大氣壓力游離法﹙ambient ionization﹚是在大氣壓力之下進行分析物離子化的方法，並結合各式質譜儀偵測分析物離子。自2004年以來，隨著脫附電噴灑游離法﹙Desorption Electrospray Ionization, DESI﹚的開發，進一步引導科學家發展出許多的新式大氣壓力游離技術，如Direct Analysis in Real Time﹙DART﹚、Electrospray-Assisted Laser Desorption Ionization﹙ELDI﹚、Atmospheric Solids Analysis Probe﹙ASAP﹚、liquid-ELDI等游離法，新式大氣壓力游離法適用於不同類形﹙固態、液態及氣態﹚的樣品，可直接進行分析，並具有簡化前處理步驟的優點。
本研究開發了一種新的大氣壓力游離技術，稱之為雷射誘導聲波脫附/電噴灑游離法﹙Laser-Induced Acoustic Desorption/Electrospray Ionization, LIAD/ESI﹚。研究中以脈衝雷射光轟擊金屬及非金屬薄片，利用雷射轟擊時產生的震波﹙shock wave﹚脫附出塗覆在薄片另一側表面的分析物。雖然在LIAD脫附樣品的過程中會產生分析物離子，但游離效率不佳，因此本研究使用ESI進行後游離﹙postionization﹚，利用電噴灑時產生的帶電荷物種﹙如質子、溶劑離子、帶多價電荷之液滴﹚與LIAD脫附出的氣相分子、粒子或微滴進行反應，形成分析物離子。
首先將LIAD/ESI/MS用於胺基酸、蛋白質、染劑、生物體液﹙膽汁、全血、血清、牛奶﹚及動物組織切片﹙豬肝﹚等固態或液態樣品的分析，樣品不需進行前處理，或是添加基質來輔助分析物的脫附及游離，即可直接進行偵測，結果可得到樣品中主要成份的離子訊號，如具單價電荷的有機小分子離子訊號﹙胺基酸、染料、藥物、酯質﹚，或是具多價電荷蛋白質大分子的離子訊號，並獲得albumin﹙66000 Da﹚的離子訊號。
接著將薄層分析法﹙TLC﹚與LIAD/ESI/MS結合，可針對混合物進行快速分離及質譜偵測。實驗時以載玻片承載TLC片，並加入甘油使載玻片與TLC片緊密貼合，以增加LIAD的脫附能力，結果可脫附出C18及silica材質的TLC片固定相，並得到分析物的離子訊號，本研究將TLC-LIAD/ESI/MS法應用於染劑、藥物標準品混合物及精油真實樣品的快速分離及偵測。
論文最後則是將ELDI及DART這兩種大氣壓力游離法應用於刑事鑑識領域，可快速篩檢尿液中所含藥物及代謝物，分析紙張表面的墨水成份，及紙張所含揮發性組成的快速分析，期望對刑事鑑識領域的發展有所助益。

none

目 錄
論文摘要...........................................................................................i
目錄.................................................................................................iii
圖目錄..............................................................................................ix
壹、緒論.........................................................................................1
一、前言........................................................................................1
二、傳統大氣壓力游離法.............................................................4
﹙一﹚大氣壓力化學游離法........................................................4
﹙二﹚電噴灑游離法....................................................................5
三、現代大氣壓力質譜法............................................................7
﹙一﹚霧化器...............................................................................8
1.融合微滴電噴灑游離法............................................................8
﹙二﹚熱脫附法..........................................................................10
1.即時直接分析游離法...............................................................10
2.脫附大氣壓力化學游離法......................................................11
3.大氣壓力固體分析探針...........................................................12
﹙三﹚熱裂解法...........................................................................14
1.電噴灑輔助熱裂解質譜法.......................................................14
﹙四﹚液滴噴射流.......................................................................15
1.脫附電噴灑游離法...................................................................15
﹙五﹚雷射脫附法......................................................................17
1.大氣壓力基質輔助雷射脫附游離法.......................................17
2.雷射脫附大氣壓力化學游離法...............................................18
3.電噴灑輔助雷射脫附游離法...................................................20
四、雷射誘導聲波脫附法............................................................26
﹙一﹚前言...................................................................................26
﹙二﹚雷射誘導聲波脫附法之原理...........................................28
﹙三﹚雷射誘導聲波脫附法於質譜技術的發展歷史...............32
1.雷射誘導聲波脫附游離法......................................................32
2.雷射誘導聲波脫附法與電子撞擊游離法或化學游離法的結合..38
3.雷射誘導聲波脫附法與光游離法的結合...............................39
五、論文目標...............................................................................41
貳、實驗.......................................................................................43
一、實驗材料...............................................................................43
﹙一﹚化學藥品及樣品................................................................43
﹙二﹚TLC片及各式薄片............................................................45
二、儀器裝置...............................................................................45
﹙一﹚XYZ 移動平台...................................................................45
﹙二﹚電噴灑游離源...................................................................46
﹙三﹚RF-DART游離源..............................................................46
﹙四﹚脈衝式紅外線雷射光.......................................................47
﹙五﹚質譜儀...............................................................................47
1.四極柱飛行時間質譜儀............................................................47
2.離子阱質譜儀...........................................................................48
3.三段式四極柱質譜儀................................................................48
﹙六﹚攝、錄影機.......................................................................48
三、雷射誘導聲波脫附/電噴灑游離質譜裝置..........................49
四、實驗流程..............................................................................52
