green chemistry approaches to develop antimicrobial textiles based on sustainable biopolymers—a...

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Green Chemistry Approaches to Develop Antimicrobial Textiles Based on Sustainable BiopolymersA 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 dierent 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 nishing of textile materials. The application of biopolymers, along with the recent impact of various green chemistrystrategies, on the antimicrobial properties of textile bers is reviewed. It also includes a brief review on dierent green pretreatment technologies used for the surface modication of textiles with a special reference to their inuence on antimicrobial properties. Finally, the advantages and future studies regarding the use of nanotechnology in the antimicrobial nishing 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 eects on all forms of life. These may result in oensive 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. 46 As a con- sequence of their importance, a number of chemicals have been employed to impart antimicrobial activity to textile materials. These chemicals include inorganic salts, organometallics, iodo- phors (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 publics enhanced awareness of eco- safety, 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 eects 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 nishers has now become increasingly demanding and has strengthened the interest in alternative ecofriendly and biodegradable nishing 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 modications. A brief list of the sources and important characteristics of some natural biopolymers explored on the textile substrates are summarized in Table 2. Generally, the natural polysaccharides used for the functional nishing 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 nishing of textiles. This is followed by a focus on some recent developmental works pertaining to antimicrobial nishing of textiles using various green chemistryapproaches 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 Table 1. Possible Toxic Eects of Some Commercially Available Synthetic Antimicrobial Agents on Human Being synthetic agent toxic eect reference quaternary ammonium compounds respiratory irritation, nausea, skin and eye irritation 141 silver argyria, contact dermatitis, mucous membrane irritation 142 zinc pyrithione developmental and neurotoxicity 143 synthetic azo dyes carcinogenic 8 triclosan endocrine disrupter, skin and eye irritation 144,145 Review pubs.acs.org/IECR © XXXX American Chemical Society A dx.doi.org/10.1021/ie303627x | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX

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Green Chemistry Approaches to Develop Antimicrobial TextilesBased on Sustainable BiopolymersA ReviewShahid-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 inthe discovery of new health and hygiene-related products for the well being of mankind. Among the possible approaches initiatedby the textile industry, the use of low-environmental impact technologies- based on sustainable biopolymers- presents a novelpossible avenue for large scale development of bioactive textiles. The purpose of this article is to review the information on therole 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. Theapplication of biopolymers, along with the recent impact of various “green chemistry” strategies, on the antimicrobial propertiesof textile fibers is reviewed. It also includes a brief review on different green pretreatment technologies used for the surfacemodification of textiles with a special reference to their influence on antimicrobial properties. Finally, the advantages and futurestudies regarding the use of nanotechnology in the antimicrobial finishing of textiles is also outlined.

1. INTRODUCTIONTextile substrates, especially of natural origin, can easily becolonized by high numbers of microbes, because these providethe ideal conditions such as moisture, temperature, oxygen, andnutrients required for their growth.1,2 Microbial pathogens havelethal effects on all forms of life. These may result in offensiveodors, color degradation, cross-infection, or transmission ofdiseases, allergic responses and deterioration of textiles.3 Tocombat these adversities it is highly desirable to impartantimicrobial 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 con-sequence of their importance, a number of chemicals have beenemployed to impart antimicrobial activity to textile materials.These chemicals include inorganic salts, organometallics, iodo-phors (substances that release iodine slowly), phenols andthiophenols, onium salts, antibiotics, heterocyclic compoundswith anionic groups, nitro compounds, urea and relatedcompounds, formaldehyde derivatives, amines and syntheticdyes.2,7 However, with the public’s enhanced awareness of eco-safety, there has been considerable debate about their use,because majority of such agents are toxic to humans and are notenvironmental friendly.3,8,9 The possible toxic effects producedby some of these agents on human beings are listed in Table 1.In addition, another big concern is that some of these agentsare being increasingly resisted by microbial pathogens.2

Therefore the role of textile finishers has now becomeincreasingly demanding and has strengthened the interest inalternative ecofriendly and biodegradable finishing agents.In view of these ecological and environmental concerns,

natural biopolymers are the only suitable and renewableproducts that have the potential to become a key resource inthe development of sustainable bioactive textiles.10 Recently,the use of natural biopolymers has been preferred for textilemodifications. A brief list of the sources and important

characteristics of some natural biopolymers explored on thetextile 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 ofenvironmentally benign technologies are rapidly expanding fortheir versatile applications in the textile industry. Hence, themajor objective of this review is to explore the role ofsustainable biopolymers in antimicrobial finishing of textiles.This is followed by a focus on some recent developmentalworks pertaining to antimicrobial finishing of textiles usingvarious “green chemistry” approaches in order to provide safeand novel antimicrobial textiles for aesthetic, hygienic, andmedical applications in the near future.

Received: December 29, 2012Revised: March 11, 2013Accepted: March 17, 2013

Table 1. Possible Toxic Effects of Some CommerciallyAvailable Synthetic Antimicrobial Agents on Human Being

synthetic agent toxic effect reference

quaternary ammoniumcompounds

respiratory irritation, nausea, skin andeye irritation

141

silver argyria, contact dermatitis, mucousmembrane irritation

142

zinc pyrithione developmental and neurotoxicity 143synthetic azo dyes carcinogenic 8triclosan endocrine disrupter, skin and eye

irritation144,145

Review

pubs.acs.org/IECR

© XXXX American Chemical Society A dx.doi.org/10.1021/ie303627x | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

2. BIOPOLYMERSAN EMERGING ALTERNATIVESOLUTION

Over the past few years, there has been enormous attention onthe use of biopolymers in different application fields.Biopolymers derived from agricultural feed stock or marinefood resources have several advantages such as abundantavailability, biocompatibility, and biodegradability, and there-fore ecological safety.11

In textile finishing, incorporation of natural polysaccharides isa new concept, which has been introduced in recent years. Thiswas brought about by the recognition that their uniqueproperties can be applied to different areas of applications suchas deodorant,12 aroma,13 insect repellent,14 fire retardant,15 UVblock,16 and water resistant and antimicrobial finishes17 whichhave recently become popular.2.1. Chitosana Million Dollar Natural Polymer.

