Chitin and Chitosan For Versatile Applications PDF

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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
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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
1
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
CONTENTS
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
2. Processing of Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3. Economic Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
4. Properties of Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
5. Derivatives of Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
5.1. Chitin Derivatives of Polysaccharides and Polypeptides . . . . . . . . 315
5.2. Tosyl and Iodo Chitins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
5.3. Ether-Type Chitin Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 316
5.4. Mixed Ester-Type Chitin Derivatives . . . . . . . . . . . . . . . . . . . . . 317
5.5. Regioselective Chlorination of Chitin . . . . . . . . . . . . . . . . . . . . . 318
5.6. N-Acyl, N-Arylidene, and N-Alkylidene Chitosan Gels . . . . . . . . 318
5.7. Maleilated Chitosan and Acrylamide Copolymers . . . . . . . . . . . . 319
5.8. Chitosan/Calcium Alginate Beads . . . . . . . . . . . . . . . . . . . . . . . 320
5.9. Calcium CarbonateChitosan Composites . . . . . . . . . . . . . . . . . 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 1532-1797 (Print); 1532-9038 (Online)
Copyright # 2002 by Marcel Dekker, Inc. www.dekker.com

308 DUTTA, RAVIKUMAR, AND DUTTA
5.10. Chitosan/Polyether Hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . 321

5.11. Polysaccharide Chitosan/PEOPPO Nanoparticles . . . . . . . . . . . 321
6. Applications of Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
6.1. Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
6.2. Applications in Chromatographic Separations. . . . . . . . . . . . . . . 331
6.3. Photography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
6.4. Food and Nutrition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
6.5. Water Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
6.6. Textile Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
6.7. Cosmetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
6.8. Paper Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
6.9. Engineering Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
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 abun-
dant 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-acet-
amido-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).

CHITIN AND CHITOSAN 309
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 water-
soluble[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.

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 strepto-
myces 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 pro-
teins 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.


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 quanti-
ties 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, solu-
tion, 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, hexauoroace-
tone,[41] and chloroalcohols in conjunction with aqueous solutions of mineral
acids[39] and dimethylacetamide (DMAc) containing 5% lithium chloride

(LiCl).[42] Recently, the dissolution of chitosan in N-methyl morpholine-N-

oxide (NMMO)/H2O has been reported by Dutta et al.[43a,b] The hydrolysis
of chitin with concentrated acids under drastic conditions produces the rela-
tively 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-phthal-
aldehydic acids.[46,47]
Chitosan and simple aldehydes produce N-alkyl chitosan upon hydro-
genation. 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 reac-
tion.[50,51] In practice, such reactions are carried out on native chitin or on

Table 1. Chitin Derivatives and Their Uses[49]
Derivatives Examples Potential Uses
N-Acylchitosans Formyl, acetyl, propionyl butyryl, hexa- Textiles, membranes, and

noyl, acetanoyl, decanoyl, dodecanoyl, medical aids like wound
tetradecanoyl, lauroyl, myristoyl, palmi- dressings
toyl, stearoyl, benzoyl, monochloroacetoyl,
dichloroacetyl, triuoroacetyl, carbamoyl,
succinyl, acetoxybenzoyl, 5-methyl pyrroli-
dinone
N-Carboxyalkyl N-Carboxybenzyl, glycine glucan (N-car- Chromatographic media
(aryl) chitosans boxymethyl chitosan), alanine glucan, phe- and metal ion collection,
nylalanine glucan, tyrosine glucan, serine functional cosmetics ingre-
glucan, glutamic acid glucan, methionine dient in hydrating creams
glucan, leucine glucan
N-Carboxyacyl From anhydrides such as maleic, itaconic, Use for collection of trace
chitosans acetylthiosuccinic, glutaric, cyclohexane transition metal ions to
1,2-dicarboxylic, phthalic, cis-tetra hydro- form lms or membranes
phthalic, 5-norbornene, 2,3-dicarboxylic and to prepare cosmetic
diphenic, salicylic, trimellitic, pyromellitic products
anhydride, N,N-dicarboxymethyl
O-Carboxyalkyl O-Carboxymethyl, crosslinked O-carboxy- Molecular sieves, viscosity
chitosans methyl builders, and metal ion
collection
Sugar derivatives 1-Deoxygalactic-1-yl-, 1-deoxyglucit-1-yl-, Expected to be useful as a
1-deoxymelibiit-1-yl, 1-deoxylactit-1-yl, 1- novel type of antimicro-
deoxylactit-1-yl-4(2,2,6,6-tetramethyl-pipe- bial agent
ridine-1-oxyl)-, 1-deoxy-60 -aldehydolactit-
1-yl-, 1-deoxy-60 -aldehydomelibiit-1-yl, cel-
lobiit-1-yl-chitosans, products obtained
from ascorbic acid
Metal ion chelates Palladium, copper, silver, iodine Catalyst, photography,
health products, and
insecticides
Semisynthetic Copolymer of chitosan with methyl Textiles
resins of chitosan methacrylate, polyureaurethane, poly
(amideester) acrylamidemaleic anhydride
Natural Chitosan glucans from various organisms Flocculation and metal
polysaccharide ion chelation
complexes,
quaternary
chitosan salts
Miscellaneous Alkyl chitin, benzyl chitin, di-O-butyryl Intermediate serine pro-
chitin tease purication, used as
drug carrier, textiles, pre-
cursor of various chitin
biomaterials
(continued )

