臺灣博碩士論文加值系統

本論文乃研究水溶性聚電解質—幾丁聚醣(chitosan)於不同pH值之丙酸水溶液中分子形態的變化。幾丁聚醣在有機酸水溶液下帶有-NH3+的正電荷，在不同pH值的丙酸水溶液中，幾丁聚醣的正電荷含量不同，所產生的電荷相斥作用會因pH值不同而改變，使得幾丁聚醣隨著pH值變化而有不同的分子形態。使用靜態光散射可以量測出分子環動半徑Rg(radius of gyration)、第二維里係數A2(second virial coefficient)和分子量(weight average molecular weight)，而歸納出幾丁聚醣分子形態和pH值之間的關聯性。使用動態光散射可求得聚合體在稀釋溶液中的傳動滲透係數Dt(translational diffiusion coefficient)進而計算其水動半徑Rh(hydrodynamic radius)分佈。實驗結果顯示，極限黏度[η]、第二維里係數(A2)、環動半徑(Rg)及水動半徑(Rh)、r(Rg/Rh)值皆隨溶劑pH值下降而增大，但分形維數隨pH值下降而下降，顯示分子形態隨著pH值下降越趨向於桿狀結構。pH值增加則幾丁聚醣分子因帶正電荷密度減少，分子內電荷排斥力下降而趨向於coil形態。我們亦取本實驗室前畢業生柏榮生論文，幾丁聚醣在乙酸水溶液之數據與本報告數據作比較。我們發現在相同pH值下，幾丁聚醣在丙酸水溶液中有較大的粒徑，分子鏈較容易伸展開。

In this study,we inverstigated the chain conformation of chitosan in propionic aqueous solutions at various pH values. The intrinsic viscosity [η] were measured using Ubbelohde viscometer. The second virial coefficient (A2), radius of gyration <Rg>, and weight average molecular weight (Mw) can be obtained from static light scattering and hydrodynamic radius <Rh> from dynamic light scattering. The experiments results revealed that [η], (A2), <Rg> and <Rh> decreased with increasing pH value. Increasing [H+] concentration resulted in an increase in the positive charge [-NH3+] group of chitosan. The charge repulsion of chitosan leads to increases both in molecular size and solubility of chitosan in water as pH decreases. The study of fractal dimesion also revealed that the molecular chain dimesion becomes more compact as pH increased. We also compared experimental data of chitosan in acetic aqueous solution with those in propionic aqueous solution. In the same pH value, we found that molecular size of chitosan in propionic aqueous solution was larger than that in acetic aqueous solution.

目錄i
表目錄iii
圖目錄v
一、前言1
1.1 動機1
1.2 幾丁聚醣簡介4
1.3 幾丁聚醣理化性質7
1.3.1 溶解性7
1.3.2 去乙醯度9
1.4 聚電解之性質9
1.5pH值、溶劑種類、流動活化能對幾丁聚醣之影響10
1.6 幾丁聚醣的光散射實驗文獻回顧11
1.6.1 靜態光散射12
1.6.2 動態光散射13
二、實驗部份17
2.1 試藥17
2.2 過濾器材20
2.3 儀器設備20
2.4 樣品配置23
2.5 原理與實驗步驟24
2.5.1 極限黏度24
2.5.2 微差折射率測定25
2.5.3 靜態光散射26
2.5.4 去極化率校正30
2.5.5 分形維數31
2.5.6 動態光散射數據分析32
三、結果與討論38
3.1 極限黏度38
3.2 微差折射率56
3.3 靜態光散射71
3.4 分形維數85
3.5 動態光散射93
四、結論106
附錄(各pH值之乙酸水溶液之性質)107
參考文獻108

Alonso I. G., Peniche-Coras C., and Nieto J. M., “Determination of
degree of acetylation of chitin by analysis”, J. Thermal Analysis., 28, 189 (1983)。
Amal R., Raper J. A., and Waite T. D. J. Colloid Interface Science., 140(1), 158-168 (1990)。
Anthonsen M. W., Varum Kjell M., and Smidsrod, O.,”Solution properties of chitosans:conformation and chain stiffness of chitosans with defferent degrees of N-acetylation,”Carbohydrate Polym.,22,193-201 (1993)。
Austin P. R., Brine C. J., Castle J. E., and Eikaksi J. P., “Chitin”, New Facets of Research Science., 212, 749 (1981)。
Borodinsky L., and King R. B., “Poly(vinyliminomethylenes)” , Maromol., 18(11), 2117-2120 (1985)。
Brown W., “Light scattering”, Chap 13, P.450, Oxford (1996)。
Chen R.H., Lin J.H. and Yang M.H., “Relationship between the chain flexibilities of chitosan molecules and physical properties of their casted films”, Carbohydrate Polymers , 24,41(1994).
