Chitin and Chitosan For Versatile Applications

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CHITIN AND CHITOSAN FOR VERSATILE APPLICATIONS
Pradip Kumar Dutta a; M. N. V. Ravikumar b; Joydeep Dutta c a Chemistry Section, Department of Applied Sciences & Humanities, Motilal Nehru Regional Engineering College, Allahabad, India b Department of Preventive Medicine & Environmental Health, University of Kentucky Medical Center, Lexington, KY, U.S.A. c School of Chemical Sciences, D. A. University, Indore, India Online Publication Date: 19 August 2002 To cite this Article: Dutta, Pradip Kumar, Ravikumar, M. N. V. and Dutta, Joydeep (2002) 'CHITIN AND CHITOSAN FOR VERSATILE APPLICATIONS', Polymer Reviews, 42:3, 307 354 To link to this article: DOI: 10.1081/MC-120006451 URL: http://dx.doi.org/10.1081/MC-120006451
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2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
JOURNAL OF MACROMOLECULAR SCIENCE Part CPolymer Reviews Vol. C42, No. 3, pp. 307354, 2002
CHITIN AND CHITOSAN FOR VERSATILE APPLICATIONS

Pradip Kumar Dutta,1,* M. N. V. Ravikumar,2,y and Joydeep Dutta3 Chemistry Section, Department of Applied Sciences & Humanities, Motilal Nehru Regional Engineering College, Allahabad 211004, India 2 Department of Applied Chemistry, Shri G. S. Institute of Technology & Science, Indore 452 003, India 3 School of Chemical Sciences, D. A. University, Indore 452 001, India
1
CONTENTS
1. 2. 3. 4. 5. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308 Processing of Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309 Economic Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311 Properties of Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311 Derivatives of Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1. Chitin Derivatives of Polysaccharides and Polypeptides . . . . . . . . 5.2. Tosyl and Iodo Chitins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3. Ether-Type Chitin Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4. Mixed Ester-Type Chitin Derivatives . . . . . . . . . . . . . . . . . . . . . 5.5. Regioselective Chlorination of Chitin . . . . . . . . . . . . . . . . . . . . . 5.6. N-Acyl, N-Arylidene, and N-Alkylidene Chitosan Gels . . . . . . . . 5.7. Maleilated Chitosan and Acrylamide Copolymers . . . . . . . . . . . . 5.8. Chitosan/Calcium Alginate Beads . . . . . . . . . . . . . . . . . . . . . . . 5.9. Calcium CarbonateChitosan Composites . . . . . . . . . . . . . . . . . 312 315 315 316 317 318 318 319 320 321
*Corresponding author. E-mail: pkd_437@yahoo.com y Current address: Department of Preventive Medicine & Environmental Health, University of Kentucky, Medical Center, Lexington, KY 40507. 307 DOI: 10.1081/MC-120006451 Copyright # 2002 by Marcel Dekker, Inc. 1532-1797 (Print); 1532-9038 (Online) www.dekker.com

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5.10. 5.11. 6.
Chitosan/Polyether Hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . 321 Polysaccharide Chitosan/PEOPPO Nanoparticles . . . . . . . . . . . 321 322 322 331 331 332 332 334 344 345 345
Applications of Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1. Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2. Applications in Chromatographic Separations. . . . . . . . . . . . . . . 6.3. Photography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4. Food and Nutrition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.5. Water Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.6. Textile Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.7. Cosmetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.8. Paper Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.9. Engineering Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
ABSTRACT
Chitin and chitosan are versatile polymers, where the interest in chitosan is due to the large variety of useful forms that are commercially available or can be made available. Chitin basically is obtained from prawn/crab shells; chemical treatment of chitin produces chitosan. This article surveys applications of chitin and chitosan in various industrial and biomedical elds. Key Words: Chitin; Chitosan; Industrial; Biomedical; Applications
1. INTRODUCTION Chitin is a white, hard, inelastic, nitrogenous polysaccharide found in the outer skeleton of insects, crabs, shrimps, and lobsters, and in the internal structure of other invertebrates. The waste of these natural polymers is a major source of surface pollution in coastal areas. Chitin is the most abundant natural and acetylamino polysaccharide and estimated to be produced annually almost as much as cellulose.[1] It has become of great interest not only as an under-utilized resource, but also as a new functional material of high potential in various elds, and the recent progress in chitin chemistry is quite noteworthy. Chitin (I) is a cellulose (II)-like polysaccharide of b-linked 2-acetamido-2-deoxy-D-glucose residues, which exhibits various dierent properties from cellulose, whose hydroxyl groups in the C2 position are substituted with acetamide groups (NHCOCH3) in chitin. Similarly, chitosan (III) is a linear polymer of a (1!4)-linked 2-amino-2-deoxy-D-glucopyranose, easily derived from chitin (I) by deacetylation (Eq. 1).

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As most polymers are synthetic materials, their biocompatibility and biodegradability are much more limited than those of natural polymers such as cellulose, chitin, chitosan, and their derivatives. While they are naturally abundant and renewable, a limitation exists in their reactivity and processability.[2,3] In this respect, chitin and chitosan are recommended as suitable resource materials, since these natural polymers have excellent properties such as biodegradability, biocompatibility, non-toxicity, and adsorption. The reaction of chitosan is considerably more versatile than cellulose due to the presence of NH2 groups. Today much attention is paid to chitosan as a potential polysaccharide resource.[4] Various eorts have been made to prepare functional derivatives of chitosan by chemical modications,[58] and only few of them are found to dissolve in conventional organic solvents.[9,10] Chitosan is only soluble in aqueous solutions of some acids, and some selective N-alkylidinations[5,6] and N-acylations[7,8] have also been attempted. Although several watersoluble[11,12] or highly swelling[8,13] derivatives are obtained, it is dicult to develop the solubility in common organic solvents by these methods. Modication of the chemical structure of chitin and chitosan to improve the solubility in conventional organic solvents has been reviewed by many authors.[14,1423] On the other hand, only a few reviews have been reported on biomedical applications of chitin/chitosan,[2433] and no comprehensive review has yet been published covering the entire range of applications. This review covers the literature from 1926 to 2000 dealing with properties, processing, and applications of chitin and chitosan.
2. PROCESSING OF CHITIN AND CHITOSAN Chitin is easily obtained from crab or shrimp shells and fungal mycelia. Chitin production is associated with food industries such as shrimp canning.

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The production of chitosanglucan complexes is associated with fermentation processes, such as those for the production of citric acid from Aspergillus niger. The processing of the fungal waste from A. niger, Mucor rouxii, and streptomyces consists of an alkali treatment that yields chitosanglucan complexes. The alkali removes the protein and deacetylates chitin simultaneously. Depending on the alkali concentration, some alkali-soluble glucans are also removed.[34] The processing of crustacean shells mainly involves the removal of proteins and the dissolution of calcium carbonate that is present in crab shells in high concentrations. The resulting chitin is deacetylated in 40% sodium hydroxide at 120 C for 13 hr. This treatment produces 70% deacetylated chitosan. Complete deacetylation can be obtained by repeating the steps, as shown in Fig. 1.
Figure 1.
Conversion of chitin to chitosan.

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3. ECONOMIC ASPECTS The production of chitin and chitosan is currently based on crab and shrimp shells discarded by the canning industries in Oregon, Washington, Virginia, and Japan, and by various nishing eets in the Antarctic. Several countries possess large unexploited crustacean resources, e.g., Norway, Mexico, and Chile.[35] The production of chitosan from crustacean shells obtained as a food industry waste is economically feasible, especially if it includes the recovery of carotenoids. The shells contain considerable quantities of astaxanthin, a carotenoid that has so far not been synthesized, and which is marketed as a sh food additive in aquaculture, especially for salmon. To produce 1 kg of 70% deacetylated chitosan from shrimp shells, 6.3 kg of HCl and 1.8 kg of NaOH are required in addition to nitrogen, process water (0.5 t), and cooling water (0.9 t). Important items in estimating the production cost include transportation, which varies depending on labor and location. In 1984 the worldwide price of chitosan was ca. US$ 10.00/kg, and the current price is ca. US$ 6.00/kg. During the past decades, the Central Institute of Fisheries Technology, Kerala, India initiated research on chitin and chitosan. In 1978, Madhavan and Nair[36] were the rst to report that dry prawn waste and dry squilla contained 23% and 15% chitin, respectively. In 1986, Madhavan et al.[37] reported that the chitinous solid waste fraction of the average Indian landing of shellsh ranged from 60,000 to 80,000 tons. Chitin and chitosan are now produced[38] commercially in India, Poland, Japan, the United States, Norway, and Australia. A considerable amount of research is in progress on chitin/chitosan all over the world, including India, to tailor and impart the required functionalities to maximize its utility.
4. PROPERTIES OF CHITIN AND CHITOSAN Most of the naturally occurring polysaccharides, e.g., cellulose, dextrin, pectin, alginic acid, agar, agarose and carragenas, are natural and acidic in nature, whereas chitin and chitosan are examples of highly basic polysaccharides. Their properties include solubility in various media, solution, viscosity, polyelectrolyte behavior, polyoxysalt formation, ability to form lms, metal chelations, optical, and structural characteristics.[39] Although the b(1!4)-anhydroglucosidic bond of chitin is also present in cellulose, the characteristic properties of chitin/chitosan are not shared by cellulose.[40] Chitin is highly hydrophobic and is insoluble in water and most organic solvents. It is soluble in hexauoroisopropanol, hexauoroacetone,[41] and chloroalcohols in conjunction with aqueous solutions of mineral acids[39] and dimethylacetamide (DMAc) containing 5% lithium chloride