Chitosan, discovered by Rouget in 1859, is a technologically

important polysaccharide biopolymer.18 It is mainly obtainedby alkaline deacetylation of chitin (Figure 1); chemically it iscomposed of glucosamine and N-acetylglucosamine unitslinked by 1−4 glucosidic bonds.19 Being nontoxic, biodegrad-able, biocompatible, and microbe resistant has given it hugepotential in a broad range of scientific areas such asbiomedical,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 thatcan affect its antimicrobial activity and mechanism of activitysuch as the type of chitosan, the degree of deacetylation,molecular weight, type of microorganism, and other physicaland chemical factors including pH, ionic strength, and additionof nonaqueous solvents.10,17,23

The antimicrobial activity of chitosan is generally welldocumented; however, its mode of action is yet not fully

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

biopolymer source characteristics

chitosan crustaceansand fungi

biocompatible, biodegradable, antimicrobial activity, antistatic activity, non toxic, chelating property, deodorizing property, filmforming ability, chemical reactivity, polyelectrolyte nature, dyeing improvement ability, cost-effectiveness, thickening property,wound healing activity

cyclodextrin starch ecofriendly nature, inclusion complex forming ability, insecticidal delivery, slow release of fragrances, solubilizing ability, ease ofproduction, cost- effectiveness, chelating activity, drug carrier ability

sericin silk worm(Bombyxmori)

biocompatible, biodegradable, uv resistant, oxidative resistant, moisture retention capacity, antibacterial, gelling property, adhesionability

alginate brown seaweeds

high moisture absorbing capacity, biocompatibility, wound healing ability, antibacterial activity

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

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understood. The most accepted mechanism is the electrostaticinteraction of the positively charged amine groups (−NH3

+) atC-2 positions in glucosamine monomers at pH lower than itspKa (∼6.3), and the negatively charged residues at the cellsurface of many fungi and bacteria. These interactionsconsequently result in extensive cell surface alteration and cellpermeability, leading to the leakage of intracellular substances,such as electrolytes, UV-absorbing material, proteins, aminoacids, glucose, and lactate dehydrogenase.24−27 This in turncauses the interruption of all essential functions of micro-organisms and finally leads to the death of these cells. Since themechanism is based on electrostatic interaction, it is worthnoting that when the positive charge density of chitosanstrengthens, the antimicrobial activity will increase conse-quently, as is the case with quaternized chitosan28,29 andchitosan metal complexes.30−32 For chitosan and its derivatives,it is quite reasonable that the antimicrobial activity is dependenton the alkyl chain length due to the change in bothconformation and charge density of the polymer, whichconsequently affect the mode of interaction with thecytoplasmic membrane.24 Several studies have confirmed thatthe degree of deacetylation (DD) and pH determine the chargedensity of chitosan and thereby the level of antimicrobialactivity. The increase in DD means an increased number ofamino groups on chitosan, and lowering the pH increases theantimicrobial effect of chitosan due to a higher proportion ofcharged amino groups.27,33 In addition, the strength and rangeof electrostatic interactions between the positively chargedamine group in chitosan and negatively charged bacteria is alsodependent upon ionic strength of the solution.17

Molecular weight plays an important role in determining theantimicrobial efficiency of chitosan. Therefore, many researchgroups have studied the molecular weight dependence.Conflicting data have been reported on the effect of molecularweight and on the susceptibility among different bacterialspecies to chitosan. No et al.34 examined antibacterial activity ofchitosan and chitosan oligomers with different molecularweights. Tokura et al.35 investigated the molecular weightdependence of chitosan against E. coli and discovered that thechitosan of average molecular weight 9.3 kDa was stacked onthe cell wall and inhibited the growth of E. coli. However, thechitosan of molecular weight 2.2 kDa, which permeated intothe cell wall, accelerated the growth of E. coli. Gerasimenko andco-workers36 examined the antimicrobial activity of low-molecular-weight chitosan with a viscosity-average molecularweight of 5−27 kDa and an equal degree of deacetylation (DD,85%). It was observed that the increase in chitosan molecularweight leads to a decrease in chitosan activity against E. coli.Zheng and Zhu37 found similar results against E. coli. Theysuggested that antimicrobial action is related to the suppressionof the metabolic activity of the bacteria as lower molecularweight chitosan enters the microbial cell more easily thanhigher molecular weight chitosan. To address the variation inpublished studies on the antibacterial activity of chitosans,Mellegard et al.38 studied the antibacterial activity of water-soluble hydrochloride salts of chitosans with weight averagemolecular weights (Mw) of 2−224 kDa and degree ofacetylation of 0.16 and 0.48 against Bacillus cereus, Escherichiacoli, Salmonella Typhimurium and three lipopolysaccharidemutants of E. coli and S. Typhimurium. They found that thechitosans with a lower degree of acetylation (FA = 0.16) weremore active than the more acetylated chitosans (FA = 0.48),and observed that chitosans of Mw 28.4 kDa, (FA = 0.16)

inhibited growth and permeabilized the membranes of all thetested strains in comparison to the other chitosans. Theyconcluded that chitosan preparation details are criticallyimportant in identifying the antibacterial features that targetdifferent test organisms.Several studies have shown that the mechanisms of the

antibacterial activity of chitosan differ for gram-positive andgram-negative bacteria or the test organism. It is well-knownthat the outer membrane (OM) of gram-negative bacteriaconsists essentially of lipopolysaccharides (LPS) containingphosphate and pyrophosphate groups which render to thebacterial surface a density of negative charges superior to thatobserved for gram-positive ones (membrane composed bypeptidoglycan associated to polysaccharides and teichoic acids(Figure 2).24 Owing to this, Chung et al.39 found more chitosan

adsorption on the cell surface of the tested gram-negativebacteria and hence a higher inhibitory effect than that on thetested gram-positive bacteria. The anionic groups likephosphate and carboxyl, of LPS and proteins in the gram-negative bacteria OM are held together by electrostaticinteractions with divalent cations that are required to stabilizethe OM. Polycationic antimicrobial agents like chitosan and itsderivatives at low pH may also compete with divalent metals forbinding with polyanions (Figure 3).24

