請用此 Handle URI 來引用此文件:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/29764
完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 劉春櫻(Chuen-Ying Liu) | |
dc.contributor.author | Huei-Chi Chen | en |
dc.contributor.author | 陳慧綺 | zh_TW |
dc.date.accessioned | 2021-06-13T01:17:55Z | - |
dc.date.available | 2009-07-13 | |
dc.date.copyright | 2007-07-25 | |
dc.date.issued | 2007 | |
dc.date.submitted | 2007-07-19 | |
dc.identifier.citation | 1. Strain, H., H. J. Am. Chem. Soc. 1939, 61, 1292.
2. Pretorius, V.; Hopkins, B. J.; Schieke, J. D. J. Chromatogr. 1974, 99, 23. 3. Jorgenson, J. W.; Lukacs, K. D. J. Chromatogr. 1981, 218, 209. 4. Knox, J. H.; Grant, I. H. Chromatographia 1987, 24, 135. 5. Knox, J. H.; Grant, I. H. Chromatographia 1991, 32, 317. 6. Freitage, R.; Hilbrig, F. Electrophoresis 2007, 28, 0000. 7. Xie, C.; Fu, H.; Hu, J.; Zou, H. Electrophoresis 2004, 25, 4095. 8. Knox, J. H.; Grant, I. H. Chromatographia 1991, 32, 317. 9. Rathore, A. S.; Horváth, C. J. Chromatogr. A 1996, 743, 231. 10. Wei, W.; Guoan, L.; Chao, Y. J. Sep. Sci 2001, 24, 203. 11. Augus, P. D. A.; Demarest, C. W.; Catalano, T.; Stobaugh, J. F. J. Chromatogr. A 2000, 887, 347. 12. Shalliker, R. A.; Broyles, B. S.; Guiochon, G. J. Chromatogr. A 2000, 878, 153. 13. Reynolds, K. J.; Maloney, T. D.; Fermier, A. M.; Colon, L. M. Analyst 1998, 123, 1493. 14. Maloney, T. D.; Colon, L. A. Electrophoresis 1999, 20, 2360. 15. Stol, R.; Mazereeuw, M.; Tjaden, U. R.; Greef, J. J. Chromatogr. A 2000, 873, 293. 16. Roulin, S.; Dmoch, R.; Carney, R.; Bartle, K. D.; Myers, P.; Euerby, M. R.; Johnson, C. J. Chromatogr. A 2000, 887, 307. 17. Zhang, X.; Huang, S. J. Chromatogr. A 2001, 910, 13. 18. Kato, M.; Dulay, M. T.; Bennett, B. D.; Quirino, J. P.; Zare, R. N. J. Chromatogr. A 2001, 924, 187. 19. Yu, C.; Svec, F.; Frechet, J. M. J. Electrophoresis 2000, 21, 120. 20. Shediac, R.; Ngola, S. M.; Throckmorton, D. J.; Anex, D. S.; Shepodd, T. J.; Singh, A. K. J.Chromatogr. A 2001, 925, 251. 21. Liao, J. L.; Chen, N.; Ericson, C.; Hjerten, S. Anal. Chem. 1996, 68, 3468. 22. Peter, E. C.; Petro, M.; Svec, F; Frechet, J. M. J. Anal. Chem. 1998, 70, 2296. 23. Zhang, S.; Huang, X.; Zhang, J.; Horvath, C. J. Chromatogr. A 2000, 887, 465. 24. Ishizuka, N.; Minakuchi, H.; Nakanishi, K.; Soga, N.; Nagayama, H.; Hosoya, K.; Tanaka, N. Anal. Chem. 2000, 72, 1275. 25. Allen, D.; El Rassi., Z. Analyst 2003, 128, 1249. 26. Chirica, G.; Remcho, V. T. Electrophoresis 2000, 21, 3039 27. Chirica, G.; Remcho, V. T. Anal. Chem. 2000, 72, 3605. 28. Garner, T. W.; Yeung, E. S. J. Chromatogr. A 1993, 640, 397. 