Abstract
In view of rapidly growing interest in the amino polysaccharide chitosan/chitin and its oligosaccharides as functional biopolymer, a recent progress of basic and application studies in chitosan/chitin oligosaccharides chemistry is reviewed as well as some basic aspects of this specialty biomass resource. A special emphasis is placed on the controlled modification reactions to prepare chitin derivatives with well-defined structures and thereby to construct sophisticated molecular architecture having various advanced functions. The reactions discussed here include acylation, quaternary ammonium salt, carboxyalkylation, graft copolymerization, quaternary salt formation, Schiff base formation, reductive alkylation, microwave modification. For conducting modification reactions in a facile and controlled manner, some soluble chitosan/chitin oligosaccharides derivatives are convenient. To fully explore the high potential of these specialty biopolymers, basic and application researches are being made extensively.
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References
Acet Ö, Baran T, Erdönmez D, Aksoy NH, Alacabey İ, Menteş A, Odabaşi M (2018) O-carboxymethyl chitosan Schiff base complexes as affinity ligands for immobilized metal-ion affinity chromatography of lysozyme. J Chromatogr A 1550:21–27
Aly AA, El-Bisi MK (2018) Chapter 11 – grafting of polysaccharides: recent advances. In: Thakur VK (ed) Biopolymer grafting. Elsevier, Cambridge, MA, pp 469–519
Avadi MR, Jalali A, Sadeghi AMM, Shamimi K, Bayati KH, Nahid E et al (2005) Diethyl methyl chitosan as an intestinal paracellular enhancer: ex vivo and in vivo studies. Int J Pharm 293(1):83–89
Aytemir MD, Ozcelik B (2011) Synthesis and biological activities of new Mannich bases of chlorokojic acid derivatives. Med Chem Res 20:443
Badawy MEI, Rabea EI (2014) Synthesis and antifungal property of N-(aryl) and quaternary N-(aryl) chitosan derivatives against Botrytis cinerea. Cellulose 21(4):3121–3137
Badawy MEI, Rabea EI, Rogge TM, Stevens CV, Smagghe G, Steurbaut W, Höfte M (2004) Synthesis and fungicidal activity of new N,O-acyl chitosan derivatives. Biomacromolecules 5(2):589–595
Baran T, Açıksöz E, Menteş A (2016) Highly efficient, quick and green synthesis of biarlys with chitosan supported catalyst using microwave irradiation in the absence of solvent. Carbohydr Polym 142:189–198
Bardajee GR, Hooshyar Z, Zehtabi F, Pourjavadi A (2012) A superabsorbent hydrogel network based on poly((2-dimethylaminoethyl) methacrylate) and sodium alginate obtained by γ-radiation: synthesis and characterization. Iran Polym J 21(12):829–836
Bhatnagar A, Sillanpää M (2009) Applications of chitin- and chitosan-derivatives for the detoxification of water and wastewater – a short review. Adv Colloid Interf Sci 152(1):26–38
Bodnar ED, Perreault H (2015) Synthesis and evaluation of carboxymethyl chitosan for glycopeptide enrichment. Anal Chim Acta 891:179–189
Bratskaya SY, Azarova YA, Matochkina EG, Kodess MI, Yatluk YG, Pestov AV (2012) N-(2-(2-pyridyl)ethyl)chitosan: synthesis, characterization and sorption properties. Carbohydr Polym 87(1):869–875
Fujii S (1980) Preparation of poly (acyl) chitosans. Carbohydr Res 83:389–393
Gedye R, Smith F, Westaway K, Ali H, Baldisera L, Laberge L, Rousell J (1986) The use of microwave ovens for rapid organic synthesis. Tetrahedron Lett 27(3):279–282
Geisberger G, Gyenge EB, Hinger D, Käch A, Maake C, Patzke GR (2013) Chitosan-thioglycolic acid as a versatile antimicrobial agent. Biomacromolecules 14(4):1010–1017
He J, Wang J, Zhong H, Ding J, Zhang L (2015) Cyanoethylated carboxymethyl chitosan as water soluble binder with enhanced adhesion capability and electrochemical performances for LiFePO4 cathode. Electrochim Acta 182:900–907
Hirano S, Zhang M (2000) Cellulose–acidic glycosaminoglycan blend fibers releasing a portion of the glycosaminoglycans in water. Carbohydr Polym 43(3):281–284
Hirano S, Ohe Y, Ono H (1976) Selective N-acylation of chitosan. Carbohydr Res 47(2):315–320
Hu F-Q, Zhao M-D, Yuan H, You J, Du Y-Z, Zeng S (2006) A novel chitosan oligosaccharide–stearic acid micelles for gene delivery: properties and in vitro transfection studies. Int J Pharm 315(1–2):158–166
Huang J, Chen W-w, Hu S, Gong J-Y, Lai H-W, Liu P et al (2013a) Biochemical activities of 6-carboxy β-chitin derived from squid pens. Carbohydr Polym 91(1):191–197
