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A Review of Chitin and Chitosan Applications

A Review of Chitin and Chitosan Applications

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Reactive & Functional Polymers 46 (2000) 1–27www.elsevier.com/locate/react
A review of chitin and chitosan applications
*Majeti N.V. Ravi Kumar
 Department of Chemistry
University of Roorkee
247 667,
Received 24 January 2000; received in revised form 20 June 2000; accepted 25 June 2000
Chitin is the most abundant natural amino polysaccharide and is estimated to be produced annually almost as much ascellulose. It has become of great interest not only as an underutilized resource, but also as a new functional material of highpotential in various fields, and recent progress in chitin chemistry is quite noteworthy. The purpose of this review is to take acloser look at chitin and chitosan applications. Based on current research and existing products, some new and futuristicapproaches in this fascinating area are thoroughly discussed.
2000 Elsevier Science B.V. All rights reserved.
Beads; Biotechnology; Chitin; Chitosan; Controlled drug delivery; Fibers; Nanoparticles; Hydrogels; Tablets; Transdermaldevices
1. Introduction
position C-2 replaced by an acetamido group.Like cellulose, it functions naturally as a struc-Chitin, a naturally abundant mucopolysac-tural polysaccharide. Chitin is a white, hard,charide, and the supporting material of crusta-inelastic, nitrogenous polysaccharide and theceans, insects, etc., is well known to consist of major source of surface pollution in coastal2-acetamido-2-deoxy-
-glucose through a
areas. Chitosan is the
-deacetylated derivative(1
4) linkage. Chitin can be degraded byof chitin, although this
-deacetylation is al-chitinase. Its immunogenicity is exceptionallymost never complete. A sharp nomenclaturelow, in spite of the presence of nitrogen. It is awith respect to the degree of 
-deacetylationhighly insoluble material resembling cellulosehas not been dened between chitin andin its solubility and low chemical reactivity. Itchitosan [1,2]. The structures of cellulose, chitinmay be regarded as cellulose with hydroxyl atand chitosan are shown in Fig. 1. Chitin andchitosan are of commercial interest due to theirhigh percentage of nitrogen (6.89%) compared
This paper is dedicated to Professor M.N.V. Prasad, Ph.D.,
to synthetically substituted cellulose (1.25%).
FNIE (New Delhi), DSc. (hc Colombo), School of Life Sciences,
This makes chitin a useful chelating agent [1].
University of Hyderabad, Hyderabad, India, who inspired me withhis scientific approach, honesty and human warmth.
As most of the present-day polymers are syn-
*Post Bag No. 29, Roorkee 247 667, India. Fax:
thetic materials, their biocompatibility and
biodegradability are much more limited than
mail address
mnvrkumar@mailcity.com (M.N.V. RaviKumar).
those of natural polymers such as cellulose,
1381-5148/00/$ – see front matter
2000 Elsevier Science B.V. All rights reserved.PII: S1381-5148(00)00038-9
Ravi Kumar 
Functional Polymers
46 (2000) 1
radability, non-toxicity, adsorption properties,etc.Recently, much attention has been paid tochitosan as a potential polysaccharide resource[5]. Although several efforts have been reportedto prepare functional derivatives of chitosan bychemical modifications [6–8], very few attainedsolubility in general organic solvents [9,10] andsome binary solvent systems [11–13]. Chemi-cally modified chitin and chitosan structuresresulting in improved solubility in general or-ganic solvents have been reported by manyworkers [14–23]. The present review is anattempt to discuss the current applications andfuture prospects of chitin and chitosan.
2. Processing of chitin and chitosan
Chitin is easily obtained from crab or shrimpshells and fungal
. In the rst case,chitin production is associated with food indus-
Fig. 1. Structures of cellulose, chitin and chitosan.
tries such as shrimp canning. In the second case,the production of chitosan–glucan complexes ischitin, chitosan and their derivatives. However, associated with fermentation processes, similarthese naturally abundant materials also exhibit a to those for the production of citric acid fromlimitation in their reactivity and processability
Aspergillus nige
Mucor rouxii
, and
-[3,4]. In this respect, chitin and chitosan are
