硒二唑类化合物的固相合成、表征及自组装
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摘要
硒(Ⅳ)与某些芳香邻二胺类化合物能定量、快速反应生成1，2，5-硒二唑类化合物(俗称苤硒脑化合物)，在分析、合成及药物化学中占有十分重要的地位。
本论文工作主要开展了包括BS、MBS、BBS、DBBS、NS、SPb、SPc、SPO、SPDO和AS等10种1，2，5-硒二唑类化合物的以下5个方面的研究：
1．固相合成 在室温下，固相合成了7个硒二唑类化合物，并用XRD，IR，EA对其过程和产物进行了表征。结果表明：与液相反应法合成相比，固相反应合成法的粗产物纯，产率高。
2．IR，UV-Vis，~1H NMR 对硒二唑类化合物的IR吸收峰进行了归类与指认，讨论了SPO、SPDO的异构体的分子结构；探讨了UV-Vis、吸收波长和摩尔吸光系数与分子结构的相对应关系，以及紫外吸收光谱性质在分析化学上的应用价值和溶液的pH值引起SPO、SPDO的结构变化。最后研究了SPO、SPDO的~1H NMR，通过计算确定了它们的结构。
3．GC／MS 用气相色谱—质谱联用仪对硒二唑化合物进行研究，发现部分硒二唑化合物具有挥发性，在气相色谱中有较好的响应；CH_3—与Br—两种取代基影响硒二唑化合物于气相色谱中的保留时间与它们的分子量成比例；同分异构体因极性和熔沸点不同，于气相色谱中保留时间完全不一样；含硒化合物在质谱裂解图中有特征分子离子或离子峰簇，其主要峰M：(M-2)约为2：1，完全不使用标准样品，也可以辨别含硒化合物。同时，对硒二唑类化合物的质谱裂解作了初步的探讨。
4．电化学性质 探讨了硒二唑化合物的循环伏安性质。硒二唑化合物的溶液体系中，电极过程主受吸附控制，为硒二二唑化合物的自组装提供了参考。
5．白组装及其单分子膜的表征与电化学性质 讨论了硒二唑化合物形成自组装膜的自组条件、自组装的表征和自组装膜的电化学性质。结果表明：自组装时，浓度以为10~(-3)mol／L数量级为佳；硒二唑化合物自组装膜的电化学信号与其溶液相似，在-600mV左右有一还原峰。
Se(IV) react with ortho aromatic diamine leads to 1,2,5-selenadiazole compounds fast and quantificationally. The selenadia- zoles have an very important role in chemistry including analysis, synthesis and medical.
The five aspects of research for BS, MBS, BBS, DBBS, NS, SPb, SPc, SPO, SPDO and AS that were done in this thesis are as follows:
1. Solid phase synthesis At room temperature, seven selenadiazoles were synthesized in solid phase, inspected and characterized with XRD, IR, EA. The results showed that the synthetical yield in solid-phase synthesis is higher than that in liquid-phase.
2. IR, UV-Vis, 1H NMR The IR, UV-Vis and 1H NMR of selenadiazoles were investigated. Their IR peaks were classified as the corresponding groups or bonds; The relation of their structure with the conjugative effects, absorbtion wavelength and molar absorb coefficients were discussed with the UV-Vis. The value of selenadiazoles in analytical chemistry and the varieties of structure with the pH were discussed. 1H NMR of SPO and SPDO were studied, and their structures were identified by the calculation.
3. GC/MS The selenadiazoles were investigated with GC/MS. In GC, some of selenadiazoles could be separated which is volatile, the effects of retention time were in direct relation in their molecular weights by the group CH3- and Br-. The retention times of isomer was different such as SPb and SPc, SPDO has two different peaks which were regarded as the isomers of SPDO. In MS, the Se-containing compounds had the characterized molecular or ion clusters, and the M: (M-2) is about 2:1 in the clusters. As the characterized molecular or ion clusters, the Se-containing compounds can be identified without the standard samples. The possible cleavage ways of selenadiazoles were discussed.
4. Electrochemical property The cyclic voltammetry of selenadiazoles were investigated, the results showed that the process of electrode was mainly dominated by adsorption. These properties provided evidence for self-assemble.