Cummins H. Z., Knable N., and Yeh Y., Phys. Res. Letts., 12, 150(1964)。
Delben F., Lapasin R., and Pricl S.,”Flow properties of N-(carboxymethyl chitosan aqueous systems in the sol and gel domains,” Int. J. Biol. Macromol., 12(2), 9-13 (1990)。
Domard A., and Rinaudo M.,”Preparation and characterization of fully
deacetylated chitasan,”Int. J. Biol. Macromol., 5(2), 49-52 (1983)。
Eric B. and Marguerite R.,“Structural and Dynamical Properties of Semirigid Polyelectrolyte Solution: A Light-Scattering Study,”Macromol., 33(6), 2098-2106 (2000)。
Filar L. J. and Wirick M. G., “Bulk and solution properties of chitosan”, Proceedings of the 1st. Int. Conf. on Chitin/Chitosan., 169 (1978)。
Holan Z., and Voyruba J., “New method of chitin determination based on deacetylation and gas-liquid chromatographic assay of liberated acetic acid”, J. Chromatography., 190, 67 (1980)。
Horkay F., Burchard W., Geissler E., and Hecht, A-M., “Thermodynamic properties of poly(vinyl alcohol) and poly(vinyl alcohol-vinyl acetate) hydrogels”, Macromol., 26, 1296 (1993-a)。
Horkay F., Burchard W., Hecht A-M., and Geissler E., “Scattering properties of poly(vinyl acetate) gels in different solvents”, Macromol., 26, 4203 (1993-b)。
Kienzle-Sterzer C., Rodriguez-Sanchez D., Karelekas D. and Rha, C. K., “Stress relaxation of a polyelectrolyte network as affected by ionic strength “ , Macromol., 15, 631 (1982)。
Kienzle-Sterzer C., and Rha C. K., “Flow behavior of a cation biopolymer”, Polymer bull., 13-1(1985)。
Knorr D., “Dye binding properties of chitin and chitosan”, J. Food Technol., 48, 36 (1983)。
Knorr D.,”Functional properties of chitin and chitosan”, J. Food
Technol., 48, 36 (1983)。
Kurita K., “Chemistry and application of chitin and chitosan” , Polymer Degradation and Stability, 59, 117-120 (1998)。
Lyubina S. Y., Strelina I. A., Nud’ga L. A., Polym. Sci. U. S. S.R., 25, 1694-1701 (1983)。
McIntyre D., and Gornick F., “Light scattering from dilute polymer solution”, Gordon and Breach, New York, 1964。
Mitchell R. F., “Recovery of synthetic polymer from solvents”,
Polym.Sci., 30, 251(1979)。
Mucha M., “Rheological characteristics of semi-dilute chitosan solution”, Macromol. Chem. Phys., 198, 471 (1997)。
Muzzarelli R . A . A ., “Chitin”, Pregamon Press. Ltd. New York, 94-
101 (1977)。
Muzzarelli R . A . A ., Parisher E. R., “MIT Sea Grant Program”, Cambrige, MA, (1978)。
Muzzarelli R. A. A., Tanfani F., Scarpini G. and Laterza G., ” The degree of acetylation of chitin by gas chromatograohy and infrared spectrophotometry”, J. Biochem. and Biophysics., Method, 2, 29(1980)。
Muzzarelli R. A. A., “Chitin and its derivatives: New trends of applied research”, Carbohydr. Polym., 3, 53-75 (1983)。
Muzzarelli R. A. A. and Rocchetti R., “Determination of the degree of acetylation of chitosan of first derivative ultraviolet spectrophotometry”, Carbohydr. Polym.. 5, 461-427 (1985)。
Muzzarelli R . A . A ., Lough C., and Emanuelli M., Carbohydr. Res., 164, 433 (1987)。
Nielsen LE. “Polymer Rheology” New York, Marcel Dekker, 1977。
Nyström B., Kjøniksen A-L., Inversn C., Macromoleculars., 31, 8142-8148 (1998)。
Onsoyen E. and Skaugrud O., “Metal recovery using chitosan” , J.
