聚合物是一高分子材料，可依照其性質分為天然與合成兩種聚合物，天然聚合物不僅構成頭髮，還組成糖、澱粉及纖維素等；合成聚合物包含有塑膠類製品，例如我們穿的衣服。最早的合成聚合物是由英國化學家帕克斯在 1850 年代發展，合成聚合物通常是高分子量的有機化合物，其結構較天然聚合物簡單，含有不同的單體單元，如：聚乙烯 (PE)、矽膠 (Silicone Rubber)、聚乙二醇 (PEG)、聚乳酸 (PLA) ⋯。如何在合成及加工過程中對各式聚合物進行結構、物性及化性的鑑定，對於民生及品管是相當重要的議題，但因高分子聚合物的蒸氣壓與溶解度通常較低，無法以質譜儀直接進行游離與偵測，所以文獻中多搭配熱裂解儀器 (Pyrolyzer) 的使用，先將化合物進行裂解與氣化，再導入氣相層析質譜儀 (Gas Chromatography/Mass Spectrometry, GC/MS) 進行分離偵測。大氣壓力游離質譜法 (Ambient Mass Spectrometry, AMS)，即在一大氣壓力下直接對樣品進行分析的質譜技術，並且不受前處理及層析分離本身系統特性的限制，能夠有效地偵測到目標分析物，具有快速、簡單操作及高通量分析的優點。

第一部分、連續式雷射脫附大氣壓力電漿化學游離質譜法結合介面之開發與測試

第一部分研究中致力於連續式雷射與大氣壓力電漿化學游離質譜法 (CW-LD plasma-APCI/MS) 結合介面之開發與測試，本研究結合雷射脫附 (Laser Desorption, LD) 及大氣壓力電漿化學游離 (Plasma Atmospheric Pressure Chemical Ionization, plasma-APCI) 技術，開發出可進行各式樣品快速分析之連續式雷射脫附結合大氣壓力電漿化學游離質譜法 (Continuous Wavelength Laser Desorption Plasma-Atmospheric Pressure Chemical Ionization Mass Spectrometry, CW-LD plasma-APCI/MS)，游離源主要包含了：(一) 取樣平台裝置、(二) 連續式雷射脫附及聚焦裝置、(三) 大氣壓力電漿化學游離裝置及 (四) 游離源本體。操作方式為將固態或液態樣品置於取樣平台裝置，再將取樣平台置入游離源本體中，平台上的樣品會因受到連續式雷射脫附進而產生中性氣相分子，經由潘寧游離 (Penning Ionization) 而得到分析物離子，再進入質量分析器進行質量鑑定，整個分析流程包含取樣、進樣、脫附以及游離，只需數十秒鐘的時間；並且分別對於雷射能量大小、雷射聚焦距離、乾燥氣體流速、進樣體積、電漿攜帶氣體流速、電漿輸出電壓強度及樣品載盤材質進行最佳化探討。

第二部分、連續式雷射脫附大氣壓力電漿化學游離質譜法在包裝材料化學組成快速篩檢之應用

研究中也將本技術應用在分析包裝材料化學成分的快速偵測，利用連續式雷射脫附結合大氣壓力化學游離質譜法，可快速偵測材料之化學組成，並且利用標準品比對來鑑定其分析結構。研究中為了模擬真實情況分別將聚乙烯 (PE)、聚丙烯 (PP)、聚乙二醇 (PEG)、聚丙二醇 (PPG)、聚甲基丙烯酸甲酯 (PMMA)、聚苯乙烯 (PS)、聚甲醛 (POM) 及矽膠 (Silicone Rubber) 等材料樣品或是標準品進行分析以得到標準圖譜。最後應用此技術對市售各家國外知名連鎖店進行食品包裝材料之聚合物組成分析，可以檢測到食品包裝材料的聚合物、塑化劑及穩定劑的訊號。