5. The characterization and electrochemical properties for self-assemble and its monolayer The results showed that the best concentration of selenadiazoles is about 10-3mol/L. The monolayers had reductive peaks at about -600mV which was consistent with the selenadiazoles in solution.
本论文工作主要开展了包括BS、MBS、BBS、DBBS、NS、SPb、SPc、SPO、SPDO和AS等10种1，2，5-硒二唑类化合物的以下5个方面的研究：
1．固相合成 在室温下，固相合成了7个硒二唑类化合物，并用XRD，IR，EA对其过程和产物进行了表征。结果表明：与液相反应法合成相比，固相反应合成法的粗产物纯，产率高。
2．IR，UV-Vis，~1H NMR 对硒二唑类化合物的IR吸收峰进行了归类与指认，讨论了SPO、SPDO的异构体的分子结构；探讨了UV-Vis、吸收波长和摩尔吸光系数与分子结构的相对应关系，以及紫外吸收光谱性质在分析化学上的应用价值和溶液的pH值引起SPO、SPDO的结构变化。最后研究了SPO、SPDO的~1H NMR，通过计算确定了它们的结构。
3．GC／MS 用气相色谱—质谱联用仪对硒二唑化合物进行研究，发现部分硒二唑化合物具有挥发性，在气相色谱中有较好的响应；CH_3—与Br—两种取代基影响硒二唑化合物于气相色谱中的保留时间与它们的分子量成比例；同分异构体因极性和熔沸点不同，于气相色谱中保留时间完全不一样；含硒化合物在质谱裂解图中有特征分子离子或离子峰簇，其主要峰M：(M-2)约为2：1，完全不使用标准样品，也可以辨别含硒化合物。同时，对硒二唑类化合物的质谱裂解作了初步的探讨。
4．电化学性质 探讨了硒二唑化合物的循环伏安性质。硒二唑化合物的溶液体系中，电极过程主受吸附控制，为硒二二唑化合物的自组装提供了参考。
5．白组装及其单分子膜的表征与电化学性质 讨论了硒二唑化合物形成自组装膜的自组条件、自组装的表征和自组装膜的电化学性质。结果表明：自组装时，浓度以为10~(-3)mol／L数量级为佳；硒二唑化合物自组装膜的电化学信号与其溶液相似，在-600mV左右有一还原峰。
Se(IV) react with ortho aromatic diamine leads to 1,2,5-selenadiazole compounds fast and quantificationally. The selenadia- zoles have an very important role in chemistry including analysis, synthesis and medical.
The five aspects of research for BS, MBS, BBS, DBBS, NS, SPb, SPc, SPO, SPDO and AS that were done in this thesis are as follows:
1. Solid phase synthesis At room temperature, seven selenadiazoles were synthesized in solid phase, inspected and characterized with XRD, IR, EA. The results showed that the synthetical yield in solid-phase synthesis is higher than that in liquid-phase.
2. IR, UV-Vis, 1H NMR The IR, UV-Vis and 1H NMR of selenadiazoles were investigated. Their IR peaks were classified as the corresponding groups or bonds; The relation of their structure with the conjugative effects, absorbtion wavelength and molar absorb coefficients were discussed with the UV-Vis. The value of selenadiazoles in analytical chemistry and the varieties of structure with the pH were discussed. 1H NMR of SPO and SPDO were studied, and their structures were identified by the calculation.
3. GC/MS The selenadiazoles were investigated with GC/MS. In GC, some of selenadiazoles could be separated which is volatile, the effects of retention time were in direct relation in their molecular weights by the group CH3- and Br-. The retention times of isomer was different such as SPb and SPc, SPDO has two different peaks which were regarded as the isomers of SPDO. In MS, the Se-containing compounds had the characterized molecular or ion clusters, and the M: (M-2) is about 2:1 in the clusters. As the characterized molecular or ion clusters, the Se-containing compounds can be identified without the standard samples. The possible cleavage ways of selenadiazoles were discussed.
4. Electrochemical property The cyclic voltammetry of selenadiazoles were investigated, the results showed that the process of electrode was mainly dominated by adsorption. These properties provided evidence for self-assemble.
5. The characterization and electrochemical properties for self-assemble and its monolayer The results showed that the best concentration of selenadiazoles is about 10-3mol/L. The monolayers had reductive peaks at about -600mV which was consistent with the selenadiazoles in solution.
