Selection of a practical assay for the determination of the entire range of acetyl content in chitin and chitosan: UV spectrophotometry with phosphoric acid as solvent

Journal of Biomedical Materials Research - Part B Applied Biomaterials

Volumn 86, Issue 2, 2008, Pages 558-568

  Hein, San ^a,b   Ng, Chuen How ^b,c   Stevens, Willem F ^b,d,e   Wang, Kean ^a  

^a Nanyang Technological University   (Singapore)

^b ASIAN INSTITUTE OF TECHNOLOGY   (Thailand)

^c Genis Ehf   (Iceland)

^d CHULALONGKORN UNIVERSITY   (Thailand)

^e MAHIDOL UNIVERSITY   (Thailand)

Author keywords

Acetyl content; Chitin chitosan; DSC; Phosphoric acid; XRD

Indexed keywords

AMINES; BIOLOGICAL MATERIALS; FOURIER TRANSFORM INFRARED SPECTROSCOPY; PELLETIZING; PHOSPHORIC ACID;

ACCURACY AND PRECISION; ACETYL CONTENT; ANALYTICAL METHODS; BIO-MEDICAL APPLICATIONS; PHYSICO-CHEMICAL CHARACTERISTICS; SOLID STATES; ULTRAVIOLET (UV) SPECTROPHOTOMETRY;

CHITIN;

ACETIC ACID DERIVATIVE; CHITIN; CHITOSAN; PHOSPHORIC ACID;

ACCURACY; ACID HYDROLYSIS; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; DIFFERENTIAL SCANNING CALORIMETRY; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; HYDROLYSIS; INFRARED SPECTROSCOPY; RELIABILITY; SPECTROPHOTOMETRY; ULTRAVIOLET SPECTROPHOTOMETRY; X RAY DIFFRACTION;

ACETYLATION; CHITIN; CHITOSAN; PHOSPHORIC ACIDS; SOLVENTS; SPECTROPHOTOMETRY, ULTRAVIOLET; SPECTRUM ANALYSIS;

EID: 47949093617     PISSN: 15524973     EISSN: 15524981     Source Type: Journal    
DOI: 10.1002/jbm.b.31056     Document Type: Article

References (84)