Polymers are macromolecules that are natural or synthetic. Naturally occurring polymers include starch, polysaccharides, and cellulose, while synthetic polymers include polyethylene, silicone rubber, polyethylene glycol and polylactic acid. The analysis of polymer structures and chemical and physical properties is very important during manufacture and quality control. Both natural and synthetic polymers have low volatilities and solubilities. Thermal gravimetric analysis mass spectrometry (TGA-MS) and pyrolysis gas chromatography mass spectrometry (Py-GC/MS) are traditionally used to analyze polymers. However, they require long analytical times and also need complex sample pretreatment. On the other hand, ambient mass spectrometry (AMS) has the advantages of direct, rapid, and high-throughput analysis, requiring little or no pretreatment.
The first part of this thesis focuses on the development of an AMS interface to connect a continuous wavelength laser (CW laser) and plasma-atmospheric pressure chemical ionization mass spectrometry (plasma-APCI/MS). A novel strategy in CW-LD plasma-APCI/MS is that sampling, desorption, and ionization are separated as three independent events. The CW-LD plasma-APCI/MS consists of: (1) a sample plate for holding solid or liquid samples, (2) a CW laser for thermally desorbing analytes from the sampling plate, and (3) a plasma-APCI ionization source for analyte ionization via Penning ionization. The total analysis time is less than 60 seconds. We optimized the laser energy, the distance between sample plate to laser, dry gas flow rate, sampling volume, discharge gas flow rate, high voltage, and the sample plate material.
The second part of this thesis focuses on the application of CW-LD plasma-APCI/MS in food safety to determine the chemical compositions of packaging materials. Polyethylene, polypropylene, polyethylene glycol, polypropylene glycol, poly(methyl)methacrylate, polystyrene, polyoxymethylene, silicone rubber, and many polymeric materials were analyzed using CW-LD plasma-APCI/MS. Results indicated that chemical components and chemical additives (DEHP, DINP, Irgafos 168, Tinuvin 770, and Irganox 1076) in packaging materials were directly characterized by CW LD-ESI/APCI MS. This technology offers a robust and viable approach for fast analysis of packaging materials (KFC, Yoshinoya, Mos Burger, McDonald’s, Starbucks, and Costco).

論文審定書 i
論文公開授權書 ii
謝誌 iv
論文摘要 v
Abstract vii
目錄 ix
圖目錄 xii
表目錄 xviii
第一章 緒論 1
一、前言 1
二、傳統質譜分析技術在聚合物上之應用 2
1、熱重分析儀 (Thermogravimetry Analyzer) 2
2、熱裂解儀 (Pyrolyzer) 3
3、基質輔助雷射脫附游離質譜法 (Matrix-assisted Laser Desorption Ionization Mass Spectrometry) 4
三、大氣壓力游離法 5
1、電噴灑游離法 (Electrospray Ionization, ESI) 5
2、大氣壓力化學游離法 (Atmospheric Pressure Chemical Ionization, APCI) 6
3、大氣壓力光游離法 (Atmospheric Pressure Photoionization, APPI) 7
四、大氣壓力電漿游離質譜法 8
1、尖端放電電漿 (Corona Discharge Plasma) 8
2、輝光放電電漿 (Glow Discharge Plasma) 10
3、介電質放電電漿 (Dielectric Barrier Discharge Plasma) 12
五、大氣壓力質譜法於聚合物之應用 14
1、熱裂解儀串聯即時直接分析游離質譜法 14
2、大氣壓力固相分析探針 14
3、即時直接分析游離質譜法 15
六、研究動機與論文目標 16
第二章 連續式雷射脫附大氣壓力電漿化學游離質譜法結合介面之開發與測試 17
一、儀器裝置 17
1、取樣平台裝置 20
2、連續式雷射脫附及聚焦裝置 22
3、大氣壓力電漿化學游離裝置 24
4、游離源本體 26
二、實驗試劑與藥品 31
三、藥品配製 31
四、連續式雷射脫附大氣壓力電漿化學游離質譜法的測試 33
第三章 連續式雷射脫附大氣壓力電漿化學游離質譜法在包裝材料化學組成快速篩檢之應用 51
一、包裝材料快速篩檢之應用 51
1、聚合物簡介 51
2、偵測不同聚合物之標準品 56
3、偵測不同聚合物之材料樣品 61
4、偵測市售食品包裝材料之聚合物組成 69
第四章 結論 76
第五章 參考文獻 77