﹙一﹚以LIAD/ESI/MS分析各種固體及液體樣品...................52
﹙二﹚以LIAD/ESI/MS分析TLC片............................................52
﹙三﹚以ELDI/MS快速篩檢尿液中所含藥物及代謝物成份....55
﹙四﹚以ELDI/MS快速分析字跡墨水的化學組成...................55
﹙五﹚以RF-DART分析紙張及鈔票中的揮發性組成.............55
參、LIAD/ESI/MS的開發............................................................56
一、兩段式游離質譜法..............................................................56
二、開發LIAD/ESI/MS進行固態樣品的分析............................57
﹙一﹚以UV laser進行LIAD脫附..............................................58
﹙二﹚以IR laser進行LIAD脫附...............................................59
﹙三﹚LIAD/ESI/MS分析固體樣品...........................................61
三、開發LIAD/ESI/MS進行液態樣品的分析............................65
﹙一﹚以LIAD脫附水溶液樣品................................................65
﹙二﹚以LIAD/ESI/MS分析蛋白質水溶液................................67
四、LIAD/ESI之脫附及游離過程..............................................69
五、LIAD/ESI之游離機制..........................................................73
肆、LIAD/ESI/MS實驗參數探討...............................................75
一、前言.....................................................................................75
二、不同雷射能量對於LIAD脫附能力的影響........................75
三、薄片材質種類與厚度差異對於LIAD脫附能力的影響.....79
四、添加基質對於LIAD/ESI/MS訊號的影響...........................85
五、偵測極限..............................................................................91
伍、以LIAD/ESI/MS分析固體及液體樣品.............................93
一、分析麥克筆染劑.................................................................93
二、以正、負離子偵測模式分析胺基酸標準品.....................93
三、以正、負離子偵測模式分析胜肽及蛋白質標準品.........96
四、分析蛋白質標準品.............................................................98
五、分析膽汁樣品..................................................................100
六、分析牛奶固體樣品..........................................................102
七、分析各種生化液體樣品..................................................103
八、分析豬肝組織..................................................................104
九、LIAD/ESI/MS應用於蛋白質結構改變之偵測................107
﹙一﹚、固體及液體樣品的比較..........................................107
﹙二﹚、液體樣品黏滯度改變對於蛋白質結構的影響......109
陸、TLC結合LIAD/ESI/MS應用於小分子的快速分離與偵測.........118
一、前言...................................................................................118
二、TLC與LIAD/ESI/MS結合.................................................119
三、以不同雷射能量密度及方法剝蝕silica TLC片..............121
四、以LIAD剝蝕C18及silica TLC片.....................................125
五、TLC-LIAD與ESI/MS的結合.............................................127
六、以LIAD/ESI/MS分析麥克筆染劑.....................................129
七、TLC-LIAD/ESI/MS偵測極限..........................................131
八、以C18 TLC-LIAD/ESI/MS分析染劑﹙負離子模式﹚...131
九、以silica TLC-LIAD/ESI/MS分析藥物............................134
十、以silica TLC-LIAD/ESI/MS分析精油樣品...................134
柒、大氣壓力質譜法在刑事鑑識領域的應用.......................140
一、ELDI/MS應用於尿液中毒品成份的快速篩檢................140
﹙一﹚前言...............................................................................140
﹙二﹚以ELDI/MS分析空白尿液樣品...................................141
﹙三﹚以ELDI/MS分析MDMA尿液樣品................................143
﹙四﹚以ELDI/MS/MS分析MDMA尿液樣品...........................144
﹙五﹚以ELDI/MS/MS分析安非他命尿液樣品.....................146
﹙六﹚以ELDI/MS/MS分析6-乙醯嗎啡尿液樣品..................148
﹙七﹚以ELDI/MS/MS分析攙假﹙漂白劑﹚尿液樣品.......149
﹙八﹚以ELDI/MS/MS分析攙假﹙清潔劑﹚尿液樣品.........152
﹙九﹚以ELDI/MS/MS分析不同pH值之尿液樣品...............154
二、ELDI/MS應用於字跡墨水化學組成的快速分析..............156
﹙一﹚以ELDI/MS分析原子筆筆劃.......................................157
﹙二﹚以ELDI/MS分析中性筆筆劃.......................................160
﹙三﹚以ELDI/MS/MS分析印表機列印文件........................160
﹙四﹚以ELDI/MS/MS分析感熱紙........................................162
三、RF-DART/MS應用於紙鈔中揮發性組成的分析............164
﹙一﹚以RF-DART/MS分析列印紙張....................................165
﹙二﹚以RF-DART/MS分析新台幣........................................166
﹙三﹚以RF-DART/MS分析各國紙鈔...................................168
捌、結論...................................................................................170
玖、參考文獻............................................................................172

1. Domon1, B.; Aebersold, R. “Mass Spectrometry and Protein Analysis” Science 2006, 312, 212–217.
2. Simoneit, B. R. T. “A Review of Current Applications of Mass Spectrometry for Biomarker/Molecular Tracer Elucidations” Mass Spectrom. Rev. 2005, 24, 719–765.
3. Lee, M. S.; Kerns, E. H. “LC/MS Applications in Drug Development” Mass Spectrom. Rev. 1999, 18, 187–279.
4. Kern, S.; Fenner, K.; Singer, H. P.; Schwarzenbach, R. P.; Hollender, J. “Identification of Transformation Products of Organic Contaminants in Natural Waters by Computer-Aided Prediction and High-Resolution Mass Spectrometry” Environ. Sci. Technol. 2009, 43, 7039–7046.
5. Peng, W. P.; Cai, Y.; Chang, H. C. “Optical Detection Methods for Mass Spectrometry of Macroions” Mass Spectrom. Rev. 2004, 23, 443–465.