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(LiCl).[42] Recently, the dissolution of chitosan in N-methyl morpholine-Noxide (NMMO)/H2O has been reported by Dutta et al.[43a,b] The hydrolysis of chitin with concentrated acids under drastic conditions produces the relatively pure amino sugar, D-glucosamine. Depending on the extent of deacetylation, chitin contains 5% to 8% (w/v) nitrogen, which is mostly in the form of primary aliphatic amino groups as found in chitosan. Chitosan undergoes the reactions typical of amines, of which N-acylation and Schi reactions are the most important. Chitosan glucans are easily obtained under mild conditions, but it is dicult to obtain cellulose glucans. N-Acylation with acid anhydrides or acyl halides introduces amido groups at the chitosan nitrogen. Acetic anhydride aords fully acetylated chitins. Linear aliphatic N-acyl groups higher than propionyl permit rapid acetylation of the hydroxyl groups in chitosan. Highly benzoylated chitin is soluble in benzyl alcohol, dimethyl sulfoxide (DMSO), formic acid, and dichloroacetic acid. The N-hexanoyl, N-decanoyl, and N-dodecanoyl derivatives have been obtained in methanesulfonic acid.[44,45] Chitosan forms aldimines and ketimines with aldehydes and ketones, respectively, at room temperature. Reaction with ketoacids followed by reduction with sodium borohydride produces glucans carrying proteic and non-proteic amino acid groups. N-Carboxymethyl chitosan is obtained from glyoxylic acid. Examples of non-proteic amino acid glucans derived from chitosan are the N-carboxybenzyl chitosans obtained from o- and p-phthalaldehydic acids.[46,47] Chitosan and simple aldehydes produce N-alkyl chitosan upon hydrogenation. The presence of the more or less bulky substituent weakens the hydrogen bonds of chitosan; therefore, N-alkyl chitosans swell in water in spite of the hydrophobicity of alkyl chains. They retain the lm-forming property of chitosan.[48]
5. DERIVATIVES OF CHITIN AND CHITOSAN Chitosan may readily be derivatized by utilizing the reactivity of the primary amino group and the primary and secondary hydroxyl groups. Glycol chitin, a partially o-hydroxyethylated chitin, was the rst derivative of practical importance; other derivatives[49] are as shown in Table 1. Derivatives of chitin may be classied into two categories; in each case, the N-acetyl groups are removed, and the exposed amino function then reacts either with acyl chlorides or anhydrides to give the group NHCOR, or is modied by reductive amination to NHCH2COOH. Of greatest potential importance are derivatives of both types formed by reaction with bi- or polyfunctional reagents, thus carrying sites for further chemical reaction.[50,51] In practice, such reactions are carried out on native chitin or on

CHITIN AND CHITOSAN Table 1. Derivatives N-Acylchitosans Chitin Derivatives and Their Uses[49] Examples Formyl, acetyl, propionyl butyryl, hexanoyl, acetanoyl, decanoyl, dodecanoyl, tetradecanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, benzoyl, monochloroacetoyl, dichloroacetyl, triuoroacetyl, carbamoyl, succinyl, acetoxybenzoyl, 5-methyl pyrrolidinone N-Carboxybenzyl, glycine glucan (N-carboxymethyl chitosan), alanine glucan, phenylalanine glucan, tyrosine glucan, serine glucan, glutamic acid glucan, methionine glucan, leucine glucan From anhydrides such as maleic, itaconic, acetylthiosuccinic, glutaric, cyclohexane 1,2-dicarboxylic, phthalic, cis-tetra hydrophthalic, 5-norbornene, 2,3-dicarboxylic diphenic, salicylic, trimellitic, pyromellitic anhydride, N,N-dicarboxymethyl O-Carboxymethyl, crosslinked O-carboxymethyl 1-Deoxygalactic-1-yl-, 1-deoxyglucit-1-yl-, 1-deoxymelibiit-1-yl, 1-deoxylactit-1-yl, 1deoxylactit-1-yl-4(2,2,6,6-tetramethyl-piperidine-1-oxyl)-, 1-deoxy-60 -aldehydolactit1-yl-, 1-deoxy-60 -aldehydomelibiit-1-yl, cellobiit-1-yl-chitosans, products obtained from ascorbic acid Palladium, copper, silver, iodine Potential Uses
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Textiles, membranes, and medical aids like wound dressings
N-Carboxyalkyl (aryl) chitosans
Chromatographic media and metal ion collection, functional cosmetics ingredient in hydrating creams Use for collection of trace transition metal ions to form lms or membranes and to prepare cosmetic products Molecular sieves, viscosity builders, and metal ion collection Expected to be useful as a novel type of antimicrobial agent
N-Carboxyacyl chitosans
O-Carboxyalkyl chitosans Sugar derivatives
Metal ion chelates
Catalyst, photography, health products, and insecticides Textiles
Semisynthetic resins of chitosan Natural polysaccharide complexes, quaternary chitosan salts Miscellaneous
Copolymer of chitosan with methyl methacrylate, polyureaurethane, poly (amideester) acrylamidemaleic anhydride Chitosan glucans from various organisms
Flocculation and metal ion chelation
Alkyl chitin, benzyl chitin, di-O-butyryl chitin
Intermediate serine protease purication, used as drug carrier, textiles, precursor of various chitin biomaterials (continued )

314 Table 1. Derivatives Examples
DUTTA, RAVIKUMAR, AND DUTTA Continued Potential Uses Desalting, ltration, dialysis, and insulating papers Enzymology, dialysis, and special papers Enzyme immobilization Food additive and anticholesterolemic
Hydroxybutyl chitin, hydroxyalkyl chitosans, cyanoethyl chitosan Glycol chitosan Glutaraldehyde chitosan Linoleic acidchitosan complex Uracylchitosan, theophylline chitosan, adenine chitosan, chitosan salts of acid, polysaccharides, chitosan streptomycin, N-cyclohexane chitosan, 2-amido-2,6diaminoheptanoic acid chitosan Chemically crosslinked glycine glucan Chitosan ascorbate reduced form Imidazole chitosan ketimine and its
Suitable for collection of carrier-free radioisotopes Used to treat parodontopathies Proposed for treatment of bone lesions
incompletely de-N-acetylated chitosan, so that the resulting polymer contains three types of monomeric units (IV).
These polyampholytes are particularly eective in removing metal cations from dilute solutions. Chitosan itself chelates metal ions, especially those of transition metals, and also nds application as a matrix for immobilization of enzymes.[49] Special attention has been given to the chemical modication of chitin, since it has the greatest potential to be fully exploited. Reactions with pure chitin have been carried out mostly in the solid state, owing to the lack of

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solubility in ordinary solvents. A 50% deacetylated chitin has been found to be soluble in water.[52,53]. This water-soluble form of chitin is a useful starting material for its smooth modications, through various reactions in solution phase. 5.1. Chitin Derivatives of Polysaccharides and Polypeptides Polysaccharide/polypeptide hybrid materials, chitin derivatives having polypeptide side chains, were prepared by the graft copolymerization of g-methyl L-glutamate N-carboxy anhydride (NCA) onto the water-soluble form of chitin in water/ethyl acetate.[1] Although NCA is very susceptible to hydrolysis, the N-acetyl groups of chitin react with NCA smoothly in solution, producing the resultant graft copolymer (V), (Eq. 2). After freezedrying, and hydrolysis in the presence of Na2CO3, the white powdery graft copolymer (VI) was obtained (Eq. 3).
5.2. Tosyl and Iodo Chitins Derivatives with tosyl and iodo groups add reactivity and bulkiness to the chitin macromolecules. The resulting derivatives are soluble reactive precursors for further regioselective modications, which can be carried out exclusively in homogeneous solution.[15] Chitin dissolved in aqueous sodium hydroxide was treated with chloroform solution of tosyl chloride, where the reaction was interfacial between the two immiscible solutions and depends on the rate of stirring. With vigorous stirring, the substitution was quite ecient and reproducible at 0 C.

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The tosyl chitins (VII) thus obtained were soluble and reactive precursors were subjected to the conversion to iodo chitins. The iodo substitution in the presence of excess sodium iodide in DMSO takes place easily due to the high solubility of both tosyl and iodo chitins. The resulting iodo chitins (VIII) were isolated by pouring the mixtures into acetone (Eq. 4). When the reactions were carried out above 100 C, the products were light tan to brown. At relatively low temperatures, e.g., at 7585 C, colorless products could be prepared in high yield.[14,15]
5.3. Ether-Type Chitin Derivatives Novel ether-type chitin derivatives were synthesized by reacting alkali salts of chitin with 1-chloropropane, propylene oxide, and 3-chloro-1,2-propanediol to prepare propyl chitin (PPC) (IX), hydroxypropyl chitin (HPC) (X), and dihydroxypropyl chitin (DHPC) (XI), respectively (Eqs. 57). The substituents were introduced primarily at the C6 position of the glucosamine unit in chitin, with a degree of substitution of approximately 0.30.5. The three chitin derivatives are soluble in weakly acidic aqueous solutions and DHPC even in pure water.[5460]

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5.4. Mixed Ester-Type Chitin Derivatives One of the ways of enhancing the solubility of chitin was the introduction of bulky acyl residues into the polymer.[16] One part powdered chitin was added to a mixture of four parts methanesulfonic acid and six parts carboxylic acid anhydrides. In the case of mixed esters, the products were obtained by varying the amount of butyric anhydride and acetic anhydride. The reaction mixture was stirred for 23 hr at 05 C and stored at 20 C overnight to complete the reaction. The products were precipitated in large quantities of crushed ice,

