對於環境中的乙硫醇的偵測，目前主要的方法是利用醋酸汞做為 吸附劑，利用汞金屬離子與環境中的硫醇形成配合物(Hg(SEt)2)，再 經由萃取或者是熱脫附等方式進行脫附，隨後利用 GC / FPD 或者是 比色法進行偵測，但這些方法中的處理步驟相當繁雜，或是需要利用 對環境汙染造成相當大危害的汞類化合物。
本研究中以 catechol 做為電化學媒介，降低乙硫醇偵測所需的氧 化電位，選用 DPV 做為偵測方法，針對 o-benzoquinone 與乙硫醇反 應後的氧化電流訊號進行乙硫醇的定量分析，此偵測方法的線性範圍 為 0.65 M - 59.3 M，其偵測極限為 0.068 M (S/N= 3)。
對真實環境中乙硫醇的濃度測定範圍與採氣量相關，當採氣量為 100 L 時，則理論測定範圍在 0.4-37 (mg/m3)內，已符合環境中乙硫醇 容許濃度的偵測標準範圍規定內。
此方法在選擇性上還沒有辦法可以避免硫化氫所造成的干擾，但 亦可做為在工作環境中含有總硫化合物濃度的檢測參考；而在環境中 乙硫醇的偵測上，雖然避免使用對環境造成危害的醋酸汞，改以丁醇 做為吸附劑，但丁醇與乙硫醇之間可能作用力較小，不能有效的吸附 環境中的乙硫醇氣體，而無法得到理論上預期的成果，希望在之後可 以更進一步的藉由在電極上進行修飾或是找尋更適當的溶劑做為吸
附劑，以改善對於環境空氣中硫醇分子的吸附及減低硫化氫在此方法 中所造成的干擾。
參考文獻
1. Patnaik, P., Handbook of Environmental Analysis: Chemical Pollutants in Air, Water, Soil, and Solid Wastes. CRC Press: 2009.
2. Heafield, M. T.; Fearn, S.; Steventon, G. B.; Waring, R. H.; Williams, A. C.; Sturman, S. G., Plasma cysteine and sulphate levels in patients with motor neurone, Parkinson's and Alzheimer's disease. Neuroscience Letters 1990, 110 (1–2), 216.
3. Seshadri, S.; Beiser, A.; Selhub, J.; Jacques, P. F.; Rosenberg, I. H.;
D'Agostino, R. B.; Wilson, P. W. F.; Wolf, P. A., Plasma Homocysteine as a Risk Factor for Dementia and Alzheimer's Disease. New England
Journal of Medicine 2002, 346 (7), 476.
4. Herzenberg, L. A.; Rosa, S. C. D.; Dubs, J. G.; Roederer, M.;
Anderson, M. T.; Ela, S. W.; Deresinski, S. C.; Herzenberg, L. A., Glutathione Deficiency is Associated with Impaired Survival in HIV Disease. Proceedings of the National Academy of Sciences of the United States of America 1997, 94 (5), 1967.
5. Roederer, M.; Staal, F. J. T.; Anderson, M.; Rabin, R. O. N.; Raju, P.
A.; Herzenberg, L. A.; Herzenberg, L. A., Disregulation of Leukocyte Glutathione in AIDS. Annals of the New York Academy of Sciences 1993, 677 (1), 113.
6. Eck, H. P.; Gmunder, H.; Hartmann, M.; Petzoldt, D.; Daniel, V.;
Droge, W., Low concentrations of acid-soluble thiol (cysteine) in the blood plasma of HIV-1-infected patients. Biological chemistry
Hoppe-Seyler 1989, 370 (2), 101.
7. Townsend, D. M.; Tew, K. D.; Tapiero, H., The importance of glutathione in human disease. Biomedicine & Pharmacotherapy
2003, 57 (3–4), 145.
8. Soria, C.; Chadefaux, B.; Coudé, M.; Gaillard, O.; Kamoun, P.,
Concentrations of total homocysteine in plasma in chronic renal failure.
