy for the development of durable multifunctional textiles. Plasma modifications are gaining popularity in the textile industry due to their numerous advantages such as low energy, no chemical requirements, and green approach over other conventional wet processing techniques. In plasma treatment, the polymer/fiber surfaces are treated with the excited and energetic plasma species (ions, radicals, electrons and metastables). The plasma introduces new hydrophilic groups into the structure, possibly due to oxidation and etching reactions, and thus may enhance functional properties such as wettability, water repellency, dyeability, and effective antimicrobial properties.116,117 The structural changes undergoing in the polymer or fiber surface has been illustrated by using advanced instrumental analysis such as FT-IR, SEM analysis, XPS, XRD, EPR, etc. Some recent studies have shown that the selection of plasma gas such as Ar, N2, O2, NH3, CO2), in addition to the operating parameters may result in various functional treatments.118 Zemljic et al.119 has reported improvement of chitosan adsorption on cellulosic fibers after treatment with oxygen plasma. The treatment resulted in high antimicrobial activity of the cellulosic fibers. Use of open air plasma has been investigated to graft chitosan polymer onto nylon textiles. It was observed that air plasma activation at a speed of (26/min) enhances the grafting of chitosan followed by improvement in antibacterial activity.120 Chang et al.121 studied the properties of polyester fabrics grafted with chitosan oligomers/polymers after being activated by atmospheric pressure and discovered that surface of fabrics activated by atmospheric pressure plasma for 60 to 120 s and grafted with chitosan oligomers results in high antibacterial efficiency. Uygun et al.122 reported the use of RF hydrazine plasma for the modification of chitosan nanopowders. It was shown that RF hydrazine plasma had a drastic effect on antibacterial action of chitosan against gram-positive strains. Use of low-temperature plasma treatment has also been investigated in the natural dyeing of textiles. The effect of lowplasma treatment in the presence of chitosan as a mordant has shown remarkable results and thus can be used as a substitute for metal mordants.123 It has also been examined to impart

Figure 11. Ionic interaction between alginate fibers and chitosan as proposed by Knill et al.111

dressings. In addition, alginate containing dressings have been demonstrated to activate macrophages within the chronic wound bed and generate a pro-inflammatory signal which may initiate a resolving inflammation characteristic of healing wounds.112 There is not much literature available on the use of these biopolymers in antimicrobial textiles. However, the role of alginate in bioactive textiles has been documented by Gorensek and Bukosek113 and Kim et al.114 Furthermore, in recent years several attempts have been made to develop novel products from these natural polysaccharides. Synthesis of novel amphiphilic alginate esters (Alg-C8, Alg-C12, or Alg-C16) graft copolymers has been reported by Yang et al.115 These alginate esters are expected to be used as protein drugs and as a carrier of hydrophobic drugs. They might offer a natural safeguard against microbial pathogens and subsequently with the advancement of innovative technologies might prove their way in the development of bioactive textiles. On the basis of the current widespread potential applications of natural biopolymers, easy availability of raw materials, and simple processing technologies, they can be explored onto the textile materials as a viable option for achieving novel functional properties. Anyway, antimicrobial textiles based on the biopolymers discussed in this review have shown energetic and environmental advantages, in comparison to the synthetic antimicrobial agents. The major drawback is their poor durability on textile materials due to the lack of strong bonding forces. However, the extensive R&D to overcome such adhesion problems in this area of biopolymer application is underway and currently there are a number of strategies employed to overcome these shortcomings.

3. ECOFRIENDLY PRETREATMENT TECHNOLOGIES FOR FUNCTIONAL FINISHING OF TEXTILES In recent years, the development of efficient green chemistry methods for functional finishing of textiles has become a major

Table 4. Summary of the Advantages and Disadvantages with Different Surface Modification Methods method

advantages

disadvantages

wet chemical

does not require any special equipment; can penetrate three-dimensional substrates

UV irradiation

enhances antimicrobial activity; increases durability; imparts other functional properties; activates fiber surface for enzyme immobilization

plasma treatment

low environmental impact method; no waste production; causes or introduces new chemical groups into the fiber structure; increases efficacy of antimicrobial properties; introduces dirt and water repellence; suitable for both natural as well as synthetic fibers; saves energy and time high dye uptake; improves shrink resistance; ecofriendly nature; need mild experimental conditions

enzyme treatment

K

nonspecific; environmental pollution; unsuitable for large scale industrial application can affect treatment consistency; affect optical properties of polymer needs careful handling to prevent detrimental action onto the substrate; high cost substrate specific; low binding