引文
[1]郑文杰，欧阳政．植物学有机硒的化学及其医学应用，广州：暨南大学出版社，2001
[2]徐辉碧，黄开勋．硒的化学生物化学及其在生命科学中的应用．武汉：华中理工大学出版社，1994
[3]L.R.McDowell, Minerals in Animal and Human Nutrition, Academic Press, New York, 1992, 294
[4]Dauchy X., Potin-G M., Struc A A and Struc M A, Fresenius, J. Anal. Chem., 1994, 348:792
[5]郭利，恽榴红，含硒化合物研究进展，中国新药杂志，2000，9(3)：155-158
[6]KASTERKA B, A study of the reaction of Se(Ⅳ) with 3,4-diaminobenzoic acid and 4-bromo-1,2-phenylenediamine, Mikrochimica acta, 1992, 106(3-6): 303-318
[7]胡雪峰，丁瑞兴．紫外分光光度法测定土壤和植物中的微量硒，土壤通报，1998，29(4)：191-194
[8]吴万征．紫外分光光度法测定了12种药材中的微量硒，广东微量元素科学，1995，2(7)：65-68
[9]杨惠芬．食品卫生理化检验标准手册．北京：中国标准出版社，1997．171
[10]董健，王秋菊，赵法兰．荧光分光光度法测定食品中硒的方法改进，微量元素与健康研究，2002，19(4)：60-61
[11]王春娜．荧光法快速测定虾皮中微量硒，北京农学院学报，2000，15(3)：52-57
[12]Qi ZH H, Zhu L Z, Chen H W, Qi W B. Spectrofluorimetric study of cyclodextrin complexation in the presence of third and fourth components, Journal of inclusion phenomena and molecular recognition in chemistry 1997,27(4): 279-289
[13]ZHENG Y X, LU D H, Synergistic enhancement of the fluorescence intensity of 4,5-benzopiaselenol by surfactants and beta-cyclodextrin in aqueous-solution, mikrochimica acta, 1992, 106 (1-2): 3-9
[14]郑文杰，曾鑫华，郭宝江，杨芳，白燕，欧阳健明．硒杂环—金属离子在乙醇溶液中的发光，光谱学与光谱分析，2004，24(1)：102-105
[15]Gomez-Ariza J L, Pozas J A, Giraldez I, et al. Speciation of volatile forms of selenium and
inorganic selenium in sediments by gas chromatography-mass spectrometry, Journal of chromatography A, 1998, 823:259-277
[16]Ashok K S, Thomas W, Tom A, et al. Analysis of selenium in bovine liver by gas chromatography with mass-selective, electron-capture and nitrogen-phosphorus detection, Journal of chromatography B, 1997,690:327-331
[17]Van Dael P, Barclay D, Longet K, et al. Determination of selenium stable isotopes by gas chromatography-mass spectrometry with negative chemical ionization, Journal of chromatography B, 715 (1998)341-347
[18]Stibil J V, Dermel J M, Byrne A R, Determination of trace amounts of selenium in poultry feedstuffs by gas-chromatography, Journal of chromatography A, 1994, 668 (2): 449-453
[19]Gomez-Ariza J L, Pozas J A, Giraldez I, et al. Comparison of three derivationzation reagents for the analysis of Se(Ⅳ) based on piazselenol formation and gas chromatography-mass spectrometry, Talanta, 1999, 49:285-292
[20]蔡乾涛，施文赵．二溴代苤硒脑的萃取及痕量硒的极谱法测定．华中理工大学学报，1989，17(1)：125-131
[21]Trivedi B V, Thakkar N V. Determination of Se(Ⅳ) and Te(Ⅳ) by differential pulse polarography. Talanta, 1989, 36(7): 786-788
[22]蔡乾涛，毛新华，施文赵．二溴代苤硒脑体系吸附溶出伏安法测定痕量硒．分析实验室，1990，9(6)：49-57
[23]蔡乾涛，施文赵．二溴代苤硒脑极谱吸附波的研究及应用．高等学校化学学报，1988，9(3)：287-289
[24]Ekmekci G, Somer G. A new selenite selective membrane electrode and its application, Talanta, 1999, 49(1): 83-89