29. Baryla, N. E.; Melanson, J. E.; Mcdermott, M. T.; Lucy, C. A. Anal. Chem. 2001, 73, 4558. 30. Kapnissi, C. P.; Akbay, C.; Schlenoff, J. B.;Warner, I. M. Anal. Chem. 2002, 74, 2328. 31. Wu, X,; Liu, H.; Zhang, S.; Haddad, P. R. Anal. Chim. Acta 2003, 478, 191. 32. Huang, X.; Zhang, J.; Horváth, C. J. Chromatogr. A 1999, 858, 91. 33. Crego, A. L.; Martinez, J.; Marina, M. J. J. Chromatogr. A 2000, 869, 329. 34. Onuska, F. I.; Comba, M. E.; Bistricki, T.; Wilkinson, R. J. J. Chromatogr. A 1977, 142, 117. 35. Pesek, J. J.; Matyska, M. T.; Tran, H. J. Sep. Sci. 2001, 24, 729. 36. Pesek, J. J.; Matyska, M. T.; Velpula S. J. Chromatogr. A 2006, 1126, 298. 37. Walden, P. Bull. Acad. Sci. St. Petersburg 1914, 405. 38. Hurley, F. H.; Wier, T. P. J. Electrochem. Soc. 1951, 98, 203. 39. Chum, H. L.; Koch, V. R.; Miller, L. L.; Osteryoung, R. A. J. Am. Chem. Soc. 1975, 97, 3264. 40. Robinson, J.; Osteryoung, R. A. J. Am. Chem. Soc. 1979, 101, 323. 41. Wilkes, J. S.; Levisky, J. A.; Hussey, C. L. Inorg. Chem. 1982, 21, 1263. 42. Scheffler, T. B.; Hussey, C. L.; Seddon, K. R.; Kear, C. M.; Armitage, P. D. Inorg. Chem. 1983, 22, 2099. 43. Laher, T. M.; Hussey, C. L. Inorg. Chem. 1983, 22, 3247. 44. Scheffler, T. B.; Hussey, C. L. Inorg. Chem. 1984, 23, 1926. 45. Hitchcock, P. B.; Mohammed, T. J.; Seddon, K. R.; Zora, J. A.; Hussey, C. L.; Ward, E. H. Inorg. Chim. Acta 1986, 113, L25. 46. Appleby, D.; Hussey, C. L.; Seddon, K. R.; Turp, J. E. Nature 1986, 323, 614. 47. Dent, A. J.; Seddon, K. R.; Welton, T. J. Chem. Soc. Chem., Commun. 1990, 315. 48. Boon, J. A.; Levisky, J. A.; Pflug, J. S. J. Org. Chem. 1986, 51, 480. 49. Chauvin, Y.; Gilbert, B.; Guibard, J. J. Chem. Soc., Chem. Commun. 1990, 1715. 50. Parshall, G. W. J. Am. Chem. Soc. 1972, 94, 8716. 51. Wilkes, J. S.; Zaworotko, M. J. J. Chem. Soc., Chem. Commun. 1992, 965. 52. Fuller, J.; Carlin, R. T.; De Long, H. C.; Haworth, D. J. Chem. Soc., Chem. Commun. 1994, 299. 53. Huddleston, J. G.; Visser, A. E.; Reichert, W. M.; Willauer, H. D.; Broker, G. A.; Rogers, R. D. Green Chemistry 2001, 3, 156. 54. Huang, X.; Luckey, J. A.; Gordon, M. J.; Zare, R. N. Anal. Chem. 1989, 61, 766. 55. Harrold, M. P.; Wojtusik, M. J.; Riviello, J.; Henson, P. J.Chromatogr. 1993, 640, 463. 56. Quang, C.; Khaledi, M. G. Anal. Chem. 1993, 65, 3354. 57. Yanes, E. G.; Gratz, S. R.; Stalcup, A. M. Analyst 2000, 125, 1919. 58. Yanes, E. G.; Gratz, S. R.; Baldwin, M. J.; Robison, S. E.; Stalcup, A. M. Anal. Chem. 2001, 73, 3838. 59. Jiang, T. F.; Gu, Y. L.; Liang, B.; Li, J. B.; Shi, Y. P.; Ou, Q. Y. Anal. Chim. Acta 2003, 479, 249. 