Chem. Tech. Biotechnol, 49, 395-404 (1990)。
Rayleigh L., Phil., May, 47, 375 (1899)。
Roberts G. A., and Domszy J. G., “Evaluation of the viscometeric constants for chitosan”, Int. J. Macromol., 4, 374 (1982)。
Sannan T., Kurita K., Ogura K., and Lwakura Y., “Studies on chitin :I. R.spectroscopic determination the degree of decacefylation”, Polymer,
19, 458 (1978)。
Sklyar A. M., Gamzazade A. L., Rogovina L. Z., Tifkova, S. A., Polym.Sci. U.S.S.R., 23, 1546-1554 (1981)。
Terbojevich M., Cosani A.; Coio G.; Marsano, E.; Bianchi, E., Carborhydr Res., 209, 251-260 (1991)。
Toei K., and Kohara T., “A conductometric method for colloid titrations”, Anal. Chem. Acta., 83, 59 (1976)。
Van Duin P. J.; Hermans, J. J., J. Polym. Sci., 36, 295 (1959)。
Wang W., Bo S., Li S., and Qin, W.,”Deternination of the Mark-Houwink equation for chitosans with different degrees of Daacetylation,”
Int. J. Biol. Macromol.,13(10),281-285 (1991)。
Wu C.and Wang W., “A dynamic laser light-scattering study of chitosan in aqueous solution”, Biopolymers., 35, 385-392 (1995)。
Yang T. C. and Zall, R.R., “Absorption of metals by natural polymers generated form seafood processing wastes”, Ind. Eng. Chem. Prod. Res. Des., 23(1), 168-172 (1984)。
Zimm, B. H., J. Chem. Phys., 16, 1093-1099 (1948a)。
Zimm, B. H., J. Chem. Phys., 16, 1099-1116 (1948b)。
李鵬程、宋金明 「甲殼質/殼聚醣及其衍生物的應用化學」，海洋科學，第5期，第25至29頁(1998)。
李育德、顏文義， 「聚合物物性」， 第44至第48頁， 高立圖書， 台北(1989)
邵惠珍，「以幾丁聚醣吸附雙成份金屬離子之平衡模式」，化工碩士論文，元智大學，桃園(2000)。
柏榮生，「幾丁聚醣乙酸水溶液之光散射研究」，化工碩士論文，
元智大學，桃園(1999)。
陳榮輝、金曉珍， 「水產甲殼類廢棄物開發高經濟價值之幾丁質、幾丁聚醣、幾丁寡醣研究之規劃報導」 ，科學發展月刊，第 23 卷
第六期 ， 第 550 至 562 頁(1995)。
陳榮輝，「水產甲殼廢棄物開發高經濟價值之幾丁質、幾丁聚醣」，科學發展月刊，第四期，第27卷，413-421頁(1999)。
曾如玲、吳豐智，「幾丁聚醣吸附銅離子螯合物溶液之研究」，第二十一屆廢水處理技術研討會論文集，第317至324頁(1996)。
劉正平，「聚乙烯醇-硼酸鹽-D2O稀釋及半稀釋溶液的動態光散射及中子散射研究」，桃園(2000)。
蔡騰龍，「聚電解質與淨水處理」，正文書局，第1至第8頁，台北(1993)。
錢明賽，「水產廢棄物蝦、蟹外殼利用之研究」，食品工業展研究所之計畫報告(1997)。
蕭瑞昌，「利用水溶性幾丁聚醣以薄膜過濾法去除微量之金屬離子」，化工碩士論文， 元智大學， 桃園(1997)。
糜福龍，「幾丁聚醣應用於藥物及疫苗傳輸系統之設計及研究」，中央大學，博士論文(1997)。