[25]Ekmekci G, Somer G. Selenite-selective membrane electrodes based on ion exchangers and application to anodic slime, Analytical sciences, 2000,16 (3):307-311
[26]Edin M, Grivas S. On the preparation of 1,2,5-selenadiazolo[3,4-e]indole and its [3,4-f] and [3,4-g] isomers through the Batcho-Leimgruber indole synthesis, Arkivoc, 2001,2:1036-1042 Part Ⅰ
[27]Grivas S. 2,1,3-benzoselenadiazoles as valuable synthetic intermediates, Currentc organic chemistry, 2000, 4(7): 707-726
[28] Grivas S, Tian W. Convenient synthesis of 4-methoxy-3-nitro-1,2- benzenedianmine and its conversion into 6-methoxy-5-nitorquinoxalines, Acta chemica scandinavica, 1992, 46(11):1109-1113
[29] Kaim W, Mono-nuclear and bi-nuclear pentacarbobyl complexes of chromium, molybdenum and tungsten with the anion radicals of 2,1,3-benzoxadiazole, 2,1,3-benzothiadia-zole and 2,1,3-benzoselenadiazole, Journal of organometallic chemistry, 1984, 264 (3): 317-326
[30] Harris M C J , Hill A F, Synthesis of 1,3-dienyl complexes of Ruthenium(Ⅱ) by facile hydroruthenation dehydration of propargylic alcohols, Journal of organometallic chemistry, 1992, 438(1-2): 209-212
[31] Heraberhold M, Hill A.F., The coordination chemistry of 2,1,3-benzothiadia-zole and 2,1,3-benzoselenadiazole- complexes of ruthenium, osmium and iridium, Journal of organometallic chemistry, 1989, 377(1): 151-156
[32] Kumari S, Sharma K S, Singh S P, Condensed heterocyclics 2,3-subsititution-reactions of 4-bromo-6-methyl-2,1,3-benzoselenadiazole, Indian journal of chemistry section B-organic chemistry including medicinal chemistry, 1990, 29 (8): 781-783
[33] Gomes A C, Biswas G, Banerjee A, et al. Structure of a planar organic-compound-2,1,3-benzoselenadiazole (piaselenole), Acta crystallographica section C-crystal structure communications, 1989, 45: 73-75
[34] Yang R Q, Tian R Y, Hou Q, Synthesis and optical and electroluminescent properties ofnovel conjugated copolymers derived from fluorene and benzoselenadiazole, Macromolecules, 2003, 36:7453-7460
[35] Fukushina T, Okazeri N, Miyashi T. First stable tetracyanodiphenoquinodimethane with a completely planar geometry: preparation, X-ray structure, and highly conductive complexes of bis[1,2,5]thiad iazolo-TCNDQ, Tetrahedron letters, 1999,40:1175-1178
[36] Yamashita Y, Ono K, Tomura M, et al. Synthesis and properties of benzobis(thiadiazole)s with nonclassical π-electron ring systems, Tetrahedron, 1997, 53:10169-10178
[37] Siddiqi S A, Aslam A, Naseem S. Study of selenium doped Bi-based superconductors by AES and SEM, Modern physics letters B, 2001, 15:973-980
[38] Ei-azhary A A, Kahtani A A, Force field scale factors of effective core potential basis sets of