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ltered o, and washed with distilled water (Eq. 8). The samples were subsequently suspended in distilled water, neutralized with ammonia water, and boiled for a few minutes to neutralize any traces of remaining acids. The acyl chitins or mixed esters (XII) were ltered, washed with distilled water, and dried in vacuum. The acetyl chitin is soluble only in acidic solvents, such as formic acid, dichloroacetic acid, and methanesulfonic acid, while butyryl chitin is reported to be soluble in methanol, ethanol, dimethylformamide (DMF), dioxin, acetone, tetrahydrofuran, and in acidic solvents such as formic acid.[16]
5.5. Regioselective Chlorination of Chitin Sakamoto et al.[61] reported chlorination of chitin with equimolar mixtures of N-chlorosuccinimide and triphenyl phosphine under homogeneous conditions in a 5% (w/v) solution of LiCl in DMAc at 7085 C. The report reveals that polymer chain scission took place to some extent, especially when the chlorination was carried out at higher temperatures with higher concentrations of reagents Carbon-13 nuclear magnetic resonance. (13C-NMR) spectroscopy of the chlorinated products and gas chromatographic-mass spectrometric (GC-MS) analysis of their hydrolyzates, both as triuoroacetyl derivatives, showed that the chlorine substitution took place regioselectively at C6. Tseng et al.[62] reported the possibility of bromination of regenerated chitin in a similar fashion. 5.6. N-Acyl, N-Arylidene, and N-Alkylidene Chitosan Gels Hirano[20] reported that the amino group at C2 is more reactive towards electrophiles than are the hydroxyl groups at C3 and C6 in the amino-2deoxy-D-glucoside residue of chitosan. Chitosan is soluble in aqueous acetic acid solution, and the solution is miscible with methanol. In this solution, N-substitution occurs selectively in reaction with carboxylic acids and

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aldehydes, to produce N-acyl, N-arylidene, and N-alkylidene derivatives (XIII), respectively.
5.7. Maleilated Chitosan and Acrylamide Copolymers The synthesis of crosslinked copolymers of maleilated chitosan and acrylamide was reported by Berkovich et al.[54] Hydrophilic three-dimensional polymers nd application as column-packing material for gel and biospecic chromatography, as well as in the immobilization of enzymes. Typical polymers used for these purposes are acrylamide, glycolmethacrylate, agar and its derivatives, dextrans, and gels based on cellulose. The threedimensional structures and gels based on chitosan are obtained either by crosslinking chitosan with bifunctional aldehydes and anhydrides of acids, or as a result of the formation of hydrogen bonds and the physical interactions between substituents in chitosan chains.[13,53,55] Recently, Sridhari and Dutta[63] used this copolymer for color removal from textile euents. An ecient procedure for the preparation of network polymers of chitosan (XIV) is achieved by copolymerizing the double bonds of substituents in chitosan chains and vinyl monomer. The double bonds were introduced into the chitosan molecule by acylating it with maleic anhydride, and acrylamide was used as the vinyl comonomer.

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5.8. Chitosan/Calcium Alginate Beads Huguet et al.[64] reported the use of chitosan and calcium alginate for the mild encapsulation of hemoglobin. The rst procedure consisted of adding dropwise a hemoglobin-containing sodium alginate mixture in a chitosan solution, then hardening the interior of capsules thus formed, in the presence of CaCl2. In the second method, the droplets were directly pulled o in a chitosanCaCl2 mixture. Both procedures led to beads containing a high concentration in entrapped hemoglobin, as more than 90% of the initial concentration was retained inside the beads provided that the chitosan concentration was great enough. The molecular weight of chitosan and the pH of its solution (2, 4, or 5.4) had only a slight eect, the best retention being obtained with beads prepared at pH 5.4. The best retention during storage in water was obtained with beads prepared with high molecular weight chitosan solution at pH 2. Ionic interactions existing between alginate and chitosan at pH 5.4 and 2.0 are shown as (XV) and (XVI), respectively.

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5.9. Calcium CarbonateChitosan Composites Zhang and Gonsalves[65] reported the crystal growth of calcium carbonate on a chitosan substrate using a supersaturated calcium carbonate solution at dierent concentrations of polyacrylic acid (PAA) as an additive via biomimetic processing. Polyacrylic acid was introduced to the system for biomimetic growth of calcium carbonate crystals on the chitosan lm surface, and protonated nitrogen and carboxylate anions were created on the chitosan lm surface. Nucleation was initiated from these charges. Nucleation and crystallization occurred at low concentrations of PAA, and crystals covered the whole lm with a spherical morphology. 5.10. Chitosan/Polyether Hydrogels Hydrogels have been widely used in controlled-release systems.[66a,b] Hydrogels which swell and contract in response to external pH are being explored.[6769] Peng et al.[70,71] reported the pH sensitivity, swelling kinetics, and modeling drug release properties of semi-IPN hydrogels from chitosan and polyether N330. 5.11. Polysaccharide Chitosan/PEOPPO Nanoparticles Hydrophilic nanoparticle carriers have important potential applications for the administration of therapeutic molecules. These recently developed hydrophobichydrophilic carriers require the use of organic solvents for their preparation and have a limited protein-loading capacity. To overcome these limitations, a new approach was described for the preparation of nanoparticles (XVII) solely from hydrophilic polymers[72] (Eq. 9). The preparation technique, based on an ionic gelation process, is extremely mild and involves the mixture of two aqueous phases at room temperature. One phase contains the polysaccharide chitosan (XVIII) and a diblock copolymer of ethylene dioxide and propylene oxide (PEOPPO) (XIX), and the other contains the polyanion sodium triphosphate (TPP) (XX) of nanoparticles. The mixture can be conveniently modulated by varying the ratio chitosan (CS)/PEOPPO.

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In order to explore fully the high potential of chitin it is necessary to establish ecient modication methods. Chemical modications of chitin are, however, generally dicult owing to the lack of solubility, and the reactions under heterogeneous conditions are accompanied by various problems such as a low extent of reaction, diculty in regioselective substitution, structural ambiguity of the products, and partial degradation due to severe reaction conditions. Recently, Kurita[73] has developed novel modes of modication reactions of chitin to make possible sophisticated molecular designs, including biodegradability and bioactivity relations of the derivatives, and applications.
6. APPLICATIONS OF CHITIN AND CHITOSAN The interest in chitin originates from the study of the behavior and chemical characteristics of lysozyme, an enzyme present in human body uids. It dissolves certain bacteria by cleaving the chitinous material of the cell walls.[74] A wide variety of medical applications for chitin and chitin derivatives have been reported over the last three decades.[7578] It has been suggested that chitosan may be used to inhibit broplasia in wound healing and to promote tissue growth and dierentiation in tissue culture.[79] The poor solubility of chitin is the major limiting factor in its utilization, and the investigation of its properties and structure. Despite these limitations, various applications of chitin and modied chitins have been reported in the literature, e.g., as raw material for man-made bers.[80] Fibers made of chitin and chitosan have been useful as absorbable sutures and wound-dressing materials.[8185] These chitin sutures resist attack in bile, urine, and pancreatic juice, which are dicult with other absorbable sutures.[85] It has been claimed that wound dressings made of chitin and chitosan bers[82] accelerate the healing of wounds by up to 75%. Apart from their applications in the medical eld, chitin and chitosan bers have potential applications in waste water treatment, where the removal of heavy metal ions by chitosan through chelation has received much attention.[81,8689] Their use in the apparel industry, with much larger scope, could be a long-term possibility.[9093]
6.1. Biomedical Applications The design of articial kidney systems has made possible repetitive hemodialysis and sustaining the life of chronic kidney failure patients. Chitosan membranes have been proposed as an articial kidney membrane because of their suitable permeability and high tensile strength.[9497] The most important part of the articial kidney is the semipermeable membrane, so far made from commercial regenerated cellulose and cuprophane. Since

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the primary action of the cellulose membrane is that of a sieve, there is little selectivity in the separation of two closely related molecules.[98] These novel membranes need to be developed for better control of transport, ease of formability, and inherent blood compatibility. A series of membranes prepared from chitin and its derivatives improved dialysis properties.[99,100] One of the most serious problems of using these articial membranes is surface-induced thrombosis, where heparization of blood is needed to prevent clotting, and people who are liable to internal hemorrhage can be dialyzed only at great risk. Hence the most challenging problem still to be solved is the development of membranes which are inherently blood compatible. From this point of view, chitosan is hemostatic, i.e., causes clots.
6.1.1. Blended Chitosan Membranes Albumin, gelatin, and collagen are being widely used for modifying the polymeric substrates to improve their blood compatibility due to their passive nature in attaching platelets.[99101] It appears that these protein-blended membranes improve permeability to small molecules like urea, creatinine, uric acid, and glucose, compared to the standard membrane of bare chitosan. These membranes also inhibit the passage of large molecules like albumin (Mw$69 000). Albumin-blended membranes have similar permeability as that of other protein blended membranes for small molecules when dialyzed for 6 hr from various isolated permeants.[102] Collagen is easily degraded in biological media, and depending on the circumstances, this can be considered either as an advantage or a drawback. A method often chosen to slow down the biodegradation of natural polymers consists of crosslinking them by various processes[103,104] in order to hinder the mechanism of recognition by the hydrolytic enzymes specic to these polymers. Chitosan in interaction with collagen can aect the mechanism of hydrolysis by collagenase in two ways: by inhibition of the process of recognition, or by direct interaction with the enzyme. Chitosan is indeed known to inhibit some proteases.[105] In 1993, Taravel and Domard[106] were the rst to report the interaction between atelocollagen and fully deacetylated chitosan. Their investigation showed that a purely electrostatic complex is formed in which all the chitosan charges are involved. The process is largely hindered by gel formation in collagen solutions at high pH, and an encapsulation of microgels of collagen is suggested. The conformation of collagen in the complex is largely modied in the solid state. Further studies show that in some circumstances another type of complex can be obtained.[106] Zhang et al.[107] reported on the properties of collagen and chitosan composites using formaldehyde as crosslinking agent. From their studies it