Clinical Chemistry 1990, 36 (12), 2137.
9. Shahrokhian, S., Lead Phthalocyanine as a Selective Carrier for
Preparation of a Cysteine-Selective Electrode. Analytical Chemistry 2001, 73 (24), 5972.
10. Nygård, O.; Nordrehaug, J. E.; Refsum, H.; Ueland, P. M.; Farstad, M.; Vollset, S. E., Plasma Homocysteine Levels and Mortality in Patients with Coronary Artery Disease. New England Journal of Medicine 1997, 337 (4), 230.
11. Refsum, M. H.; Ueland, M. P. M.; Nygård, M. O.; Vollset, M. D. D. P.
H. S. E., HOMOCYSTEINE AND CARDIOVASCULAR DISEASE.
Annual Review of Medicine 1998, 49 (1), 31.
12. Hwang, C.; Sinskey, A.; Lodish, H., Oxidized redox state of glutathione in the endoplasmic reticulum. Science 1992, 257 (5076), 1496.
13. Dalton, T. P.; Shertzer, H. G.; Puga, A., REGULATION OF GENE EXPRESSION BY REACTIVE OXYGEN. Annual Review of
Pharmacology and Toxicology 1999, 39 (1), 67.
14. Trabesinger, A. H.; Weber, O. M.; Duc, C. O.; Boesiger, P., Detection of glutathione in the human brain in vivo by means of double quantum coherence filtering. Magnetic Resonance in Medicine 1999, 42 (2), 283.
15. Dieckhaus, C. M.; Fernández-Metzler, C. L.; King, R.; Krolikowski, P. H.; Baillie, T. A., Negative Ion Tandem Mass Spectrometry for the Detection of Glutathione Conjugates. Chemical Research in Toxicology
2005, 18 (4), 630.
16. Wang, W.; Rusin, O.; Xu, X.; Kim, K. K.; Escobedo, J. O.; Fakayode, S. O.; Fletcher, K. A.; Lowry, M.; Schowalter, C. M.; Lawrence, C. M.;
Fronczek, F. R.; Warner, I. M.; Strongin, R. M., Detection of
Homocysteine and Cysteine. Journal of the American Chemical Society
2005, 127 (45), 15949.
17. Huo, F.-J.; Sun, Y.-Q.; Su, J.; Chao, J.-B.; Zhi, H.-J.; Yin, C.-X., Colorimetric Detection of Thiols Using a Chromene Molecule. Organic Letters 2009, 11 (21), 4918.
18. Chen, X.; Zhou, Y.; Peng, X.; Yoon, J., Fluorescent and colorimetric probes for detection of thiols. Chemical Society Reviews 2010, 39 (6), 2120.
19. Assessment, S. R. C. C. f. C. H.; Santodonato, J.; Etiology, N. C. I. D.
o. C., Monograph on Human Exposure to Chemicals in the Workplace : Mercaptans: Final Report. National Cancer Institute, Division of Cancer Etiology: 1985.
20. ACGIH., Documentation of the Threshold Limit Values & Biological Exposure Indices (7th edition). Amer Conf of Governmental: Cincinnati,
2001.
21. Kangas, J.; JÄ Ppinen, P.; Savolainen, H., Exposure to Hydrogen Sulfide, Mercaptans and Sulfur Dioxide in Pulp Industry. American Industrial Hygiene Association Journal 1984, 45 (12), 787.
22. Goyer, N., Evaluation of Occupational Exposure to Sulfur
Compounds in Paper Pulp Kraft Mills. American Industrial Hygiene Association Journal 1990, 51 (7), 390.
23. RTECS, Methanethiol Methanethiol, Ed. NIOSH: 2004.
24. 液化石油氣. In CNS 12951, 中國國家標準: 2003.
25. Persson, S.; Edlund, M.-B.; Claesson, R.; Carlsson, J., The formation of hydrogen sulfide and methyl mercaptan by oral bacteria. Oral
Microbiology and Immunology 1990, 5 (4), 195.