Chitosan also possesses excellent metal-binding capacity, actsas a water binding agent, and inhibits various enzymes.27 Itselectively binds with Mg2+ and Ca2+ ions present in the cellwall, and hence disrupts the integrity of the cell wall orinfluence the activity of degradative enzymes. The disruption ofcell wall integrity has been testified by several methods.Chelation mechanism is generally more efficient at high pH inwhere the amine groups are unprotonated and the electron pairon 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 (whichmainly contribute to the stability of gram-negative outermembrane) resulted in destabilization of the outer membraneof E. coli. It was possible to observe and identify under fluorescespectroscopy the changes in amino acid namely phenylalaninewhich was located at the surface and inside of the proteinspresent in the membrane of E. coli. On the other hand; it is alsoclaimed that the positively charged chitosan interacts withcellular DNA of some fungi and bacteria, which consequentlyinhibits the mRNA and protein synthesis.24,27,41

2.1.2. Chitosan in Antimicrobial Finishing. Due to itsantimicrobial property, chitosan provides increasing interest toresearchers working on adding functionalities to the textilesurfaces; it has been used in wool, cotton, cellulose, andpolyester finishing.17 Unfortunately, the weak binding of

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

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chitosan with the textile fibers constitutes the main problems inits application. To address this issue, various cross-linkingagents have been used such as glutaric dialdehyde or otherformaldehyde reactant-based cross-linkers.42−44 However, therelease of toxic and irritant formaldehyde vapors from thesesubstances, besides several other constraints like the reductionof mechanical properties and fiber degradation, have increasedthe desirability of finding new cross-linking agents, which donot release formaldehyde. Recently, in some studies, poly-carboxylic acids, particularly 1,2,3,4- butantetracarboxylic acid(BTCA) and citric acid have been used as safer cross-linkingagents between chitosan and cellulose fibers. The hydroxylfunctional group interactions with the carboxyl groups of thepolycarboxylic acids greatly improve the antimicrobial durabilityand other fiber properties.43,45−47 The cross-linking mechanismof BTCA with cellulose in the presence of chitosan is shown inFigure 4.46 Likewise, the surface modification of wool fabricsusing anhydrides, succinic anhydride (SA), and phthalicanhydride (PA), to graft the chitosan have delivered betterantimicrobial results, in an environmentally friendly manner.48

Citric acid and low toxic oxidizing agents, such as potassiumpermanganate and sodium hypophosphite, have been shown topromote an effective cross-linking between chitosan and textilesubstrates such as cotton cellulose45 and woolen fabrics49 in anesterification reaction. This greatly improves antimicrobial andantiseptic effects of the treated fabrics. The antimicrobial effectwas attributed to the formation of quaternary ammonium saltby the amino groups of chitosan in the treatment which canbind to the negatively charged bacterial surface therebyinhibiting their vital functions.

Nowadays, a safe, healthy and comfortable living environ-ment becomes more important; as a result, special focus onvarious “green chemistry” approaches by researchers is stronglycreated. In this sense, UV irradiation has been proposed as asuitable nontoxic procedure for producing durable antimicro-bial finished textiles. Alonso et al.50 studied the application ofchitosan to previously UV-irradiated cellulose fibers for thepreparation of antimicrobial textiles (Figure 5). They utilizedcitric acid as a cross-linking agent, and sodium phosphate(NaH2PO4) as reaction catalyst and found that treated fibersignificantly decreases the spore germination percentage ofPenicillium chrysogenum and colony forming units per milliliterfor E. coli in comparison to raw cellulose fiber. Recently,chitosan has been applied on cotton and synthetic fabrics byradical UV-curing, and high values of antimicrobial activity werereported by Ferrero and Periolatto.51 Likewise, Periolatto etal.52 developed antimicrobial chitosan finish based on radicalUV-curing with 2-hydroxy-2-methylphenylpropane-1-one oncotton and silk fabrics. They found that chitosan UV-curingyields strong antimicrobial properties against E. coli on cottonand silk fabrics at low polymer add-on, with a high washdurability 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 adrastic change on the antimicrobial properties of the fabrics. Inaddition, it resulted in high dye uptake of the fabric.53 Thestudies performed using chitosan-coated fabrics have demon-strated better inhibition against gram-negative bacteria thangram-positive. This variation could be attributed to their

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 El-tahlawy et al.46

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differences in cell wall structure and outer membranepermeability.The effectiveness of antimicrobial functionalization on

textiles has been shown to be dependent upon the pretreatmentway and chitosan application methods.54 In a recent study,Ibrahim et al.55 claimed that a new environmental friendlytreatment using the incorporation of chitosan and otherbioactive ingredients into pigment pastes results in thedevelopment of antibacterial cellulose fabrics. They reportedthat the antibacterial activity by the modified pigment printsagainst S. aureus and E. coli was maintained for more than 20washings. The printability and antibacterial activity was alsofound 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 ofmarine crustaceans, such as crabs, shrimps, prawns, lobsters,and the cell walls of some fungi (Figure 1). Currently, it is mostoften produced by deacetylation of chitin from exoskeleton ofshellfish, because these are abundantly available, and have beenabandoned as waste products by the worldwide seafoodcompanies. Teli and Sheikh56 has reported the extraction ofchitosan from shrimp shells waste and its use in thedevelopment of antibacterial rayon. The antibacterial rayonfabric portrayed promising results against gram positive andgram negative bacteria with a high wash durability. The highdurability in antibacterial activity by the lignocellulosic rayonfiber was maintained by the use of acrylic acid as a graftingagent. It was demonstrated that acrylic acid has high ability toreact with amine groups of chitosan.Nowadays, the commercial production of chitosan by the

deacetylation of chitin from crustaceans appears to have limitedpotential for industrial acceptance. This fact is due to theirseasonal and limited supply, requirement of harsh chemicals,such as concentrated NaOH, either in alcohol or aqueoussolution for deacetylation, and their inconsistent physicochem-ical properties.57 On the other hand, the recent advances infermentation technology suggest that the cultivation of fungican provide an alternatives to produce chitosan because ofmany advantages,58,59 such as abundant availability, no need ofany aggressive treatment, and physiochemical properties that

