Encyclopedia of Polymeric Nanomaterials

DOI 10.1007/978-3-642-36199-9_322-1
# Springer-Verlag Berlin Heidelberg 2014

Chitin and Chitosan

Hiroshi Tamura* and Tetsuya Furuike
Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita, Osaka, Japan

Synonyms
Polysaccharide; Polyose

Definition
Chitin and chitosan are found as supporting materials in many aquatic organisms, insects, mush-
rooms, and microorganisms and are biocompatible, biodegradable, nontoxic, and antimicrobial in
nature. Historical parts, properties, and applications in chitin and chitosan are mainly argued.

Historical Parts
In 1811, French chemist and pharmacist Henri Braconnot discovered the alkaline-insoluble fraction
from mushrooms by treatment with dilute warm alkali. He analyzed nitrogen content in the liquid
obtained from distillation of alkali-insoluble fraction and found out that ammonia contained in the
liquid. He gave the name alkaline-insoluble fraction as “fungine” (the ancient name of chitin)
[1, 2]. In 1823, Antoine Odier isolated the alkaline-insoluble fraction from cuticles of insects
(May bug) by repeated treatments with hot KOH solutions, and he gave the name of the alkaline-
insoluble fraction as chitine. The word was derived from Greek word “wito n” (chiton; the meaning
is tunic, covering or envelope). The English word “chitin” comes from this French word [2–4]. In
1824, Children also got the same fraction from May bug elytra and found nitrogen in the fraction by
elemental analysis [3].
In 1859, Rouget treated chitin with concentrated KOH solution and he found that the resultant
compound was soluble in dilute organic acids. He gave the name of the product as “modified chitin”
[3, 4]. In 1894, Hoppe-Seyler treated the shells of crabs, scorpions, and spiders with KOH solution at
180  C and the resultant product dissolved in dilute acetic acid and hydrochloric acid solution, and
then this product could be recovered by addition of alkaline to the reaction solution. Hoppe-Seyler
gave the name of product as “chitosan” [3].
At the same time, Ledderhose (1878) proposed that glucosamine and acetic acid are composed of
chitin and Gilson (1894) confirmed the presence of glucosamine in chitin [2]. Later years, chitin and
chitosan are known as copolymers of N-acetyl-D-glucosamine and D-glucosamine units linked with
b-(1–4)-glycosidic bonds. Nowadays the names of chitins and chitosans are usually defined with
their degree of acetylation (DA, number of N-acetyl-D-glucosamine in the polymer) or degree of
deacetylation (DD, number of D-glucosamine in the polymer).
Nowadays, chitin and chitosan are produced from shells of shrimps and crabs and bone plates of
squids for commercial and laboratory scale, and fungal mycelia, insect cuticles, and mushrooms are

*Email: tamura@kansai-u.ac.jp

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Encyclopedia of Polymeric Nanomaterials
DOI 10.1007/978-3-642-36199-9_322-1
# Springer-Verlag Berlin Heidelberg 2014

used for the production of chitin and chitosan in laboratory scale. Chitin and chitosan have been used
in many sectors such as in agriculture, as food and feed supplement, in waste water treatment, in
medical and pharmaceutical products, etc.

Properties
Chitin is a copolymer of N-acetyl-D-glucosamine and D-glucosamine units linked with b-(1–4)
glycosidic bonds; here N-acetyl-D-glucosamine units are predominant in that polymer chain.
Crystalline form of chitin occurs in nature as a-, b-, and g-chitin [5]. a-Chitin can be obtained
from shells of crabs and shrimps and from cell walls of fungi, and b-chitin can be isolated from the
bone plates of squids and cuttlefishes. In a-chitin the chains run in antiparallel fashion bound by
strong hydrogen bonding. In b-chitin the chains run in parallel and are connected by weak
intermolecular forces. Solubility properties of chitin and chitosan are highly dependent on the
number of free amino groups in the molecules. Chitin possesses a low content of amino groups.
Therefore most chitins are not soluble and do not swell in common solvents; however very partially
deacetylated chitin (DA 25 %) and b-chitin can be swollen in water. Chitins dissolve in concentrated
acids (HCl, H2SO4, formic, acetic, dichloroacetic, and trichloroacetic acid), in
(dimethylformamide)-N2O4 mixtures, in hexafluoro-2-propanol, in hexafluoroacetone, in
dimethylacetamide-LiCl, in N-methylpyrrolidone-LiCl, and in CaCl2.2H2O-methanol [6].
The deacetylated form of chitin refers to chitosan. Chitin usually refers to a copolymer with a
degree of acetylation (DA) of more than 40 % [i.e., degree of deacetylation (DD) of less than 60 %]
and insoluble in dilute acids. The name chitosan is used for a copolymer with less than 40 % DA (i.e.,
more than 60 % DD).
The amino group in chitosan has a pKa value of 6.5, which leads to a protonation in acidic to
neutral solution with a charge density dependent on pH and the %DA value. This makes chitosan
water soluble and a bioadhesive which readily binds to negatively charged surfaces such as mucosal
membranes.
Chitosan is soluble in dilute inorganic acids, HCl; in organic acids, acetic acid, ascorbic acid,
citric, formic, lactic, acetic, and pyruvic acid; in tetrahydrofuran; in ethyl acetate; and in
1,2-dichloroethane, but it is insoluble in benzoic acid, in cinnamic acid, and in oxalic acid [3].
Chitin and chitosan are found as supporting materials in many aquatic organisms (shells of
shrimps and crabs and bone plates of squids and cuttlefish), in many insects (May bug, cicada,
mosquitoes, cockroach, honeybees, silkworms, drosophila, Extatosoma, and Sipyloidea), in terres-
trial crustaceans, in mushrooms (Agaricus bisporus, Auricularia auricula-judae, Lentinula edodes,
Trametes versicolor, Armillaria mellea, Pleurotus ostreatus, Pleurotus sajor-caju, and Pleurotus
eryngii), and in some of microorganisms (yeast, fungal mycelia, and algae) [7].