26. Awano, S.; Koshimune, S.; Kurihara, E.; Gohara, K.; Sakai, A.; Soh, I.; Hamasaki, T.; Ansai, T.; Takehara, T., The assessment of methyl
mercaptan, an important clinical marker for the diagnosis of oral malodor.
Journal of Dentistry 2004, 32 (7), 555.
27. ETHYL MERCAPTAN. H.H.S., U. S., Ed. 1988.
28. Waller, R. L., Methanethiol inhibition of mitochondrial respiration.
Toxicology and Applied Pharmacology 1977, 42 (1), 111.
29. Sandmeyer, E. E., Organic Sulfur Compounds, in Patty's Industrial Hygiene and Toxicology. John Wiley and Sons: New York, 1981; p 2063.
30. Jaakkola, J. J. K.; Vilkka, V.; Marttila, O.; Jäppinen, P.; Haahtela, T., The South Karelia Air Pollution Study: The Effects of Malodorous Sulfur Compounds from Pulp Mills on Respiratory and Other Symptoms.
American Journal of Respiratory and Critical Care Medicine 1990, 142 (6 Pt 1), 1344.
31. 陳成裕, 95
年作業環境有害物容許濃度標準建議值訂定計畫
IOSH95-A304. 勞委會安全衛生研究所: 台灣, 2007; p 73.32. Wroński, M., Determination of volatile thiols by gas chromatography using separation astributyltin mercaptides. Journal of Chromatography A
1991, 555 (1–2), 306.
33. Tcherkas, Y. V.; Denisenko, A. D., Simultaneous determination of several amino acids, including homocysteine, cysteine and glutamic acid, in human plasma by isocratic reversed-phase high-performance liquid chromatography with fluorimetric detection. Journal of Chromatography A 2001, 913 (1–2), 309.
34. Amarnath, K.; Amarnath, V.; Amarnath, K.; Valentine, H. L.;
Valentine, W. M., A specific HPLC-UV method for the determination of cysteine and related aminothiols in biological samples. Talanta 2003, 60 (6), 1229.
35. Ogasawara, Y.; Mukai, Y.; Togawa, T.; Suzuki, T.; Tanabe, S.; Ishii, K., Determination of plasma thiol bound to albumin using affinity chromatography and high-performance liquid chromatography with fluorescence detection: Ratio of cysteinyl albumin as a possible
biomarker of oxidative stress. Journal of Chromatography B 2007, 845 (1), 157.
36. Ivanov, A. R.; Nazimov, I. V.; Baratova, L. A., Determination of biologically active low-molecular-mass thiols in human blood: II.
High-performance capillary electrophoresis with photometric detection.
Journal of Chromatography A 2000, 895 (1–2), 167.
37. Chen, G.; Zhang, L.; Wang, J., Miniaturized capillary electrophoresis system with a carbon nanotube microelectrode for rapid separation and detection of thiols. Talanta 2004, 64 (4), 1018.
38. Zinellu, A.; Sotgia, S.; Scanu, B.; Usai, M.; Fois, A.; Spada, V.;
Deledda, A.; Deiana, L.; Pirina, P.; Carru, C., Simultaneous detection of N-acetyl-l-cysteine and physiological low molecular mass thiols in plasma by capillary electrophoresis. Amino Acids 2009, 37 (2), 395.
39. Fei, S.; Chen, J.; Yao, S.; Deng, G.; He, D.; Kuang, Y.,
Electrochemical behavior of l-cysteine and its detection at carbon
nanotube electrode modified with platinum. Analytical biochemistry 2005, 339 (1), 29.
40. Potesil, D.; Petrlova, J.; Adam, V.; Vacek, J.; Klejdus, B.; Zehnalek, J.; Trnkova, L.; Havel, L.; Kizek, R., Simultaneous femtomole
determination of cysteine, reduced and oxidized glutathione, and phytochelatin in maize (Zea mays L.) kernels using high-performance liquid chromatography with electrochemical detection. Journal of Chromatography A 2005, 1084 (1–2), 134.