6. Van Bocxlaer, J. F.; Clauwaert, K. M.; Lambert, W. E.; Deforce, D. L.; Van den Eeckhout, E. G.; Leenheer, A. P. D. “Liquid Chromatography-Mass Spectrometry in Forensic Toxicology” Mass Spectrom. Rev. 2000, 19, 165–214.
7. Yang, L. “Accurate and Precise Determination of Isotopic Ratios by MC-ICP-MS: A Review” Mass Spectrom. Rev. 2009, 28, 990–1011.
8. Yinon, J. “Forensic Applications of Mass Spectrometry” Mass Spectrom. Rev. 1991, 10, 179–224.
9. Nier, A. O. “Electron Impact Mass Spectrometry” Rev. Sci. Instrum. 1947, 18, 415–427.
10. Munson, M. S. B.; Field, F. H. “Chemical Ionization Mass Spectrometry. I. General Introduction.” J. Am. Chem. Soc. 1966, 88, 2621–2630.
11. Munson, B. “Chemical Ionization Mass Spectrometry” Anal. Chem., 1971, 43, 28A–43A.
12. Barber, M.; Bordoli, R. S.; Sedgwick, R. D.; Tyler, A. N. “Fast Atom Bombardment of Solids as An Ion Source in Mass Spectrometry” Nature 1981, 293, 270–275.
13. Barber, M.; Bordoli, R. S.; Sedgwick, R. D.; Tyler, A. N. “Fast Atom Bombardment of Solids (F.A.B.): A New Ion Source for Mass Spectrometry” J. Chem. Soc. Chem. Commun. 1981, 325–327.
14. Tabet, J. C.; Cotter, R. J. “Laser Desorption Time-of-Flight Mass Spectrometry of High Mass Molecules” Anal. Chem. 1984, 56, 1662–1667.
15. Zakett, D.; Schoen, A. E.; Cooks, R. G.; Hemberger, P. H. “Laser-Desorption Mass Spectrometry/Mass Spectrometry and the Mechanism of Desorption Ionization” J. Am. Chem. Soc. 1981, 103, 1295–1297.
16. Posthumus, M. A.; Kistemaker, P. G.; Meuzelaar, H. L. C.; Ten Noever de Brauw, M. C. “Laser Desorption-Mass Spectrometry of Polar Nonvolatile Bio-Organic Molecules” Anal. Chem. 1978, 50, 985–991.
17. Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. “Electrospray Ionization for Mass Spectrometry of Large Biomolecules” Science 1989, 246, 64–71.
18. Yamashita, M.; Fenn, J. “Electrospray Ion Source. Another Variation on the Free-Jet Theme” J. Phys. Chem. 1984, 88, 4451–4459.
19. Tanaka, K.; Waki, H.; Ido, Y.; Akita, S.; Yoshida Y.; Yoshida, T. “Protein and Polymer Analysis up to m/z 100,000 by Laser Ionization Time-of-Flight Mass Spectrometry” Rapid Commum. Mass Spectrom. 1988, 2, 151–153.
20. Karas, M.; Bachmann, D.; Hillenkamp, F. “Influence of the Wavelength in High-Irradiance Ultraviolet Laser Desorption Mass Spectrometry of Organic Molecules” Anal. Chem. 1985, 57, 2935–2939.
21. Karas, M.; Hillenkamp, F. “Laser Desorption Ionization of Proteins with Molecular Masses Exceeding 10,000 Daltons” Anal. Chem. 1988, 60, 2299–2301.
22. Moini M. “Atmospheric pressure chemical ionization: principles, instrumentation, and applications” In Encyclopedia of Mass Spectrometry, Vol. 6, Gross, M. L.; Caprioli, R. M. Eds.; Elsevier: Amsterdam, The Netherlands, 2007; pp 344.
23. Horning, E. C.; Horning, M. G.; Carroll, D. I.; Dzidic, I.; Stillwell, R. N. “New Picogram Detection System Based on a Mass Spectrometer with a External Ionization Source at Atmospheric Pressure” Anal. Chem. 1978, 45, 936–943.
24. Carroll, D. I.; Dzidic, I.; Stillwell, R. N.; Horning, M. G.; Horning, E. C. “Subpicogram Detection System for Gas Phase Analysis Based upon Atmospheric Pressure Ionization (API) Mass Spectrometry” Anal. Chem. 1978, 46, 706–710.
25. Pichini, S.; Altieri, I.; Pellegrini, M.; Zuccaro, P.; Paciifci, R. “The Role of Liquid Chromatography-Mass Spectrometry in the Determination of Heroin and Related Opioids in Biological Fluids” Mass Spectrom. Rev. 1999, 18, 119–130.
26. Dole M.; Mack L. L.; Hines R. L.; Mobley R. C.; Ferguson L. D.; Alice M. B. “Molecular Beams of Macroions” J. Chem. Phys. 1968, 49, 2240–2249.
27. Kerbale, P.; Tang, L. “From Ions in Solution to Ions in the Gas Phase - the Mechanism of Electrospray Mass Spectrometry” Anal. Chem. 1993, 65, 972A–986A.
28. Schmelzeisen-Redeker, G.; Bütfering, L.; Röllgen, F. W. “Desolvation of Ions and Molecules in Thermospray Mass Spectrometry” Int. J. Mass Spectrom. Ion Processes, 1989, 90, 139–150.
29. Nehring, H.; Thiebes, S.; Bütfering, L. Röllgen, F. W. “Cluster Ion Formation in Thermospray Mass Spectrometry of Ammonium Salts” Int. J. Mass Spectrom. Ion Processes, 1993, 128, 123–132.
30. Iribarne, J. V.; Thomson, B. A. “On the Evaporation of Small Ions from Charged Droplets” J. Chem. Phys. 1976, 64, 2287–2294.