1. Chandy R, Sharma CP. Chitosan - as a biomaterial. Biomater Artif Cells Artif Organs 1990;8:1-24.
2. Hirano S. Chitin biotechnology applications. Biotechnol Annu Rev 1996;2:237-258.
3. Khor E, Lim LY. Implantable applications of chitin and chitosan. Biomaterials 2003;24:2339-2349.
4. Kumar MN, Muzzarelli RA, Muzzarelli C, Sashiwa H, Domb AJ. Chitosan chemistry and pharmaceutical perspectives. Chem Rev 2004;104:6017-6084.
5. Kato Y, Onishi H, Machida Y. Contribution of chitosan and its derivatives to cancer chemotherapy. In Vivo 2005;19:301-310.
6. Thein-Han WW, Stevens WF. Transdermal delivery controlled by a chitosan membrane. Drug Dev Ind Pharm 2004;30:397-404.
7. Anal AK, Stevens WF. Chitosan-alginate multilayer beads for controlled release of ampicillin. Int J Pharm 2005;290:45-54.
8. Roy K, Mao HQ, Huang SK, Leong KW. Oral gene delivery with chitosan-DNA nanoparticles generates immunologic protection in a murine model of peanut allergy. Nat Med 1999;5:387-391.
9. Koping-Hoggard M, Mel'nikova YS, Vårum KM, Lindman B, Artursson P. Relationship between the physical shape and the efficiency of oligomeric chitosan as a gene delivery system in vitro and in vivo. J Gene Med 2003;5:130-141.
10. Azad AK, Sermsintham N, Chandrkrachang S, Stevens WF. Chitosan membrane as a wound-healing dressing: Characterization and clinical application. J Biomed Mater Res B Appl Biomater 2004;69:216-222.
11. Kojima K, Okamoto Y, Kojima K, Miyatake K, Fujise H, Shigemasa Y, Minami S. Effects of chitin and chitosan on collagen synthesis in wound healing. J Vet Med Sci 2004;66:1595-1598.
12. Qi L, Xu Z, Jiang X, Li Y, Wang M. Cytotoxic activities of chitosan nanoparticles and copper-loaded nanoparticles. Bioorg Med Chem Lett 2005;15:1397-1399.
13. Kimura Y, Sawai N, Okuda H. Antitumour activity and adverse reactions of combined treatment with chitosan and doxorubicin in tumour-bearing mice. J Pharm Pharmacol 2001;53:1373-1378.
14. Harish Prashanth KV, Tharanathan RN. Depolymerized products of chitosan as potent inhibitors of tumor-induced angiogenesis. Biochim Biophys Acta 2005;1722:22-29.
15. Saiki I, Murata J, Nakajima M, Tokura S, Azuma I. Inhibition by sulfated chitin derivatives of invasion through extracellular matrix and enzymatic degradation by metastatic melanoma cells. Cancer Res 1990;50:3631-3637.
16. Roberts GAF. Chitin Chemistry. London: Macmillan; 1992.
17. Muzzarelli RAA, Peter MG, editors. Chitin Handbook. Grottammare: Atec; 1997.
18. Hirano S. Production and application of chitin and chitosan in Japan. In: Skjåk-Bræk G, Anthonsen T, Sanford PA, editors. Chitin and Chitosan: Sources, Chemistry, Biochemistry, Physical Properties and Applications. London: Elsevier; 1989. pp 37-43.
19. Hein S, Ng CH, Chandrkrachang S, Stevens WF. A systematic approach to quality assessment system of chitosan. In: Uragami T, Kurita K and Fukamizo T, editors. Chitin and Chitosan in Life Science. Tokyo: Kodansha; 2000. pp 332-335.
20. Hein S, Ng CH, Stevens WF. Development of analytical protocols for quality assessment of chitin and chitosan: Protein content, crystallinity and assay of insolubles. In: Boucher I, Jamieson K, Retnakaran A, editors. Advances in Chitin Science, Vol. 7. Montreal: ISM Biopolymer; 2004. pp 13-18.
21. Terayama H. Method of colloid titration (a new titration between polymer ions). J Polym Sci 1952;8:243-253.
22. Broussignac P. Chitosan: A natural polymer not well known by the industry. Chim Ind Genie Chim 1968;99:1241-1247.
23. Hayes ER, Davies DH. Characterization of chitosan. II. The determination of degree of acetylation of chitosan and chitin. In: Pariser ER, Muzzarelli RAA, editors. Proceedings of 1st International Conference on Chitin/Chitosan. MIT Sea Grant Report MITSG 78-7; 1978. pp 406-420.
24. Rutherford FA, Austin PR. Marine chitin properties and solvents. Pariser ER, Muzzarelli RAA, editors. Proceedings of 1st International Conference on Chitin/Chitosan. MIT Sea Grant Report MITSG 78-7; 1978. pp 182-192.
25. Gummow BD, Roberts GAF. Studies on chitosan-induced metachromasy, Part 1: Metachromatic behaviour of sodium 2′-hydroxy-1,1′-azo-naphthalene- 4-sulfonate in the presence of chitosan. Makromol Chem 1985;186:1239-1244.
26. Domszy JG, Roberts GAF. Evaluation of infrared spectroscopic techniques for analyzing chitosan. Makromol Chem 1985;186:1671-1677.
27. Raymond L, Morin FG, Marchessault RH. Degree of deacetylation of chitosan using conductometric titration and solid-state NMR. Carbohydr Res 1993;246:331-336.
28. Jiang X, Chen L, Zhong W. A new linear potentiometric titration method for the determination of deacetylation degree of chitosan. Carbohydr Polym 2003;54:457-463.
