本論文主要是以簡單製作方式製作微片，並利用此微片進行電噴灑的相關研究。論文的第一部份是以壓克力做為微片材質的製作過程與電噴灑性質的探討。由於壓克力容易在其上進行各式加工，因此成功地利用美工刀在壓克力上刻劃微管道，並發現只要溶液能由樣品槽流到微管道出口端，而出口端經直角的修飾後，就可以在微管道出口尖端產生電噴灑，實驗證實此裝置可成功地得到肌紅蛋白帶多價電荷的電噴灑質譜圖。

第二部份則是設計輻射狀的多管道微片電噴灑裝置，並研究此裝置自動化的可行性，實驗中藉由三種不同的樣品在不同的微管道進行電噴灑，證明此裝置的確具有自動化的潛力。此外在實驗中以簡單的前處理直接對市售的藥錠進行分析，也可成功地得到含有微小顆粒的電噴灑質譜圖，證實本研究中所設計的微管道不會被樣品中的顆粒所堵塞而無法分析，因此可以大大的節省複雜樣品前處理的時間，增加樣品分析的速度，提供對大量樣品作例行分析的新選擇。

第三部份是對於微片電噴灑流速的大小所進行的相關研究，其目的是希望將本研究中電噴灑的流速降低，以降低樣品的使用量。實驗中將竹子纖維製成的探針放置在管道中使得樣品溶液順著竹子纖維流到尖端，而在尖端所形成的泰勒錐較小，得到較低的電噴灑流速，但是仍無法與電泳流速匹配。

none

目 錄

論文摘要 ....................................................................................... I
目錄 ....................................................................................... III
圖目錄 ....................................................................................... IV
表目錄 ....................................................................................... VI
壹、 緒論 ................................................................................ 1
一、質譜游離法的發展 ....................................................... 1
二、電噴灑游離質譜法的沿革與發展 ................................. 3
三、電噴灑游離直譜法之原理 ............................................. 6
1.帶電液滴的生成 ........................................................... 6
2.溶劑揮發與液滴再爆裂 ............................................. 7
3.氣相離子生成原因 ...................................................... 8
四、發展微片電噴灑游離法的因素 ..................................... 9
五、目前微片電噴灑游離法的發展與產生的問題 .............. 12
六、論文目標 ........................................................................ 16
貳、 實驗 ................................................................................ 19
一、儀器裝置 ......................................................................... 19
二、微片電噴灑裝置製作過程 ............................................. 20
三、顯微觀測、攝影設備的操作 ......................................... 22
參、 結果與討論 ................................................................................ 25
一、設計製作簡單方便的電噴灑微片 ................................... 25
二、微片電噴灑游離法自動化潛力研究 .............................. 38
三、微片電噴灑流速之改良 .................................................. 45
肆、 結論 ................................................................................ 56
伍、 參考文獻 ................................................................................ 58

伍、參 考 文 獻

1. Thomson, J. J. Rays of Positive Electricity and their Application to Chemical Analysis Green and Co., 1998.
2. Nier, A. O. Rev. Sci. Instrum. 1947, 18, 415. "Electro Impact Mass Spectrometry"
3. Munson, M. S. B.; F. H. Field, J. Am. Chem. Soc. 1960, 88, 2621. "Chemical Ionization Mass Spectrometry"
4. Unsold, E.; Hillenkamp, F.; Nitsche, R. Analysis 1990, 4, 115. "Mass Group Spectrometry of peptides and Proteins by Matrix Assisted Ultraviolet Laser Desorption/ Ionization in Methods in Enzymology"
5. Barber, M.; Bordoli, R. S.; Ellott, G. J.; Sedgwick, R. D.; Tyler, A. N. Anal. Chem. 1982, 54, 645A. "Fast Atom Bombardment Mass Spectrometry"
6. Benninghoven, A.; Rudenauer, F. G.; Werner, H. W. Secondary Ion Mass Spectrometry: Basic Concepts, Instrumental Aspects, Applications and Trends Wiley, 1987.
7. Cotter, R. J. Anal. Chem. 1988, 60, 781A. "Plasma Desorption Mass Spectrometry: Coming of Age"
8. Beckey, H. D. Principles of Field Ionization and Field Desorption Mass Spectrometry Pergamon, 1977.