can be manipulated and standardized by controlling theparameters of fermentation.Several fungi, such as Mucor rouxi, Absidia glauca, Aspergillus

niger, Gongronella butleri, Rhizopus oryzae, and different speciesof Basidiomycetes have been explored to upgrade the possiblealternative sources of chitosan for biomedical, textile, and otherapplications.58 Recently, Moussa et al.60 isolated a chitosan-richfraction termed the acetic acid soluble material (AcSM) fromthe cell wall of Mucor rouxii DSM-1191. The predominantcomponent of the fractions have demonstrated excellentantibacterial properties, and such fractions have been appliedas finishing agents for cotton fabrics. The treated fabric showedhigh antimicrobial efficacy against Escherichia coli and Micro-coccus leteus, with a significant enhancement in other physicalproperties. Furthermore, they proposed that Mucor rouxiiDSM-1191 has the excellent potential to be used for cell wallAcSM production on an industrial scale. Likewise, isolation ofchitosan from Aspergillus niger mycelial waste, subsequent to itsproduction of citric acid, has been proven to developantimicrobial cotton textiles. It was examined that the highantimicrobial activity of such fabrics against both infectioncausing 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 onan industrial scale, besides these may initiate new researchopportunities in the development of bioactive textiles forvarious medical and hygienic applications.

2.1.4. Chitosan DerivativesDo They Really Make Sense?The use of chitosan to impart the antimicrobial property totextiles has been the focus of textile antimicrobial finishing overthe last few decades. In fact, it has been described that chitosancan be used as a multifunctional textile finishing agent, becauseits antimicrobial activity can be combined with other functions,such as dyeing improvement, antistatic property, and deodorantactivity.17 However, in its native form, the loss of biologicalactivity and low solubility at neutral or alkaline conditions, inaddition to its poor durability on textiles due to poor adhesionare the main problems, which hinder its use as an antimicrobialtextile finishing agent.To overcome this, a number of chitosan derivatives that are

soluble in water over a wide pH range have been synthesizedand used as antimicrobial agents on textiles. These include N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride,62

chito-oligosaccharide, N-p-(N-methylpyridinio)methylated chi-tosan chloride and N-4-[3-(trimethyl-ammonio) propoxy]benzylated chitosan chloride.2 Kim et al.62 applied N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride(HTCC) (Figure 6a) as an antimicrobial agent to cottonfabrics and observed a lower minimum inhibition concentration(MIC) against Staphylococcus aureus, Klebsiella pneumoniae, andEscherichia coli compared to that of native chitosan; however,the imparted antibacterial activity was lost on laundering. Byusing BTCA cross-linker, they found that the antibacterialactivity of HTCC was maintained over 90% even after beingexposed to 20 consecutive laundering cycles. The impartedlaundering durability of antimicrobial cotton fabrics wasbecause of the introduced covalent bond formation betweenthe cellulose molecule and HTCC via the esterification ofBTCA catalyzed by sodium acetate. Likewise Montazer andAfjeh63 used the very same derivative of chitosan (HTCC) toachieve a multifunctional finishing on the cotton fabric in thepresence 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.

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

inhibitory rate of HTCC against Staphylococcus aureus andEscherichia coli was more than 95%.64 Interestingly, thereactivity of the HTCC has been improved by the introductionof functional acrylamidomethyl groups to the primary alcoholgroups by Lim and Hudson.65 They reported that such areactive chitosan derivative can be covalently bonded to textile

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

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fibers having nucleophilic groups, especially to cellulose. In asubsequent publication, the same group studied the applicationof their synthesized fiber reactive chitosan derivative O-acrylamidomethyl-N-[(2-hydroxy-3-trimethylammonium)-propyl] chitosan chloride (NMA-HTCC) (Figure 6b), as anantimicrobial textile finish for cotton fabrics and discovered thatthe antimicrobial activity against Staphylococcus aureus wasmaintained over 99% even after being exposed to 50consecutive home laundering cycles.7 On the other hand, thecotton treated with native chitosan in the same study showedrelatively low antibacterial activity (about 70%) only after 10home launderings. They also reported that the antimicrobialfunction of NMA-HTCC treated fabric arises from attractiveinteractions between the quaternary ammonium groups on thefabric and the negatively charged cell membrane of themicrobe. The slight decrease in the antibacterial activity afterlaundering was attributed to the fact that anionic groups of thesurfactant present in the detergent interact ionically with thecationic groups of NMA-HTCC and reduce the chance ofNMA-HTCC to interact with negatively charged bacterialmembranes. The results from their both studies also showedthat antibacterial activity against Staphylococcus aureus increasesafter one laundering than before laundering. It could be due tothe high amount of protonated chitosan on the fabric beforelaundering, which may coat the bacterial cell surface and thusprevent the leakage of intracellular components.More recently, Gupta and Haile66 synthesized carboxymethyl

derivatives of chitosan by carboxymethylation (Figure 6c), witha view to develop a multifunctional finish on cotton. Theyobserved very high inhibitory activity of such cotton fabricsagainst bacterial pathogens with improved wash durability. El-Shafei and co-workers67 also reported synthesis of carbox-ymethyl chitosan by chemical reaction of chitosan withmonochloroacetic acid under alkaline conditions, followed byits treatment on precationized cotton using a cold-batch-method (Figure 7). It was interesting to observe that the

carboxymethyl chitosan was more effective in the presence ofcationized cotton against Escherichia coli DSMZ 498 andMicrococcus luteus ATCC 9341 strains. The possible mode ofaction was attributed to the polycationic nature of carbox-ymethyl chitosan in addition to the permanent positive chargeraised from the cationized cotton, both interact with thenegative charged residues present at the cell wall of bacterialeading to alteration of the cell wall permeability andconsequently, interfere with the bacterial metabolism andresult in the death of cells.In 2011, Fu and his co-workers68 synthesized three water-