29. Muzzarelli RAA, Rocchetti R. Determination of the degree of acetylation of chitosans by first derivative ultraviolet spectrophotometry. Carbohydr Polym 1985;5:461-472.
30. Aiba S. Studies on chitosan, Part 1: Determination of the degree of N-acetylation of chitosan by ultraviolet spectrophotometry and gel permeation chromatography. Int J Biol Macromol 1986;8:173-176.
31. Muraki E, Yaku F, Iyoda J, Kojima H. Measurement of degree of deacetylation in D-glucosamine oligosaccharides by UV absorption. Biosci Biotech Biochem 1993;57:1929-1930.
32. Tan SC, Khor E, Tan TK, Wong SM. The degree of deacetylation of chitosan: Advocating the first derivative UV spectrophotometry method of determination. Talanta 1998;45:713-719.
33. Pedroni VI, Gschaider ME, Schulz PC. UV Spectrophotometry: Improvements in the study of the degree of acetylation of chitosan. Macromol Biosci 2003;3:531-534.
34. Liu D, Wei Y, Yao P, Jiang L. Determination of the degree of acetylation of chitosan by UV spectrophotometry using dual standards. Carbohydr Res 2006;341:782-785.
35. Domard A. Determination of N-acetyl content in chitosan samples by c.d. measurements. Int J Biol Macromol 1987;9:333-336.
36. Ferreira MC, Marvão MR, Duarte ML. Determination of the degree of acetylation of chitin/chitosan using IR spectroscopy. In: Stevens WF, Rao MS, Chandrkrachang S, editors. The Proceedings of the Second Asia Pacific Symposium: Chitin and Chitosan. Bangkok: Asian Institute of Technology; 1996. p 107.
37. Vårum KM, Anthonsen MW, Grasdalen H, Smidsrød O. Determination of the degree of N-acetylation and the distribution of N-acetyl groups in partially N-deacetylated chitins (chitosans) by high-field n.m.r. spectroscopy. Carbohydr Res 1991;211:17-23.
38. 1H NMR spectroscopy. Polym Bull 1992;26:87-94.
39. 13C NMR. Int J Biol Macromol 1992;14:122-128.
40. 1H NMR method for the determination of the degree of deacetylation of chitosan. J Pharm Biomed Anal 2003;32:1149-1158.
41. 1H-NMR. Carbohydr Polym 2005;61:155-161.
42. Nanjo F, Katsumi R, Sakai K. Enzymatic method for determination of the degree of deacetylation of chitosan. Anal Biochem 1991;193:164-167.
43. Maghami GG, Roberts GAF. Studies on the adsorption of anionic dyes on chitosan. Makromol Chem 1988;189:2239-2243.
44. Roberts GAF. Determination of the degree of N-acetylation of chitin and chitosan. In: Muzzarelli RAA, Peter MG, editors. Chitin Handbook. Grottammare: Atec; 1997. pp 127-132.
45. Neugebauer WA, Neugebauer E, Brzezinski R. Determination of the degree of N-acetylation of chitin-chitosan with picric acid. Carbohydr Res 1989;189:363-367.
46. Prochazkova S, Vårum KM, Ostgaard K. Quantitative determination of chitosans by ninhydrin. Carbohydr Polym 1999;38:115-122.
47. Muzzarelli RAA, Tanfani F, Scarpini G, Laterza G. The degree of acetylation of chitins by gas chromatography and infrared spectroscopy. J Biochem Biophys Methods 1980;2: 299-306.
48. Holan I, Votruba J, Vlasakova VJ. New method of chitin determination based on deacetylation and gas-liquid chromatographic assay of liberated acetic acid. J Chromatogr 1980;190:67-76.
49. Stoev G, Velichkov A. Direct determination of acetic acid in strongly acidic hydrolysates of chitin and chitin-containing biological products by capillary gas chromatography. J Chromatogr 1991;538:431-434.
50. Rathke TD, Hudson SM. Determination of the degree of N-deacetylation in chitin and chitosan as well as their monomer sugar ratios by near infrared spectroscopy. J Polym Sci Part A: Polym Chem 1993;31:749-753.
51. Vårum KM, Egelandsdal B, Ellekjær MR. Chracterization of partially N-acetylated chitosans by near infra-red spectroscopy. Carbohydr Polym 1995;28:187-193.
52. Mattai J, Hayes ER. Characterization of chitosan by pyrolysis-mass spectrometry. J Anal Appl Pyrolysis 1982;3:327-334.
53. Lal GS, Hayes ER. Determination of the amine content of chitosan by pyrolysis-gas chromatography. J Anal Appl Pyrolysis 1984;6:183-193.
54. Sato H. Mizutani S, Tsuge S, Ohtani H, Aoi K, Takasu A, Okada M, Kobayashi S, Kiyosada T, Shoda S. Determination of the degree of acetylation of chitin/chitosan by pyrolysis-gas chromatography in the presence of oxalic acid. Anal Chem 1998;70:7-12.
55. 15N NMR. Macromolecules 1999;32:518-520.
56. Heux L, Brugnerotto J, Desbrières J, Versali MF, Rinaudo M. Solid state NMR for determination of degree of acetylation of chitin and chitosan. Biomacromolecules 2000;1:746-751.
57. Kittur FS, Prashanth H, Sankar KVH, Tharanathan RN. Characterization of chitin, chitosan and their carboxymethyl derivatives by differential scanning calorimetry. Carbohydr Polym 2002;49:185-193.