1. J. Dempster, The Ionization and Dissociation of Hydrogen Molecules and the Formation of H3. Phil. Mag. 1916, 31, 438-443.
2. M. S. B. Munson, F. H. Field, Chemical ionization Mass Spectrometry. I. Generation Introduction. J. Am. Chem. Soc. 1966, 88, 2621-2630.
3. Dzidic, I.; Carroll, D. I.; Stillwell, R. N.; Horning, E. C., Comparison of Positive Ions Formed in Nickel-63 and Corona Discharge Ion Sources Using Nitrogen, Argon, Isobutane, Ammonia and Nitric Oxide as Reagents in Atmospheric Pressure Ionization Mass Spectrometry. Anal. Chem. 1976, 48 (12), 1763-1768.
4. http://www.perkinelmer.com/catalog/family/id/tg gcms
5. http://www.perkinelmer.com/catalog/family/id/tg ir
6. https://science-math.wright.edu/chemistry/research/facilities
7. Saraji-Bozorgzad, M.; Geissler, R.; Streibel, T.; Mühlberger, F.; Sklorz, M.; Kaisersberger, E.; Denner, T.; Zimmermann, R., Thermogravimetry Coupled to Single Photon Ionization Quadrupole Mass Spectrometry:  A Tool To Investigate the Chemical Signature of Thermal Decomposition of Polymeric Materials. Anal. Chem. 2008, 80 (9), 3393-3403.
8. Tsuge, S.; Ohtani, H.; Watanabe, C., Pyrolysis - GC/MS Data Book of Synthetic Polymers: Pyrograms, Thermograms and MS of Pyrolyzates. Elsevier Science. 2011.
9. Tanaka, K.; Waki, H.; Ido, Y.; Akita, S.; Yoshida, Y.; Yoshida, T.; Matsuo, T., Protein and Polymer Analyses up to m/z 100,000 By Laser Ionization Time-of-Flight Mass Spectrometry. Rapid Common. Mass Sp. 1988, 2 (8), 151-153.
10. http://www.sigmaaldrich.com/china-mainland/zh/technical-documents/.html
11. Yamashita, M.; Fenn, J. B., Electrospray Ion Source. Another Variation on the Free-Jet Theme. J. Phys. Chem. 1984, 88 (20), 4451-4459.
12. Carroll, D. I.; Dzidic, I.; Stillwell, R. N.; Haegele, K. D.; Horning, E. C., Atmospheric Pressure Ionization Mass Spectrometry. Corona Discharge Ion Source for Use in a liquid Chromatograph-Mass Spectrometer-Computer Analytical System. Anal. Chem. 1975, 47 (14), 2369-2373.
13. Robb, D. B.; Covey, T. R.; Bruins, A. P., Atmospheric Pressure Photoionization:  An Ionization Method for Liquid Chromatography−Mass Spectrometry. Anal. Chem. 2000, 72 (15), 3653-3659.
14. http://www.jeolusa.com/PRODUCTS/AnalyticalInstruments/MassSpectrometers/AccuTOFDART/AccuTOFDARTTechnology/tabid/449/Default.aspx
15. Cody, R. B.; Laramée, J. A.; Durst, H. D., Versatile New Ion Source for the Analysis of Materials in Open Air under Ambient Conditions. Anal. Chem. 2005, 77 (8), 2297-2302.
16. McEwen, C. N.; McKay, R. G.; Larsen, B. S., Analysis of Solids, Liquids, and Biological Tissues Using Solids Probe Introduction at Atmospheric Pressure on Commercial LC/MS Instruments. Anal. Chem. 2005, 77, 7826-7831.
17. Smith, M. J.; Cameron, N. R.; Mosely, J. A., Evaluating Atmospheric pressure Solids Analysis Probe (ASAP) Mass Spectrometry for the Analysis of Low Molecular Weight Synthetic Polymers. Analyst 2012, 137 (19), 4524-30.
18. Wang, H.; Sun, W.; Zhang, J.; Yang, X.; Lin, T.; Ding, L., Desorption Corona Beam Ionization Source for Mass Spectrometry. Analyst 2010, 135 (4), 688-695.
19. Ratcliffe, L. V.; Rutten, F. J. M.; Barrett, D. A.; Whitmore, T.; Seymour, D.; Greenwood, C.; Aranda-Gonzalvo, Y.; Robinson, S.; McCoustra, M., Surface Analysis under Ambient Conditions Using Plasma-Assisted Desorption/Ionization Mass Spectrometry. Anal. Chem. 2007, 79 (16), 6094-6101.
20. Shelley, J. T.; Ray, S. J.; Hieftje, G. M., Laser Ablation Coupled to a Flowing Atmospheric Pressure Afterglow for Ambient Mass Spectral Imaging. Anal. Chem. 2008, 80 (21), 8308–8313.
