摘要
巯基化合物普遍存在于生物体内,具有重要的生理功能;它也广泛用于有机合成。人们对它的研究兴趣愈来愈浓厚。
我们利用银微盘电极对一些巯基化合物的电化学性质进行了研究,发现巯基化合物多能在银微盘电极上有灵敏的伏安响应。
全文共分六章。着重研究了还原型谷胱甘肽(GSH)、谷胱甘肽降解产物和6-巯基嘌呤的电化学行为。在选定的实验条件下,分别于-0.65V、-0.47V和-0.81V处出现灵敏的阴极还原峰。采用合适的方法,还原峰电流分别与三种巯基化合物的浓度于1.0×10~(-5)~1.0×10~(-3)mol/L、9.0×10~(-7)~4.0×10~(-5)mol/L和1.0×10~(-8)~2.0×10~(-6)mol/L范围内呈良好的线性关系。检测限分别为1.0×10~(-6)mol/L、5.0×10~(-8)mol/L和5.0×10~(-9)mol/L。用于模拟样品的测定,结果令人满意。
同时,我们还对对苄二硫醇、头孢噻肟钠降解产物和巯基乙酸在银微盘电极上的电化学性质进行了研究,也取得了较为满意的结果。
我们还将6-巯基嘌呤修饰于银微盘电极表面,并对其电化学性质作了初步探讨。
Thiol derivatives were of particular interest in biosphere and synthetical chemistry because of their physiological properties and their importance as chemical materials.
The silver microdisk electrode was prepared and utilized to study the electrochemical behaviors of some thiols. It had been observed that there were sensitive voltammetric responses of most of thiols at silver microdisk electrode.
In this thesis, we studied the electrochemical behaviors of reduced glutathione, the degradation products of glutathione and 6-mercaptopurine at silver microdisk electrode in detail. In the negative potential range (for example from 0.1V to -1.0V), there was a sensitive cathodic peak at -0.65V, -0.47V and -0.81 respectively on the cyclic voltammograms of reduced glutathione, the degradation product of glutathione and 6-mercaptopurine. Under the proper condition, the cathodic peak currents were proportional to the concentrations in the range of 1.0X 10-5-1.0X 10-3mol/L , 9.0 X 10-7-4.0 X 10-5mol/L and 1.0 X 10-8-2.0 X 10-6mol/L respectively. The method had been successfully applied to determination of the thiols in simulant samples.
On the other hand, we have also studied the electrochemical behaviors of other thiol derivatives with the silver microdisk electrode, such as 1,4-dimercaptomethyl benzene, degradation product of cefotaxime and thioglycolic acid, and obtained some useful information.
At last, we modified silver microdisk electrode by 6-mercaptopurine and earned gut some abecedarian studies of its electrochemical behavior.
引文
1.Bond A. M., Oldham K. B., Zoski C. G., Anal. Chim. Acta, 1989,216:177
2.Niwa O., Horiuchi T., Morita M., et al, Anal. Chim. Acta, 1996,318:167
3.Zhong H. Q., Lin X. Q., J. Electroanal. Chem., 1997,434:55
4.Chao M. H., Huang H. J., Anal. Chem., 1997,69:463
5.Wightman R. M., Anal. Chem., 1981,53:1125A
6.林心如.电分析化学.1989,3(1):12
7.李长明.化学通报.1987,1:33
8.吴持平,陈洪渊,方惠群.分析化学.1988,16:566
9.鞠熀先,陈洪渊.化学传感器.1990,10(1):1
10.傅业伟,郑建斌.分析化学.1990,18:485
11.Pons S., Fleischmann M., Anal. Chem., 1987,59:1391A
12.鞠熀先,陈洪渊.分析化学.1992,20:107
13.张学记,周性尧.痕量分析.1992,8(3~4):10