41. Huang, S.-T.; Ting, K.-N.; Wang, K.-L., Development of a long-wavelength fluorescent probe based on quinone–methide-type reaction to detect physiologically significant thiols. Analytica Chimica Acta 2008, 620 (1–2), 120.
42. Shibata, A.; Furukawa, K.; Abe, H.; Tsuneda, S.; Ito, Y., Rhodamine-based fluorogenic probe for imaging biological thiol.
Bioorganic & Medicinal Chemistry Letters 2008, 18 (7), 2246.
43. Duan, L.; Xu, Y.; Qian, X.; Wang, F.; Liu, J.; Cheng, T., Highly selective fluorescent chemosensor with red shift for cysteine in buffer solution and its bioimage: symmetrical naphthalimide aldehyde.
Tetrahedron Letters 2008, 49 (47), 6624.
44. Rafii, M.; Elango, R.; Courtney-Martin, G.; House, J. D.; Fisher, L.;
Pencharz, P. B., High-throughput and simultaneous measurement of homocysteine and cysteine in human plasma and urine by liquid chromatography–electrospray tandem mass spectrometry. Analytical biochemistry 2007, 371 (1), 71.
45. Burford, N.; Eelman, M. D.; Mahony, D. E.; Morash, M., Definitive identification of cysteine and glutathione complexes of bismuth by mass spectrometry: assessing the biochemical fate of bismuth pharmaceutical agents. Chemical Communications 2003, (1), 146.
46. Zeng, Y.; Zhang, G.; Zhang, D., A selective colorimetric chemosensor for thiols based on intramolecular charge transfer mechanism. Analytica Chimica Acta 2008, 627 (2), 254.
47. Zhang, D.; Zhang, M.; Liu, Z.; Yu, M.; Li, F.; Yi, T.; Huang, C., Highly selective colorimetric sensor for cysteine and homocysteine based on azo derivatives. Tetrahedron Letters 2006, 47 (39), 7093.
48. Shao, N.; Jin, J. Y.; Cheung, S. M.; Yang, R. H.; Chan, W. H.; Mo, T., A Spiropyran-Based Ensemble for Visual Recognition and Quantification of Cysteine and Homocysteine at Physiological Levels. Angewandte Chemie International Edition 2006, 45 (30), 4944.
49. Wen, M.; Liu, H.; Zhang, F.; Zhu, Y.; Liu, D.; Tian, Y.; Wu, Q., Amorphous FeNiPt nanoparticles with tunable length for electrocatalysis and electrochemical determination of thiols. Chemical Communications
2009, (30), 4530.
50. Zacharis, C. K.; Tzanavaras, P. D.; Themelis, D. G., Ethyl-propiolate as a novel and promising analytical reagent for the derivatization of thiols:
Study of the reaction under flow conditions. Journal of Pharmaceutical and Biomedical Analysis 2009, 50 (3), 384.
51. Heyrovský, M.; Vavřička, S., Electrochemical reactivity of homocysteine at mercury electrodes as compared with cysteine.
Bioelectrochemistry and Bioenergetics 1999, 48 (1), 43.
52. Çakır, S.; Biçer, E.; Çakır, O., Square-wave adsorptive stripping voltammetric behaviour of fresh and aged cystine solutions at
physiological pH. Electrochemistry Communications 1999, 1 (7), 257.
53. Ç akir, S.; Biçer, E.; Ç akir, O., Binary and ternary complexes of Cu(II) ions with saccharin and cysteine. Electrochemistry Communications 2000, 2 (2), 124.
54. Hart, J. P.; Hartley, I. C., Voltammetric and amperometric studies of thiocholine at a screen-printed carbon electrode chemically modified with cobalt phthalocyanine: studies towards a pesticide sensor. The Analyst
1994, 119 (2), 259.
55. Retamal, B. A.; Vaschetto, M. E.; Zagal, J., Catalytic
electro-oxidation of 2-mercaptoethanol using cobalt phthalocyanine + poly(2-chloroaniline) modified electrodes. Journal of Electroanalytical Chemistry 1997, 431 (1), 1.
