新型多吡啶功能配合物的微波合成、表征及与DNA作用的光谱研究
|
摘要
本文简要介绍了微波辐射作用机理和特点，以及微波辐射技术在有机和无机合成中的应用，并对近年来多吡啶配合物的电化学与光谱性质的研究，和多吡啶配合物与DNA的键合模式及其影响因素作了简要评述，还介绍了紫外光谱、荧光光谱、核磁共振谱及电化学测定等一些常用的研究配合物和DNA作用机制的实验方法。
通过微波辐射加热方式，快速合成了[Co(H_2bzimpy)_2](ClO_4)_2{H_2bzimpy=2，6-bis(benzimidazol-2-yl)pyridine，2，6-二(苯并咪唑-2)吡啶}和[Co(5-NO_2-phen)_2dppz](ClO_4)_3{5-NO_2-phen=5-Nitro-1，10-phenanthroline，5-硝基-1，10-菲咯啉；dppz=dipyrido[3，2-a；2，3-c]phenazine，二吡啶吩嗪}两种新型多吡啶钴功能配合物，利用循环伏安法和微分脉冲伏安法等电化学方法测定了配合物的电化学行为，并用紫外可见和荧光光谱法研究了配合物的谱学性质。络果表明，配合物[Co(H_2bzimpy)_2](ClO_4)_2的中心离子由+3价还原为+2价的半波电位为E_(1/2)=0.601V(vs SCE)，对应的电极反应为准可逆过程，由+2价还原为+1价的半波电位为E_(1/2)=-0.908V(vs SCE)，对应的电极反应为可逆过程，此外，配合物在-1.593V和-1.978V有两个明显的不可逆还原峰，对应的电极反应可能是配体H_2bzimpy的还原反应；配合物[Co(H_2bzimpy)_2](ClO_4)_2在乙腈溶液中于308nm和345nm处有两个吸收峰，而在N-N-二甲基甲酰胺(DMF)溶液中只有334nm处一个吸收峰；配合物在乙腈溶液中能产生荧光，其最大发射波长为443nm。
配合物[Co(5-NO_2-phen)_2dppz](ClO_4)_3的中心离子由+3价还原为+2价的半波电位为E_(1/2)=0.567V(vs SCE)，对应的电极反应为准可逆过程，此外，配合物在-0.551V有一个不可逆还原峰，对应的电极反应可能是+2价离子被还原为0价金属；配合物在甲醇溶液中于232，271，341，357，375nm(logε4.77，4.83，3.94，3.90，3.86)处有五个吸收峰；并在甲醇溶液中能产生荧光，其最大发射波长分别为476nm和538nm。
采用紫外光谱法和荧光光谱法考察了这两种新型多吡啶钴配合物[Co(5-NO_2-phen)_2dppz](ClO_4)_3和[Co(H_2bzimpy)_2](ClO_4)_2与DNA的相互作用。研究发现，两种配合物与DNA作用时吸收强度都减小，
且吸收峰红移，表明两种配合物都能以插入方式与DNA结合。
In this paper, the mechanism and properties of microwave irradiation and its applications in both organic and inorganic synthesizing field were introduced. Studies on the electrochemical and spectral characteristics of polypyridly complexes, binding-modes of polypyridly complexes binding to DNA and factors affecting the binding of complexes to DNA are reviewed. Experimental methods for
studying mechanisms of complexes binding to DNA are introduced, including UV, Fluorescence, NMR and Electrochemistry.
Two novel functional polypyridly cobalt complexes of [Co(H2bzimpy)2](ClO4)2 ( H2bzimpy = 2,6-bis(benzimidazol-2-yl) pyridine) and [Co(5-NO2-phen)2dppz](ClO4)3 (5-NO2-phen = 5-Nitro-1.10-phenanthroline, dppz = dipyrido[3,2-a;2 , 3 -cjphenazine) was synthesized by microwave irradiation method. The electrochemical behaviors of the complexes have been investigated by cyclic voltammetry and differential pulse voltammetry techniques, and the
electronic absorption spectroscopy and fluorescence spectroscopy of
the complexes were determined at room temperatu e.
The cyclic voltammpgram of the complex [Co(H2bzimpy)2]2+ have shown a quasi-reversible Co(III)/ Co(II) redox couple at 0.601V vs SCE and a reversible Co(II)/Co( I ) redox couple at -0.908V vs SCE. In addition, the complex [Co(H2bzimpy)2]2+ displayed two irreversible reduction waves for its H_(2)bzimpy ligands at -1.593V and -1.978V, respectively. The two maxima of adsorption of the complex in acetonitrile occur respectively at 308nm and 345nm, and that of adsorption of it in DMF does at 334nm. That of emission of the complex in acetonitrile occurs at 443nm.
The cyclic voltammogram of the complex [Co(5-NO2-phen)2 dppz]3+ have shown a quasi-reversible Co(III)/Co( II) redox couple at 0.567V vs SCE, and a irreversible Co(II)/Co(0) reduction reaction at -0.551V vs SCE. The five maxima of adsorption of the complex in
CH3OH occur respectively at 232, 271, 341, 357nm and 375nm, and those of emission of the complex in CHsOH occur at 476nm and 538nm, respectively.