14.Fleischmann M., et al(Eds.). Ultramicroelectrode, Datatech Systems, Morganton, Science Publishers, 1987
15.Montenegro M., et al., Microelectrodes: Theory and Applications, Kluwer Academic Publishers, Dordrecht, The Netherlands. 1991
16.Andrieux C. P., et al, Chem. Rev., 1990,90(5):723
17. 陈洪渊,鞠熀先.分析化学.1992,20(9):997
18.Russell A., Anal. Chem., 1986,58:2961
19.Oldham K. B., J. Electroanal. Chem., 1989:270:79
20.Tutty O. R., J. Electroanal. Chem., 1994:377:39
21.Zhuang Qiankun, Chen Hongyuan. Chinese Chemical Letters. 1992,3(9):723
22.Winkler K., Baranski A., J. Electroanal. Chem., 1993:346:197
23.Tait R. J., et al, Anal. Chem., 1993,65:3252
24.Garreau D., Sav'eant J., J. Electroanal Chem., 1974,50:1
25.Bond A. M., Lay P. A., J. Electroanal. Chem., 1986,199:285
26.Cooper J. B., Bond A. M., J. Electroanal. Chem., 1991,315:143
27.Bond A. M., Pfund V. B., J. Electroanal. Chem., 1992,335:281
28.陈洪渊,鞠熀先.高等学校化学学报.1991,12(10):1459
29.Beriet C., Pletcher D., J. Electroanal. Chem., 1994,375:213
30.Bowyer W. J., Evans D. H., J. Org. Chem., 1988,53:5234
31.Safford L. K., Weaver M. J., J. Electroanal. Chem., 1992,331:857
32.Robinaon R. S., Mecreery C. W., Anal. Chem., 1981
33.Andrieux C. P., J. Electroanal. Chem., 1988,243:321
34.Amatore C. A., Jutano A., J. Electroanal. Chem., 1987,218:361
35.蔡称心,陈洪渊.化学学报.1995,3:286
36.方禹之,于雁灵.分析化学.1995,3:332
37.Genxi Li, Hongyuan Chen, Dexi Zhu. Anal. Lett., 1996,8:1273
38.邹建平,陈克潜.有机硫化学.苏州大学出版社.苏州.1998:1
39.徐汉生,奚农葆.湖北化工.2000,5:1
40.Kagi J., Vallee B., J. Bio. Chem., 1960,235:3460
41.Hamer DH., Am. Rev. Biochem., 1986,55:913
42.Namerkin N. S., Tyurin V. D., Kukin M. A., J. Organomet. Chem., 1978,149:355
43.Winter A., Zuoloni L., Huttner G., et al, Org. Chem., 1982,37B:1430
44.宋礼成,黄耀曾,钱延龙编.金属有机化学进展.化工出版社.北京.1987:181
45.Wilkinson G., Gillard R. D., McCleverty J. A.(Eds), Comprehensive Coordination Chemistry, Vol.6, New York, Pergamon Press, 1987:541
46.Williams J. M., Schultz A. J., Science, 1991,252:1501
47.Demole E., Enggist P., OhloffG., Helv. Chim. Acta., 1982,65:1785
48.Flament I., Chevallier C., Chem. Ind. (London), 1988:592
49.Ames J. M., Chem. Ind. (London), 1988:558
50.关贵民.中华劳动卫生与职业病杂志.1986,1:47
51.郑泽武,黄韶清,唐学林等.医学综述.1995,2:83
52.陈志康,朱桐君,陈醒言等.温州医学院学报.1980,10(2):23
53.Nagawa Y., Saji Y., Chiba S., et al, Jpn. J. Pharmaeol, 1971,21:185
54.Youn S. C., Jeong M. K., Young J. L., et al, J. Pharmacol Exp. Ther, 1997,280:1335
55.Kuninori T., Nishiyama J., Anal. Bioehem., 1991,191(1):19
56.Erdmam G.R., Steury J. C., et al, J. Chomatogr. Biomed. Appl., 1991,109:149
57.Russel J., Mckeown J. A., J. Pharm. Biomed. Anal., 1997,15(11):1757