60. Mwongela, S. M.; Numan, A.; Gill, N. L.; Agbaria, R. A.; Warner, I. M. Anal. Chem. 2003, 75, 6089. 61. Qin, W.; Li, S. F. Y. Electrophoresis 2002, 23, 4110. 62. Qin, W.; Li, S. F. Y. Analyst 2003, 128, 37. 63. Qin, W.; Wei, H.; Li, S. F. Y. J. Chromatogr. A 2003, 985, 447. 64. Qin, W.; Li, S. F. Y. J. Chromatogr. A 2004, 1048, 253. 65. Kašička, V. Electrophoresis 2006, 27, 142. 66. Corradini, D.; Cogliandro, E.; D’Alessandro, L.; Nicoletti, I. J. Chromatogr. A 2003, 1013, 221. 67. Quang, C. Y.; Malek, A.; Khaledi, M. G. Electrophoresis 2003, 24, 824. 68. Cobb, K. A.; Dolník, V.; Novotny, M. Anal. Chem. 1990, 62, 2478. 69. Gilges, M.; Kleemiss, M. H.; Schomburg, G. Anal. Chem. 1994, 66, 2038. 70. Chiu, R. W.; Jimenez, J. C.; Monnig, C. A. Anal. Chem. Acta 1995, 307, 193. 71. Zhang, S.; Zhang, J.; Horváth, C. J. Chromatogr. A 2001, 914, 189. 72. Ye, M.; Zou, H.; Liu, Z.; Ni, J. J. Chromatogr. A 2000, 869, 385. 73. Zhang, J.; Huang, X.; Zhang, S.; Horváth, C. Anal. Chem. 2000, 72, 3022. 74. Li, Y.; Xiang, R.; Horváth, C.; Wilkins, J. A. Electrophoresis 2004, 25, 545. 75. Okanda, F. M.; El Rassi, Z. Electrophoresis 2005, 26, 1988. 76. Stroink, T.; Schravendijk, P.; Wiese, G.; Teeuwsen, J.; Lingeman, H.; Waterval, J. C. M.; Bult, A.; de Jong, G. J.; Underberg, W. J. M. Electrophoresis 2003, 24, 1126. 77. Catai, J. R.; Somsen, G. W.; de Jong, G. J. Electrophoresis 2004, 25, 817. 78. Johannesson, N.; Wetterhall, M.; Markides, K. E.; Bergquist, J. Electrophoresis 2004, 25, 809. 79. Šolínová, V.; Kašička, V.; Barth, T.; Hauzerová, L.; Fanali, S. J. Chromatogr. A 2005, 1081, 9. 80. Huang, Y.; Duan, J.; Jiang, X.; Chen, H.; Chen, G. J. Sep. Sci. 2005, 28, 2534. 81. Huang, Y.; Duan, J.; Chen, Q.; Chen, G. Electrophoresis 2004, 25, 1051. 82. Koezuka, K.; Ozaki, H.; Matsubara, N.; Terabe, S. J. Chromatogr. B 1997, 689, 3. 83. Zhang, B.; Soukup, R.; Armstrong, D. W. J. Chromatogr. A 2004, 1053, 89. 84. Anderson, J. L.; Ding, J.; Welton, T.; Armstrong, D. W. J. Am. Chem. Soc. 2002, 124, 14247. 85. Suchánková, J.; Soukupová, K.; Tesařová, E.; Bosákov á, Z.; Coufal, P. Chromatographia Supplement 2004, 60, S119. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/29764 | - |