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was clear that the chitosan network can interpenetrate into the collagen network, and that the mechanical and swelling properties were enhanced. They reported that the crosslinking conditions, such as time, concentration, and pH, can aect the swelling degree and tensile strength of these composites. Fibrinogen adsorption kinetics and platelet attachment to various protein-blended chitosan membranes were also investigated to demonstrate their blood compatibility.[30] The adhesion of platelets to protein-blended chitosans can be modied to variable degrees when tyrode-washed calf platelets are exposed to those membranes. Albumin-blended membrane demonstrates a maximum reduction in platelet adhesion in comparison to other membranes studied.[30] It is well understood that the nature of the surface-bound protein can alter the subsequent platelet adhesion and thrombosis.[99] Hence, reduced brinogen binding to certain protein-blended membranes may be one of the parameters for reduced plateletsurface binding via the modulation of brinogen receptors. Thus, it appears, albumin-blended chitosan membranes have superior permeability and blood compatibility compared to chitosan or standard cellulose membranes.
6.1.2. Enzyme Immobilization One of the most important applications of chitin is the immobilization of enzymes and whole cells.[108] A limited number of enzymes are of practical interest for industrial needs,[109] and some of the enzymes that have been immobilized are given in Table 2. There are many methods of immobilization of enzymes, such as entrapment and absorption, xing by crosslinking chitosan solutions and
Table 2. Uses[38] Enzymes/Cell Immobilized on Chitin and Its Derivatives and Proposed Proposed Uses AMP to IMP Starch and glycogen to D-glucose Plastein synthesis Hydrolysis of lactose D-glucose to D-fructose, preparation of D-gluconic acid Hydrolysis of cellobiose Preparation of pharmaceuticals, cosmetics, and food protein Urea to ammonia and CO2 Synthesis of L-tryptophan, nitrication of waste water
Enzyme/Cells AMP deaminase Amylase diastase and glucoamylase a-Chymotripsin b-D-Galactosidase D-Glucose isomerase b-D-Glucosidase Lysozyme, Pronase, Subtilisin, and Tripsin Urease E. coli cells, Nitrosomonas europea cells

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crosslinking insolubilized chitosan.[110] The most common method of xing enzymes to chitosan is by using crosslinking reagents such as dialdehydes (e.g., glyoxal and glutaraldehyde). The amino group of chitosan and the enzyme forms aldimine bonds with the dialdehyde and is reduced by sodium borohydride or sodium cyanoborohydride to form stable gels of active immobilized enzymes.[110112] In order to improve the mechanical stability and density with high resistance to attrition and compression, an inorganic support such as silica gel is coated with chitosan and subsequently used for the immobilization of enzymes. Such a system has all the advantages of support, such as exibility, elasticity, and high coupling eciency. Enzyme immobilization can also be done on porous surfaces of chitosan beads, giving good cell carriers, because surface area, density, and compressive strength are not changed during sterilization of these beads.[113] The advantages of using immobilized enzymes are: the enzymic reaction can be stopped at any desired time, a small amount of enzyme is sucient for large amounts of substrates, the enzyme is not lost in the product, there is no inhibition to limit the extent of the reaction, there is no self-digestion of the enzyme, enzymes from pathogenic organisms can be used, and a batch process can be made into a continuous process. In recent years the practice of using non-growing whole or lysed microbial cells, rather than puried enzymes, has gained in popularity. Advantages of immobilized cells are simple product isolation and repeated use in a continuous process.[114]
6.1.2.1. Bioactive Complex Immobilized Albumin-Blended Chitosan Membranes While chitosan membrane is thrombogenic, N-acetyl and N-hexanoyl chitosan membranes are more non-thrombogenic. So attempts were made to improve the blood compatibility of chitosan membranes via surface modications with least interference to their permeability properties.[115118] A complex having brinolytic, anticoagulant, and antiplatelet activities was prepared by the modication of urokinase with antithrombin-III, methyldopa, and polyglycolethylene. A non-thrombogenic, albumin-blended chitosan membrane was derived by immobilizing this bioactive complex via carbodiimide.[119] This novel membrane demonstrated good permeability for small molecules and showed a dramatic reduction in platelet attachment. It appears that membranes carrying immobilized drug complexes may have wider applications, such as in the hemodialysis of patients with hypertension, as well as for improved permeability and blood compatibility. This may also be useful for patients who are liable to internal hemorrhage on heparinization, which may reduce or prevent the use of heparin during

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dialysis. These membranes have to be sterilized before clinical use. So, the variation in permeability, mechanical, and surface properties was studied due to dierent sterilization techniques on chitosan membranes.[30] Reports are available regarding the permeability of various molecules through chitosan membranes[30,120,121] which contain dierent immobilized and modied biomolecules, such as: 1. Bioactive molecules immobilized to liposome-modied, albuminblended chitosan membrane. 2. Phosphoryl choline bilayer immobilized on albumin-blended chitosan membrane. 3. Chondratin sulfate and phosphoryl choline immobilized on chitosan surfaces treated with glow discharge and albumin. Various modications are suggested to dramatically improve the blood compatibility of chitosan membrane without altering its superior permeability. The development of a smaller articial kidney may be possible if these approaches are successful.
6.1.3. Chitosan as an Articial Skin Individuals who suer extensive losses of skin are acutely ill and are exposed to massive infection or to severe uid loss. Patients who survive these early symptoms must often cope with problems of rehabilitation arising from deep, disguring scars and crippling contractures. Malette et al.[122] studied the eect of treatment with chitosan and saline solution on healing and broplasia of wounds made by scalpel insersions in skin and subcutaneous tissue in the abdominal surface of dogs. Yannas and Burke[123] proposed a design for articial skin, applicable to long-term chronic use, and focused on a non-antigenic membrane which performs as a biodegradable template for the synthesis of neodermal tissue. It appears that chitosan polysaccharides having structural characteristics similar to glycosamino glycans can be considered for developing such a substratum for skin replacement.[123126]
6.1.4. Chitin and Chitosan-Based Dressings Chitin and chitosan have many distinctive biomedical properties and have been applied in many dierent industrial areas. However, chitin-based wound-healing products are still at the early stage of research.[127] A dressing made of a chitosangelatin complex was developed by Sparkes and Murray.[128] The procedure involves dissolving chitosan in water in the presence of a suitable acid, maintaining the pH of the solution at about 23, followed by addition of gelatin dissolved in water. The weight ratio of chitosan

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and gelatin is 3:1 to 1:3. To reduce the stiness of the resulting dressing, plasticizers such as glycerol and sorbitol are added into the mixture. A dressing lm was cast from this solution on a at plate and dried at room temperature. It was claimed that, in contrast to conventional biological dressings, this experimental dressing, displayed excellent adhesion to subcutaneous fat. Nara et al.[129] patented a wound dressing comprising a non-woven fabric composed of chitin bers made by a wet spinning technique. In one of the examples, chitin powder was ground to 100 mesh and treated in 1 N HCl for 1 hr at 4 C. It was then heated to 90 C where it was treated for 3 hr in a 3% NaOH solution to remove calcium and protein in the chitin powder, and rinsed repeatedly followed by drying. The resultant chitin had a viscosity of 256 cP at 30 C when it was dissolved in a DMAc solution containing 8% LiCl (w/v) to form a 0.2% solution (w/v). After ltering and holding to allow defoaming to occur, the dope was transported to a nozzle under pressure and extruded into butanol at 60 C. The chitin was coagulated, collected, and the resultant strand was rinsed with water and dried to obtain a lament of 0.74 dtex with a strength of 2.8 g/d. The laments were then cut into staple bers. Non-woven dressings were made by using polyvinyl alcohol as a brous binder. In 1988, Kifune et al.[130] developed a new wound dressing, composed of chitin non-woven fabric, which has been proved to be benecial in clinical practice. Kim and Min[131] have developed a wound covering material from polyelectrolyte complexes of chitosan with sulfonated chitosan. It is proposed that wound healing is accelerated by the oligomers of degraded chitosan by tissue enzymes, and this material was found to be eective in regeneration of the skin tissue in the wound area. Biagini et al.[132] developed a chitosan derivative, N-carboxybutyl chitosan, used in dressings to treat plastic surgery donor sites. The solution of N-carboxybutyl chitosan was dialyzed and freeze-dried to produce a soft and exible pad, which was sterilized and applied to the wound. They reported that this dressing could promote ordered tissue regeneration compared to control donor sites. Further, the dressing may show better histoarchitectural order and better vascularization. While the absence of inammatory cells was observed at the dermal level, fewer aspects of proliferation of the malpigihan layer were reported at the epidermal level. Researchers at the British Textile Technology Group (BTTG) patented a procedure for making chitin-based brous dressing.[133136] In their method the chitin/chitosan bers were not made by the traditional ber-spinning technique, and the raw materials were not derived from shrimp shell, but instead from microfungi. Their procedure can be summarized as follows: Microfungal mycelia preparation from culture of Mucor mucedo growing in a nutrient solution. II. Culture washing and treatment with NaOH to remove protein and precipitate chitin/chitosan. I.