31. Thomson, B. A.; Iribarne, J. V. “Field Induced Ion Evaporation from Liquid Surfaces at Atmospheric Pressure” J. Chem. Phys. 1979, 71, 4451–4463.
32. Hirabayashi, A. “Evaporation of Charged Fine Droplets” Int. J. Mass Spectrom. Ion Processes, 1998, 175, 241–245.
33. Takáts, Z.; Wiseman, J. M.; Gologan, B.; Cooks, R. G. “Mass Spectrometry Sampling Under Ambient Conditions with Desorption Electrospray Ionization” Science 2004, 306, 471–473.
34. Shiea, J.; Huang, M. Z.; Hsu, H. J.; Lee, C. Y.; Yuan, C. H.; Beech, I.; Sunner, J. “Electrospray-assisted laser desorption/ionization mass spectrometry for direct ambient analysis of solids” Rapid Commun. Mass Spectrom. 2005, 19, 3701–3704.
35. 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, 2297–2302.
36. 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.
37. Song, Y.; Cooks, R. G. “Atmospheric Pressure Ion/Molecule Reactions for the Selective Detection of Nitroaromatic Explosives Using Acetonitrile and Air as Reagents” Rapid. Commun. Mass Spectrom. 2006, 20, 3130–3138.
38. Covey, T. R.; Thomson, B. A.; Schneider, B. B. “Atmospheric Pressure Ion Sources” Mass Spectrom. Rev. 2009, 28, 870– 897.
39. Chen, H.; Gamez, G.; Zenobi, R. “What Can We Learn from Ambient Ionization Techniques? ” J. Am. Soc. Mass Spectrom. 2009, 20, 1947–1963.
40. Van Berkel, G. J.; Pasilis, S. P.; Ovchinnikova, O. “Established and Emerging Atmospheric Pressure Surface Sampling/Ionization Techniques for Mass Spectrometry” J. Mass Spectrom. 2008, 43, 1161–1180.
41. Venter, A.; Nefliu, N.; Cooks, R. G. “Ambient Desorption Ionization Mass Spectrometry” Trends Anal. Chem. 2008, 27, 284–290.
42. Lee, C. C.; Chang, D. Y.; Jeng, J.; Shiea, J. “Generating Multiply Charged Protein Ions via Two-Step Electrospray Ionization Mass Spectrometry” J. Mass Spectrom. 2002, 37, 115–117.
43. Shiea, J.; Chang, D. Y.; Lin, C. H.; Jiang, S. J. “Generating Multiply Charged Protein Ions by Ultrasonic Nebulization/Multiple Channel-Electrospray Ionization Mass Spectrometry” Anal. Chem. 2001, 73, 4983–4987.
44. Chang, D. Y.; Lee, C. C.; Shiea, J. “Detecting Large Biomolecules from High-Salt Solutions by Fused-Droplet Electrospray Ionization Mass Spectrometry” Anal. Chem. 2002, 74, 2465–2469.
45. Shieh, I. F.; Lee, C. Y.; Shiea, J. “Eliminating the Interferences from TRIS Buffer and SDS in Protein Analysis by Fused-Droplet Electrospray Ionization Mass Spectrometry” J. Proteome Res. 2005, 4, 606–612.
46. Chen, H.; Venter, A.; Cooks, R. G. “Extractive Electrospray Ionization for Direct Analysis of Undiluted Urine, Milk and Other Complex Mixtures Without Sample Preparation. Chem. Commun. 2006, 2042–2044.
47. Chen, H.; Wortmann, A.; Zhang, W.; Zenobi, R. “Rapid in Vivo Fingerprinting of Nonvolatile Compounds in Breath by Extractive Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry” Angew. Chem. Int. Ed. 2007, 46, 580–583.
48. Chen, H.; Hu, B.; Hu, Y.; Huan, Y.; Zhou, Z.; Qiao, X. “Neutral Desorption Using a Sealed Enclosure to Sample Explosives on Human Skin for Rapid Detection by EESI-MS” J. Am. Soc. Mass Spectrom. 2009, 20, 719–722.
49. Nilles, J. M.; Connell, T. R.; Durst, H. D. “Quantitation of Chemical Warfare Agents Using the Direct Analysis in Real Time (DART) Technique” Anal. Chem. 2009, 81, 6744–6749.
50. Jagerdeo, E.; Abdel-Rehim, M. “Screening of Cocaine and Its Metabolites in Human Urine Samples by Direct Analysis in Real-Time Source Coupled to Time-of-Flight Mass Spectrometry After Online Preconcentration Utilizing Microextraction by Packed Sorbent” J. Am. Soc. Mass Spectrom. 2009, 20, 891–899.
51. Petucci, C.; Diffendal, J.; Kaufman, D.; Mekonnen, B.; Terefenko, G.; Musselman, B. “Direct Analysis in Real Time for Reaction Monitoring in Drug Discovery” Anal. Chem. 2007, 79, 5064–5070.
52. 陳亮村, “開發以大氣壓力質譜法對各式樣品中揮發性成分的分析” 國立中山大學碩士論文, 2007.
53. Yang, S.; Ding, J.; Zheng, J.; Hu, B.; Li, J.; Chen, H.; Zhou, Z.; Qiao, X. “Detection of Melamine in Milk Products by Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry” Anal. Chem. 2009, 81, 2426–2436.
54. Cotte-Rodriguez , I.; Hernandez-Soto, H.; Chen, H.; Cooks, R. G. “In Situ Trace Detection of Peroxide Explosives by Desorption Electrospray Ionization and Desorption Atmospheric Pressure Chemical Ionization” Anal. Chem. 2008, 80, 1512–1519.