dc.description.abstract | 本研究以共價鍵結的方式,將咪唑陽離子鍵結於毛細管的內壁,作為開管式毛細管電層析的靜相,用於分離結構相似的神經降壓素 (neurotensin,NT)與腦啡肽(enkephalin)。首先以3-(chloropropyl)- trimethoxysilane (CPTMS)將毛細管矽烷化,再將咪唑溶於甲苯或DMF,與CPTMS的活性基反應,繼而以ㄧ溴辛烷進行烷化反應。所製備的管柱經電滲流的測定,發現以DMF為溶劑之鍵結量優於甲苯,顯示溶解度增加與吡啶的催化,可改進咪唑鍵結量,使管柱在pH 4~7的條件下,電滲透流皆為逆向。而製備管柱通入磷酸緩衝溶液時,管壁 dialkylimidazolium與磷酸會形成離子對 (ion-pair)或產生反應,使靜相較易脫落,因而改用醋酸緩衝溶液及Tris作為移動相。由研究發現,以電壓-20 kV,添加10%(v/v) 正丙醇於醋酸緩衝溶液 (pH 4, 100 mM)時,兩者可於十分鐘內達到基線分離,RSD值均 < 3.31% (n=5);而以電壓-20 kV,添加10 % (v/v)甲醇於醋酸緩衝溶液 (pH 5.0, 10 mM)為最佳分離條件時,可使(Gln4)-NT、(D-Trp11)-NT、(D-Tyr11)-NT與(L-Tyr11)-NT出現三支吸收峰,僅掌性異構物無法分離,RSD值均 < 7.8 % (n=5)。此外,本研究亦比較咪唑鍵結管柱與不同碳鏈長度之咪唑陽離子靜相對分離的影響,發現咪唑鍵結管柱與靜相之作用力較強,且分析物在異相系統中擴散性較差,波峰拖尾較嚴重;而咪唑陽離子碳鏈較短 (C4)時,滯留效果不佳,分析物無法分離;碳鏈長度較長(C8, or C12)時,分析物滯留效果較佳,且隨碳鏈長度增長分析物的滯留時間亦無明顯的延長。綜上所述,此離子液體不僅提供管柱表面的正電荷,使其具逆向電滲透流,還可減少分析物在管柱表面的吸附,且靜相具凡德瓦力 (分散力與偶極力)、π-π電子作用力、氫鍵與靜電交互作用力等機制,故即使構造甚為相似,電荷/質量比雷同的分析物均可達成功的分離。 | zh_TW |
dc.description.abstract | Two peptides enkephalins and neurotensins were carried out with supported-ionic liquid open-tubular columns. To prepare ionic liquid columns, the capillary was first silanzed with 3-(chloropropyl)- trimethoxysilane (CPTMS). Imidazole was then subjected to be bond covalently to the CPTMS in the presence of toluene or DMF as solvent. Finally imidazole was linked with 1-bromooctane to form a positively charged diakylimidazolium layer for the generation of reversed electroosmotic flow (EOF) over a pH range of 4 to 7. Using phosphate as background electrolyte (BEG) the strong ion-pair interaction between diakylimidazolium and phosphate caused the bleeding of stationary phase. With running buffer of acetate (pH 4, 100 mM)/10% (v/v) 1-propanol, [Leu]-enkephalin and [Met]-enkephalin were baseline separated within 10 min with RSD < 3.31% (n=5). With running buffer of acetate (pH 5, 10 mM)/10% (v/v) methanol, four closely related neurotensins showed three absorbed peaks within 15 min with RSD < 7.8% (n=5). In this study, the migration pattern of imidazole coated column was also compared with those of different carbon length of substituent on ionic liquid column. Because of the strong hydrogen bond interaction, the peaks of imidazole coated column showed more tailing. For C8 or C12 of substituent of ionic liquid, the hydrophobic force and hydrogen bond interaction were stronger, and the column efficiency was better than the short carbon chain length (C4) . | en |
dc.description.provenance | Made available in DSpace on 2021-06-13T01:17:55Z (GMT). No. of bitstreams: 1 ntu-96-R94223023-1.pdf: 2605579 bytes, checksum: aa3c7bb775a34538bf89044147388df6 (MD5) Previous issue date: 2007 | en |
dc.description.tableofcontents | 中文摘要 I