some selenium and tellurium heterocylic molecules, selenophene, 1,2,5-selenadiazole, tellurophene and, 1,2,5-telluradiazole, Journal of molecular structure(theochem), 2001.572: 81-87
[39] Ei-azhary A A, Vibrational analysis of the spectra of 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,2,5-oxadiazole and 1,2,5-thiadiazole comparison between DFT, MP2 and HF force fields, Spectrochimcca acta (part A), 1996,(52): 33-44
[40] Kwiatkowski J S, Leszczynski J, Teca I, Molecular structure and infrared spectra of furan, thiophene, selenophene and their 1,2-N and 3,4-N derivatives: density functional theory and converntional post-Hartree-Fock MP2 studies, Journal of molecular structure, 1997, 436-437: 451-480
[41] 周益明，忻新泉．低热固相合成化学，无机化学学报，1999，15(3)：273-292
[42] 卢毅，邱咏梅，林辉，纲合化学中的绿色同相合成研究概况，海峡药学，2002，14(5)：1-5
[43] 刘海林，马晓燕，袁莉，黄韵．分子自组装研究进展，材料科学与工程学报，2004，22(2)：308-311
[44] 张祺，黄惠忠，何惠新等．角分辨XPS对自组装单分子层厚度和官能团位置的定性及定量研究．化学物理学报，1997，10(3)201～204
[45] 董献堆，陆君涛，查全性．巯基化合物自组装单分子层的研究进展．电化学，1995，1(3)：248～258
[46] Dishner M H, Hemminger J C, Feher F J. Scanning tunneling microscopy characterization of organselenium monolayers on Au(111), Langmuir, 1997, 13:4788～4790
[47] Nakano K, Sato T, Tazaki M, et al. Self-assembled monolayer formation from decanesenol on polycrystalline gold as characterized by electrochemical measurements, quartz-crystal microbalance, XPS, and IR spectroscopy, Langmiur, 2000,16:2225～2229
[48] Huang F K, Horton R C J, Myles D C, et al. Selenolates as alternative to thiolates for self-assembled monolayers: A SERS study, Langmiur, 1998, 14:4802～4808
[49] Bandyopadhyay K, Vijayamohanan K. Formation of a self-assembled monolayer of diphenyl diselenide on polycrystalline gold, Langmiur, 1998, 14:625～629
[50] 郑文杰，曾鑫华，白燕，杨芳，欧阳健明．硒杂环化合物(4，52苯并苤硒脑)在金表面上
的自组装，物理化学学报，2002，15(6)：461-464
[51]徐静娟，汪云，方惠群，陈洪渊．多巴胺在硫堇衍生化自组装膜修饰金电极上的伏安行为及其安培测定，分析化学，1998，26(4)：428-430
[52]张修华，王升富．2-巯基乙醇自组装膜电极对多巴胺电催化氧化及其分析应用，分析化学，2002，28(11)：1312-1315
[53]Kondo, Toshihir O, Kana. Effects of alkyl chain length on the efficiency of photoinduced electron transfer at gold electrodes modified with SAMs of molecules containing porphyrin, ferrocene, and thiol separated each other by alkyl chains, Phys Chem (muenchen), 1999, 212 (1): 23-30
[54]王俊，曾百肇，周性尧．自组装膜技术在电分析化学中的应用．分析科学学报，2000，16(3)：253～258
[55]韦天新，翟锦，葛俊豪，甘良兵，黄春辉．两种C60吡咯环多羧基衍生物自组装膜的制备及其光电转换性质研究，高等学校化学学报，1999，20(10)：1515-1519
[56]李添宝，李新海，黄克雄，蒋汉瀛，李晶，蔡志光．乙二胺改性的玻璃基片上C_(60)自组装薄膜的制备及其光致发光，高等学校化学学报，1999，20(5)：680～683
[57]Haussling L, Knoll W, Ringsdorf H, et al. Makromol Chem Macromol Symp, 1991, 46:145.
[58]Harrison D J, Fluri K, Chiem N, et al. Micromachining chemical and biochemical analysis and reaction systems on glass substrates, Sensors and Actuators B Chemical, 1996, 33: 105-109
[59]Schierbaum K D, Weiss T, Thoden van Velzen E U. Science, 1994,265: 1413.
