甲殼素(Chitin)主要是從甲殼類動物中所萃取出來的高分子，而幾丁聚醣(Chitosan)則是甲殼素的衍生物之一，其結構為N-乙醯-2-胺基-2-脫氧-D-葡萄糖。當去乙醯化程度低於百分之五十時，稱之為甲殼素，反之當去乙醯化程度高於百分之五十，則稱之為幾丁聚醣。幾丁聚醣本身不具毒性且有良好的生物相容性與生物可分解性，但因只能溶解在酸的水溶液中，故近年來已有不少學者希望能藉著化學改質進而改善其溶解性與增加其應用性。
在論文中，我們以甲磺酸當溶劑，讓幾丁聚醣上的羥基與胺基和丁醯氯或丁酐進行醯化反應。由於(1)將丁醯基導入幾丁聚醣的高分子鏈中，(2)因強酸導致幾丁聚醣分子量降解，而改善了幾丁聚醣的溶解性質，並藉著改變反應條件，探討對丁醯化幾丁聚醣的影響。之後使用核磁共
振光譜(NMR)和紅外線光譜(FT-IR)鑑定其化學結構，並利用核磁共振光譜的吸收峰面積，推算出幾丁聚醣的丁醯基接枝量。在改質成丁醯化幾丁聚醣後，除了可溶於酸性溶劑外，還可微溶於四氫口夫喃(THF)、氯仿(CHCl3)。最後再以熱重分析儀(TGA)、微差掃描熱卡儀(DSC)探討幾丁聚
醣分子經過改質後的熱性質變化。

Chitosan is a derivative of chitin, which is mainly obtained fromcrustacean. This natural polymer composed of a mixed repeatingstructural unit of 2-acetamido-2-deoxy-β-D-glucose and
2-amino-2-deoxy-β-D-glucose. Chitosan is the copolymer name when its glucosamine ratio is over 50%. Chitosan itself is nontoxic, biocompatible,
and biodegradable with the action of glycosidase such as chitosanase,chitinase, but it is only soluble in dilute organic acids. The uses and
applications of chitosan are limited by its insolubility in organic solvents due to its hydrophilic primary and secondary hydroxyl groups. Therefore,chemical modification of chitosan is necessary to improve its solubility.
In this study, we report a synthesis for the N,O-acylation of chitosan in MeSO3, and butyryl group had been introduced to the hydroxyl group
and amino group in various experiment conditions. Butyrylation of chitosan improved the solubility, owing to (1) hydrophobic moiety with an ester linkage; (2) the decrease of molecular weight by MeHSO3 as a strong acid. H-NMR and FT-IR are used to identify its chemical structural after butyrylation reaction. And the degree of butyrated
substitution is characterized by H-NMR. The thermodynamics properties of butyrated chitosan were examined by TGA and DSC as well.

參考文獻
1. Severian D,“Polymeric Biomaterials”, Marcel Dekker, New York
2. 美國飼料穀物協會, “生物可分解塑膠”, 美國飼料穀
物協會, 台北市
3. Rantner BD, Hoffman AS, “Biomaterials science
an introduction to materials in medicine”, Academic Press, San Diego, 1996
4. 蔣挺大, “甲殼素”, 中國環境科學出版社, 北京,
1996
5. Shigemasa Y, Minami S, “Application of chitin
and chitosan for biomaterials”, 13, 383, 1995
6. Kurita K, “Chemistry and application of chitin
and chitosan”,polymer degradation and stability, 59, 117, 1998
7. Chatelet C, Damour O, Domard A, “Influence of
the degree of acetylation on some Biological properties of chitosan films ”,Biomaterials, 22, 261, 2001
8. 田蔚城, “生物產業與製藥產業”, 九州圖書文物有限
公司, 台北市, 1998
9. Peter MG, “Applications and environmental aspects of chitin and chitosan”, J M S-Pure Appl Chem, A32, 629, 1995
10.Ge J et. al., “The effect of structure on pervaporation of chitosan memberane”, J Member Sci, 165, 75, 2000
11.Rao SB, Sharma CP, “Use of chitosan as a
biomaterial : studies on its safety and hemostatic potential”, Biomater Appl, 10, 136, 1995
12.Chandy T, Sharma CP, “Chitosan as a biomaterial”, Biomat, Art Cell, Art Org, 18, 1, 1990
13.Terbojevich M, Cosani A, Muzzare RAA,“Molecular