英文摘要 III 目錄 V 圖目錄 IX 表目錄 XII 第一章 緒論 1 第一節 毛細管電層析簡介 1 1.1 前言 1 1.2 帶電物質於CEC之分離 2 1.3 毛細管電層析管柱種類 5 1.3.1填充式管柱 5 1.3.2整體式管柱 6 1.3.3開管式管柱 7 第二節 離子液體 12 2.1 離子液體的歷史 12 2.2 離子液體的特性 13 2.3 離子液體於毛細管電泳之應用 15 第三節 胜肽與蛋白質分子的分析 20 3.1 前言 20 3.2 胜肽與蛋白質的分離 20 3.3 分析物 23 第四節 研究動機 28 第二章 實驗部份 38 第一節 儀器部分 38 1.1 毛細管電泳儀器裝置 38 1.2 其他實驗操作儀器 39 第二節 藥品部分 40 2.1 管柱製備 40 2.2 緩衝溶液 40 2.3 電滲流標記物與分析物 40 第三節 毛細管靜相製備 41 3.1 毛細管內部前處理 41 3.2 支撐性離子液體管柱製備 41 3.2.1 矽烷基衍生化反應 41 3.2.2 咪唑官能基衍生化反應 42 3.2.3 一溴辛烷衍生化反應 42 第四節 毛細管電層析之實驗操作 43 4.1 試劑之配製 43 4.2 毛細管電層析之操作條件 44 第三章 結果與討論 50 第一節 管柱製備條件的探討 50 1.1 溶劑對於咪唑鍵結量的影響 50 1.2 管柱飽和鍵結量 51 1.3 緩衝溶液種類對靜相穩定度的影響 52 1.4 管柱逆向電滲流測定 53 第二節 腦啡肽的分離 59 2.1 甲硫胺酸腦啡肽與白胺酸腦啡肽之分離 59 2.2 醋酸緩衝溶液pH 值的影響 60 2.3 醋酸緩衝溶液離子濃度的影響 61 2.4 有機修飾劑的影響 61 2.5 分離機制的探討 63 第三節 神經降壓素的分離 76 3.1 神經降壓素 76 3.2 動相pH 值的影響 77 3.3 動相離子濃度的影響 78 3.4 有機修飾劑含量的影響 79 3.5 不同種類有機修飾劑的影響 80 3.6 分離機制的探討 81 第四節 離子液體之碳鏈長度的影響 95 4.1 碳鏈長度對分離的影響 95 第四章 結論 102 參考文獻 104 圖目錄 Fig. 1-1. Scanning electron micrograph of a continuous monolithic silica prepared in a fused-silica capillary. 29 Fig. 1-2. Reaction pathways used for the preparation of silica-based monolithic column with both quaternary ammonium and alkyl functionalities. 29 Fig. 1-3. Scheme of typical PEM-coated capillary using a cationic polymer and an anionic polymer (or an anionic polymeric surfactant). 30 Fig. 1-4. Reaction scheme for the preparation of the p-tert-butylcalix[8]-arene bonded phase. 30 Fig. 1-5. Typical scanning electron micrographs of the PLOT column. 31 Fig. 1-6. Most common structures of ionic liquid. 32 Fig. 1-7. Separation Mechanism of polyphenols using 1-alkyl-3-methyl-imidazolium-based ionic liquids. 33 Fig. 1-8. Chemical structures of the three chiral binaphthyl derivatives. 33 Fig. 1-9. The synthesis of the strong anion-exchanger function at the chromatographic surface. 34 Fig. 1-10. Schematic diagram of the parting filling method. 34 Fig. 2-1. Homemade capillary washing kits. 47 Fig. 2-2. Capillary filling and washing kits. 47 Fig. 2-3. The procedures for the preparation of supported ionic liquid. 48 Fig. 2-4. Capillary detection window. 49 Fig. 3-1. Electroosmotic mobility of IL-C8 columns preparaed at different condition. 55 Fig. 3-2. Bleeding of stationary phase after electrophoretic process. 56 Fig. 3-3. The structures of peptides. 66 Fig. 3-4. Electrochromatographic separation of enkephalins at different pH value. 67 Fig. 3-5. Effect of pH value on the separation of enkephalins. 68 Fig. 3-6. Electrochromatographic separation of enkephalins at different buffer concentration. 69 Fig. 3-7. Effect of buffer concentration on the separation of enkephalins. 70 Fig. 3-8. Effect of different organic modifiers on the separation of enkephalins. 71 Fig. 3-9. Effect of 1-propanol content on the separation of enkephalins. 