soluble chitosan derivatives bearing dual-antibacterial functional

groups with 2,3-epoxypropyltrimethylammonium chloride andbenzaldehyde as modifiers through formation of Schiff base,reduction, N-methylation and O-quaternization for producingdurable antimicrobial finished cotton fabric. They found thatsynthesized derivatives O-quaternized-N,N-biethyl-N-benzy-lammonium 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) (Figure6f) in the presence of citric acid as a cross-linking agent displaystrong antibacterial activities and fairly good durability.Following the application of the derivatives on the cottonfabric, the O-QCTS-DEBn derivative exhibited particularly highactivity due to its high cationic charge density (two cationiccharges of ammonium salt), which is known to act on thebacterial cell membrane, making the cell membrane lose itbarrier function and finally the death of bacteria. It was alsofound that the O-QCTSS derivative at a concentration of 3%made the antibacterial rate reach nearly 100% against bothgram-positive and gram-negative bacteria. Its antibacterialactivity arises because of the presence of two differentantimicrobial groups such as a quaternary ammonium groupand a Schiffs base group in its structure. Furthermore, the O-QCTS derivative made the finished fabric durable for 20 timesof home laundering due to its lower water solubility than that ofthe other two derivatives.Klaykruayat et al.69 grafted cationic hyperbranched dendritic

polyamidoamine (PAMAM), a dendrimer analogue to thereactive amino group of chitosan (Figure 6g). The modifiedchitosan with PAMAM after application onto cotton fabrics washighly active against microbes, in particular bacterial species,even at a near neutral pH. However, there was no antibacterialmechanism suggested for PAMAM-modified chitosan-fiber, butit 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 textilefinishing. In addition to overcoming the limitations of nativechitosan, further research may be focused on the use of moreefficient and novel agents that can impart multifunctionalproperties to the finished fabrics before such technologies canbe adopted on a large practical scale.

2.1.5. ChitosanMetal Complexes in AntimicrobialTextiles. Chitosan can form coordinate or chelate complexeswith metal ions like copper, zinc, iron, and cobalt, etc. Some ofthese complexes are reported to have potent antimicrobialactivity.70 This complex forming ability of chitosan withtransition and other heavy metal ions have portrayed manifoldsadvantages, in textile applications. Chitosan-metal complexeshave successfully been used in the development of antimicrobialfibers. Gouda and Keshk71 studied the feasibility of using metalsuch as zirconium, titanium, and chitosan films on cottonfabrics to impart multifunctional properties. The resultant fabricshowed antibacterial activity in addition to the UV protectionproperties. Furthermore, it was shown that inhibitory activity oftreated cotton fabrics depends upon the nature of metal oxide.Nowadays, with the consumer’s enhanced awareness about

the contaminations associated with food products, there hasbeen a growing need for alternative safe food packagingsubstrates. In this context, antimicrobial jute fibers forpackaging applications based on chitosan and chitosan−metalcomplexes have delivered promising results.31 Therefore, asearch for more innovative ways, and further research on thechitosan-metal complexes, may result in high value utilization ofthese antimicrobial fibers for food preservation applications.

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

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2.2. Cyclodextrins (CD). Cyclodextrins (CDs) are a familyof cyclic oligosaccharides; they are produced during enzymaticdegradation of starch by the enzyme, namely cyclodextringlycosyltransferase. CDs are composed of alpha-1,4-linkedglucopyronase sub units, the most commonly available typesare α-CD, β-CD, and γ-CD having 6, 7, and 8 glucopyronasemoieties, respectively. These substances, and in particular β-CD(Figure 8) have shown huge potential in textiles, because of

their ability to selectively form inclusion complexes with othersubstances72,73 through host−guest interactions. The complex-

ation strength and longevity of host−guest complexes mainlydepends upon the size of incoming guest molecule and the typeof interaction such as hydrogen bonding, van der Waalsinteraction, charge transfer and hydrophobic.

2.2.1. Inclusion with Antimicrobial Agents. Cyclodextrininclusion complexes can be formed in solutions, in a solid stateas well as when cyclodextrins are linked to various surfaces.They can act as permanent or temporary hosts for smallmolecules. Inclusion in cyclodextrins exerts a profound effecton the physicochemical properties of guest molecules which arenot achievable otherwise.74 The principal advantages of naturalcyclodextrins as carriers for biologically active guests, such asdrugs, insect repellents, and antimicrobial agents, etc., are asfollows:75

• well- defined chemical structure, yielding many potentialsites 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 biode-

gradation• controlled release of drugs and flavours.

The release of enthalpy-rich water molecules from the cavityof CDs is the main driving force of complex formation. It hasbeen proposed that water molecules are displaced by morehydrophobic guest molecules present in the solution to attainan apolar−apolar association and decrease of cyclodextrin ring

Figure 8. β-Cyclodextrin.

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

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strain resulting in a more stable lower energy state.76 Some ofthe antimicrobial agents used for inclusion compounds ontextiles are given in Table 3.2.2.2. CyclodextrinRole in Functional Finishing of

Textiles. The toxicological studies have shown that CDs donot give rise to skin irritation, skin sensation, or mutageni-cicity.77 In the USA α-, β-, and γ-CDs have obtained the GRASlist (FDA list of food additives that are “generally recognized assafe”) status,78 and since 2000, Germany has also approved theuse β-CD as a food additive.79 Owing to these facts they areincreasing being researched all around the globe as newauxiliaries for textile finishing. Several studies have reported thattextiles containing CDs fixed on their surfaces can be used forfragrance 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 thearchitecture of CDs that they cannot form direct covalentbonds with textile fibers; however, this problem has been solvedby the grafting of CDs using polycarboxylic acid (non-formaldehyde cross-linking agents) and other bindingagents.83−85 These properties enable them to be used in awide variety of medical, technical, and geotextiles products.Bajpai et al.86 have described antibacterial properties of fabricsobtained by a novel method, based on the grafting of CDloaded with silver(I) ions onto cellulose backbone of cottonfabrics using citric acid as a cross-linker. It was observed thatincorporating silver(I) ions into the cavity of CDs depictsexcellent antibacterial action with slow release mechanism afterapplication onto the fabric. The results showed that silver(I)ions can be conveniently loaded into CD cavities for their useas slow release devices for antimicrobial applications.In the year 1996, the first reactive cyclodextrin derivative,

namely monochlorotriazinyl-β-cyclodextrin (MCT-β-CD) hav-ing a monochlorotriazinyl group as a reactive anchor wasintroduced for permanent surface modification of textiles.73