58. Zhang Y, Xue C, Xue Y, Gao R, Zhang X. Determination of the degree of deacetylation of chitin and chitosan by X-ray powder diffraction. Carbohydr Res 2005;11:1914-1917.
59. Sannan T, Kurita K, Ogura K, Iwakura Y. Studies on chitin: 7. I.R. spectroscopic determination of degree of deacetylation. Polymer 1978;19:458-459.
60. Moore GK, Roberts GAF. Determination of the degree of N-acetylation of chitosan. Int J Biol Macromol 1980;2:115-116.
61. Miya M, Iwamoto R, Ohta K, Iwakura Y. IR spectroscopic determination of CONH content in highly deacetylated chitosan. Int J Biol Macromol 1980;2:323-324.
62. Baxter A, Dillon M, Taylor KD, Roberts GAF. Improved method for IR determination of the degree of N-acetylation of chitosan. Int J Biol Macromol 1992;14:166-169.
63. Shigemasa Y, Matsuura H, Sashiwa H, Saimoto H. Evaluation of different absorbance ratios from infrared spectroscopy for analyzing the degree of deacetylation in chitin. Int J Biol Macromol 1996;18:237-242.
64. Sabnis S, Block LH. Improved infrared spectroscopic method for the analysis of degree of N-acetylation of chitosan. Polym Bull 1997;39:67-71.
65. Brugnerotto J, Lizardib J, Goycoolea FM, Arguelles-Monal W, Desbrières J, Rinaudo M. An infrared investigation in relation with chitin and chitosan characterization. Polymer 2001;42:3569-3580.
66. Khor E. Chitin: Fulfilling a biomaterials promise. Oxford: Elsevier; 2001. pp 127-130.
67. Duarte ML, Ferreira MC, Marvão MR, Rocha J. An optimized method to determine the degree of acetylation of chitin and chitosan by FTIR spectroscopy. Int J Biol Macromol 2002;31:1-8.
68. 13C NMR. Carbohydr Polym 2004;58:409-416.
69. Niola F, Basora N, Chornet E, Vidal PF. A rapid method for the determination of the degree of N-acetylation of chitin-chitosan samples by acid hydrolysis and HPLC. Carbohydr Res 1993;238:1-9.
70. Ng CH, Hein S, Chandrkrachang S, Stevens WF. Evaluation of an improved acid hydrolysis-HPLC assay for the acetyl content in chitin and chitosan. J Biomed Mater Res B Appl Biomater 2006;76:155-160.
71. 13C cross polarization/magic angle spinning (CP/MAS) NMR spectroscopy. Chem Lett (The Chemical Society of Japan) 1981:1479-1482.
72. 13C CP/MAS NMR spectroscopy. Int J Biol Macromol 2001;28:359-363.
73. Hsiao H-Y, Tsai C-C, Chen S, Hsieh B-C, Chen RLC. Spectrophotometric determination of deacetylation degree of chitinous materials dissolved in phosphoric acid. Macromol Biosci 2004;4:919-921.
74. Stevens WF. Production of chitin and chitosan: Refinement and sustainability of chemical and biological processing. In: Uragami T, Kurita K, Fukamizo T, editors. Chitin and Chitosan in Life Science. Tokyo: Kodansha; 2001. pp 293-300.
75. Trung ST, Ng CH, Stevens WF. Characterization of decrystallized chitosan and its application in biosorption of textile dyes. Biotechnol Lett 2003;25:1185-1190.
76. Kurita K, Sannan T, Iwakura Y. Studies on chitin, Part 4: Evidence for formation of block and random copolymers of N-acetyl-D-glucosamine and D-glucosamine by hetero- and homogeneous hydrolyses. Makromol Chem 1977;178:3197-3202.
77. Jang M-K, Kong B-G, Jeong Y-I, Lee CH, Nah J-W. Physicochemical characterization of α-chitin, β-chitin and γ-chitin separated from natural resources. J Polym Sci Part A: Polym Chem 2004;42:3423-3432.
78. Chen RH, Lui CS. Effect of recovery methods and conditions on the yield, solubility, molecular weight, and creep compliance of regenerated chitosan. J Appl Polym Sci 2002;84:193-202.
79. Jaworska M, Sakurai K, Gaudon P, Guibal E. Influence of chitosan characteristics on polymer properties, Part 1: Crystallographic properties. Polym Int 2003;52:198-205.
80. Ng C-H, Hein S, Ogawa K, Chandrkrachang S, Stevens WF. Distribution of D-glucosamine moieties in heterogeneously deacetylated cuttlefish chitin. Carbohydr Polym 2007;69:282-390.
81. Chen RH, Shyur JS, Chang JR. The effects of ultrasonic-heating and heating only on the changes in intrinsic viscosity, degree of deacetylation and maximum melting point temperature of treated chitosan. In: Stevens WF, Rao MS, Chandrkrachang S, editors. Chitin and Chitosan: Environmental Friendly and Versatile Biomaterials. Thailand: Asian Institute of Technology; 1996. pp 90-97.
82. Tsaih ML, Chen RH. Effect of degree of deacetylation of chitosan on the kinetics of ultrasonic degradation of chitosan. J Appl Polym Sci 2003;90:3526-3531.
83. Hasegawa M, Akira I, Onabe F. Preparation of low-molecular-weight chitosan using phosphoric acid. Carbohydr Polym 1993;20:279-283.
84. Vincendon M. Regenerated chitin from phosphoric acid solutions. Carbohydr Polym 1997;32:233-237.