9. Yamashita, M.; Fenn, J. B. J. Phys. Chem. 1984, 88, 4451. "Electrospray Ion Source: Another Variation on The Free-Jet Theme"
10. Karas, M.; Hillenkamp, F. Anal. Chem. 1988, 60, 2299. "Laser Desorption Ionizaion of Proteins with Molecular Masses Exceeding 10,000 Daltons"
11. Zeleny, J. Phys. Rev. 1917, 10, 1. "Industry Application of Electrospray Technology"
12. Dole, M.; Mack, L. L.; Hines, R. L. J. Chem. Phys. 1968, 49, 2240. "Molecular Beams of Macroions"
13. Mack, L. L.; Kralic, P.; Rheude, A.; Dole, M. J. Chem. Phys. 1970, 52, 4977. "Molecular Beams of Macroions II"
14. Wong, S. F.; Meng, C. K.; Fenn, J. B. J. Phys. Chem. 1988, 92, 546. "Mutiple Charging in Electrospray Ionization for Poly(ehtylene glycols)"
15. Fenn, J. B.; Mann, M.; meng, C. K.; Wong, S. F.; Whitehouse, G. M. Science 1989, 246, 64. "Electrospray Ionization for Mass Spectrometry of Large Biomolecules"
16. Meng, C. K.; Mann, M.; Fenn, J. B. Z. Phys. D. 1988, 10, 361. "On Protons of Proteins - A Beams a Beam for a That"
17. Smith,R. D.; Loo, J. A.; Edmonds, C. G.; Barinaga, C. J.; Udseth, H. R. Anal. Chem. 1990, 62, 882. "New Developments in Biochemical Mass Spectrometry"
18. Loo, J. A.; Edmonds, C. G.; Udseth, H. R.; Smith, R. D. Anal. Chem. 1990, 62, 693. "Effect of Reducinig Disulfid - Containing Protein on Electrospray Ionization Mass Spectrometry"
19. Aleksandrov, M. L.; Gall, L. N.; Shkurov, V. A.; Pavlenko, V. A.; Krasnov, N. V.; Nikolaev, V. I. J. Anal. Chem. USSR 1984, 39, 1268. "Mechanism of Ion Formation During The Electrohydrodynamic Sputtering of a Liquid into a Vacuum"
20. Bruins, A. P.; Covey, T. R.; Henion, J. D. Anal. Chem. 1987, 59, 2642. "Ion-Spray Interface for Combind Liquid Chromatography/ Atmospheric Pressure Ionization Mass Spectrometry"
21. Olivares, J. A.; Nguyen, N. T.; Yonker, C. R.; Smith, R. D. Anal. Chem. 1987, 59, 1232. "On-Line Mass Spectrometric Detection for Capillary Zone Electrophoresis"
22. Wahl, J. H.; Goodlett, D. R.; Useth, H. R.; Smith, R. D. Anal. Chem. 1992, 64, 3194. "Attomole Level Capillary Electrophoresis-Mass Spectrometric Protein Analysis using 5-μm-i.d. Capillaries"
23. Gale, D. C.; Smith, R. D. Rapid Commun. Mass Spectrom. 1993, 7, 1017. "Small Volume and Low Flow-Rate Electrospray Ionization Mass Spectrometry of Aqueous Samples"
24. Wilm, S.; Mann, M. J. Mass Spectrom. Ion Processes 1994, 136, 167. "Electrospray and Taylor-Cone Theory Dole's Beam of Macromolecules at Last?"
25. Wilm, S.; Mann, M. Anal. Chem. 1996, 68, 1. "Analytical Properties of The Nanoelectrospray Ion-Source"
26. Xue, Q.; Foret, F.; Dunayevskiy, Y. M.; Zavracky, P. M.; McGruer, N. E.; Karger, B. L. Anal. Chem. 1997, 69, 426. "Multichannel Microchip Electrospray Mass Spectrometry"
27. Ramsey, R. S.; Ramsey, J, M. Anal. Chem. 1997, 69, 1174. "Generating Electrospray form Microchip Devices Using Electroosmotic Pumping"
28. Kuo, C. P.; Shiea, J. Anal. Chem. 1999, 71, 4413. "Application of Direct Electrospray Probe to Analyze Biological Compounds and to Couple to Solid-Phase Microextraction to Dectect Trace Surfactants in Aqueous-Solution"
29. Hong, C. M.; Lee, C. T.; Lee, Y. M.; Kuo, C. P.; Yuan, C. H.; Shiea, J. Rapid Commun. Mass Spectrom. 1999, 13, 21. "Generating Electrospray from Solution Predeposited on a Copper Wire"
30. Gomez, A.; Tang, K. Phys. Fluid 1994, 65, 404. "On The Structure of An Electrostatic Spray of Monodispers Droplets"
31. Dole, D.; Mack, L. L.; Hines, R. L.; Mobley, R. C.; Ferguson, L. D.; Alice, M. B. Chem. Phys. 1968, 49, 2240. "Evidence of Charge inversion in The Reaction of Single Charged Anions with Multiply Charged Macroions"

32. Iribarne, J. V.; Thornson, B. A. J. Chem. Phys. 1976, 64, 15. "On The Evaporation of Small Ion from Charged Droplets"
33. Rollgen, F. W.; Wegner, B. W.; Buttering, L. J. Phys. Colloq. 1984, 45, C9~297. "A New Approach for The Study of Gas Phase Ion-Ion Reactions Using Electrospray Ionization"
34. Watson, J. D. Science 1990, 248, 44. "The Human Genome Project: Past, Present, and Future"
35. Czarnik, A. W. Anal. Chem. 1998, 70, 378A. "Combinatorial Chemistry - Whats in It for Analytical Chemists"
36. Kyranos, J. N.; Hogan, J. C. Anal. Chem. 1998, 70, 389A. "High- Throughput Characterization of Combinatorial Libraries Generated by Parallel Synthesis"
37. Li, J.; Thibault, P.; Bings, N. H.; Skinner, C. D.; Theng, C.; Colyer, C.; Karrison, J. Anal. Chem. 1999, 71, 3306. "Integration of Microfabricated Devices to Capillary Electrophoresis - Electrospray Mass Spectrometry using a Low Dead Volume Connection: Application to Rapid Analysis of Proteolytic Digests"
38. Zhang, B.; Liu, H.; Karger, B. L.; Foret, F. Anal. Chem. 1999, 71, 3258. "Microfabricated Devices for Capillary Electrophoresis - Electrospray Mass Spectrometry"


39. Licklide, L.; Wang, X. Q.; Desai, A.; Rai, Y. C.; Lee, T. D. Anal. Chem. 2000, 72, 367. "A Micromachined Chip-Based Electrospray Source for Mass Spectrometry"