[60]曾鑫华，若干硒芳香杂环化合物的谱学、电化学和自组装，硕士毕业论文，暨南大学，2003．6
[61]Merrifield R B. Journal of American chernistry society, 1963, 85:2159
[62]Alvert C, Eugene S, Francis E R. 8-Selenapurine, Journal of organic chemistry, 1958,23:1940-1942
[63]郑文杰，曾鑫华，杨芳，白燕，贺鸿志，欧阳健明．硒芳香杂环化合物的光谱和电化学性质，分析科学学报，2003，19(1)：36
[64]刘清福，张冬亭，王秀玲.，次黄嘌呤和黄嘌呤与卤化镍配合物的IR光谱特征，光谱实验室，2003，20(6)：845-847
[65] Brown N M D, Peter B. Synthesis and spectroscopy of 1,2,5-selenadiazolo-[3,4-b]-pyridine and 1,2,5-selenadiazolo-[3,4-c]-pyridine, Tetrahedron, 1968, 24:6577-6582
[66] Pretsch E, Buhlmanm P著，荣国斌译．波谱数据表——有机化合物的结构解析(Structure determination of organic compounds tables of spectral data),上海：华东理工大学出版社，2002.9
[2]徐辉碧，黄开勋．硒的化学生物化学及其在生命科学中的应用．武汉：华中理工大学出版社，1994
[3]L.R.McDowell, Minerals in Animal and Human Nutrition, Academic Press, New York, 1992, 294
[4]Dauchy X., Potin-G M., Struc A A and Struc M A, Fresenius, J. Anal. Chem., 1994, 348:792
[5]郭利，恽榴红，含硒化合物研究进展，中国新药杂志，2000，9(3)：155-158
[6]KASTERKA B, A study of the reaction of Se(Ⅳ) with 3,4-diaminobenzoic acid and 4-bromo-1,2-phenylenediamine, Mikrochimica acta, 1992, 106(3-6): 303-318
[7]胡雪峰，丁瑞兴．紫外分光光度法测定土壤和植物中的微量硒，土壤通报，1998，29(4)：191-194
[8]吴万征．紫外分光光度法测定了12种药材中的微量硒，广东微量元素科学，1995，2(7)：65-68
[9]杨惠芬．食品卫生理化检验标准手册．北京：中国标准出版社，1997．171
[10]董健，王秋菊，赵法兰．荧光分光光度法测定食品中硒的方法改进，微量元素与健康研究，2002，19(4)：60-61
[11]王春娜．荧光法快速测定虾皮中微量硒，北京农学院学报，2000，15(3)：52-57
[12]Qi ZH H, Zhu L Z, Chen H W, Qi W B. Spectrofluorimetric study of cyclodextrin complexation in the presence of third and fourth components, Journal of inclusion phenomena and molecular recognition in chemistry 1997,27(4): 279-289
[13]ZHENG Y X, LU D H, Synergistic enhancement of the fluorescence intensity of 4,5-benzopiaselenol by surfactants and beta-cyclodextrin in aqueous-solution, mikrochimica acta, 1992, 106 (1-2): 3-9
[14]郑文杰，曾鑫华，郭宝江，杨芳，白燕，欧阳健明．硒杂环—金属离子在乙醇溶液中的发光，光谱学与光谱分析，2004，24(1)：102-105
[15]Gomez-Ariza J L, Pozas J A, Giraldez I, et al. Speciation of volatile forms of selenium and
inorganic selenium in sediments by gas chromatography-mass spectrometry, Journal of chromatography A, 1998, 823:259-277
[16]Ashok K S, Thomas W, Tom A, et al. Analysis of selenium in bovine liver by gas chromatography with mass-selective, electron-capture and nitrogen-phosphorus detection, Journal of chromatography B, 1997,690:327-331
[17]Van Dael P, Barclay D, Longet K, et al. Determination of selenium stable isotopes by gas chromatography-mass spectrometry with negative chemical ionization, Journal of chromatography B, 715 (1998)341-347
[18]Stibil J V, Dermel J M, Byrne A R, Determination of trace amounts of selenium in poultry feedstuffs by gas-chromatography, Journal of chromatography A, 1994, 668 (2): 449-453
[19]Gomez-Ariza J L, Pozas J A, Giraldez I, et al. Comparison of three derivationzation reagents for the analysis of Se(Ⅳ) based on piazselenol formation and gas chromatography-mass spectrometry, Talanta, 1999, 49:285-292
[20]蔡乾涛，施文赵．二溴代苤硒脑的萃取及痕量硒的极谱法测定．华中理工大学学报，1989，17(1)：125-131
[21]Trivedi B V, Thakkar N V. Determination of Se(Ⅳ) and Te(Ⅳ) by differential pulse polarography. Talanta, 1989, 36(7): 786-788
[22]蔡乾涛，毛新华，施文赵．二溴代苤硒脑体系吸附溶出伏安法测定痕量硒．分析实验室，1990，9(6)：49-57