The interaction of the complexes [Co(H2bzimpy)2](CIO_(4))2 and [Co(5-NO2-phen)2dppz](ClO4)_(3) with DNA have been studied by absorption spectra and fluorescence spectra. The results indicate that both of the new polypyridly cobalt complexes interact with DNA by intercalative binding.
通过微波辐射加热方式，快速合成了[Co(H_2bzimpy)_2](ClO_4)_2{H_2bzimpy=2，6-bis(benzimidazol-2-yl)pyridine，2，6-二(苯并咪唑-2)吡啶}和[Co(5-NO_2-phen)_2dppz](ClO_4)_3{5-NO_2-phen=5-Nitro-1，10-phenanthroline，5-硝基-1，10-菲咯啉；dppz=dipyrido[3，2-a；2，3-c]phenazine，二吡啶吩嗪}两种新型多吡啶钴功能配合物，利用循环伏安法和微分脉冲伏安法等电化学方法测定了配合物的电化学行为，并用紫外可见和荧光光谱法研究了配合物的谱学性质。络果表明，配合物[Co(H_2bzimpy)_2](ClO_4)_2的中心离子由+3价还原为+2价的半波电位为E_(1/2)=0.601V(vs SCE)，对应的电极反应为准可逆过程，由+2价还原为+1价的半波电位为E_(1/2)=-0.908V(vs SCE)，对应的电极反应为可逆过程，此外，配合物在-1.593V和-1.978V有两个明显的不可逆还原峰，对应的电极反应可能是配体H_2bzimpy的还原反应；配合物[Co(H_2bzimpy)_2](ClO_4)_2在乙腈溶液中于308nm和345nm处有两个吸收峰，而在N-N-二甲基甲酰胺(DMF)溶液中只有334nm处一个吸收峰；配合物在乙腈溶液中能产生荧光，其最大发射波长为443nm。
配合物[Co(5-NO_2-phen)_2dppz](ClO_4)_3的中心离子由+3价还原为+2价的半波电位为E_(1/2)=0.567V(vs SCE)，对应的电极反应为准可逆过程，此外，配合物在-0.551V有一个不可逆还原峰，对应的电极反应可能是+2价离子被还原为0价金属；配合物在甲醇溶液中于232，271，341，357，375nm(logε4.77，4.83，3.94，3.90，3.86)处有五个吸收峰；并在甲醇溶液中能产生荧光，其最大发射波长分别为476nm和538nm。
采用紫外光谱法和荧光光谱法考察了这两种新型多吡啶钴配合物[Co(5-NO_2-phen)_2dppz](ClO_4)_3和[Co(H_2bzimpy)_2](ClO_4)_2与DNA的相互作用。研究发现，两种配合物与DNA作用时吸收强度都减小，
且吸收峰红移，表明两种配合物都能以插入方式与DNA结合。
In this paper, the mechanism and properties of microwave irradiation and its applications in both organic and inorganic synthesizing field were introduced. Studies on the electrochemical and spectral characteristics of polypyridly complexes, binding-modes of polypyridly complexes binding to DNA and factors affecting the binding of complexes to DNA are reviewed. Experimental methods for
studying mechanisms of complexes binding to DNA are introduced, including UV, Fluorescence, NMR and Electrochemistry.
Two novel functional polypyridly cobalt complexes of [Co(H2bzimpy)2](ClO4)2 ( H2bzimpy = 2,6-bis(benzimidazol-2-yl) pyridine) and [Co(5-NO2-phen)2dppz](ClO4)3 (5-NO2-phen = 5-Nitro-1.10-phenanthroline, dppz = dipyrido[3,2-a;2 , 3 -cjphenazine) was synthesized by microwave irradiation method. The electrochemical behaviors of the complexes have been investigated by cyclic voltammetry and differential pulse voltammetry techniques, and the
electronic absorption spectroscopy and fluorescence spectroscopy of
the complexes were determined at room temperatu e.
The cyclic voltammpgram of the complex [Co(H2bzimpy)2]2+ have shown a quasi-reversible Co(III)/ Co(II) redox couple at 0.601V vs SCE and a reversible Co(II)/Co( I ) redox couple at -0.908V vs SCE. In addition, the complex [Co(H2bzimpy)2]2+ displayed two irreversible reduction waves for its H_(2)bzimpy ligands at -1.593V and -1.978V, respectively. The two maxima of adsorption of the complex in acetonitrile occur respectively at 308nm and 345nm, and that of adsorption of it in DMF does at 334nm. That of emission of the complex in acetonitrile occurs at 443nm.
The cyclic voltammogram of the complex [Co(5-NO2-phen)2 dppz]3+ have shown a quasi-reversible Co(III)/Co( II) redox couple at 0.567V vs SCE, and a irreversible Co(II)/Co(0) reduction reaction at -0.551V vs SCE. The five maxima of adsorption of the complex in
CH3OH occur respectively at 232, 271, 341, 357nm and 375nm, and those of emission of the complex in CHsOH occur at 476nm and 538nm, respectively.