Huang J, Jiang H, Qiu M, Geng X, Yang R, Li J, Zhang C (2013b) Antibacterial activity evaluation of quaternary chitin against Escherichia coli and Staphylococcus aureus. Int J Biol Macromol 52:85–91
Huang W, Wang Y, Zhang S, Huang L, Hua D, Zhu X (2013c) A facile approach for controlled modification of chitosan under γ-ray irradiation for drug delivery. Macromolecules 46(3):814–818
Jenkins DW, Hudson SM (2001) Heterogeneous chloroacetylation of chitosan powder in the presence of sodium bicarbonate. J Polym Sci A Polym Chem 39(23):4174–4181
Jenkins DW, Hudson SM (2002) Heterogeneous graft copolymerization of chitosan powder with methyl acrylate using trichloroacetyl−manganese carbonyl co-initiation. Macromolecules 35(9):3413–3419
Jia Z, shen D, Xu W (2001) Synthesis and antibacterial activities of quaternary ammonium salt of chitosan. Carbohydr Res 333(1):1–6
Kaifu K, Nishi N, Komai T, Tokura S, Somorin O (1981) Studies on chitin. V. formylation, propionylation, and butyrylation of chitin. Polym J 13:241
Karrer P, White SM (1930) Polysaccharide XLIV. Weitere Beiträge zur Kenntnis des Chitins. Helv Chim Acta 13(5):1105–1113
Konwar A, Kalita S, Kotoky J, Chowdhury D (2016) Chitosan–iron oxide coated graphene oxide nanocomposite hydrogel: a robust and soft antimicrobial biofilm. ACS Appl Mater Interfaces 8(32):20625–20634
Kurita K (2001) Controlled functionalization of the polysaccharide chitin. Prog Polym Sci 26(9):1921–1971
Kurita K (2006) Chitin and chitosan: functional biopolymers from marine crustaceans. Mar Biotechnol 8(3):203
Kurita K, Ichikawa H, Ishizeki S, Fujisaki H, Iwakura Y (1982) Studies on chitin, 8. Modification reaction of chitin in highly swollen state with aromatic cyclic carboxylic acid anhydrides. Die Makromol Chem 183(5):1161–1169
Kurita K, Ishii S, Tomita K, Nishimura S-I, Shimoda K (1994) Reactivity characteristics of squid β-chitin as compared with those of shrimp chitin: high potentials of squid chitin as a starting material for facile chemical modifications. J Polym Sci A Polym Chem 32(6):1027–1032
Kurita K, Mori S, Nishiyama Y, Harata M (2002) N-alkylation of chitin and some characteristics of the novel derivatives. Polym Bull 48(2):159–166
Li C, Tian H, Rong N, Liu K, Liu F, Zhu Y, Jiang Y (2011) Chitosan grafted with macrocyclic polyamines on C-2 and C-6 positions as nonviral gene vectors: preparation, characterization, and in vitro transfection studies. Biomacromolecules 12(2):298–305
Lin Y-H, Liang H-F, Chung C-K, Chen M-C, Sung H-W (2005) Physically crosslinked alginate/N,O-carboxymethyl chitosan hydrogels with calcium for oral delivery of protein drugs. Biomaterials 26(14):2105–2113
Liu L, Li Y, Li Y, Fang Y-E (2004) Rapid N-phthaloylation of chitosan by microwave irradiation. Carbohydr Polym 57(1):97–100
Liu X, Xia W, Jiang Q, Xu Y, Yu P (2014) Synthesis, characterization, and antimicrobial activity of Kojic acid grafted chitosan oligosaccharide. J Agric Food Chem 62(1):297–303
Liu X, Jiang Q, Xia W (2018a) One-step procedure for enhancing the antibacterial and antioxidant properties of a polysaccharide polymer: Kojic acid grafted onto chitosan. Int J Biol Macromol 113:1125–1133
Liu X, Xia W, Jiang Q, Yu P, Yue L (2018b) Chitosan oligosaccharide-N-chlorokojic acid mannich base polymer as a potential antibacterial material. Carbohydr Polym 182:225–234
LogithKumar R, KeshavNarayan A, Dhivya S, Chawla A, Saravanan S, Selvamurugan N (2016) A review of chitosan and its derivatives in bone tissue engineering. Carbohydr Polym 151:172–188
Loubaki E, Sicsic S, Le Goffic F (1989) Modification chimique du chitosane avec la δ-gluconolactone, la β-propiolactone et le glycidol. Eur Polym J 25(4):379–384
Muzzarelli RAA, Tanfani F, Emanuelli M, Mariotti S (1982) N-(carboxymethylidene)chitosans and N-(carboxymethyl)chitosans: novel chelating polyampholytes obtained from chitosan glyoxylate. Carbohydr Res 107(2):199–214
Ning Ma AW (2004) Progress in chemical modification of chitin and chitosan. Prog Chem 16(4):643–653. In Chinese
Nishimura S-I, Kai H, Shinada K, Yoshida T, Tokura S, Kurita K et al (1998) Regioselective syntheses of sulfated polysaccharides: specific anti-HIV-1 activity of novel chitin sulfates. Carbohydr Res 306(3):427–433
Pillai CKS, Paul W, Sharma CP (2009) Chitin and chitosan polymers: chemistry, solubility and fiber formation. Prog Polym Sci 34(7):641–678