[23]蔡乾涛，施文赵．二溴代苤硒脑极谱吸附波的研究及应用．高等学校化学学报，1988，9(3)：287-289
[24]Ekmekci G, Somer G. A new selenite selective membrane electrode and its application, Talanta, 1999, 49(1): 83-89
[25]Ekmekci G, Somer G. Selenite-selective membrane electrodes based on ion exchangers and application to anodic slime, Analytical sciences, 2000,16 (3):307-311
[26]Edin M, Grivas S. On the preparation of 1,2,5-selenadiazolo[3,4-e]indole and its [3,4-f] and [3,4-g] isomers through the Batcho-Leimgruber indole synthesis, Arkivoc, 2001,2:1036-1042 Part Ⅰ
[27]Grivas S. 2,1,3-benzoselenadiazoles as valuable synthetic intermediates, Currentc organic chemistry, 2000, 4(7): 707-726
[28] Grivas S, Tian W. Convenient synthesis of 4-methoxy-3-nitro-1,2- benzenedianmine and its conversion into 6-methoxy-5-nitorquinoxalines, Acta chemica scandinavica, 1992, 46(11):1109-1113
[29] Kaim W, Mono-nuclear and bi-nuclear pentacarbobyl complexes of chromium, molybdenum and tungsten with the anion radicals of 2,1,3-benzoxadiazole, 2,1,3-benzothiadia-zole and 2,1,3-benzoselenadiazole, Journal of organometallic chemistry, 1984, 264 (3): 317-326
[30] Harris M C J , Hill A F, Synthesis of 1,3-dienyl complexes of Ruthenium(Ⅱ) by facile hydroruthenation dehydration of propargylic alcohols, Journal of organometallic chemistry, 1992, 438(1-2): 209-212
[31] Heraberhold M, Hill A.F., The coordination chemistry of 2,1,3-benzothiadia-zole and 2,1,3-benzoselenadiazole- complexes of ruthenium, osmium and iridium, Journal of organometallic chemistry, 1989, 377(1): 151-156
[32] Kumari S, Sharma K S, Singh S P, Condensed heterocyclics 2,3-subsititution-reactions of 4-bromo-6-methyl-2,1,3-benzoselenadiazole, Indian journal of chemistry section B-organic chemistry including medicinal chemistry, 1990, 29 (8): 781-783
[33] Gomes A C, Biswas G, Banerjee A, et al. Structure of a planar organic-compound-2,1,3-benzoselenadiazole (piaselenole), Acta crystallographica section C-crystal structure communications, 1989, 45: 73-75
[34] Yang R Q, Tian R Y, Hou Q, Synthesis and optical and electroluminescent properties ofnovel conjugated copolymers derived from fluorene and benzoselenadiazole, Macromolecules, 2003, 36:7453-7460
[35] Fukushina T, Okazeri N, Miyashi T. First stable tetracyanodiphenoquinodimethane with a completely planar geometry: preparation, X-ray structure, and highly conductive complexes of bis[1,2,5]thiad iazolo-TCNDQ, Tetrahedron letters, 1999,40:1175-1178
[36] Yamashita Y, Ono K, Tomura M, et al. Synthesis and properties of benzobis(thiadiazole)s with nonclassical π-electron ring systems, Tetrahedron, 1997, 53:10169-10178
[37] Siddiqi S A, Aslam A, Naseem S. Study of selenium doped Bi-based superconductors by AES and SEM, Modern physics letters B, 2001, 15:973-980
[38] Ei-azhary A A, Kahtani A A, Force field scale factors of effective core potential basis sets of
some selenium and tellurium heterocylic molecules, selenophene, 1,2,5-selenadiazole, tellurophene and, 1,2,5-telluradiazole, Journal of molecular structure(theochem), 2001.572: 81-87
[39] Ei-azhary A A, Vibrational analysis of the spectra of 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,2,5-oxadiazole and 1,2,5-thiadiazole comparison between DFT, MP2 and HF force fields, Spectrochimcca acta (part A), 1996,(52): 33-44