56. Inoue, T.; Kirchhoff, J. R., Electrochemical detection of thiols with a coenzyme pyrroloquinoline quinone modified electrode. Analytical Chemistry 2000, 72 (23), 5755.
57. Lawrence, N. S.; Davis, J.; Compton, R. G.; Jiang, L.; Jones, T. G. J.;
Davis, S. N., Selective determination of thiols: a novel electroanalytical approach. The Analyst 2000, 125 (4), 661.
58. Lawrence, N. S.; Davis, J.; Compton, R. G., Electrochemical detection of thiols in biological media. Talanta 2001, 53 (5), 1089.
59. Gong, K. P.; Zhu, X. Z.; Zhao, R.; Xiong, S. X.; Mao, L. Q.; Chen, C.
F., Rational attachment of synthetic triptycene orthoquinone onto carbon nanotubes for electrocatalysis and sensitive detection of thiols. Analytical Chemistry 2005, 77 (24), 8158.
60. Wang, W.; Li, L.; Liu, S. F.; Ma, C. P.; Zhang, S. S., Determination of physiological thiols by electrochemical detection with piazselenole and its application in rat breast cancer cells 4T-1. Journal of the American Chemical Society 2008, 130 (33), 10846.
61. 乙硫醇採樣分析方法建議. In CLA 5017, 行政院勞工委員會:
2008.
62. OSHA, METHYL MERCAPTAN. In OSHA 26, OSHA: 1981.
63. MERCAPTANS, METHYL-, ETHYL-, and n-BUTYL-. In NIOSH 2542, NIOSH: 1994.
64. 空氣中硫化氫、甲硫醇、二硫化碳、硫化甲基、及二硫化甲基檢 驗方法-氣相層析/火焰光度偵測法. In NIEA A701.11C, 行政院環境保 護署: 2008.
65. 排放管道中硫醇檢驗法-吸收光度法. In NIEA A703.71C, 行政院 環境保護署: 2005.
66. Pariente, F.; Tobalina, F.; Moreno, G.; Hernández, L.; Lorenzo, E.;
Abruña, H. D., Mechanistic Studies of the Electrocatalytic Oxidation of NADH and Ascorbate at Glassy Carbon Electrodes Modified with Electrodeposited Films Derived from 3,4-Dihydroxybenzaldehyde.
Analytical Chemistry 1997, 69 (19), 4065.
67. Zare, H. R.; Nasirizadeh, N., Electrocatalytic Characteristics of
Hydrazine and Hydroxylamine Oxidation at Coumestan Modified Carbon Paste Electrode. Electroanalysis 2006, 18 (5), 507.
68. Tse, D. C. S.; McCreery, R. L.; Adams, R. N., Potential oxidative pathways of brain catecholamines. Journal of Medicinal Chemistry 1976,
19 (1), 37.
69. Tse, D. C.-S.; Kuwana, T., Electrocatalysis of dihydronicotinamide adenosine diphosphate with quinones and modified quinone electrodes.
Analytical Chemistry 1978, 50 (9), 1315.
70. Carlson, B. W.; Miller, L. L., Mechanism of the oxidation of NADH by quinones. Energetics of one-electron and hydride routes. Journal of the American Chemical Society 1985, 107 (2), 479.
71. Shahrokhian, S.; Bozorgzadeh, S., Electrochemical oxidation of dopamine in the presence of sulfhydryl compounds: Application to the square-wave voltammetric detection of penicillamine and cysteine.
Electrochimica Acta 2006, 51 (20), 4271.
72. Shahrokhian, S.; Saberi, R. S., Differential pulse voltammetric determination of propylthiouracil and methylthiouracil using their catalytic effects on the electrochemical oxidation of catechol.
International Journal of Electrochemical Science 2007, 2 (2), 158.
73. Raoof, J. B.; Ojani, R.; Amiri-Aref, M.; Chekin, F., Catechol as an electrochemical indicator for voltammetric determination of
N-acetyl-l-cysteine in aqueous media at the surface of carbon paste electrode. Journal of Applied Electrochemistry 2010, 40 (7), 1357.