55. McEwen, C.; Gutteridge, S. “Analysis of the Inhibition of the Ergosterol Pathway in Fungi Using the Atmospheric Solids Analysis Brobe (ASAP) Method” J. Am. Soc. Mass Spectrom. 2007, 18, 1274–1278.
56. Lloyd, J. A.; Harron, A. F.; McEwen, C. N. “Combination Atmospheric Pressure Solids Analysis Probe and Desorption Electrospray Ionization Mass Spectrometry Ion Source” Anal. Chem. 2009, 81, 9158–9162.
57. Hong, C.M.; Tsai, F. C.; Shiea, J. “A Multiple Channel Electrospray Source Used to Detect Highly Reactive Ketenes From a Flow Pyrolyzer” Anal. Chem. 2000, 72, 1175–1178.
58. Hsu, H. J.; Kuo, T. L.; Wu, S. H.; Oung, J. N.; Shiea, J. “Characterization of Synthetic Polymers by Electrospray-Assisted Pyrolysis Ionization-Mass Spectrometry” Anal. Chem. 2005, 77, 7744–7749.
59. Hsu, H. J.; Oung, J. N.; Kuo, T. L.; Wu, S. H.; Shiea, J. “Using Electrospray-Assisted Pyrolysis Ionization/Mass Spectrometry for the Rapid Characterization of Trace Polar Components in Crude Oil, Amber, Humic Substances, and Rubber Samples” Rapid Commun. Mass Spectrom. 2007, 21, 375–384.
60. Venter, A.; Sojka, P. E.; Cooks, R. G. “Droplet Dynamics and Ionization Mechanisms in Desorption Electrospray Ionization Mass Spectrometry” Anal.Chem. 2006, 78, 8549–8555.
61. Takáts, Z. Wiseman, J. M.; Cooks, R. G. “Ambient Mass Spectrometry Using Desorption Electrospray Ionization (DESI): Instrumentation, Mechanisms and Applications in Forensics, Chemistry, and Biology” J. Mass Spectrom. 2005, 40, 1261–1275.
62. Green, F. M.; Stokes, P.; Hopley, C.; Seah, M. P.; Gilmore, I. S.; O'connor, G. “Developing Repeatable Measurements for Reliable Analysis of Molecules at Surfaces Using Desorption Electrospray Ionization” Anal. Chem. 2009, 81, 2286–2293.
63. Leuthold, L. A.; Mandscheff, J. F.; Fathi, M.; Giroud, C.; Augsburger, M.; Varesio, E.; Hopfgartner, G. “Desorption Electrospray Ionization Mass Spectrometry: Direct Toxicological Screening and Analysis of Illicit Ecstasy Tablets” Rapid Commun. Mass Spectrom. 2006, 20, 103–110.
64. Wiseman, J. M.; Ifa, D. R.; Song, Q.; Cooks, R. G. “Tissue Imaging at Atmospheric Pressure Using Desorption Electrospray Ionization (DESI) Mass Spectrometry” Angew. Chem. Int. Ed. 2006, 45, 7188–7192.
65. Chen, H.; Talaty, N. N.; Takáts, Z.; Cooks, R. G. “Desorption Electrospray Ionization Mass Spectrometry for High-Throughput Analysis of Pharmaceutical Samples in The Ambient Environment” Anal. Chem. 2005, 77, 6915–6927.
66. Wiseman, J. M.; Ifa, D. R.; Zhu, Y.; Kissinger, C. B.; Manicke, N. E.; Kissinger, P. T.; Cooks, R. G. “Desorption Electrospray Ionization Mass Spectrometry: Imaging Drugs and Metabolites in Tissues” Proc. Natl. Acad. Sci. 2008, 105, 18120–18125.
67. Van Berkel, G. J.; Ford, M. J.; Deibel, M. A. “Thin-Layer Chromatography and Mass Spectrometry Coupled Using Desorption Electrospray Ionization” Anal. Chem. 2005, 77, 1207–1215.
68. Ifa, D. R.; Gumaelius, L. M.; Eberlin, L. S.; Manicke, N. E.; Cooks, R. G. “Forensic Analysis of Inks by Imaging Desorption Electrospray Ionization (DESI) Mass Spectrometry” Analyst 2007, 132, 461–467.
69. Haddad, R.; Sparrapan, R.; Eberlin, M. N. “Desorption Sonic Spray Ionization for (High) Voltage-Free Ambient Mass Spectrometry” Rapid Commun. Mass Spectrom. 2006, 20, 2901–2905.
70. Haddad, R.; Milagre, H. M. S.; Catharino, R. R.; Eberlin, M. N. “Easy Ambient Sonic-Spray Ionization Mass Spectrometry Combined with Thin-Layer Chromatography” Anal. Chem. 2008, 80, 2744–2750.
71. Sérgio, A. S.; Patrícia, V. A.; Rodrigo, R. C.; George, N.; Eberlin, M. N. “Fabric Softeners: Nearly Instantaneous Characterization and Quality Control of Cationic Surfactants by Easy Ambient Sonic-Spray Ionization Mass Spectrometry” Rapid Commun. Mass Spectrom. 2009, 23, 357–362.
72. McLean, J. A.; Russell, W. K.; Russell, D. H. “A High Repetition Rate (1 kHz) Microcrystal Laser for High Throughput Atmospheric Pressure MALDI-Quadrupole-Time-of-Flight Mass Spectrometry” Anal. Chem. 2003, 75, 648–654.