Application
Chitin and chitosan are biocompatible, biodegradable, and nontoxic and are antimicrobial and
hydrating agents. These properties can be exploited into biomedical purpose to prepare chitin/
chitosan matrices in various forms. Chitin and chitosan are easily processed into gels [6, 8],
membranes [9, 10], micro- and nano-nanoparticles [11], scaffolds, and sponges [12] forms. There
are a number of promising applications of nanoscale thin films and fibers of chitin/chitosan [13].

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Encyclopedia of Polymeric Nanomaterials
DOI 10.1007/978-3-642-36199-9_322-1
# Springer-Verlag Berlin Heidelberg 2014

In addition to the biomedical application, chitin/chitosan is applied as follows. Chitosan causes

the fine sediment particles to bind together and is subsequently removed with the sediment during
sand filtration. It also removes phosphorus, heavy minerals, and oils from the water. Chitosan has a
long history for use as a fining agent in winemaking [14]. Fungal source chitosan has shown an
increase in settling activity, reduction of oxidized polyphenolics in juice and wine, chelation and
removal of copper (post-racking), and control of the spoilage yeast Brettanomyces. These products
and uses are approved for European use by the EU and OIV standards [15].
Elicitors are compounds, which activate chemical defense in plants. Various biosynthetic path-
ways are activated in treated plants depending on the compound used. Chitosan and its oligomers are
typical elicitors and had been used in the agricultural and horticultural purpose, primarily for plant
defense and yield increase. The biocontrol mode of action of chitosan elicits natural innate defense
responses within plant to resist insects, pathogens, and soil-borne diseases when applied to foliage or
the soil [16]. Chitosan increases photosynthesis, promotes and enhances plant growth, stimulates
nutrient uptake, increases germination and sprouting, and boosts plant vigor.
Electric Double-Layer Capacitor (EDLC) received much attention because it has a high-power
density electro-device compared to the conventional lithium ion second battery. Since it is a kind of
condenser, conventional EDLC is composed of liquid electrolyte. New approach for EDLC is to use
the gel electrolyte in which several polymers have been suggested. Recently, polysaccharides are
used as supporting materials for EDLC. One example is a cellulose-chitin hybrid gel with ion liquid
as electrolyte. Quite interestingly, electrochemical properties of gel electrolyte system were superior
to that of conventional liquid electrolyte system. The chitosan gel system was also examined and
found that chitosan gel electrolyte is preferable for EDLC due to the formation of preferable
interface structure [17].
Recently, much attention has been paid to electro-spinning process as a unique technique because
it can produce polymer nanofibers with diameter in the range from several micrometers down to tens
of nanometers, depending on the polymer and processing conditions. In electro-spinning, a high
voltage is applied to create electrically charged jets of a polymer solution. These jets dry to form
nanofibers, which are collected on a target as a nonwoven fabric. These nanofibers are of consid-
erable interest for various kinds of applications, because they have several useful properties such as
high specific surface area and high porosity. Nanofibers containing chitin or chitosan yield potential
applications in areas such as filtrations, recovery of metal ions, drug release, dental, tissue engi-
neering, catalyst and enzyme carriers, wound healing, protective clothing, cosmetics, biosensors,
medical implants, and energy storage [18, 19]. Chitin nanofiber with diameter around 10–20 nm has
been reported based on the same concept of cellulose nanofiber [20] and several researches are now
underway.