58.Abu-Izza K., Lu D. R., J. Chromatogr. B., Biomed. Appl., 1994, 660(2):347
59.Raggi M. A., Nobile L., Giovannini A. G., J. Pharm. Biomed. Anal., 1991,9:1037
60.Ciesislski W., Chem. Anal.(Warsaw), 1991, 36(3):555
61.Tsuruta Y., Moritani K., Anal. Sci., 1992,8(3):393
62. Compagnone D., Massoud R., Di Ilio C., et al., Anal. Lett., 1991,24(6):993
63. Schours M., Hellendoom L., Gooijer C., et al, J. Chromatogr., 1991,552(1/2):625
64. Lin Ling B., Baeyens W. R. G., Dewaele C., Anal. Chim. Acta, 1991,255:283
65. Sandhyarani N., Pradeep T., J. Colloid Interface Sci., 1999,218(1):176
66. Martin J., White I. N. H., J. Chromator. Biomed. Appl., 1991,106:219
67. Zhao Y., Baeyens W. R. G., Chromatographia., 1997,44(1/2):31
68. Kaniowska E., Chwatko G., J. Chromatogr., A., 1998,798(1/2):27
69. Mills B. J., Stinson C. T., J. Food Compos. Anal., 1997,10(2):90
70. Tsikas D., Sandmann J., J. Chromatogr., B: Biomed. Appl., 1998,708(1/2):55
71. Nozal M. J., Bemal J. L., J. Chromatogr., A., 1997,778(1/2):347
72. Raggi M. A., Mandrioli R., Chromatographia, 1997,46(1/2):17
73.程敬君,匡培根.色谱.1998,16(2):167
74. Narahari Reddy M., Behnke C., J. Liq. Chromatogr. Relat. Technal., 1997,20(9):1391
75. Taneja D. K., Jain N. K., Indian Drugs, 1996,33(8):403
76. Raggi M. A., Schiavone P., Pharmazie, 1998,53(4):239
77. Eid M. A., Mikrochim. Acta, 1998,129(1/2):91
78. Morioka Y., Kobayshi K., Biol. Pharm. Bull., 1997,20(8):825
79. Fogg A. G., Ismail R., Talanta, 1997,44(3):399
80. Ciesielski W., Zakrzewski R., Chem. Anal. (Warsaw), 1996,41 (6): 1083
81.刘斌,孙向英.华侨大学学报(自).1997,18(1):27
82. Komljenovic J., Radic N., Analysis, 1996,24(3):63
83.马俊义,余荣珍.信阳师范学院学报(自).1998,11(1):51
84. Limson J., Ngokomg T., Electroanlysis, 1997,9(3):255
85. Mishra U., Prasad B. B., J. Indian Chem. Soc., 1998,75(1):56
86. Ciesielski W., Zakrzewski R., Chem. Anal.(Warsaw)., 1996,41(3):399
87. Kamidate T., Watanabe H., Talanta, 1996,43(10):1733
88.李怀娜,慈云祥.分析化学.1997,25(6):679
89. Thomson J. S., Green J. B., Energy Fuels, 1997,11(4):909
90. Mestres M., Busto O., J. Chromatogr. A., 1997,773(1/2):261
91. Takagi K., Kataoka H., Biosci. Biotechnol. Biochem., 1996,60(4):729
92.徐光利,邓兆永.中国药科大学学报.1998,29(1):49
93. Capote R. G., J. Radioanal. Nucl. Chem., 1997,223(1/2):221
94. Bain C. D., Troughton E. B., Tao Y. T., et al, J. Am. Chem. Soc., 1989,111:321
95.Uiban A., Chem. Rev., 1996,96:1533
96.李景虹,程广金,懂绍俊.化学学报.1995,10:11
97.Nuzzo R. G., Zegarski B. R., Dubois L. H., J. Am. Chem. Soc., 1987,109:733
98.Forster R. J., Anal. Chem., 1996,68:3143
99.Iarnes L., A., Louis A., Coury Jr., et al, Anal. Chem., 1998,70:519R