73. Laiko, V. V.; Moyer, S. C.; Cotter, R. J. “Atmospheric Pressure MALDI / Ion Trap Mass Spectrometry”Anal. Chem. 2000, 72, 5239–5243.
74. Kolaitis, L.; Lubman, D. K. “Detection of Nonvolatile Species by Laser Desorption Atmospheric Pressure Mass Spectrometry” Anal. Chem. 1986, 58, 2137–2142.
75. Coon, J. J.; McHale, K. J.; Harrison, W. W. “Atmospheric Pressure Laser Desorption/Chemical Ionization Mass Spectrometry: A New Ionization Method Based on Existing Themes” Rapid Commun. Mass Spectrom. 2002, 16, 681–685.
76. Coon, J. J.; Harrison, W. W. “Laser Desorption-Atmospheric Pressure Chemical Ionization Mass Spectrometry for the Analysis of Peptides from Aqueous Solution” Anal. Chem. 2002, 74, 5600–5605.
77. Coon, J. J.; Steele H. A.; Laipis, P. J.; Harrison, W. W. “Direct Atmospheric Pressure Coupling of Polyacrylamide Gel Electrophoresis to Mass Spectrometry for Rapid Protein Sequence Analysis” J. Proteome Res. 2003, 2, 610–617.
78. Peng, S.; Edler, M.; Ahlmann, N.; Hoffmann, T.; Franzke, J. “A New Interface to Couple Thin-Layer Chromatography with Laser Desorption/Atmospheric Pressure Chemical Ionization Mass Spectrometry for Plat Scanning” Rapid Commun. Mass Spectrom. 2005, 19, 2789–2793.
79. Huang, M. Z.; Hsu, H. J.; Lee, J. Y.; Jeng, J.; Shiea, J. “Direct Protein Detection from Biological Media Through Electrospray-Assisted Laser Desorption Ionization/Mass Spectrometry” J. Proteome Res. 2006, 5, 1107–1116.
80. Huang, M. Z.; Hsu, H. J.; Wu, C. I.; Lin, S. Y.; Ma. Y. L.; Cheng, T. L.; Shiea, J. “Characterization of the Chemical Components on the Surface of Different Solids with Electrospray-Assisted Laser Desorption Ionization Mass Spectrometry” Rapid Commun. Mass Spectrom. 2007, 21, 1767–1775.
81. Cheng, S. C.; Lin, Y. S.; Huang, M. Z.; Shiea, J. “Applications of Electrospray Laser Desorption Ionization Mass Spectrometry for Document Examination” Rapid Commun. Mass Spectrom. 2010, 24, 203–208.
82. Lin, S. Y.; Huang, M. Z.; Chang, H. C.; Shiea, J. “Using Electrospray-Assisted Laser Desorption/Ionization Mass Spectrometry To Characterize Organic Compounds Separated on Thin-Layer Chromatography Plates” Anal. Chem. 2007, 79, 8789–8795.
83. Shiea, J.; Yuan, C. H.; Huang, M. Z.; Cheng, S. C.; Ma, Y. L.; Tseng, W. L.; Chang, H. C.; Hung, W. C. “Detection of Native Protein Ions in Aqueous Solution under Ambient Conditions by Electrospray Laser Desorption/Ionization Mass Spectrometry ” Anal. Chem. 2008, 80, 4845–4852.
84. Cheng, C. Y.; Yuan, C. H.; Cheng, S. C.; Huang, M. Z.; Chang, H. C.; Cheng, T. L.; Yeh, C. S.; Shiea, J. “Electrospray-Assisted Laser Desorption/Ionization Mass Spectrometry for Continuously Monitoring the States of Ongoing Chemical Reactions in Organic or Aqueous Solution under Ambient Conditions” Anal. Chem. 2008, 80, 7699–7705.
85. Sampson, J. S.; Hawkridge, A. M.; Muddiman, D. C. “Generation and Detection of Multiply-Charged Peptides and Proteins by Matrix-Assisted Laser Desorption Electrospray Ionization (MALDESI) Fourier Transform Ion Cyclotron Resonance Mass Spectrometry” J. Am. Soc. Mass Spectrom. 2006, 17, 1712–1716.
86. Sampson, J. S.; Hawkridge, A. M.; Muddiman, D. C. “Development and Characterization of an Ionization Technique for Analysis of Biological Macromolecules: Liquid Matrix-Assisted Laser Desorption Electrospray Ionization” Anal. Chem. 2008, 80, 6773–6778.
87. Sampson, J. S.; Murray, K. K.; Muddiman, D. C. “Intact and Top-Down Characterization of Biomolecules and Direct Analysis Using Infrared Matrix-Assisted Laser Desorption Electrospray Ionization Coupled to FT-ICR Mass Spectrometry” J. Am. Soc. Mass Spectrom. 2009, 20, 667–673.
88. Nemes, P.; Vertes, A. “Laser Ablation Electrospray Ionization for Atmospheric Pressure, in Vivo, and Iimaging Mass Spectrometry” Anal. Chem. 2007, 79, 8098–8106.
89. Nemes, P.; Barton, A. A.; Li, Y.; Vertes, A. “Ambient Molecular Imaging and Depth Profiling of Live Tissue by Infrared Laser Ablation Electrospray Ionization Mass Spectrometry” Anal. Chem. 2008, 80, 4575–4582.
90. Sripadi, P.; Nazarian, J.; Hathout, Y.; Hoffman, E. P.; Vertes, A. “In vitro Analysis of Metabolites from the Untreated Tissue of Torpedo Californica Electric Organ by Mid-Infrared Laser Ablation Electrospray Ionization Mass Spectrometry” Metabolomics 2009, 5, 263–276.