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III. Bleaching and further washing. IV. Preparation of the dispersion of the bers using paper-making equipment. V. Filtration and wet-laid matt preparation; mixing with other bers to give mechanical strength. This is a novel method which uses non-animal sources as the raw material, and the resulting microfungal bers are totally dierent from the normal spun bers. They have highly branched and irregular structures. The bers are unmanageably brittle when they are allowed to dry, and a plasticizer has to be associated with the whole process. A wet-laid matt is the basic product. Muzzarelli[137] recently introduced another chitosan derivative which was believed to be very promising in medical applications. This derivative is 5-methylpyrrolidinone chitosan, which was made by a series of chemical reactions. It was claimed that this polymer is compatible with other polymer solutions, including gelatin, poly(vinyl alcohol), poly(vinyl pyrrolidone), and hyaluronic acid. The advantages claimed by the inventor include healing of wounded mensical tissues, healing of decubitus ulcers, depression of capsule formation around prostheses, limitation of scar formation, and retraction during healing. Some wound dressing samples were also prepared from the aqueous solution of this 5-methylpyrrolidinone chitosan, which was dialyzed and laminated between stainless steel plates and freeze-dried to yield eeces. It was also claimed that this material could be fabricated into many dierent forms, such as laments, non-woven fabrics, etc. Once applied to a wound, 5-methylpyrrolidinone chitosan becomes immediately available in the form of oligomers produced under the action of lysozyme. Another chitin derivative, dibutyrylchitin, was spun into a ber recently by a research group[138] at the University of Leeds. Dibutyryl chitin was prepared by treatment of krill chitin with butyric anhydride at 2530 C in the presence of perchloric acid as a catalyst. Samples of polymers with the molecular weights high enough to form bers were obtained, and dibutyryl chitin bers were made by a simple method of dry-spinning in acetone. The results showed that the bers had tensile properties similar to or better than those of chitin and some chitin derivatives. An attempt to convert dibutyryl chitin bers to chitin bers was made. It was claimed that chitin bers with good tensile properties could be obtained by alkaline hydrolysis of dibutyryl chitin bers without destroying the ber structure. However, no more information was given about the uses of this ber. As far as chitin-based commercial wound dressings are concerned, one product (Beschitin , Unitika) is commerically available in Japan. This is a non-woven fabric manufactured from chitin laments. At present, very few commercial dressings based on chitin or chitosan ber are available in the market.

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6.1.5. Opthalmology Chitosan possesses all the characteristics required for an ideal contact lens: optical clarity, mechanical stability, sucient optical correction, gas permeability, partially towards oxygen, wettability, and immunological compatibility. Contact lenses are made from partially depolymerized and puried squid pen chitosan by spin-casting technology, and these contact lenses are clear, tough, and possess other required physical properties such as modulus, tensile strength, tear strength, elongation, water content, and oxygen permeability. Antimicrobial and wound-healing properties of chitosan, along with excellent lm-forming capability, make chitosan suitable for the development of an ocular bandage lens.[139]
6.1.6. Biodegradable Drug Delivery Systems The eciency of drugs would increase enormously if they were directed selectively to their cellular targets, a concept rst introduced by Paul Ehrich at the beginning of the twentieth century. However, it is only for the last 30 years that the development of natural science has initiated projects in several laboratories to try to translate this dream into reality. There are several ways of approaching this problem.[140146] The applicability of natural polysaccharides such as agar, konjac, and pectin in the design of dosage forms for sustained release has been reported.[147149] Despite the medical applications of chitin/chitosan described above, they are still utilized in the pharmaceutical eld.[41] It is known that compounds having a molecular weight lower than 2900 pass through membranes derived from chitosan.[150] Since chitin and chitosan do not cause any biological hazard and are inexpensive, these polymers might be suitable for use in the preparation of dosage forms of commercial drugs.[151155] Controlled-release technology emerged during the 1980s as a commercially sound methodology (Fig. 2). The achievement of predictable and reproducible release of an agent into a specic environment over an extended period of time has many signicant merits. The most signicant merit would be to create a desired environment with optimal response, minimum side eect, and prolonged ecacy. This is a relatively new technology and requires an interdisciplinary scientic approach. Chitin/chitosan controlled delivery systems are being developed further, and used for a wide variety of reagents in a number of environments.[72,156158] Draget et al.[104] described a procedure for preparing homogeneous chitosan gels by in situ molybdate crosslinking. The gels are obtained by dispersing solid MoO3 in a buered chitosan solution, and the polymer is crosslinked by formation of heavily negatively charged molybdate polyoxyanions. The resulting ionic gels are transparent, thermoirreversible, and can be made at low

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Figure 2. delivery.
Repeated dose vs. controlled delivery: (a) repeated dose delivery, (b) controlled
polymer concentrations. Depending on the ionic strength, these gels are able to swell to several times their original size in aqueous solutions. Chandy and Sharma[159] showed the possibility of modifying the formulation to obtain the desired controlled release of the drug in an oral sustained-delivery system. They prepared chitosan beads for oral sustained delivery in 2% acetic acid, blowing through nozzles into NaOHmethanol solution by compressed air. The regenerated porous beads were washed with hot, and then cold, water. Nishimura et al.[160] reported the properties of these beads. The in vitro evaluations of nifedipine-loaded chitosan beads were monitored by ultraviolet (UV) spectrophotometer. Thacharodi and Rao[161] have developed transdermal propranolol hydrochloride (prop-HCl) delivery systems which are controlled by membrane permeation. Various chitosan membranes with dierent crosslink densities were used as drug release controlling membranes, and chitosan gel as the drug reservoir. The physicochemical properties of the membranes have been well characterized, and the permeability characteristics of these membranes to both lipophilic and hydrophilic drugs have been reported.[162a,b] A procedure for preparing a homogeneous chitosan gel in NMMO/H2O has been developed in the authors laboratory for sustained dosages.[43] Chitosan gel was obtained at 120oC in NMMO/H2O, which is transparent and suitable for sustained dosages. (Caution! NMMO detonates readily at 130 C.) The swelling and thermal behavior of the new gelling system have also been studied by the authors.[163a,b]
6.1.7. Microcapsules/Microspheres Related to Chitosan Since the introduction of microcapsules by Green et al.[164] in the 1950s, interest in the preparation, characterization, and application of

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microcapsules/microspheres has increased immensely. Syntheses of microcapsules/microspheres have been widely reviewed.[164167] Due to the attractive properties and wide applications of chitosan-based microcapsules and microspheres, a survey of their preparation, characteristics, and applications is very useful.[168171] Natural polymeric microcapsules/microspheres are generally manufactured via dierent microencapsulation processes, e.g., polymerization techniques. The choice of technique is largely dependent on the nature of the starting materials and the desired compositional and morphological characteristics of the resultant microcapsules/microspheres. It is not easy, for example, to use the solvent evaporation and the polymer melt solidication methods to prepare chitosan microcapsules due to diculties in obtaining complete solvent evaporation and due to the lack of a melting point for chitosan. Yao et al.[165] reviewed microencapsulating methods employed for chitosan microcapsules/microspheres. All types of chitosan microcapsules/microspheres have a wide range of applications. They may be employed, for example, to solve numerous problems in environmental and biomedical engineering. Chitosan microcapsules/ microspheres are being studied for the controlled release of drugs.[165]
6.2. Applications in Chromatographic Separations The characteristics of chitin and chitosan make them of great value for chromatographic supports. They can interact with organic substances like proteins and act as electron donors toward transition metal ions. Townsley,[172a] and Takeda and Tomida[172b] used chitin powder as a chromatographic support in thin layer chromatography for the separation of nucleic derivatives. Chitin thin layers have higher Rf than for cellulose layers. The superiority of chitin to silica gel and polyamide for the thin layer chromatography of some phenols and amino acids has also been reported elsewhere.[173] Chitosan has also been used by Muzzarelli and Rocchetti[174a] for the determination of molybdenum and vanadium in sea water. Thus, several elds of chromatography are open to industrial applications of chitin, chitosan, and their derivatives,[174b,c] like ion exchange chromatography, chelation chromatography, ligand exchange chromatography, anity chromatography, high pressure chromatography, and gel chromatography.
6.3. Photography Chitosan plays an important role in the eld of photography due to its resistance to abrasion, optical characteristics, lm-forming ability, and behavior with silver complexes, which are easily carried from one to another

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layer of a lm. Furthermore, due to the presence of regular amino groups, chitosan can easily form mixtures with gelation and thus prevent lateral diusion of acidic dyes.[175] 6.4. Food and Nutrition[176188] Chitosan has been used as an eective agent for coagulation of suspended solids from various food processing waste, and the potential food application of chitin and chitosan and some of their functional properties have been presented in recent years. The use of chitinous material to improve nutritional value has been well studied by dierent workers. The presence of chitin in marine invertebrates, insects, fungi, yeast, and in cell walls of certain plants, and of chitosan in various fungi, indicates that chitin and chitosan are already part of our food supply. Furthermore, the toxicity studies have showed that chitosan is as safe as salt and sugar. According to the U.S. Environmental Protection Agency, chitosan is acceptable for portable water applications. Chitosan also has hypolipidemic and hypocholersterolemic activity.
6.5. Water Engineering As environmental protection is becoming an important global issue, the relevant industries should pay attention to developing such a technology which would be free from all sorts of environmental problems.[189,190] Nair et al.[191] used chitosan obtained from prawn waste for removal of mercury from solutions. In order to nd the eect of particle size of chitosan on adsorption of Hg2, chitosan of two dierent particle sizes, namely, 1020 mesh and 40 mesh, was employed. The results of their investigation are given in Fig. 3, which clearly indicates that the eciency of adsorption of chitosan depends upon the period of treatment, particle size, initial concentration of the Hg2, and quantity of the chitosan used. The study on adsorption of metal ions using chitosan as an adsorbent by various workers is listed in Table 3. Recently, Bhavani and Dutta[193] reported the removal of color from dyehouse euents using chitosan as an adsorbent. Hydroxymethyl chitin and other water-soluble derivatives are useful occulants for anionic waste streams.[74] Chitosan N-benzyl sulfonate derivatives are used as sorbents for removal of metal ions in acidic medium by Weltrowski et al.[194] The selective adsorption capacity for metal ions of amidoximated chitosan bead-g-PAN copolymer has been studied by Kang et al.[195] These investigations have clearly indicated that chitosan has a natural selectivity for the heavy metal ions and is useful for the treatment of waste water. Maleilated chitosan and chitosan bers in

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Figure 3. Inuence of quantity of chitosan on the adsorption of mercury from lower and higher concentrations.
Table 3. Removal of Metal Ions Cd2
Waste Water Treatment from Chitosan as an Adsorbent by Various Workers Conc. Range (ppm) 110 Parameters for Adsorption Particle size of adsorbent Temperature variation, pH 7 Particle size 0.44 Kinetics study Research Group Jha et al. Rower et al. Makay et al. Yang et al. Maruce et al. Udayshankar et al. Peniche-covas et al. Ref. [192a] [192b] [192c] [192d] [192e] [192f] [192g]
Cd2 Cu2, Hg2, Ni2, Zn2 Cr3 Cr6 Hg2