Popescu V, Muresan A, Popescu G, Balan M, Dobromir M (2016) Ethyl chitosan synthesis and quantification of the effects acquired after grafting it on a cotton fabric, using ANOVA statistical analysis. Carbohydr Polym 138:94–105
Qizhi Dong ZG (2001) O-alkylation of chitosan under microwave irradiation. Nat Sci J Xiangtan Univ 23(2):57–59. in Chinese
Rahmani S, Mohammadi Z, Amini M, Isaei E, Taheritarigh S, Rafiee Tehrani N, Rafiee Tehrani M (2016) Methylated 4-N,N dimethyl aminobenzyl N,O carboxymethyl chitosan as a new chitosan derivative: synthesis, characterization, cytotoxicity and antibacterial activity. Carbohydr Polym 149:131–139
Ravi Kumar MNV (2000) A review of chitin and chitosan applications. React Funct Polym 46(1):1–27
Rúnarsson ÖV, Holappa J, Malainer C, Steinsson H, Hjálmarsdóttir M, Nevalainen T, Másson M (2010) Antibacterial activity of N-quaternary chitosan derivatives: synthesis, characterization and structure activity relationship (SAR) investigations. Eur Polym J 46(6):1251–1267
Sahariah P, Gaware V, Lieder R, Jónsdóttir S, Hjálmarsdóttir M, Sigurjonsson O, Másson M (2014) The effect of substituent, degree of acetylation and positioning of the cationic charge on the antibacterial activity of quaternary chitosan derivatives. Mar Drugs 12(8):4635
Sahariah P, Benediktssdóttir BE, Hjálmarsdóttir MÁ, Sigurjonsson OE, Sørensen KK, Thygesen MB, Másson M (2015) Impact of chain length on antibacterial activity and hemocompatibility of quaternary N-alkyl and N,N-dialkyl chitosan derivatives. Biomacromolecules 16(5):1449–1460
Sangeetha Y, Meenakshi S, SairamSundaram C (2015) Corrosion mitigation of N-(2-hydroxy-3-trimethyl ammonium)propyl chitosan chloride as inhibitor on mild steel. Int J Biol Macromol 72:1244–1249
Setia A (2018) Chapter 1 – Applications of graft copolymerization: a revolutionary approach. In: Thakur VK (ed) Biopolymer grafting. Elsevier, Cambridge, MA, pp 1–44
Shin-Ichiro N, Yoshiaki M, Longdi R, Manabu S, Akihiko Y, Norio N et al (1993) An efficient method for the syntheses of novel amphiphilic polysaccharides by regio- and thermoselective modifications of chitosan. Chem Lett 22(9):1623–1626
Shoda S-i, Uyama H, Kadokawa J-i, Kimura S, Kobayashi S (2016) Enzymes as green catalysts for precision macromolecular synthesis. Chem Rev 116(4):2307–2413
Singh DK, Ray AR (2000) Biomedical applications of chitin, chitosan, and their derivatives. J Macromol Sci C 40(1):69–83
Singh V, Kumar P, Sanghi R (2012) Use of microwave irradiation in the grafting modification of the polysaccharides – a review. Prog Polym Sci 37(2):340–364
Sini TK, Santhosh S, Mathew PT (2005) Study of the influence of processing parameters on the production of carboxymethylchitin. Polymer 46(9):3128–3131
Thanou M, Nihot MT, Jansen M, Verhoef JC, Junginger HE (2001) Mono-N-carboxymethyl chitosan (MCC), a polyampholytic chitosan derivative, enhances the intestinal absorption of low molecular weight heparin across intestinal epithelia in vitro and in vivo. J Pharm Sci 90(1):38–46
Uragami T, Matsuoka Y, Miyata T (2016) Removal of dilute benzene in water through ionic liquid/poly(vinyl chloride) membranes by pervaporation. J Membr Sci Res 2(1):20–25
Wang Y, Zhang X, Qiu D, Li Y, Yao L, Duan J (2018) Ultrasonic assisted microwave synthesis of poly (chitosan-co-gelatin)/polyvinyl pyrrolidone IPN hydrogel. Ultrason Sonochem 40:714–719
Wei L, Zhaoyang L, Wenshen L, Feng X-D (1993) Chemical modification of biopolymers-mechanism of model graft copolymerization of chitosan. J Biomater Sci Polym Ed 4(5):557–566
Wu D (2017) Synthesis and characterization of O-carboxymethyl chitosan grafted colorants and supported catalysts. PhD thesis. Tianjin University
Zargar V, Asghari M, Dashti A (2015) A review on chitin and chitosan polymers: structure, chemistry, solubility, derivatives, and applications. Chem Bio Eng Rev 2(3):204–226
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Liu, X., Jiang, Q. (2019). Modification of Chitosan/Chitin and Its Oligosaccharides. In: Zhao, L. (eds) Oligosaccharides of Chitin and Chitosan. Springer, Singapore. https://doi.org/10.1007/978-981-13-9402-7_7
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DOI: https://doi.org/10.1007/978-981-13-9402-7_7
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