91. Eliezer, S.; Gilath, I. “Laser-Induced Spall in Metals: Experiment and Simulation” J. Appl. Phys. 1990, 67, 715–724.
92. Linder, B.; Seydel, U. “Laser Desorption Mass Spectrometry of Nonvolatiles under Shock Wave Conditions” Anal. Chem. 1985, 57, 895–899.
93. Golovlev, V. V.; Allman, S. L.; Garrett, W. R.; Chen, C. H. “Laser-Induced Acoustic Desorption of Electrons and Ions” Appl. Phys. Lett. 1997, 71, 852–854.
94. Paltauf, G.; Dyer, P. E. “Photomechanical Processes and Effects in Ablation” Chem. Rev. 2003, 103, 487–518.
95. Golovlev, V. V.; Allman, S. L.; Garrett, W. R.; Taranenko, N. I.; Chen, C. H. “Laser-Induced Acoustic Desorption” Int. J. Mass. Spectrom. Ion. Processes 1997, 169, 69–78.
96. Peng, W. P.; Yang, Y. C.; Lin, C. W.; Chang, H. C. “Molar Mass and Molar Mass Distribution of Polystyrene Particle Size Standards” Anal. Chem. 2005, 77, 7084–7089.
97. Shea, R. C.; Petzold, C. J.; Campbell, J. L.; Li, S.; Aaserud, D. J.; Kenttämaa, H. I. “Characterization of Laser-Induced Acoustic Desorption Coupled with a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer” Anal. Chem. 2006, 78, 6133–6139.
98. Zinovev, A. V.; Veryovkin, I. V.; Moore, J. F.; Pellin, M. J. “Laser-Driven Acoustic Desorption of Organic Molecules from Back-Irradiated Solid Foils” Anal. Chem. 2007, 79, 8232–8241.
99. Cheng, S. C.; Cheng, T. L.; Chang, H. C.; Shiea, J. “Using Laser-Induced Acoustic Desorption/Electrospray Ionization Mass Spectrometry To Characterize Small Organic and Large Biological Compounds in the Solid State and in Solution Under Ambient Conditions” Anal. Chem. 2009, 81, 868–874.
100. Peng, W. P.; Yang, Y. C.; Kang, M. W.; Tzeng, Y. K.; Nie, Z. X.; Chang, H. C.; Chang, W.; Chen, C. H. “Laser-Induced Acoustic Desorption Mass Spectrometry of Single Bioparticles” Angew. Chem., Int. Ed. 2006, 45, 1423–1426.
101. Peng, W. P.; Lin, H. C.; Lin, H. H.; Chu, M. L.; Yu, A. L.; Chang, H. C.; Chen, C. H. “Charge-Monitoring Laser-Induced Acoustic Desorption Mass Spectrometry for Cell and Microparticle Mass Distribution Measurement” Angew. Chem., Int. Ed. 2007, 46, 3865–3869.
102. Nie, Z.; Tzeng, Y. K.; Chang, H. C.; Chiu, C. C.; Chang, C. Y.; Chang, C. M.; Tao, M. T. “Microscopy-Based Mass Measurement of a Single Whole Virus in a Cylindrical Ion Trap” Angew. Chem., Int. Ed. 2006, 45, 8131–8134.
103. Nie, Z.; Cui, F.; Tzeng, Y. K.; Chang, H. C.; Chu, M. L.; Lin, H. C.; Chen, C. H.; Lin, H. H.; Yu, A. L. “High-Speed Mass Analysis of Whole Erythrocytes by Charge-Detection Quadrupole Ion Trap Mass Spectrometry” Anal. Chem. 2007, 79, 7401–7407.
104. Peng, W. P.; Lin, H. C.; Chu, M. L.; Chang, H. C.; Lin, H. H.; Yu, A. L.; Chen, C. H. “Charge Monitoring Cell Mass Spectrometry” Anal. Chem. 2008, 80, 2524–2530.
105. Pérez, J.; Ramîrez-Arizmendi, L. E.; Petzold, C. J.; Guler, L. P.; Nelson, E. D.; Kenttämaa, H. I. “Laser-induced Acoustic Desorption/Chemical Ionization in Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry” Int. J. Mass Spectrom. 2000, 198, 173–188.
106. Habicht, S. C.; Amundson, L M.; Duan, P.; Vinueza, N. R.; Kenttämaa, H. I. “Laser-Induced Acoustic Desorption Coupled with a Linear Quadrupole Ion Trap Mass Spectrometer” Anal. Chem. In Press
107. Shea, R. C.; Petzold, C. J.; Campbell, J. L.; Li, S.; Aaserud, D. J.; Kenttämaa, H. I. “Characterization of Laser-Induced Acoustic Desorption Coupled with a Fourier Transform Ion Cyclotron Resonance Mass Spectrometry” Anal. Chem. 2006, 78, 6133–6139.
108. Shea, R. C.; Habicht, S. C.; Vaughn, W. E.; Kenttämaa, H. I. “Design and Characterization of a High-Power Laser-Induced Acoustic Desorption Probe Coupled with a Fourier Transform Ion Cyclotron Resonance Mass Spectrometry” Anal. Chem. 2007, 79, 2688–2694.
109. Campbell, J. L.; Fiddler, M. N.; Crawford, K. E.; Gqamana P. P.; Kenttämaa, H. I. “Analysis of Polyethylene by Using Cyclopentadienyl Cobalt Chemical Ionization Combined with Laser-Induced Acoustic Desorption/Fourier Transform Ion Cyclotron Resonance Mass Spectrometry” Anal. Chem. 2005, 77, 4020–4026.