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various forms have been used for the removal of dyes from the euent of textile industries.[196a,b]
6.6. Textile Industry 6.6.1. Introduction to Chitin and Chitosan Fibers Utilization of chitin as a resource is extremely limited because of the poor solubility and poor reactivity, which are due to the strong micelle structure which was formed through hydrogen bonds between aminoacetyl groups. The spinnability and lm-forming ability, like those in cellulose, are obtained in chitin when it dissolves at high concentrations without degradation of the molecules. The polyamide-type micelle should be broken up prior to solubilization of chitin into a solvent or prior to being subjected to chemical reactions. The preparation of chitin viscose was reported previously through the xanthation of alkali chitin by the application of a freezing procedure.[197] Chitin ber was obtained from chitin viscose using the spinning conditions of rayon ber at a lower temperature, but it was not suitable for practical use because of the weakness of both its tenacity and its knot strength in the wet state. However, the freezing procedure would seem to be useful to break up the micelle structure of a chitin molecule. On this basis several solvents for polyamides were applied to dissolve the chitin. The formic aciddichloroacetic acid system was found to be a suitable solvent for obtaining a viscous chitin solution when the freezing procedure was employed.[197] Chitosan bers were made by wet spinning of the polymers solution in 2% aqueous acetic acid.[198] The ber properties were aected by processing conditions, such as spin strength ratio, coagulation bath composition, and drying conditions. The chitosan bers were acetylated with acetic anhydride in methanol, producing regenerated chitin bers. The acetylation process was aected by the reaction temperature, treatment time, and the molar ratio of anhydride of amine groups. The properties of the acetylated chitosan bers were studied in terms of thermal stability, solubility, and mechanical properties. It was found that, after acetylation, the bers had an improved thermal stability and tensile strength. There have been many attempts to produce chitin and chitosan bers.[197,199205] In the case of chitin, the major problem has been to nd a suitable solvent. Although a number of solvents, such as formic acid,[197] concentrated mineral acid,[201] trichloroacetic acid (TCA),[205] DMAcLiCl,[200,205] and a 40/40/20 mixture of TCA, chloral hydrate, and dichloromethane[204] can dissolve chitin, the solvents are not convenient and in some cases degradation of the polymer is unavoidable. Nonetheless, chitin bers with a tenacity of up to 0.44 N/tex (4.5 g/dtex) have been reported.[204,206,207]

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6.6.1.1. Solvent and Solution Properties Chitin and chitosan degrade before melting, which is typical for polysaccharides with extensive hydrogen bonding. This makes it necessary to dissolve chitin and chitosan in an appropriate solvent system to spin bers. Residual solvent must then be either leached or evaporated out of the ber. Solvent systems for chitin and chitosan have been studied extensively. Although many solvents have been used, only a handful are practical for industrial applications due to lack of toxicity, corrosiveness, or mutagenic properties.[208] Potentially useful solvents include certain acids [aqueous acetic acid, formic acid (FA)], halogenated solvents, amides with Li complexes, and combinations thereof. Solution properties of chitin and chitosan have also been studied extensively. For ber spinning, the objective is to obtain a homogeneous non-gel solution with a maximum polymer-to-solvent ratio. For each solvent system, polymer concentration, pH, counterion concentration, and temperature eects on the solution viscosity must be known. Examples of these are measured mostly for chitosan and reported by various workers elsewhere.[209220] In the case of bers, comparative data from solvent to solvent are unavailable. As a general rule, researchers dissolve the maximum amount of polymer in a given solvent system that still retains homogeneity and then spin bers without any further characterization of the solution. To spin bers out of solution requires a coagulant to allow for polymer regeneration or solidication. The nature of the coagulant is also highly dependent on the solvent and solution properties as well as the polymer used.
6.6.1.2. Natural Microbrillar Arrangement Chitin has been known to form microbrillar arrangements in living organisms. These brils are usually embedded in a protein matrix and have diameters from 2.5 to 2.8 nm. Crustacean cuticles possess chitin microbrils with diameters as large as 25 nm. These microbrillar arrangements were reviewed by Muzzarelli,[221] and by Brine and Austin.[222]
6.6.1.3. Fiber Formationin Retrospection Von Weimarn[223,224] reported the rst solution of chitin that could be formed into a ropy-plastic state in 1926. These solutions were using readily soluble salts capable of strong hydration. In the order of ease of solubility of chitin, they are: LiCN > CaCNS2 > CaI2 > CaBr2 > CaCl2

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No tensile evaluations were formed on these ropy materials. Kunike[225] pointed out as early as 1926 the problems in dissolving chitin. To help in the dissolution of chitin, it was N-deacetylated in 5% caustic at 60oC for 14 days. Another procedure for N-deacetylation was to place the chitin in an autoclave for 3 hr at 180oC and 10 atm pressure. He also pointed out that 6% to 10% solids of N-deacetylated chitin can be brought into acidic solutions at room temperature. Aqueous acetic acid was found to be suitable for this purpose. Fibers were spun by removing impurities of these acidic solutions through lter presses. Chemicals incompatible with chitin were suggested as coagulants. The resultant bers were washed and dried under tension. The nal product bers had a round to heart-shaped cross-section with a tensile breaking load of 35 kg/mm2 (345 Pa). The bers possessed a dull luster similar to natural silk, leading to the suggestion that the N-deacetylated chitin bers would make good articial hair. The collection and recycling of chitin from small-scale consumers was also suggested. An early patent application on plastic masses of chitin was made on this procedure by Kunike[225] at the Kaiser Wilhem Institute fuer Fasertochemie in 1926. Clark and Smith[226] produced bers by dissolving chitin at 95 C in presaturated solutions of lithium thiocyanate (saturated at 60 C). Their investigation showed no tensile properties or solution concentrations, however, x-ray analysis showed a high degree of orientation. Solvent removal was not successful, even at 200 C. Lithium iodide was implied to have behaved in the same manner. A ratio of ve molecules lithium thiocyanate per mole and hydroglucose unit was found to exist. This is comparable to the celluloselithium thiocyanate compound, and the role of solvent/salt complexes in terms of cellulose solubility has been reviewed in detail.[227,228]
6.6.2. Novel Solvent Spin Systems 6.6.2.1. Halogenated Solvent Spin System In 1975, Austin[229] suggested organic solvents containing acids for the direct dissolution of chitin. Such a system was chloroethanol and sulfuric acid, where the precipitation of chitin in brillar form in water, methanol, or aqueous ammonium hydroxides was mentioned, but no ber tensile data were presented. In 1975, Brine and Austin[222] suggested TCA as a chitin solvent. Chitin was pulverized and two parts by weight were added to 87 parts by weight of a solvent mixture containing 40% TCA, 40% chloral hydrate, and 20% methylene chloride over a period of 3045 min. A lament was extruded from this solution using a hypodermic needle and acetone as the coagulant.

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The lament was then neutralized with potassium hydroxide (KOH) in 2-propanol followed by washing in deionized water. The laments were then cold drawn. Two tensile breaks were taken at 60% relative humidity and room temperature. The rst break was from a lament with a crosssection of 0.08 0.10 mm2, yielding a tensile strength of 72 kg/mm2 (710 Pa) and a breaking elongation of 13%. The second lament had a cross-section of 0.014 0.740 mm2, indicating a collapsed core structure. It had a tensile strength of 104 kg/mm2 (1026 Pa) and a breaking elongation of 44%.[185,203,230] Syringing a lament should not be interpreted as conclusive evidence for a possible wet-spinning process. While syringe extrusion might indicate the selection of a coagulant, it would be surprising to obtain meaningful tensile data. Shear forces in a spinneret are much greater than those experienced in a syringe tip. Kifune et al.[231] suggested dissolving chitin in TCA and a chlorinated hydrocarbon such as chloromethane, dichloromethane, 1,1,2-trichloroethane. The TCA concentration should be kept between 2.5% and 75% by weight. A concentration range between 1% and 10% chitin was suggested, as well as dissolution below room temperature. Fiber extrusion occurred through a spinneret of between 0.04 and 0.06 mm diameter into an acetone coagulation bath followed by a methanol bath. The dried laments ranged in tensile strength from 1.67 to 3.1 g/d and an elongation from 8.7% to 20%, respectively. The strength of the bers was improved by leaving them in 0.5 g/L aqueous caustic solution for 1 h. The resultant tensile strengths were 2.25 to 3.20 g/d with elongations of 19.2% to 27.3%, respectively. Kifune et al.[83,232] further suggested that these chitin laments were suitable as adsorbable surgical sutures. However, TCA is very corrosive and degrades the polymer molecular weight. The breaking elongations suggest that the halogenated solvents act as plasticizers. Fuji Spinning Company[233] dissolved chitosan in a mixture of water and dichloroacetic acid (DCA). The 6.44% chitosan acetate salt solution viscosity was 410 poise. The dope was extruded through a platinum nozzle into basic CuCO3/NH4OH solution to form bers. Denier and tensile properties were unavailable. Capozza[94,234236] suggested hexauoroisopropanol and hexauoroacetone sesquihydrate as a solvent system. Chitin was spun into bers using this system. Dry spinning was accomplished by heating a solution containing chitin and 97 parts hexauoroisopropanol at 55 C and extruding through a spinneret. The bers were autoclaved by steam but no tensile properties were given. Wet spinning was accomplished by extruding a 3% solution of chitin in hexauoroacetone sesquihydrate into an acetone coagulation bath. The solution was further washed with acetone and then dried and drawn. Comparative tensile strengths were not reported. Solvents used by these systems were highly toxic,[237] which made complete solvent recovery imperative.