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cotton fabrics imparts excellent antibacterial and UV protection properties. More recently researchers working in the field of adding functionalities to textile surfaces are investigating the possible applications of biopolymers in the form of nanoparticles. Coating the surfaces of textiles or incorporating the fibers with biopolymers in the nano form is the latest approach for the production of highly active textiles. Biopolymers in the form of nanoparticles display unique properties, such as higher stability, improved antimicrobial action, and better affinity for the fabrics. Consequently, a dramatic improvement in the finish durability on textiles has been achieved.138,139 Recent studies have also demonstrated that the antibacterial methanolic extract of the leaves of Ocimum sanctum can be loaded inside the sodium alginate chitosan nanoparticles. The use of these loaded extracts for the finishing of cotton fabric showed excellent antibacterial and wash durability results.9 Therefore, it can be predicted that biopolymer-based nanoparticles can improve functional, environmental, and economical benefits in the development of antimicrobial textiles. Meanwhile, such promising results warrants exploitation of more such biopolymer-based nanoparticles with distinct functionalities, and in future may provide innovative ways to develop new functional textiles.

remarkable antimicrobial properties to cotton fabrics in the presence of cellulase enzyme.124 Demir et al.116 has suggested the use of argon and air plasma for modifying the knitted wool surface in order to enhance its adsorption capacity for chitosan and hence to improve antimicrobial properties. 3.2. Enzyme Treatment. In recent years, the enzymes socalled biological catalysts with polypeptide chains have been used in textile applications in cost-effective and environmentally sensitive ways.125 The use of enzymes has been documented to improve some physical properties of the fibers for better adhesion.126,127 Considering special advantages and high potentialities of the application of enzymes in the textile industry, especially for producing high value-added textiles, this paper reviews the application of enzymes for antibacterial modification of textiles. Recently the immobilization technique, which is based on enzymes, has been incorporated in the textile industry to increase the activity and to build new functionalized textile products. Wang et al.128 has immobilized lysozymes onto wool fabrics. The immobilization of the enzyme was done at 40 °C and pH 7.0 for 6 h with 5 g/L lysozyme concentration in order to impart a better antibacterial effect to wool fabric. Various industrial enzymes such as α-amylase, alkaline pectinase, and laccase enzymes have been incorporated onto ester-cross-linked as well as Cu-chelated cotton fabrics for developing high durable antimicrobial fabrics.129 Hebeish et al.47 has reported the preparation of multifinishing formulations consisting of BTCA and chitosan having different molecular weights by chitosanolysis using pectinase enzyme, and impregnating them on the cotton fabrics. The resultant cotton fabrics showed high antimicrobial activity with durability up to 10 washings. To explore the future potential applications of enzymes in antimicrobial textiles, it is essential to understand the dosage and efficacy of the enzymes, as well as their interaction with the textile substrates.

5. CONCLUSION The current efforts in the development of new technologies for implementation of sustainable biopolymers in the real market of antimicrobial textiles do not guarantee economical viability yet. Nevertheless, application of these agents in the development of bioactive textiles is a promising prospect. Further research is yet to be carried out to translate the potential of biopolymers into industrial reality. The promising results can boost additional studies oriented to the search of new sources, cost-effective extraction methodologies, and innovative application methods that could provide alternatives to toxic synthetic antimicrobial agents. If significantly improved, sustainable biopolymers may minimize the negative effects of synthetic agents in the textile industry. Likewise, these bioactive textiles may be able to fulfill the consumer’s desire for a healthier and a more productive lifestyle by reducing stress and promoting comfort and relaxation in the near future.

4. BIOPOLYMERS AND NANOTECHNOLOGYTHE FUTURE PROSPECT In recent years, nanotechnology has been booming in many areas, including material science, mechanics, electronics, optics, medicine, plastics, energy, electronics, and aerospace. Nowadays, it is playing an extraordinary role in the functional finishing of textiles.130 It has been sought to improve existing material performances and develop fibers, composites, and novel finishing methods. The literature shows that nanoparticles, due to their diverse functions, may impart flame retardation, UV-blocking,131 water repellence,132 self-cleaning,130 and antimicrobial properties79 to the textile fibers. From an ecological point of view, the introduction of green chemistry principles into nanotechnology is one of the hot topics in nanoscience research today. Up to date, several studies have been carried out dealing with the use of biopolymers such as chitosan,133 hyaluronan,134 starch,135 and cyclodextrin,92 as both the reducing and stabilizing agents for nanoparticle formation. Abdel-Mohsen and co-workers136 reported synthesis of core−shell nanoparticles by using silver nanoparticles as core and chitosan-O-methoxy polyethylene glycol as shell. They suggested that such nanoparticles can be used for the development of multifunctional cotton fabrics. Likewise, ElShafei and Abou-Okeil.137 developed a simple method to prepare nano-ZnO by using ZnO/carboxymethyl chitosan bionanocomposites system for their application to textiles. Their finding made evident that coating of the same on the

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AUTHOR INFORMATION

Corresponding Author

*Tel.: +91-9350114878. E-mail: faqeermohammad@rediffmail. com. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Financial support provided by University Grants Commission, Govt. of India; through Central University Ph.D. Students Fellowship (Shahid-ul-Islam) and BSR Research Fellowship in Sciences for Meritorious Students (Mohammad Shahid) is highly acknowledged.

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