, which involves alkali treatment yield-recommended as suitable functional materials, ing chitosan–glucan complexes. The alkali re-because these natural polymers have excellent moves the protein and deacetylates chitin simul-properties such as biocompatibility, biodeg- taneously. Depending on the alkali concentra-
Scheme 1.
Ravi Kumar 
Functional Polymers
46 (2000) 1
tion, some soluble glycans are removed [24].
4. Properties of chitin and chitosan
The processing of crustacean shells mainlyMost of the naturally occurring polysac-involves the removal of proteins and the disso-charides, e.g. cellulose, dextran, pectin, alginiclution of calcium carbonate which is present inacid, agar, agarose and carragenans, are neutralcrab shells in high concentrations. The resultingchitin is deacetylated in 40% sodium hydroxideor acidic in nature, whereas chitin and chitosanat 120
C for 1–3 h. This treatment producesare examples of highly basic polysaccharides.70% deacetylated chitosan (Scheme 1).Their unique properties include polyoxysaltformation, ability to form films, chelate metalions and optical structural characteristics [29].
3. Economic aspects
Like cellulose, chitin functions naturally as astructural polysaccharide, but differs from cellu-The production of chitin and chitosan islose in its properties. Chitin is highly hydro-currently based on crab and shrimp shellsphobic and is insoluble in water and mostdiscarded by the canning industries in Oregon,organic solvents. It is soluble in hexafluoro-Washington, Virginia and Japan and by variousisopropanol, hexafluoroacetone, chloroalcoholsfinishing fleets in the Antarctic. Several coun-in conjugation with aqueous solutions of miner-tries possess large unexploited crustacean re-al acids [24] and dimethylacetamide containingsources, e.g. Norway, Mexico and Chile [25].5% lithium chloride. Chitosan, the deacetylatedThe production of chitosan from crustaceanproduct of chitin, is soluble in dilute acids suchshells obtained as a food industry waste isas acetic acid, formic acid, etc. Recently, the geleconomically feasible, especially if it includesforming ability of chitosan in
-methylmor-the recovery of carotenoids. The shells containpholine
-oxide and its application in controlledconsiderable quantities of astaxanthin, a carot-drug release formulations has been reportedenoid that has so far not been synthesized, and[30–32]. The hydrolysis of chitin with concen-which is marketed as a fish food additive intrated acids under drastic conditions producesaquaculture, especially for salmon.relatively pure
-glucosamine.To produce 1 kg of 70% deacetylatedThe nitrogen content of chitin varies from 5chitosan from shrimp shells, 6.3 kg of HCl andto 8% depending on the extent of deacetylation,1.8 kg of NaOH are required in addition towhereas the nitrogen in chitosan is mostly in thenitrogen, process water (0.5 t) and coolingform of primary aliphatic amino groups.water (0.9 t). Important items for estimating theChitosan, therefore, undergoes reactions typicalproduction cost include transportation, whichof amines, of which
-acylation and Schifvaries depending on labor and location. In India,reaction are the most important. Chitosan de-the Central Institute of Fisheries Technology,Kerala, initiated research on chitin and chitosan. rivatives are easily obtained under mild con-From their investigation, they found that dry ditions and can be considered as substitutedprawn waste contained 23% and dry squilla glucans.contained 15% chitin [26]. They have also
-Acylation with acid anhydrides or acylreported that the chitinous solid waste fraction halides introduces amido groups at the chitosanof the average Indian landing of shell fish nitrogen. Acetic anhydride affords fullyranges from 60 000 to 80 000 tonnes [27,28]. acetylated chitins. Linear aliphatic
-acylChitin and chitosan are now produced commer- groups above propionyl permit rapid acetylationcially in India, Japan, Poland, Norway and of hydroxyl groups. Higher benzoylated chitin isAustralia. The worldwide price of chitosan (in soluble in benzyl alcohol, dimethylsulfoxide,small quantities) is ca. US$7.5/10 g (Sigma and formic acid and dichloroacetic acid. The
-Aldrich price list). hexanoyl,
-decanoyl and
-dodecanoyl deriva-

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