21. Kogelschatz, U.; Eliasson, B.; Egli, W., From Ozone Generators to at Television Screens: History and Future Potential of Dielectric-Barrier Discharges. Pure Appl. Chem. 1999, 71 (10), 1819-1828.
22. Na, N.; Zhao, M.; Zhang, S.; Yang, C.; Zhang, X., Development of a Dielectric Barrier Discharge Ion Source for Ambient Mass Spectrometry. J. Am. Soc. Mass. Spectrom. 2007, 18 (10), 1859-1862.
23. Harper, J. D.; Charipar, N. A.; Mulligan, C. C.; Zhang, X.; Cooks, R. G.; Ouyang, Z., Low-Temperature Plasma Probe for Ambient Desorption Ionization. Anal. Chem. 2008, 80 (23), 9097-9104.
24. Jones, R. W.; Reinot, T.; McClelland, J. F., Molecular Analysis of Primary Vapor and Char Products during Stepwise Pyrolysis of Poplar Biomass. Energy Fuels 2010, 24 (9), 5199-5209.
25. Smith, M. J.; Cameron, N. R.; Mosely, J. A., Evaluating Atmospheric pressure Solids Analysis Probe (ASAP) Mass Spectrometry for the Analysis of Low Molecular Weight Synthetic Polymers. Analyst. 2012, 137 (19), 4524-30.
26. Haunschmidt, M.; Klampfl, C. W.; Buchberger, W.; Hertsens, R., Rapid identification of stabilisers in polypropylene using time-of-flight mass spectrometry and DART as ion source. Analyst. 2010, 135 (1), 80-85.
27. https://zh.wikipedia.org/wiki/塑膠分類標誌
28. Iribarne, J. V.; Thomson, B. A., On the Evaporation of Small Ions from Charged Droplets. J. Chem. Phys. 1976, 64 (6), 2287-2294.
29. Konermann, L.; Ahadi, E.; Rodriguez, A. D.; Vahidi, S., Unraveling the Mechanism of Electrospray Ionization. Anal. Chem. 2013, 85 (1), 2-9.
30. Langmuir, I., Oscillations in Ionized Gases. Proc. Natl. Acad. Sci. U. S. A. 1928, 14 (8), 627-637.
31. Schutze, A.; Jeong, J. Y.; Babayan, S. E.; Park, J.; Selwyn, G. S.; Hicks, R. F., The Atmospheric-Pressure Plasma Jet: a Review and Comparison to Other Plasma Sources. IEEE Tran. Plasma Sci. 1998, 26 (6), 1685-1694.
32. Pappas, D., Status and Potential of Atmospheric Plasma Processing of Materials. J. Vac. Sci. Technol. A. 2011, 29 (2).
33. Ding, X.; Duan, Y., Plasma-Based Ambient Mass Spectrometry Techniques: The Current Status and Future Prospective. Mass Spectrom. Rev. 2014.
34. Andrade, F. J.; Shelley, J. T.; Wetzel, W. C.; Webb, M. R.; Gamez, G.; Ray, S. J.; Hieftje, G. M., Atmospheric Pressure Chemical Ionization Source. 1. Ionization of Compounds in the Gas Phase. Anal. Chem. 2008, 80 (8), 2646-2653.
35. Ovchinnikova, O. S.; Van Berkel G. J., Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemical ionization. Rapid Commun. Mass Spectrom. 2010, 24, 1721–1729.
36. Basile F.; Zhang S.; Shin Y. S.; Drolet B., Atmospheric pressure-thermal desorption (AP-TD)/electrospray ionization-mass spectrometry for the rapid analysis of Bacillus spores. Analyst. 2010, 135, 797–803.
37. Ovchinnikova, O. S.; Nikiforov, M. P.; Bradshaw, J. A.; Jesse, Stephen., Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer-Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry. ACSNANO. 2011, 5 (7), 5526-5531.
38. Chen H.; Ouyang Z.; Cooks R. G., Thermal Production and Reactions of Organic Ions at Atmospheric Pressure. Angew. Chem. Int. Ed. 2006, 45, 3656 –3660.
39. Hanton, S. D., Mass Spectrometry of Polymers and Polymer Surfaces. Chem. Rev. 2001, 101 (2), 527-570.
40. Jecklin, M. C.; Gamez, G.; Zenobi, R., Fast Polymer Fingerprinting Using Flowing Afterglow Atmospheric Pressure Glow Discharge Mass Spectrometry. Analyst. 2009, 134 (8), 1629-1636.
41. Ackerman, L. K.; Noonan, G. O.; Begley, T. H., Assessing Direct Analysis in Real-time-mass Spectrometry (DART-MS) for the Rapid Identification of Additive in Food Packaging. Food Addit. Contam. Part A. 2009, 26 (12), 1611-1618.