72 Fig. 3-10. Separation resolution of enkephalins at different 1-propanol content. 73 Fig. 3-11. Structure of neurotensins. 84 Fig. 3-12. Electrochromatographic separation of neurotensins at different pH value. 86 Fig. 3-13. Effect of pH value on the separation of neurotensins. 87 Fig. 3-14. Electrochromatographic separation of neurotensins at different buffer concentration. 88 Fig. 3-15. Effect of concentrarion on the separation of neurotensins. 89 Fig. 3-16. Effect of different organic modifiers on the separation of neurotensins. 90 Fig. 3-17. Electrochromatographic separation of neurotensins at different methanol content. 91 Fig. 3-18. Effect of methanol content on the separation of neurotensins. 92 Fig. 3-19. Electrochromatographic separation of different organic modifiers on the separation of neurotensins. 93 Fig. 3-20. CEC separation of enkephalins with different carbon length of substituents on ionic liquid. 98 Fig. 3-21. CEC separation of neurotensins with different carbon length of substituents on ionic liquid. 99 表目錄 Table 1-1. Structures and properties of the pure ionic liquids 35 Table. 1-2. Thermal decomposition temperatures of several ILs 36 Table 1-3. Viscosity data for several ILs 37 Table 2-1. The concentration of stocked and analytical samples 44 Table 3-1. Characterization of the IL-C8 column at different preparaed conditions 57 Table 3-2. Effect of buffer composition on the stability of the IL-C8 column 58 Table 3-3. The physical properities of the enkephalins 74 Table 3-4. The physico-chemical properties of various solvents at 20℃ 75 Table 3-5. The physical properties of neurotensins 94 Table 3-6. Relative mobility of neurotensins 94 Table 3-7. Retention time of analytes at different substituent of supported ionic liquid column 100 Table 3-8. Separation efficiencies of analytes using supported ionic liquid column with C8 substituent 101 | |
dc.language.iso | zh-TW | |
dc.title | 支撐性離子液體於毛細管電層析神經降壓素與腦啡肽的應用 | zh_TW |
dc.title | Supported Ionic Liquid for the CEC Separation of Enkephalins and Neurotensins | en |
dc.type | Thesis | |
dc.date.schoolyear | 95-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 桂椿雄(Chun-Hsiung Kuei),張煥宗(Huan-Tsung Chang) | |
dc.subject.keyword | 離子液體,毛細管電層析, | zh_TW |
dc.subject.keyword | ionic liquid,CEC, | en |
dc.relation.page | 109 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2007-07-19 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
文件中的檔案:
檔案 | 大小 | 格式 | |
---|---|---|---|
ntu-96-1.pdf 目前未授權公開取用 | 2.54 MB | Adobe PDF |
系統中的文件,除了特別指名其著作權條款之外,均受到著作權保護,並且保留所有的權利。