parameters of chitosans depolymerized with the aid of papin”, Carbohydr Polym, 29, 63, 1996
14.Allan GG, Peyron M, “Molecular weight manipulation of chitosan Ⅱ: prediction and control of extent depolymerization by nitrous acid”, Carbohydr Res, 277, 273, 1995
15.Allan GG, Peyron M, “Molecular weight manipulation of chitosanⅠ: kinetics of depolymerization by nitrous acid”, Carbohydr Res,277, 257, 1995
16.Rege PR, Block LH, “Chitosan processing : influence of process parameters during acidic and alkaline hydrolysis and effect of the processing sequence on the resultant chitosan's properties”,Carbohydr Res, 321, 235, 1999
17.Oungbho K, Miller BW, “Chitosan sponges as
sustained release drug carriers”, Int J Pharma, 156, 229, 1997
18.Senel S, Ikinci G, Kas S, Yousefi-Rad A, Sargon
MF, Hincal AA,“Chitosan films and hydrogels of
chlorhexidine gluconate for oral mucosal delivery”, Int J Pharma, 193, 197, 2000
19.Malette WG et. al., “Method for the therapeutic
occlusion”, US Patent, 4, 785, 1984
20.Amiji MM, “Platelet adhesion and activation on
an amphoteric chitosan derivative bearing sulfonate groups”, Colloids and Surfaces B: Biointerfaces, 10, 263, 1998
21.Amiji MM, “Synthesis of anionic poly(ethylene glycol)derivative for chitosan surface modification in blood-contacting applications”,Carbohydr Polym, 32, 193, 1997
22.Kurita K,“Controlled functionalization of the
polysaccharide chitin”,prog. polym. sci., 26, 1921, 2001
23.Kurita K, Ishii S, Tomita K, Nishimura S, Shimoda K, “Reactivity Characteristics of Squid
Beta-Chitin as Compared with Those of Shrimp Chitin - High Potentials of Squid Chitin as a
Starting Material for Facile Chemical Modifications”, J Polym Sci: Part A:Polym Chem, 32, 1027, 1994
24.Goosen MFA, “Applications of chitin and chitosan”, Technomic Pub.,Lancaster, p79, 1997
25.Fujii S, Kumagai H, Noda M, Carbohydr Res, 83, 389, 1980
26.Hirano S, Ohe Y, Agric Biol Chem, 39, 1337, 1975
27.Moore GK, Roberts GAF, Int J Biol Macromol, 2,
73, 1980
28.Nishi N, Noguchi J, Tokura S, Shiota H,“Studies
on chitin. I.acetylation of chitin”, Polym J, 11, 27, 1979
29.Kaifu K, Nishi N, Komai T, Tokura S, Somorin O,”Studies on chitin.V. formation, propionylation, and butyrylation of chitin”, Polym J, 13, 241, 1981
30.Kurita K, Inoue S, Nishimura S, “Preparation of soluble chitin derivatives as reactive precursors for controlled modifications -tosyl-Chitins and iodo-chitins”, J Polym Sci: Part A: Polym Chem, 29,937, 1991
31.Kurita K, Yoshino H, Yokota K, Ando M, Inoue S,
Ishii S, Nishimura SI, “Preparation of tosylchitins as precursors for facile chemical
modifications of chitin”, Macromolecules, 25, 3786, 1992
32.Kurita K, Yoshino H, NishimuraSI, “Mercapto-chitins: a new type of supports for effective immobilization of acid phosphatase”,Carbohyd Polym, 32, 171, 1997
33.Nishimura SI, Kohgo O, Kurita K, Vittavatvong C,
Kuzuhara H,“Syntheses of novel chitosan derivatives soluble in organic-solvents by regioselective chemical modifications”, Chem