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Tokura et al.[198] used a combination of FA, DCA, and isopropylether as a solvent system. Chitin was cycled several times from 20 C to room temperature in FA, after which a small amount of DCA was added. Isopropylether was then added to reduce the solution viscosity to below 199 poise. Dierent coagulation systems were used. The lament tensile properties[198] show that dry tenacities were below 1.59 g/d and no elongations above 4.3%. It is noteworthy that the wet strength drops to below 0.50 g/d, but that the elongation increases to as high as 13%. A TCA/dichloromethane spin system[238] is also described by Unitika Co. Ltd. Three parts chitin were dissolved in 50 parts TCA and 50 parts dichloromethane by weight. The defoamed dope was extruded into acetone before wind-up. The bobbins were neutralized with KOH, washed with water, and dried. The bers had a tensile strength of 2 g/d and 0.520 denier. Unitika Co. Ltd. also used the TCAchloral hydrate dichloroethane solvent system[239] for chitin. Five parts chitin were dissolved in 100 parts of a 4:4:2 TCA:chloral hydrate:dichloroethane solvent mixture and extruded through a 0.06-mm nozzle into acetone. The bers were treated with methanolic NaOH. The ber gave optimum tenacity of 3.2 g/d with an elongation of 20%. Unitika Co. Ltd. followed this up with another patent using a 60:40 TCA:trichloroethylene spin dope mixture.[240] Tensile properties were unavailable. In 1983, Unitika Co. Ltd.[241] showed that a dope consisting of three parts chitin, 50 parts TCA, and 50 parts dichloromethane could be spun at a rate of 1.7 mL/min under 25 kg/cm2 pressure into acetone to form laments. The extrusion die had 50 holes of 0.07 mm diameter each. This indicates a jet velocity of 8.8 m/min and a take-up of 5 m/min. The coagulation bath was maintained at 18 C. The laments were washed with acetone at 18 C for 10 min, rewound at 4.5 m/min, then neutralized, washed, and dried. The multilament product had a total denier of 150 with a tenacity of 2.65 g/d. A similar system using four parts of chitin in the same solvent, but a 40-hole die of 0.08 mm diameter each, was also used.[242] The jet velocity was 10.4 m/min into a 25 C acetone bath. The rst take-up roll at 5 m/min was followed by a rewinding at 7 m/min. The total denier was 175; however, no tensile properties were reported. Some of the halogenated solvent systems approached dry tenacities of above 3 g/d; however, the low wet tenacities were still undesirable. Although the ber characterization was much better for these systems, the polymer characterization lacked molecular weight as well as degree of N-acetylation formation. Solution properties would be hard to obtain due to rapid chitin degradation in these solvents. Although anhydrous coagulation baths were used and compared, bers were neutralized in aqueous media. A study in completely anhydrous systems would be of interest, since it may lead to more densely consolidated bers. The implementation of these spin systems represents a problem due to the nature of the solvents: TCA and DCA are corrosive and degrade the polymer upon short exposures.

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6.6.2.2. AmideLiCl System In 1977, Rutherford and Austin[42] published marine chitin properties and solvents. This summarized the problems encountered in nding a solvent system for chitin. Austin[243] suggested DMAc and 5% LiCl or N-methyl-2pyrrolidone (NMP) and 5% LiCl as solvents for chitin. A solution of 5% w/v was obtained within 2 hr with these systems. A lament was extruded from the solution using a 15-gauge needle into an acetone coagulation bath. This was followed by more washing and drawing in acetone. The nal lament was washed in deionized water. Tensile properties were obtained at 60% relative humidity and room temperature at an applied stress of 0.1 cm/min. The resultant dry tensile strengths for dierent crab and shrimp species ranged from 24 to 60 kg/mm2 (236592 Pa). Austin[244] published another comprehensive paper in which he elaborated on chitin solvents, but not bers. Nakajima et al.[83] also dissolved chitin in an amideLiCl solution. The solution was extruded through a 0.05-mm spinneret into a butylalcohol coagulant. The dry tensile strength of the bers was 50 kg/mm2 (493 Pa). Kifune et al.[245,246] elaborated on this spin system. A spin dope concentration of 1% to 10% in NMP and DMAcLiCl is suggested, with an alcohol coagulation bath followed by a draw bath and further washing. Several other Japanese patents[247,248] also used the DMAcLiCl spin system. Unitika Co. Ltd. claimed bers spun from a solution containing 0.5 g chitin, 8 g LiCl, and 100 g DMF. The viscosity of the solution was 50600 cP at 30 C depending on the chitin concentration. A 3% chitin dope in a 20:1 DMF:LiCl solvent was spun through a die of 50 holes of 0.08 mm diameter each into an isobutanol coagulation bath at 10 m/min. This gave 61-denier bers with tenacities of 3.81 g/d after washing and drying. This was followed by spinning a 3.5% chitin solution dissolved in a 25:3 NMP:LiCl solution into 70 C isobutanol. No tensile properties were reported. Unitika Co. Ltd.[248] also reported a 58-denier lament with a tenacity of 4.25 g/d by spinning a dope consisting of 11 g chitin and 200 g of 8% LiCl in NMP solution. The coagulant was isobutanol. Along the same lines,[249] a dope was prepared containing 3 g chitin and 200 g of saturated LiCl in DMAc solution. To this dope, another 0.5 g LiCl was added before spinning into isobutanol. The nal 65-denier lament had a tenacity of 4.18 g/d. It is not clear if this high denier was for bers or multilaments; in general, highdenier bers result in poor tensile properties. A group of Russian researchers[250] spun chitin bers out of DMAc/ NMP solutions containing 5% chitin and 5% LiCl (based on chitin content). The bers were drawn in a 50:50 ethanol:ethylene glycol bath, giving an average yield strength of 390 MPa with 3% elongation. An initial modulus of 2 GPa was also reported. Scanning electron microscopy showed bers with a round brillar cross-section. A follow-up study showed that as the degree

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of N-acetylation increased (1230%), the modulus of elasticity and relative elongation decreased. X-ray analysis showed that as the degree of acetylation increased, the amount of amorphous regions also increased.[251] The amidelithium systems showed some of the best dry tenacities, although they still lack adequate wet tenacities. The low wet tenacities are probably due to low crystallinity and poor consolidation of the ber. The bers and spin dopes were well characterized, but the polymers used to prepare these dopes were not properly characterized. Some coagulation studies were carried out, but a clear comparison could not be made. A very real problem with this spin system is the removal and recovery of lithium from the ber. The lithium acts as a Lewis acid by solvating the chitin amide group.
6.6.2.3. NMMO/H2O System Attempts have been made by the authors[252] to develop a process for chitosan bers by direct dissolution using a novel solvent system (NMMO/ H2O). In this process, a mixture of 5% chitosan to NMMO/H2O was kept for 48 hr at room temperature and then heated to elevated temperature until gel formation is complete.[163] The resulting chitosan gel was then allowed to cool to the ambient temperature. The almost transparent and brownish gel obtained was insoluble in water and in common organic solvents. The Tg of the gel was observed about 6 C higher than that of chitosan, i.e., 150 C, and the increased Tg of the gel was due to the restricted molecular movement, owing to formation of NO bonding at the C2 position of chitosan. The thermal behavior of chitosan and gel is conrmed by evaluation of enthalpy changes, from 163 to 169 cal/g. The ber was made from the gel following melt spinning. The precipitation of chitosan in brillar form in water was obtained.
6.6.3. Fiber Summary Early recognition of chitins microbrillar arrangement pointed to berforming possibilities. Chitin was found to be intractable in common organic solvents. This led to the parallel development of the xanthate process as it was established for cellulose. Resultant ber properties were below 2 g/d in tensile strength. The low tensile strength values and environmental concerns with the xanthate process led to the development of novel halogenated and amideLi(halide) solvent systems in the 1970s. Breaking strengths of 4.25 g/d MPa for bers were reported.[253] A combination of solvent removal represents some of the major obstacles with these systems. To avoid these solvent problems, chitosan can be dissolved with ease in dilute non-corrosive aqueous acids such as formic and acetic acids. Fibers obtained from these

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aqueous acid solutions exhibited breaking strength of 3.81 g/d MPa. A wide range of chitosan derivatives has also been synthesized, of which mixed ester derivatives gave the most promising results.[44,253257] Fiber properties of 7.1 g/d are found from liquid crystal solutions.[257] Each of these chitosan derivatives still had a 10-fold loss of wet tensile strength. Several attempts at crosslinking chitosan improved the wet strength slightly, while sacricing elongation. Careful attention should be paid to dierentiate the eects of degree of N-acetylation, molecular weight, casting solution, thermal drying, coagulation, and solvent removal. In this respect, the direct dissolution of chitosan in NMMO/H2O may give a promising prospect for new-generation bers.[252]
6.6.4. Chitosan in Degree of Polymerization (DP) Finishing for Improved Dyeability The applicability of chitin and chitosan has been investigated in various areas of the textile industries. In the textile nishing eld, they are used to improve the soil release property, shrink-proong of wool, and dyeability of immature cotton. Shin and Dong[258] reported the eect of molecular weight of chitosan on dyeability of DP nished cotton. They treated cotton fabrics with a mixture of chitosan and DMDHEU (dimethylol dihydroxyethylene urea) or DMeDHEU (dimethyl dihydroxyethylene urea) in one step. Treated fabrics were dyed with direct, acid, and reactive dyes, and their performance properties and color fastness were studied.
6.6.4.1. Eect of Molecular Weight of Chitosan on Performance Properties Chitosan of higher molecular weight, i.e., higher DP, causes a decrease in wrinkle recovery angle (WRA) of DMDHEU or DMeDHEU/chitosantreated samples.[258] However, as the molecular weight of chitosan decreases, the WRA increases to a similar level as for DMDHEU or DMeDHEUtreated samples, as shown in Table 4. Also, higher molecular weight chitosan gives higher breaking strength retention (BS, Rtn.) due to the binding eect of the fabric structure.
6.6.4.2. Eect of Molecular Weight of Chitosan on the Uptake of Direct, Acid, and Reactive Dyes[258] All the DMDHEU/chitosan-treated samples give higher color yields than DMDHEU-treated samples. Direct dye uptakes of the