110. Crawford, K. E.; Campbell, J. L.; Fiddler, M. N.; Duan, P.; Qian, K.; Gorbaty, M. L. Kenttämaa, H. I. “Laser-Induced Acoustic Desorption/Fourier Transform Ion Cyclotron Resonance Mass Spectrometry for Petroleum Distillate Analysis” Anal. Chem. 2005, 77, 7916–7923.
111. Campbell, J. L.; Crawford, K. E.; Kenttämaa, H. I. “Analysis of Saturated Hydrocarbons by Using Chemical Ionization with Laser-Induced Acoustic Desorption/Fourier Transform Ion Cyclotron Resonance Mass Spectrometry” Anal. Chem. 2004, 76, 959–963.
112. Duan, P.; Fu, M.; Pinkston, D. S.; Habicht, S. C.; Kenttämaa, H. I. “Gas-Phase Reactions of ClMn(H2O)+ with Polar and Nonpolar Hydrocarbons in a Mass Spectrometer” J. Am. Chem. Soc. 2007, 129, 9266–9267.
113. Zinovev, A. V.; Veryovkin, I. V.; Moore, J. F.; Pellin, M. J. “Laser-Driven Acoustic Desorption of Organic Molecules from Back-Irradiated Solid Foils” Anal. Chem. 2007, 79, 8232–8241.
114. Kawai, Y.; Miyoshi, M.; Moon, J. H.; Terao, J. “Detection of Cholesteryl Ester Hydroperoxide Isomers Using Gas Chromatography-Mass Spectrometry Combined with Thin-Layer Chromatography Blotting” Anal. Biochem. 2007, 360, 130–137.
115. Didonato, G. C.; Busch, K. L. “Phase-Transition Matrix for Chromatography/Secondary Ion Mass Spectrometry” Anal. Chem. 1986, 58, 3231–3232.
116. Monaghan, J. J.; Morden, W. E.; Johnson, T.; Wilson, I. D.; Martin, P. “Thin Layer Chromatography/Mass Spectrometry: The Advantages of Tandem Mass Spectrometry” Rapid Commun. Mass Spectrom. 1992, 6, 608–615.
117. Danigel, H.; Schmidt, L.; Jungclas, H.; Pfluger, K. H. “Combined Thin Layer Chromatography/Mass Spectrometry: an Application of 252Cf Plasma Desorption Mass Spectrometry for Drug Monitoring” Biomed. Mass Spectrom. 1985, 12, 542–544.
118. Kubis, A. J.; Somayajula, K. V.; Sharkey, A. G.; Hercules, D. M. “Laser Mass Spectrometric Analysis of Compounds Separated by Thin-layer Chromatography” Anal. Chem. 1989, 61, 2516–2523.
119. Mehl, J. T.; Hercules, D. M. “Direct TLC-MALDI Coupling Using a Hybrid Plate” Anal. Chem. 2000, 72, 68–73.
120. Pellegrini, M.; Rosati, F.; Pacifici, R.; Zuccaro, P.; Romolo, F. S.; Lopez, A. “Rapid Screening Method for Determination of Ecstasy and Amphetamines in Urine Samples Using Gas Chromatography-Chemical Ionization Mass Spectrometry” J. Chromatogr. B 2002, 769, 243–251.
121. Lord, H. L.; Pawliszyn, J. “Method Optimization for the Analysis of Amphetamines in Urine by Solid-Phase Microextraction” Anal. Chem. 1997, 69, 3899–3906.
122. Jaffee, W. B.; Trucco, E.; Levy, S.; Weiss, R. D. “Is This Urine Really Negative? A Systematic Review of Tampering Methods in Urine Drug Screening and Testing” J. Subst. Abuse Treat. 2007, 33, 33–42.
123. Xu, Y.; Wang, J.; Yao, L. “Dating the Writing Age of Black Roller and Gel Inks by Gas Chromatography and UV-Vis Spectrophotometer” Forensic Sci. Int. 2006, 162, 140–143.
124. Wilson, J. D.; LaPorte, G. M.; Cantu, A. A. “Differentiation of Black Gel Inks Using Optical and Chemical Techniques” J. Forensic Sci. 2004, 49, 364–370.
125. Weyermann, C.; Marquis, R.; Mazzella, W.; Spengler, B. “Differentiation of Blue Ballpoint Pen Inks by Laser Desorption Ionization Mass Spectrometry and High-Performance Thin-Layer Chromatography” J. Forensic Sci. 2007, 52, 216–220.
126. Liu, Y. Z.; Yu, J.; Xie, M. X.; Liu, Y.; Han, J.; Jing, T. T. “Classification and Dating of Black Gel Pen Ink by Ion-Pairing High-Performance Liquid Chromatography” J. Chromatogr. A 2006, 1135, 57–64.
127. Fakhari, A. R.; Breadmore, M. C.; Macka, M.; Haddad, P. R. “Non-Aqueous Capillary Electrophoresis with Red Light Emitting Diode Absorbance Detection for the Analysis of Basic Dyes” Anal. Chim. Acta 2006, 580, 188–193.
128. Papson, K.; Stachura, S.; Boralsky, L.; Allison, J. “Identification of Colorants in Pigmented Pen Inks by Laser Desorption Mass Spectrometry” J. Forensic Sci. 2008, 53, 100–106.
129. Siegel, J.; Allison, J.; Mohr, D.; Dunn, J. “The Use of Laser Desorption/Ionization Mass Spectrometry in the Analysis of Inks in Questioned Documents” Talanta 2005, 67, 425–429.
130. Vu, D. T. “Characterization and Aging Study of Currency Ink and Currency Canine Training Aids Using Headspace SPME/GC-MS” J. Forensic Sci. 2003, 48, 754–770.