Recently, cellulase enzyme treatment has been done to raise thegrafting yield of MCT-β-CD on organic cotton. The inclusionof antibacterial agent thymol on biopolished MCT-β-CDgrafted fabric has shown high efficiency against Staphylococcusaureus and Escherichia coli. Durability to the antibacterialproperty was maintained up to several repeated washing cyclesby the treatment.87

Wang and Cai.88 reported incorporation of miconazolenitrate (antibacterial agents) into the β-CD cavities perma-nently bound to cellulose fabrics. The optimal reactionconditions for grafting of β-cyclodextrin to cellulose fabricswere found to be MCT-β-CD 60−100 g/L, catalyst Na2CO350−60 g/L, the reaction temperature of 150−160 °C and thereaction time 5−8 min. According to their findings, the MCT-β-CD grafted cellulose retained the antibacterial abilities morethan 70% even after washing 10 cycles, while the antibacterialactivity of the unmodified textile was almost lost. Likewise,Cabrales et al.89 investigated the grafting of monochlorotria-zinyl-β-cyclodextrin (MCT-β-CD) onto cotton fabrics followedby their inclusion formation with triclosan (a powerfulantibacterial agent). They observed excellent antibacterialresults. Abdel-Halim et al.90 used linear electron beam radiationto graft glycidyl methacrylate/monochlorotriazinyl-β-CD mix-ture onto cotton fabrics. They loaded the grafted fabrics with acommercially available antimicrobial agent (chlorohexidindiacetate). Grafted cotton loaded with an antimicrobial agentwas found to show very good antimicrobial activity in contrary

to control and grafted fabrics not loaded with antimicrobialagent. The results reported in this study demonstrate also thatthe GMA/MCT-CD grafted fabrics loaded with antimicrobialagent retain good durability toward antimicrobial activity afterfive washings. This is due to the cavities present in cyclodextrinmoieties 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 withbifunctional moieties and have been introduced into textileapplications.91

CDs have the potential to act as reducing and stabilizingagents for green nanoparticles synthesis; nanoparticles hold thecurrent increasing interest of textile researchers.92 Furthermore,CDs have the unique ability to reversibly complex with a rangeof nanoinorganic materials, and hence can carry and stabilizethem on the fabric surfaces.93 On the basis of these facts, CDsrepresent a great potential to be used in novel applications,particularly in the area of medical and hygienic textiles.Therefore, these may provide immediate opportunities fordeveloping novel functional textiles in the near future.

2.3. Sericin Protein. Sericin is a natural macromolecularprotein derived from silk worm, Bombyx mori. It generallyconstitutes between 20 and 30% of silk protein and ranges insize from 65 to 400 kDa. Sericin envelopes the fibroin fiberwhich forms the main silk filament content with successivesticky layers that help in the formation of a cocoon. Being anamorphous glue-like substance, it helps in the cohesion of thecocoon by gluing silk threads together.94,95 Because of itsseveral inherent properties, such as biocompatibility, biodegrad-ability, antibacterial, UV resistance, oxidative resistance, andmoisture absorption ability, sericin has become an appealingproduct for its versatile applications in different fields, includingpharmaceuticals, cosmetics, and textiles.96

Generally, the sericin protein has been studied to increase thefunctional properties of many synthetic fibers.97,98 Some recentstudies have also demonstrated its potential for application onnatural fibers. Although, sericin has not really shown anyantimicrobial properties on textiles, it has been suggested thatsilk sericin may act as a functional agent for cotton and woolfabrics.99 Rajendran et al.100 successfully applied silk sericin asan antibacterial finishing agent onto cotton fabrics. It wasobserved that the resultant fabric displays a reduction rate of89.4% and 81% against S. aureus and E. coli, respectively. Theyconcluded to increase the durability of the finish in order toretain the antimicrobial property by using cross-linking agentsin the near future. More recently, Doakhan and co-workers101

prepared sericin/TiO2 nanocomposite as a new finishing agentfor cotton fabrics by extraction of sericin from raw silk usinghot water followed by dispersion of nano-TiO2 in its solution.They found that the antibacterial activity of the finishing againstStaphylococcus aureus was more effective than Escherichia coli.They claimed laundering durability of the antimicrobialtreatment up to 40 cycles by using polycarboxylic acid cross-linking agents. On the basis of their findings, the same authorsproposed that the antibacterial activity of sericin could originatefrom its polycationic nature, conveyed by its positively chargedNH3

+ groups at acidic pH. The polycationic nature might be afundamental factor contributing to its interaction with thenegatively charged bacterial cell membrane, causing leakage ofproteinaceous and other intracellular constituents, ultimatelyresulting in the death of bacteria. Low molecular weight sericincould also penetrate the cell wall of bacteria, complex withanionic materials in the cells, inhibit the normal physiological

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activities of bacteria, and finally may lead to the death of thesecells.Despite the promising use of sericin in value-added products

in the biomedical, pharmaceutical, cosmetic, food, and textileindustries,95 at present sericin is mostly discarded in silkprocessing wastewaters. Recovery of silk sericin fromdegumming liquor or cocoons could provide significanteconomic and social benefits. Unfortunately, an extensiveliterature survey revealed that there are only relatively fewspecific and objective research studies to support the manyclaims made about sericin and sericin modified materials. Inview of its many beneficial effects, particularly the antimicrobialactivity, in-depth research needs to be carried out on itsantimicrobial mode of action in addition to the stability,biocompatibility, and other functional characteristics of itsfinished products.Therefore, it can be concluded that use of sericin for

antimicrobial modifications are in the phase of basicinvestigations. Nevertheless, sericin protein also has recentlyrevealed its potential to be used as a capping agent fornanoparticles synthesis. The synthesized silver nanoparticleswere further used in the development of antimicrobial silkfabric.102 In this context, sericin protein provides an evidence tosatisfy the current consumer’s demand for natural bioactivetextiles, 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 thedevelopment of bioactive textiles using other biopolymers aswell, including alginate (Figure 9), collagen,103 and hyaluronan(Figure 10). There have been several reports about theirversatile applications in the biomedical field.104