Table 1. Continued
Derivatives Examples Potential Uses
Hydroxybutyl chitin, hydroxyalkyl chito- Desalting, ltration, dialy-

sans, cyanoethyl chitosan sis, and insulating papers
Glycol chitosan Enzymology, dialysis, and
special papers
Glutaraldehyde chitosan Enzyme immobilization
Linoleic acidchitosan complex Food additive and anti-
cholesterolemic
Uracylchitosan, theophylline chitosan,
adenine chitosan, chitosan salts of acid,
polysaccharides, chitosan streptomycin,
N-cyclohexane chitosan, 2-amido-2,6-
diaminoheptanoic acid chitosan
Chemically crosslinked glycine glucan Suitable for collection of
carrier-free radioisotopes
Chitosan ascorbate ketimine and its Used to treat parodonto-
reduced form pathies
Imidazole chitosan 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 immo-
bilization 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

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 freeze-
drying, 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 chloro-
form solution of tosyl chloride, where the reaction was interfacial between
the two immiscible solutions and depends on the rate of stirring. With vigor-
ous stirring, the substitution was quite ecient and reproducible at 0 C.

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 reac-
tions 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-pro-
panediol 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]

5.4. Mixed Ester-Type Chitin Derivatives
One of the ways of enhancing the solubility of chitin was the introduc-
tion 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,

ltered o, and washed with distilled water (Eq. 8). The samples were sub-
sequently 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 homo-
geneous 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 chromato-
graphic-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 bromi-
nation 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-2-
deoxy-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

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-dimen-
sional 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 three-
dimensional 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 interac-
tions 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 chi-
tosan (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 acry-
lamide was used as the vinyl comonomer.

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 chi-
tosan 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 con-
centration 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.

5.9. Calcium CarbonateChitosan Composites
Zhang and Gonsalves[65] reported the crystal growth of calcium carbo-

nate on a chitosan substrate using a supersaturated calcium carbonate solu-
tion 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 pre-
paration 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 con-
tains the polyanion sodium triphosphate (TPP) (XX) of nanoparticles. The
mixture can be conveniently modulated by varying the ratio chitosan
(CS)/PEOPPO.
9

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 limita-
tions, 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-dres-
sing 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

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 hepar-
ization 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 pas-
sive 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
(Mw69 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

was clear that the chitosan network can interpenetrate into the collagen net-
work, 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 plate-
lets are exposed to those membranes. Albumin-blended membrane demon-
strates 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. Enzymes/Cell Immobilized on Chitin and Its Derivatives and Proposed

Uses[38]
Enzyme/Cells Proposed Uses
AMP deaminase AMP to IMP

Amylase diastase and glucoamylase Starch and glycogen to D-glucose
a-Chymotripsin Plastein synthesis
b-D-Galactosidase Hydrolysis of lactose
D-Glucose isomerase D-glucose to D-fructose, preparation of
D-gluconic acid
b-D-Glucosidase Hydrolysis of cellobiose
Lysozyme, Pronase, Subtilisin, and Preparation of pharmaceuticals, cosmetics,
Tripsin and food protein
Urease Urea to ammonia and CO2
E. coli cells, Nitrosomonas Synthesis of L-tryptophan, nitrication of
europea cells waste water

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 ster-
ilization 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 pro-
cess can be made into a continuous process.
In recent years the practice of using non-growing whole or lysed micro-
bial cells, rather than puried enzymes, has gained in popularity. Advantages
of immobilized cells are simple product isolation and repeated use in a con-
tinuous 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 modi-
cations 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 hyper-
tension, 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

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, albumin-
blended 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

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:
I. 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.

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.

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 chi-
tosan, 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 mem-
branes 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 commer-
cially sound methodology (Fig. 2). The achievement of predictable and repro-
ducible 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 chit-
osan 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 result-
ing ionic gels are transparent, thermoirreversible, and can be made at low

Figure 2. Repeated dose vs. controlled delivery: (a) repeated dose delivery, (b) controlled
delivery.
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 for-
mulation 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 mem-
brane permeation. Various chitosan membranes with dierent crosslink den-
sities 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 mem-
branes 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

microcapsules/microspheres has increased immensely. Syntheses of micro-

capsules/microspheres have been widely reviewed.[164167] Due to the attrac-
tive 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 manufac-
tured via dierent microencapsulation processes, e.g., polymerization techni-
ques. The choice of technique is largely dependent on the nature of the
starting materials and the desired compositional and morphological charac-
teristics of the resultant microcapsules/microspheres. It is not easy, for exam-
ple, 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 pro-
blems 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 chroma-
tographic 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 chromato-
graphy of some phenols and amino acids has also been reported elsewhere.[173]
Chitosan has also been used by Muzzarelli and Rocchetti[174a] for the determi-
nation 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 chroma-
tography, 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