100.李景虹,程广金,董绍俊.分析化学.1996,24(9):1093
101.Evertt W. R., Fritsch-Faules I., Anal. Chim. Acta., 1995,307(2/3):253
102.Arrigan D. W. M., Bihan L. L., Mark J. P., Analyst(U. K.), 1999,124:17
103.Daisuke H., Kazuhiro U., Shin I. I., et al, Electrochemisty(Tokyo), 1999,67(12):1218
104.Bain C. D., Whitesides G. M., J. Am. Chem. Soc., 1989,111:7155
105.Frisbie C. D., Fritsch-Faules I., Wollman E. W., et al, Thin Solid Films, 1992,210:341
106.Laibinis P. E., Hiskman J. J., Wrighton M. S., et al, Science, 1989,245:845
107.Jin W. R., Wei H. Y., Zhao X., Electroanalysis(N.Y.), 1997,9:770
108.顾凯,朱俊杰,陈洪渊.分析化学.1999,27(10):1172
109.冶保献,方程,周性尧.高等学校化学学报.1998,19(9):1405
110.陈健,赵文涛,胡继明等.高等学校化学学报.1995,16(11):1697
111.Zeng B., Purdy W. C., Electroanalysis(N.Y.), 1998,10(4):236
112.Gen-Xi Li, Xiang-Min Liao, Hui-Qun Fang, et al, J. Electroanal. Chem., 1994,369:267
113.方宾,方惠群,陈洪渊.高等学校化学学报.1996,17:1384
114.方宾,朱英贵,张玉忠等.分析化学.1997,25(5):505
115.方宾,李蜀萍,方惠群等.分析化学.1997,25(1):59
116.Barker J. E., Heales S. J. R., Caseidy A., et al, Brain Res., 1996,716:718
117.Bains J. S., Shaw C. A., Brain Res. Rev., 1997,25:335
118.Chaudiere J., Tappel A., J. Inorg. Biochem., 1984,29:318
119.Jenner P., Olanow C. W., Ann Neurol., 1998,44:572
120.Jouini M., Laplage G., Huet J., J. Inorg. Biochem., 1986,86:269
121.中华人民共和国卫生部药典委员会编.药典注释.北京:化学工业出版社.1993:845
122.杨藻寰主编.医用药理学(第三版).北京:人民卫生出版社.1994:1011
123.Kirk O., Encyl. Chem. Technol., 1983,22(3):933
124.王华.精细石油化工.1988,3:49
125.黄德才.辽宁化工.1988,6:39
126.中华人民共和国卫生部.化装品卫生标准(GB7916-87).1987:21
127.宋春华.工业卫生与职业病.1990,16(3):145
128.袁勒生.现代酶学.上海:华东理工大学出版社,2001:298
129.Yang C., Chon S., J. Chromatogr B; Biomem. Appl., 1994,661(2):231
130.Russel J., Rabenstein D. L., Anal. Biochem., 1996,242(11):136
131.Matsumoto S., Texhigawara M., Anal. Sci., 1996,12(1):91
132.Ueno S., Ishizak M. Jpn., J. Toxicol., Environ. Health, 1994,40(1):96
133.Takehara K., Ide Y., Bioelectrochem. Bioenerg., 1992,29:103
134.Touche M. L. D., Williams D. R., J. Chem. Soc. Dalton Trans., 1976,98:1355
135.U. Kela, R. Vijayrargiya. Biochem. J., 1981, 193:799
136.Albertion F., Pettersson B., Ohlman S., et al, J. Liq. Chromatogr., 1995, 18(20):3991
137.Chrzamowska M., Sloderbach A., Chem. Anal. (Warsaw), 1997,42(3):381
138.韩秀文,屈铭,缪希茄等.谷胱甘肽在水溶液中的构象研究.化学通报.1994,3:36
139.Ciesielski W., Chem. Anal. (Warsaw), 1991,36(3):555
140.王晓清,由天艳,杨秀荣,汪尔康,分析化学,1999,27(10):1141
141.Errington J., McDonald W. S., Shaw B. L., J. Chem. Soc., Dalton Trans., 1980,11:2312
142.Luening U., Wangnick C., Peters K., et al, Chem. Ber., 1991,124(2):397
143.李启隆,陈寿爱,尚军.高等学校化学学报.1994,15(3):339
144.郑星泉主编,化妆品卫生检验.天津:天津大学出版社.1994:93
145.孙汝东,葛忠明.日用化学工业.1997,1:48