342 Table 4.
DUTTA, RAVIKUMAR, AND DUTTA Properties of DMDHEU/Chitosan (DMeDHEU/Chitosan)-Treated Fabrics[258] Color Strength Values (K/S)
Sample Untreated DMDHEUtreated (DMeDHEUtreated) DMDHEU/ chitosan (DMeDHEU/ chitosan)treated F (185,300) A (73,200) B (59,000) C (21,000) D (14,000) E (3,800)
a b
Add-on (%)
WRA (oWf )
BS Rtn. (%)
Direct Red 81 41 0.3 (3.3)
Acid Reactive Reactive Red 266 Red 183 Red 183* 0.2 6.6 0.3 0.3 (0.4) 0.4 (2.2) 1.1 (3.0)
176 100 4.4 ( 4.8 ) 294 (271) 56 (76)
7.3 7.2 7.8 8.6 7.0 7.7
(7.4) (7.2) (8.1) (8.2) (7.4) (6.7)
257 289 285 306 305 302
(207) (219) (215) (252) (269) (264)
80 73 64 62 68 61
(91) (101) (97) (89) (94) (82)
9.1 7.2 6.2 6.0 3.7 1.9
(11.2) (13.2) (11.0) (10.8) (9.0) (5.8)
5.8 6.1 4.5 4.0 2.7 1.3
(5.7) (7.4) (5.6) (4.0) (2.3) (0.8)
0.4 0.4 0.4 0.5 0.5 1.2
(5.2) (4.8) (4.9) (5.3) (5.4) (6.3)
2.3 2.1 2.4 3.0 2.4 2.5
(9.1) (9.0) (10.4) (12.4) (9.7) (5.2)
WRA: wrinkle recovery angle. BS Rtn.: binding strength retention.
DMDHEU-treated samples were negligible. Except for the samples treated with chitosan of molecular weight below 1.4 104, all the DMDHEU/ chitosan-treated samples give higher color yields than the untreated samples. As shown in Table 4, the dye uptake of direct dye increases as the molecular weight of chitosan increases. Uptake of acid dyes of the untreated, DMDHEU/chitosan-treated, and DMeDHEU/chitosan-treated samples showed higher dye uptake than the untreated as well as DMDHEU or DMeDHEU-treated samples. Again the dye uptake of acid dyes increases as the molecular weight of chitosan decreases. The results showed that reactive dye uptakes of DMDHEU or DMeDHEU/chitosan-treated samples are much lower than those of the untreated. Dye uptake of CI reactive red 183 is higher than that of DMDHEU-treated sample, regardless of chitosan molecular weight. In the case of DMeDHEU/chitosan-treated samples, dye uptakes are higher than those of DMDHEU-treated sample, regardless of chitosan molecular weight. The dye uptake of DMDHEU or DMeDHEU-treated samples tends to increase as the molecular weight of chitosan decreases, though the dierence in dye uptake is small and just opposite when compared with the results of direct and acid dyes.

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6.6.5. Color Removal from Textile Mill Euents Color, which contributes so much to the beauty of nature, is essential to the attractiveness and acceptability of most products used by modern society.[259] Textile wet-processing operations produce high volumes of euent waste water of varied composition, often containing salts plus organic surfactants, solvents, and dyes. Color pollution regulations have been on the books in the United States since the mid 1970s, but until recently have not been enforced. The textile industrys continuing concern for the environment, and desire to be better corporate citizens, has brought reviewed emphasis on environmentally friendly products and production using technologies focusing on either source reduction or improved waste treatment.[260] Much can still be done on both fronts, and no single technique is likely to solve all problems, especially in the area of color pollution control.[261] Mounting pressure on the textile industry to treat dyehouse euents has led to a host of new and old technologies competing to provide cost-eective solutions. Among the oldest of methods for treatment of waste water is the use of adsorbents derived from biological matter or biomass. Because of its low-cost, widespread availability, biomass has often been investigated with some promising results.[262271]
6.6.5.1. Dye Binding and Water Uptake In 1982, Knorr[272] examined dye binding and water uptake properties of chitin and chitosan followed by Sosulskis method.[273] The absorbance of the supernatant was measured at 505 nm using deionized water as blank. The weight of supernatant was used as a basis for the calculation of the total amount of dye bound or released. The pH adjustment was carried out by using either 10 mL of a commercial buer solution or by adding 0.1 N HCl to a slurry of 0.5 g chitin/chitosan and 10 mL of dye solution. After stirring for 15 min the pH was readjusted and deionized water added to reach 20.5 g of total weight. Chitosan gels were formed at pH values below 5.5, and no dye binding measurements could be performed. The eects of dye concentration in chitin/chitosan dye solution ratios on dye binding capacity and water uptake of chitin and chitosan have been studied.[272] A marked dierence between water uptake of chitin and chitosan was found, with chitosan having higher water uptake than chitin. This dierence can be due to dierences in the crystallinity of the products or dierences in the amount of salt-forming groups. Dierences in the amount of covalently bound protein residues might also aect water uptake.[39]

344
An eect of chitin/chitosan dye solution ratio on water uptake was also observed as being higher at a 0.5 g : 20 mL ratio than at a 2.0 g : 20 mL ratio. Similar trends were found with dye binding capacity. This dierence could be caused by dierences in rate of water uptake (wettability) at dierent chitin to aqueous dye solution ratios. Dye concentration had no marked eect on water uptake, but signicantly aected the dye binding capacity of chitin and chitosan. The results of regression and correlation analyses examined the dye binding capacity of chitin and chitosan as a function of dye concentration.[274] The results indicate that the dye binding capacity of both chitin and chitosan correlated signicantly with dye concentration. The eect of pH on the dye binding capacity of chitin and chitosan is also reported.[274] These data indicate a decline in the dye binding capacity of chitin and chitosan above pH 7.0. Within a pH range of 2.07.0 the dye binding capacity of chitin was shown to be stable, while chitosan formed gels below pH 5.5 and could not be evaluated. With the exception of chitin at pH 9, the dye binding capacity was not aected by adjusting the pH either with hydrochloric acid or with a buer solution. The authors physicochemical study[193] of the adsorption on chitosan is also noteworthy in this context. It is important to consider the methods of containing the solid adsorbent and the waste water when applying the adsorption system to large-scale treatment. Two major classes of contacting systems exist, namely, the batchtype process and the bed or column systems. The bed-type processes may be xed-bed or uidized-bed systems; the detailed procedure is described elsewhere.[275] Chitosan can be spun into bers,[276] which apparently have much improved adsorption kinetics. Chemically crosslinking the chitosan bers allows the bers to be used at low pH, which improves their dye binding capacity, without solubilizing the chitosan.[196] Chitosan can also be cast into membranes and then crosslinked to produce lters with excellent physical and chemical stability and high water permeability.[277] Chitosan membranes would thus be expected to have very rapid dye adsorption kinetics, in addition to high capacity, although no reports are found in the literature on this eect.
6.7. Cosmetics Organic acids are usually good solvents for cosmetic applications. Chitin and chitosan have fungicidal and fungistatic properties. Chitosan is the only natural cationic gum that becomes viscous on being neutralized with acid. These materials are used in creams, lotions, and permanent waving lotions, and several derivatives have also been reported as nail lacquers.[278]

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6.8. Paper Industry 6.8.1. Paper Finishing Chitosan has been reported to impart wet strength to paper.[279] Hydroxymethyl chitin and other water-soluble derivatives are useful end additives in paper making. This polymer, although potentially available in large quantities, has never become a commercially signicant product. 6.9. Engineering Applications 6.9.1. Solid State Batteries Chitosan is insoluble in water, which poses a problem in the fabrication of solid state proton-conducting polymer batteries. A lack of water present in the chitosan obviates the presence of hydrogen ions. Consequently, the proton-conducting polymer needed for solid state battery application cannot be obtained from chitosan alone. Chitosan is a biopolymer which can provide some ionic conductivity when dissolved in acetic acid. The conductivity is due to the presence of proton from the acetic acid solution. The transport of these protons is thought to occur through the many microvoids in the polymer, since the dielectric constants from piezoelectric studies are small, suggesting the polymer structures to contain many microvoids. The choice of a more suitable electrode material may produce a better battery system.[280]
7. CONCLUSION From the foregoing sections it is clear that chitin and chitosan can readily be derivatized by utilizing the reactivity of the primary amino group and the primary and secondary hydroxyl groups to nd applications in diversied areas. In this review various aspects, including the properties, processing, and applications, have been critically emphasized. Further, in this review an attempt has been made to increase the understanding of the importance and characteristics of chitin and chitosan. In view of this, this review will be of great interest both for industrial and academic institutions.
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Chitin and Chitosan For Versatile Applications

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CHITIN AND CHITOSAN FOR VERSATILE APPLICATIONS

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Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345

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Conversion of chitin to chitosan.

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Textiles, membranes, and medical aids like wound dressings

N-Carboxyalkyl (aryl) chitosans

O-Carboxyalkyl chitosans Sugar derivatives

Metal ion chelates

Catalyst, photography, health products, and insecticides Textiles

Flocculation and metal ion chelation

Alkyl chitin, benzyl chitin, di-O-butyryl chitin

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314 Table 1. Derivatives Examples

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aldehydes, to produce N-acyl, N-arylidene, and N-alkylidene derivatives (XIII), respectively.

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CHITIN AND CHITOSAN