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 proper-
ties 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 hypo-
cholersterolemic 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 con-
centration 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 deri-
vatives 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

Figure 3. Inuence of quantity of chitosan on the adsorption of mercury from lower and
higher concentrations.
Table 3. Waste Water Treatment from Chitosan as an Adsorbent by Various Workers
Removal of Conc. Range Parameters for Research

Metal Ions (ppm) Adsorption Group Ref.
Cd2 110 Particle size of Jha et al. [192a]

adsorbent
Cd2 Rower et al. [192b]
Cu2, Hg2, Temperature variation, Makay et al. [192c]
Ni2, Zn2 pH 7
Yang et al. [192d]
Cr3 Particle size 0.44 Maruce et al. [192e]
Cr6 Udayshankar et al. [192f]
Hg2 Kinetics study Peniche-covas et al. [192g]

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 degrada-
tion 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 condi-
tions 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 poly-
amides were applied to dissolve the chitin. The formic aciddichloroacetic acid
system was found to be a suitable solvent for obtaining a viscous chitin solu-
tion 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 proper-
ties. 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] con-
centrated 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 degrada-
tion 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]

6.6.1.1. Solvent and Solution Properties
Chitin and chitosan degrade before melting, which is typical for poly-
saccharides 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 com-
plexes, and combinations thereof.
Solution properties of chitin and chitosan have also been studied exten-
sively. 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 mea-
sured mostly for chitosan and reported by various workers elsewhere.[209220]
In the case of bers, comparative data from solvent to solvent are unavail-
able. 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 solidica-
tion. 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

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 auto-
clave 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% methy-
lene chloride over a period of 3045 min. A lament was extruded from
this solution using a hypodermic needle and acetone as the coagulant.

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 cross-
section 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 mean-
ingful 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-trichloro-
ethane. 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 proper-
ties were unavailable.
Capozza[94,234236] suggested hexauoroisopropanol and hexauoro-
acetone 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 coagu-
lation 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.

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 elonga-
tions 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 metha-
nolic 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 una-
vailable. 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 velo-
city 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.

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-2-
pyrrolidone (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 coa-
gulant. 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, high-
denier 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

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 stu-
dies 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 ber-

forming 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

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/chitosan-
treated samples.[258] However, as the molecular weight of chitosan decreases,
the WRA increases to a similar level as for DMDHEU or DMeDHEU-
treated 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

Table 4. Properties of DMDHEU/Chitosan (DMeDHEU/Chitosan)-Treated Fabrics[258]
Color Strength Values (K/S)

a b
Add-on WRA BS Rtn. Direct Acid Reactive Reactive
Sample (%) (oWf ) (%) Red 81 Red 266 Red 183 Red 183*
Untreated 176 100 41 0.2 6.6 0.3

DMDHEU- 4.4 ( 4.8 ) 294 (271) 56 (76) 0.3 (3.3) 0.3 (0.4) 0.4 (2.2) 1.1 (3.0)
treated
(DMeDHEU-
treated)
DMDHEU/
chitosan
(DMeDHEU/
chitosan)-
treated
F (185,300) 7.3 (7.4) 257 (207) 80 (91) 9.1 (11.2) 5.8 (5.7) 0.4 (5.2) 2.3 (9.1)
A (73,200) 7.2 (7.2) 289 (219) 73 (101) 7.2 (13.2) 6.1 (7.4) 0.4 (4.8) 2.1 (9.0)
B (59,000) 7.8 (8.1) 285 (215) 64 (97) 6.2 (11.0) 4.5 (5.6) 0.4 (4.9) 2.4 (10.4)
C (21,000) 8.6 (8.2) 306 (252) 62 (89) 6.0 (10.8) 4.0 (4.0) 0.5 (5.3) 3.0 (12.4)
D (14,000) 7.0 (7.4) 305 (269) 68 (94) 3.7 (9.0) 2.7 (2.3) 0.5 (5.4) 2.4 (9.7)
E (3,800) 7.7 (6.7) 302 (264) 61 (82) 1.9 (5.8) 1.3 (0.8) 1.2 (6.3) 2.5 (5.2)
a
WRA: wrinkle recovery angle.
b
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.

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]

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 signi-
cantly 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 indi-
cate 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 physicochem-
ical study[193] of the adsorption on chitosan is also noteworthy in this context.
It is important to consider the methods of containing the solid adsor-
bent and the waste water when applying the adsorption system to large-scale
treatment. Two major classes of contacting systems exist, namely, the batch-
type process and the bed or column systems. The bed-type processes may be
xed-bed or uidized-bed systems; the detailed procedure is described else-
where.[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]

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 con-
ductivity 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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