2.4.1. Alginate Fibers in Wound Dressing. Alginate fibersdue to their recently discovered ion-exchange and gel-formingabilities have been extensively used in wound dressing

applications.105,106 Moreover, alginate fibers are particularlyuseful due to their excellent biocompatibility, nontoxicity, andpotential bioactivity, and thus may offer many advantages overtraditional cotton and viscose gauzes.107 Alginate fibers,typically as insoluble calcium salt, upon contact with woundexudates, may cause an exchange of sodium ions in the woundexudates with calcium ions in the fiber.108 As a result of the ionexchange between the calcium ions in the fiber and the sodiumions in exudates, the fibers are transformed from water-insoluble calcium alginate into water-soluble sodium alginate,resulting in the absorption of a large amount of water by thefibers. Such gelation provides the wound with a moistenvironment, which promotes healing and leads to a bettercosmetic repair of the wounds.109

Owing to their low antibacterial activity, alginate fibers canbe incorporated with broad-spectrum antimicrobial agents toenhance the overall antimicrobial activity, and thus may formhighly absorbent alginate wound dressings having antimicrobialproperties. Qin.110 observed that the silver-containing alginatefibers can maintain the white physical appearances whileproviding a sustained release of silver ions when in contact withwound exudates. Fan and co-workers107 prepared antibacterialfibers from a mixture of alginate, carboxymethyl chitosan andsilver nitrate. Carboxymethyl chitosan was found to improvethe water-retention of the blend fibers and silver nitrate-enhanced activity against gram-positive S. aureus. Knill et al.111

studied the modification of alginate with hydrolyzed andunhdrolysed chitosan. Their results showed that the hydrolyzedchitosan could penetrate the alginate fibers and had the abilityto provide a slow release/leaching of antibacterial activecomponents (presumably hydrolyzed chitosan fragments). Itis interesting that the hydrolyzed chitosan fragmenting intobase alginate fibers perhaps via ionic interactions (Figure 11)results in some reinforcement and thus increases the tensileproperties of the fibers for their potential applications in wound

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

Figure 10. Hyaluronan.

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dressings. In addition, alginate containing dressings have beendemonstrated to activate macrophages within the chronicwound bed and generate a pro-inflammatory signal which mayinitiate a resolving inflammation characteristic of healingwounds.112 There is not much literature available on the useof these biopolymers in antimicrobial textiles. However, therole of alginate in bioactive textiles has been documented byGorensek and Bukosek113 and Kim et al.114

Furthermore, in recent years several attempts have beenmade to develop novel products from these naturalpolysaccharides. Synthesis of novel amphiphilic alginate esters(Alg-C8, Alg-C12, or Alg-C16) graft copolymers has beenreported by Yang et al.115 These alginate esters are expected tobe used as protein drugs and as a carrier of hydrophobic drugs.They might offer a natural safeguard against microbialpathogens and subsequently with the advancement ofinnovative technologies might prove their way in thedevelopment of bioactive textiles.On the basis of the current widespread potential applications

of natural biopolymers, easy availability of raw materials, andsimple processing technologies, they can be explored onto thetextile materials as a viable option for achieving novel functionalproperties. Anyway, antimicrobial textiles based on thebiopolymers discussed in this review have shown energeticand environmental advantages, in comparison to the syntheticantimicrobial agents. The major drawback is their poordurability on textile materials due to the lack of strong bondingforces. However, the extensive R&D to overcome suchadhesion problems in this area of biopolymer application isunderway and currently there are a number of strategiesemployed to overcome these shortcomings.

3. ECOFRIENDLY PRETREATMENT TECHNOLOGIESFOR FUNCTIONAL FINISHING OF TEXTILES

In recent years, the development of efficient green chemistrymethods for functional finishing of textiles has become a major

focus of researchers. The ecological and economic restrictionsimposed on the textile industry have led to the development ofmodern strategies based on environment friendly approaches.Nowadays, surface modification of polymer surfaces isconsidered one of the most promising treatments. Surfacemodification increases the functional group accessibility of thefiber without affecting other bulk properties. Some of theimportant surface modification treatment methods (Table 4)adopted recently are discussed below.

3.1. Plasma Treatment. Plasma treatment is a novel andan ecofriendly strategy for the development of durablemultifunctional textiles. Plasma modifications are gainingpopularity in the textile industry due to their numerousadvantages such as low energy, no chemical requirements, andgreen approach over other conventional wet processingtechniques. In plasma treatment, the polymer/fiber surfacesare treated with the excited and energetic plasma species (ions,radicals, electrons and metastables). The plasma introducesnew hydrophilic groups into the structure, possibly due tooxidation and etching reactions, and thus may enhancefunctional properties such as wettability, water repellency,dyeability, and effective antimicrobial properties.116,117 Thestructural changes undergoing in the polymer or fiber surfacehas been illustrated by using advanced instrumental analysissuch as FT-IR, SEM analysis, XPS, XRD, EPR, etc. Some recentstudies have shown that the selection of plasma gas such as Ar,N2, O2, NH3, CO2), in addition to the operating parametersmay result in various functional treatments.118 Zemljic et al.119

has reported improvement of chitosan adsorption on cellulosicfibers after treatment with oxygen plasma. The treatmentresulted in high antimicrobial activity of the cellulosic fibers.Use of open air plasma has been investigated to graft chitosanpolymer onto nylon textiles. It was observed that air plasmaactivation at a speed of (26/min) enhances the grafting ofchitosan followed by improvement in antibacterial activity.120

Chang et al.121 studied the properties of polyester fabricsgrafted with chitosan oligomers/polymers after being activatedby atmospheric pressure and discovered that surface of fabricsactivated by atmospheric pressure plasma for 60 to 120 s andgrafted with chitosan oligomers results in high antibacterialefficiency. Uygun et al.122 reported the use of RF hydrazineplasma for the modification of chitosan nanopowders. It wasshown that RF hydrazine plasma had a drastic effect onantibacterial 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 low-plasma treatment in the presence of chitosan as a mordant hasshown remarkable results and thus can be used as a substitutefor metal mordants.123 It has also been examined to impart