74. Nematollahi, D.; Golabi, S. M., Electrochemical study of catechol and 4-methylcatechol in methanol. Application to the electro-organic synthesis of 4,5-dimethoxy-and 4-methoxy-5-methyl-o-benzoquinone.
Journal of Electroanalytical Chemistry 1996, 405 (1–2), 133.
75. Golabi, S. M.; Nematollahi, D., Electrochemical study of catechol and some 3-substituted catechols in the presence of 4-hydroxy coumarin:
application to the electro-organic synthesis of new coumestan derivatives.
Journal of Electroanalytical Chemistry 1997, 420 (1–2), 127.
76. Nematollahi, D.; Forooghi, Z., Electrochemical oxidation of
catechols in the presence of 4-hydroxy-6-methyl-2-pyrone. Tetrahedron
2002, 58 (24), 4949.
77. Nematollahi, D.; Rahchamani, R. A., Electro-oxidation of catechols in the presence of benzenesulfinic acid. Application to electro-organic synthesis of new sulfone derivatives. Journal of Electroanalytical Chemistry 2002, 520 (1-2), 145.
78. Nematollahi, D.; Alimoradi, M.; Husain, S. W., Cyclic Voltammetric Study of the Oxidation of Catechols in the Presence of Cyanide Ion.
Electroanalysis 2004, 16 (16), 1359.
79. Nematollahi, D.; Rafiee, M., Electrochemical oxidation of catechols in the presence of acetylacetone. Journal of Electroanalytical Chemistry
2004, 566 (1), 31.
80. Moghaddam, A. B.; Kobarfard, F.; Fakhari, A. R.; Nematollahi, D.;
Davarani, S. S. H., Mechanistic study of electrochemical oxidation of o-dihydroxybenzenes in the presence of
4-hydroxy-1-methyl-2(1H)-quinolone - Application to the
electrochemical synthesis. Electrochimica Acta 2005, 51 (4), 739.
81. Fotouhi, L.; Khakpour, M.; Nematollahi, D.; Heravi, M. M., Investigation of the electrochemical behavior of some catechols in the presence of 4,6-dimethylpyrimidine-2-thiol. Arkivoc 2008, 43.
82. Nematollahi, D.; Rafiee, M.; Fotouhi, L., Mechanistic Study of Homogeneous Reactions Coupled with Electrochemical Oxidation of Catechols. Journal of the Iranian Chemical Society 2009, 6 (3), 448.
83. Nematollahi, D.; Bamzadeh, M.; Shayani-Jam, H., Electrochemical Oxidation of Catechols in the Presence of Phenyl-Meldrum's Acid.
Synthesis and Kinetic Evaluation. Chemical & Pharmaceutical Bulletin
2010, 58 (1), 23.
84. Varmaghani, F.; Nematollahi, D.; Mallakpour, S.; Esmaili, R., Electrochemical oxidation of 4-substituted urazoles in the presence of arylsulfinic acids: an efficient method for the synthesis of new
sulfonamide derivatives. Green Chemistry 2012, 14 (4), 963.
86. Wang, J., Lü, Hui Sun, Qiaohua Li, Rongzhi Zhong, Yan Zhao, Jian Liu, Min Jia, Xiang Method of Electrochemical Determination of
Glutathione. Acta Chim. Sinica 2009, 67 (5), 415.
87. Zanello, P.; Chemistry, R. S. o., Inorganic Electrochemistry: Theory, Practice and Applications. Royal Society of Chemistry: 2003.
88. Shahrokhian, S.; Ghalkhani, M., Simultaneous voltammetric detection of ascorbic acid and uric acid at a carbon-paste modified
electrode incorporating thionine–nafion ion-pair as an electron mediator.
Electrochimica Acta 2006, 51 (13), 2599.
89. 採樣分析方法通則. 行政院勞工委員會: 1995.
90. 勞工作業環境空氣中有害物容許濃度標準. In