Lett, 243, 1990
34.Allan GG, Peyron M, “Molecular weight manipulation of chitosan .1.kinetics of depolymerization by nitrous acid”, Carbohy Res,
277, 257,1995
35.Pavia DL, Lampman GM, Kriz GS,“Introduction to
spectroscopy”,Brooks/Cole, Thomson Learning,
Australia, 13, 2001
36.Hamaguchi K, Funatsu M, J Bio chem, 46, 1659,
1959
37.Skjak-Bræk G, Anthonsen T, Sandford P, “Chitin
and chitosan”,Elsevier, Barking, p389, 1989
38.Muzzarelli RAA, Peter MG, “Chitin handbook”,
Atec Edizioni,Grottammare, p61,1997
39.Moore GK, Roberts GAF, Int J Bio Macromol, 4,
246, 1982
40.Miyazaki T, Matsushima Y, Bull Chem Soc Jpn, 41,
2723, 1968
41.Carolan CA, Blair HS, Allen SJ, Mckay G, “N,O-carboxymethyl chitosan, a water-soluble derivative and potential green food preservative”, Chem Eng Res Des, 69, 195, 1991
42.Rinaudo M, Ledung P, Gey C, Milas M, “Substituent distribution on O,N-carboxymethylchitosans by H-1-NMR and C-13 NMR”, Int J Bio Macromol, 14, 122, 1992
43.Sashiwa H, Kawasaki N, Nakayama A, Muraki E,
Yamamoto N, Zhu H, Nagano H, Omura Y, Saimoto H,
Shigemasa Y, Aiba S-I,“Chemical modification of
chitosan. 13. Synthesis of organosoluble,
palladium adsorbable, and biodegradable chitosan
derivatives toward the chemical plating on
plastics”, Biomacromolecules, 3, 1120,2002
44.Muzzarelli RAA, Tanfani F, Emanuelli M, Mariotti
S, Carbohydr Res,107, 199, 1982
45.Kurita K, Hirakawa M, Nishiyama Y, “Silylated
chitin - a new organosoluble precursor for
facile modifications and film casting”, Chem
Lett, 771, 1999
46.夏篤禕, “高聚物結構分析”, 化學工業出版社, 北
京, 1990
47.孫逸民, 陳玉舜, 趙敏勳, 謝明學, 劉興鑑, “儀器分
析”, 全威圖書有限公司, 台北縣, 1999
48. Mellor JD 著, 張志純譯, “冰凍乾燥法”, 徐氏基
金會, 1983
49. Wang W, Qin W, Bo SQ, “Influence of the degree
of deacetylation of chitosan on its Mark-Houwink
equation parameters”, Macromol Rapid Commun., 12, 559, 1991
50.Luyen DV, Rossbach V, “Mixed esters of chitin”, J App Polym Sci, 55, 679, 1995
51.Sashiwa H, Kawasaki N, Nakayama A, Muraki E,
Yamamoto N, Zhu H, Nagano H, Omura Y, Saimoto H,
Shigemasa Y, Aiba Sei-ichi,“ Chemical
modification of chitosan. 13. synthesis of organosoluble, palladium adsorbable, and biodegradable chitosan derivatives toward the
chemical plating on plastics”, Biomacromolecules, 3,1120, 2002
52.Heux L, Brugnerotto J, Desbriéres J, Versali M.-F., Rinaudo M,“ Solid state NMR for determination of degress of acetylation of chitin and chitosan”, Biomacromolecules, 1, 746, 2000
53.Capitan D, Angelis AAD, Crescenzi V, Masci G,
Segre AL,“NMRstudy of a novel chitosan-based hydrogel”, Carbohydr Polym, 45, 245, 2001
54.Hirai A, Odani H, Nakajima A, “Determinationn
of degree of deacetylation of chitosan by 1H-NMR
spectroscopy”, Polym Bull, 26,87, 1991
55.Capitan D, Crescenzi V, Angelis AAD, Segre AL,“Water in hydrogel. An NMR study of water/polymer interactions in weakly crosslinked
chitosan network”, Macromolecules, 34, 4136, 2001
56.Mayer KM, Pankow GW, Helv Chim Acta, 18, 589,
1935