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

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

method advantages disadvantages

wetchemical

does not require any special equipment; can penetrate three-dimensional substrates nonspecific; environmentalpollution; unsuitable for largescale industrial application

UVirradiation

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

can affect treatment consistency;affect optical properties ofpolymer

plasmatreatment

low environmental impact method; no waste production; causes or introduces new chemical groups into the fiberstructure; increases efficacy of antimicrobial properties; introduces dirt and water repellence; suitable for bothnatural as well as synthetic fibers; saves energy and time

needs careful handling to preventdetrimental action onto thesubstrate; high cost

enzymetreatment

high dye uptake; improves shrink resistance; ecofriendly nature; need mild experimental conditions substrate specific; low binding

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remarkable antimicrobial properties to cotton fabrics in thepresence of cellulase enzyme.124 Demir et al.116 has suggestedthe use of argon and air plasma for modifying the knitted woolsurface in order to enhance its adsorption capacity for chitosanand hence to improve antimicrobial properties.3.2. Enzyme Treatment. In recent years, the enzymes so-

called biological catalysts with polypeptide chains have beenused in textile applications in cost-effective and environmentallysensitive ways.125 The use of enzymes has been documented toimprove some physical properties of the fibers for betteradhesion.126,127 Considering special advantages and highpotentialities of the application of enzymes in the textileindustry, especially for producing high value-added textiles, thispaper reviews the application of enzymes for antibacterialmodification of textiles.Recently the immobilization technique, which is based on

enzymes, has been incorporated in the textile industry toincrease the activity and to build new functionalized textileproducts. Wang et al.128 has immobilized lysozymes onto woolfabrics. The immobilization of the enzyme was done at 40 °Cand pH 7.0 for 6 h with 5 g/L lysozyme concentration in orderto impart a better antibacterial effect to wool fabric. Variousindustrial enzymes such as α-amylase, alkaline pectinase, andlaccase enzymes have been incorporated onto ester-cross-linkedas well as Cu-chelated cotton fabrics for developing highdurable antimicrobial fabrics.129 Hebeish et al.47 has reportedthe preparation of multifinishing formulations consisting ofBTCA and chitosan having different molecular weights bychitosanolysis using pectinase enzyme, and impregnating themon the cotton fabrics. The resultant cotton fabrics showed highantimicrobial activity with durability up to 10 washings. Toexplore the future potential applications of enzymes inantimicrobial textiles, it is essential to understand the dosageand efficacy of the enzymes, as well as their interaction with thetextile substrates.

4. BIOPOLYMERS AND NANOTECHNOLOGYTHEFUTURE PROSPECT

In recent years, nanotechnology has been booming in manyareas, including material science, mechanics, electronics, optics,medicine, plastics, energy, electronics, and aerospace. Nowa-days, it is playing an extraordinary role in the functionalfinishing of textiles.130 It has been sought to improve existingmaterial performances and develop fibers, composites, andnovel finishing methods. The literature shows that nano-particles, due to their diverse functions, may impart flameretardation, UV-blocking,131 water repellence,132 self-clean-ing,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 hottopics in nanoscience research today. Up to date, several studieshave been carried out dealing with the use of biopolymers suchas chitosan,133 hyaluronan,134 starch,135 and cyclodextrin,92 asboth the reducing and stabilizing agents for nanoparticleformation. Abdel-Mohsen and co-workers136 reported synthesisof core−shell nanoparticles by using silver nanoparticles as coreand chitosan-O-methoxy polyethylene glycol as shell. Theysuggested that such nanoparticles can be used for thedevelopment of multifunctional cotton fabrics. Likewise, El-Shafei and Abou-Okeil.137 developed a simple method toprepare nano-ZnO by using ZnO/carboxymethyl chitosanbionanocomposites system for their application to textiles.Their finding made evident that coating of the same on the

cotton fabrics imparts excellent antibacterial and UV protectionproperties.More recently researchers working in the field of adding

functionalities to textile surfaces are investigating the possibleapplications of biopolymers in the form of nanoparticles.Coating the surfaces of textiles or incorporating the fibers withbiopolymers in the nano form is the latest approach for theproduction of highly active textiles. Biopolymers in the form ofnanoparticles display unique properties, such as higher stability,improved antimicrobial action, and better affinity for the fabrics.Consequently, a dramatic improvement in the finish durabilityon textiles has been achieved.138,139 Recent studies have alsodemonstrated that the antibacterial methanolic extract of theleaves of Ocimum sanctum can be loaded inside the sodiumalginate chitosan nanoparticles. The use of these loaded extractsfor the finishing of cotton fabric showed excellent antibacterialand wash durability results.9

Therefore, it can be predicted that biopolymer-basednanoparticles can improve functional, environmental, andeconomical benefits in the development of antimicrobialtextiles. Meanwhile, such promising results warrants exploita-tion of more such biopolymer-based nanoparticles with distinctfunctionalities, and in future may provide innovative ways todevelop new functional textiles.

5. CONCLUSIONThe current efforts in the development of new technologies forimplementation of sustainable biopolymers in the real marketof antimicrobial textiles do not guarantee economical viabilityyet. Nevertheless, application of these agents in the develop-ment of bioactive textiles is a promising prospect. Furtherresearch is yet to be carried out to translate the potential ofbiopolymers into industrial reality. The promising results canboost additional studies oriented to the search of new sources,cost-effective extraction methodologies, and innovative appli-cation methods that could provide alternatives to toxicsynthetic antimicrobial agents. If significantly improved,sustainable biopolymers may minimize the negative effects ofsynthetic agents in the textile industry. Likewise, these bioactivetextiles may be able to fulfill the consumer’s desire for ahealthier and a more productive lifestyle by reducing stress andpromoting comfort and relaxation in the near future.

■ AUTHOR INFORMATIONCorresponding Author*Tel.: +91-9350114878. E-mail: [email protected] authors declare no competing financial interest.

■ ACKNOWLEDGMENTSFinancial support provided by University Grants Commission,Govt. of India; through Central University Ph.D. StudentsFellowship (Shahid-ul-Islam) and BSR Research Fellowship inSciences for Meritorious Students (Mohammad Shahid) ishighly acknowledged.

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Industrial & Engineering Chemistry Research Review

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