[40] Kwiatkowski J S, Leszczynski J, Teca I, Molecular structure and infrared spectra of furan, thiophene, selenophene and their 1,2-N and 3,4-N derivatives: density functional theory and converntional post-Hartree-Fock MP2 studies, Journal of molecular structure, 1997, 436-437: 451-480
[41] 周益明，忻新泉．低热固相合成化学，无机化学学报，1999，15(3)：273-292
[42] 卢毅，邱咏梅，林辉，纲合化学中的绿色同相合成研究概况，海峡药学，2002，14(5)：1-5
[43] 刘海林，马晓燕，袁莉，黄韵．分子自组装研究进展，材料科学与工程学报，2004，22(2)：308-311
[44] 张祺，黄惠忠，何惠新等．角分辨XPS对自组装单分子层厚度和官能团位置的定性及定量研究．化学物理学报，1997，10(3)201～204
[45] 董献堆，陆君涛，查全性．巯基化合物自组装单分子层的研究进展．电化学，1995，1(3)：248～258
[46] Dishner M H, Hemminger J C, Feher F J. Scanning tunneling microscopy characterization of organselenium monolayers on Au(111), Langmuir, 1997, 13:4788～4790
[47] Nakano K, Sato T, Tazaki M, et al. Self-assembled monolayer formation from decanesenol on polycrystalline gold as characterized by electrochemical measurements, quartz-crystal microbalance, XPS, and IR spectroscopy, Langmiur, 2000,16:2225～2229
[48] Huang F K, Horton R C J, Myles D C, et al. Selenolates as alternative to thiolates for self-assembled monolayers: A SERS study, Langmiur, 1998, 14:4802～4808
[49] Bandyopadhyay K, Vijayamohanan K. Formation of a self-assembled monolayer of diphenyl diselenide on polycrystalline gold, Langmiur, 1998, 14:625～629
[50] 郑文杰，曾鑫华，白燕，杨芳，欧阳健明．硒杂环化合物(4，52苯并苤硒脑)在金表面上
的自组装，物理化学学报，2002，15(6)：461-464
[51]徐静娟，汪云，方惠群，陈洪渊．多巴胺在硫堇衍生化自组装膜修饰金电极上的伏安行为及其安培测定，分析化学，1998，26(4)：428-430
[52]张修华，王升富．2-巯基乙醇自组装膜电极对多巴胺电催化氧化及其分析应用，分析化学，2002，28(11)：1312-1315
[53]Kondo, Toshihir O, Kana. Effects of alkyl chain length on the efficiency of photoinduced electron transfer at gold electrodes modified with SAMs of molecules containing porphyrin, ferrocene, and thiol separated each other by alkyl chains, Phys Chem (muenchen), 1999, 212 (1): 23-30
[54]王俊，曾百肇，周性尧．自组装膜技术在电分析化学中的应用．分析科学学报，2000，16(3)：253～258
[55]韦天新，翟锦，葛俊豪，甘良兵，黄春辉．两种C60吡咯环多羧基衍生物自组装膜的制备及其光电转换性质研究，高等学校化学学报，1999，20(10)：1515-1519
[56]李添宝，李新海，黄克雄，蒋汉瀛，李晶，蔡志光．乙二胺改性的玻璃基片上C_(60)自组装薄膜的制备及其光致发光，高等学校化学学报，1999，20(5)：680～683
[57]Haussling L, Knoll W, Ringsdorf H, et al. Makromol Chem Macromol Symp, 1991, 46:145.
[58]Harrison D J, Fluri K, Chiem N, et al. Micromachining chemical and biochemical analysis and reaction systems on glass substrates, Sensors and Actuators B Chemical, 1996, 33: 105-109
[59]Schierbaum K D, Weiss T, Thoden van Velzen E U. Science, 1994,265: 1413.
[60]曾鑫华，若干硒芳香杂环化合物的谱学、电化学和自组装，硕士毕业论文，暨南大学，2003．6
[61]Merrifield R B. Journal of American chernistry society, 1963, 85:2159
[62]Alvert C, Eugene S, Francis E R. 8-Selenapurine, Journal of organic chemistry, 1958,23:1940-1942
[63]郑文杰，曾鑫华，杨芳，白燕，贺鸿志，欧阳健明．硒芳香杂环化合物的光谱和电化学性质，分析科学学报，2003，19(1)：36
[64]刘清福，张冬亭，王秀玲.，次黄嘌呤和黄嘌呤与卤化镍配合物的IR光谱特征，光谱实验室，2003，20(6)：845-847
[65] Brown N M D, Peter B. Synthesis and spectroscopy of 1,2,5-selenadiazolo-[3,4-b]-pyridine and 1,2,5-selenadiazolo-[3,4-c]-pyridine, Tetrahedron, 1968, 24:6577-6582
[66] Pretsch E, Buhlmanm P著，荣国斌译．波谱数据表——有机化合物的结构解析(Structure determination of organic compounds tables of spectral data),上海：华东理工大学出版社，2002.9