Related Entries
▶ Biodegradability
▶ Biodegradable Materials
▶ Biodegradable Polymers
▶ Nanofibres and Electrospinning

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Encyclopedia of Polymeric Nanomaterials
DOI 10.1007/978-3-642-36199-9_322-1
# Springer-Verlag Berlin Heidelberg 2014

References
1. Braconnot H (1811) Sur la nature des champignons. Ann Chim 79:261–304
2. Muzzarelli RAA (1977) Chitin. Pergamon Press, Oxford
3. Roberts GAF (1992) Chitin chemistry. Macmillan Press, London
4. Winterowd JG, Sandford PA (1995) Chitin and chitosan. In: Stephen AM (ed) Food poly-
saccharides and their applications. Marcel Dekker, New York, pp 441–461
5. Nwe N, Stevens WF (2008) Production of chitin and chitosan and their applications in the
medical and biological sector. In: Tamura H (ed) Recent research in biomedical aspects of chitin
and chitosan. Research Signpost, Kerala, pp 161–176
6. Tamura H, Nagahama H, Tokura S (2006) Preparation of chitin hydrogel under mild conditions.
Cellulose 13:357–364
7. Tauber OE (2005) The distribution of chitin in an insect. J Morphol 56:51
8. Nagahama H, Kashiki T, Nwe N, Jayakumar R, Furuike T, Tamura H (2008) Preparation of
biodegradable chitin/gelatin membranes with GlcNAc for tissue engineering applications.
Carbohydr Polym 73:456–463
9. Jayakumar R, Nwe N, Tokura S, Tamura H (2007) Sulfated chitin and chitosan as novel
biomaterials. Int J Biol Macromol 40:175–181
10. Jayakumar R, Divya Rani VV, Shalumon KT, Sudhessh Kumar PT, Nair SV, Furuike T, Tamura
H (2009) Bioactive and osteoblast cell attachment studies of novel a-, and b-chitin membranes
for tissue engineering applications. Int J Biol Macromol 45:260–264
11. Anitha A, Divya Rani VV, Krishna R, Sreeja V, Selvamurugan N, Nair SV, Tamura H, Jayakumar
R (2009) Synthesis, characterization, cytotoxicity and antibacterial studies of chitosan,
O-carboxymethyl, N, O-carboxymethyl chitosan nanoparticles. Carbohydr Polym 78(4):672–677
12. Portero A, Teijeiro-Osorio D, Alonso MJ, Remunan-Lopez C (2007) Development of chitosan
sponges for buccal administration of insulin. Carbohydr Polym 68:617–625
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fiber formation. Progr Polym Sci 34:641–678
14. Quintela S, Villarán MC, López De Armentia I, Elejalde E (2012) Ochratoxin A removal from
red wine by several oenological fining agents: bentonite, egg albumin, allergen-free adsorbents,
chitin and chitosan. Food Addit Contam Part A 29(7):1168–1174
15. Escudero-Abarca BI, Escudero-Abarca MG, Aguilar-Uscanga PM, Hayward-Jones P,
Mendoza M, Ramírez L (2004) Selective antimicrobial action of chitosan against spoilage
yeasts in mixed culture fermentations. J Ind Microbiol Biotechnol 31(1):16–22
16. Goosen MFA (1996) Applications of chitin and chitosan. CRC, Boca Raton, pp 132–139
17. Yamagata M, Soeda K, Ikebe S, Yamazaki S, Ishikawa M (2013) Chitosan- based gel electrolyte
containing an ionic liquid for high- performance nonaqueous supercapacitors. Electrochim Acta
100:275–280
18. Shalumon KT, Binulal NS, Selvamurugan N, Nair SV, Menon D, Furuike T, Tamura H,
Jayakumar R (2009) Electrospinning of carboxymethyl chitin/poly(vinyl alcohol) nanofibrous
scaffolds for tissue engineering applications. Carbohydr Polym 77:863–869
19. Watthanaphanit A, Supaphol P, Tamura H, Tokura S, Rujiravanit R (2008) Fabrication of chitin
whisker-reinforced alginate nanocomposite fibers for wound dressing application. J Appl
Polym 110:890–899
20. Ifuku S, Nogi M, Abe K, Yoshioka M, Morimoto M, Saimoto H, Yano H (2009) Preparation of Chitin
Nanofibers with a Uniform Width as α-Chitin from Crab Shells. Biomacromolecules 10:1584–1588

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