The interaction of the complexes [Co(H2bzimpy)2](CIO_(4))2 and [Co(5-NO2-phen)2dppz](ClO4)_(3) with DNA have been studied by absorption spectra and fluorescence spectra. The results indicate that both of the new polypyridly cobalt complexes interact with DNA by intercalative binding.
引文
[1]Gedye R.N., Smith F.E., Westaway K.C., et al. The use of microwave ovens for rapid organic synthesis. Tetrahedron Lett., 1986, 27(3): 279.
[2]徐勇，陈克巧，国内微波化学应用研究现状及进展，上海化工，1998，23(2)：56．
[3]金钦汉，戴树珊，黄卡玛等编，《微波化学》，科学出版社(北京)，1999：118．
[4]Bose A.K., Manhas M., Gosh M., et al. Microwave-induced organic reaction enhancement chemistry. 2. Simplified techniques, J. Org. Chem.,1991, 56(25): 6968.
[5]丁金昌，杨建鸿，傅敏，微波辐射下巴比妥的N-烃基化反应，合成化学，1997，5(3)：309．
[6]Chen S., Chiou S., Wang K., Improvement of microwave oven used for reflux chemical reaction, J. Chem. Soc. Chem. Commun., 1990: 807.
[7]Cablewski T., Faux A.F., Stauss C.R., Development and Application of a Continuous Microwave Reactor for Organic Synthesis, J. Org. Chem.,1994, 59(12): 3408.
[8]张迈生，李莉，杨燕生等，MCM-41中孔分子筛的全微波辐射快速合成，中山大学学报(自然科学版)，1998，37(2)：128．
[9]戴德昌，李沅英，蔡少华等，(CeO．67TbO．33)MgA111019和BaMgA110017：Eu2~+荧光体的微波辐射合成及其发光性能，中国稀土学报，1998，16(3)：284．
[10]贾殿赠，杨立新，夏熙等，微波技术在固相配位化学反应中的应用研究(Ⅰ)--Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)配合物在微波条件下的固相合成，高等学校化学学报，1997，18(9)：1432．
[11]曹左英，赖声礼，微波辐射下壳聚糖Zn(Ⅱ)配合物的合成，现代化工，1999，19(11)：24．
[12]Xiao Xiaoming, Jun Sakamoto, Masahiro Tanabe, et al.
Microwave synthesis and electrospectrochemical study on ruthenium(Ⅱ) polypyridine complexes, J. Electroanal. Chem., 2002, 527(1): 33.
[13]Donald P. Segers, M. Keith DeArmond, Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 2. Tris complexes of ruthenium(Ⅱ), J. Phys. Chem., 1982, 86(19): 3768.
[14]樊兴君，尤进茂，谭干祖等，微波促进有机化学反应研究进展，化学讲展，1998，10(3)：285．
[15]E.G.E. Jahngen, Ronald R. Lentz, Peter S. Pesheck, et al, Hydrolysis of adenosine triphosphate by conventional or microwave heating, J. Org. Chem., 1990, 55(10):3406.
[16]胡希明，赖声礼，张华莲等，微波诱导快速磷酸锌合成研究，化学通报，1998，12：33．
[17]Stephen D.P., Gary B., Richard B., et al, The influence of microwaves on the rate of reaction of propan-1-ol with ethanoic acid, J. Org. Chem., 1991, 56(3): 1313.
[18]Wei C.S., Pamela M. G., Jessica H. J., et al, Microwave-induced hydrolysis of phospho anhydride bonds in nucleotide triphosphates, J. Org. Chem., 1988, 53(18):4414.
[19]Juris A., Balzani V., Barigelletti F., et al., Ru(Ⅱ) polypyridine complexes: photophysics, photochemistry, and electrochemistry, and chemiluminescence. Coord. Chem. Rev.,1988,84:85.
[20]De Silva A.P., Gunaratne H. Q.N.,Gunnlaudasson T., et al., Signaling recognition event switch fluorescent sensor and switches, Chem. Rev., 1997,97:151.
[21]Balzani V., Juris A., Venturi M., et al., Luminesent and redox-Active polynuclear transition metal complexes, Chem. Rev., 1996,96:759.
[22]刘劲刚，计亮年，多吡啶钌配合物作为DNA结构探针的研究，无机化学学报，2000，16(2)：195．
[23]敬炳文，吴韬，张曼华等，功能性多吡啶配体的合成，高等学校化学学报，2000，21(3)：395．
[24]Haga M., Ali M.M., Koseki S., et al., Proton-Induced Tuning of Electrochemical and Photophysical Properties in Mononuclear and Dinuclear Ruthenium Complexes Containing 2,2'-Bis(benzimidazol-2-yl)-4,4'-bipyridine: Synthesis, Molecular Structure, and Mixed-Valence State and Excited-State Properties, Inorg. Chem.,1996, 35(11):3335.
[25]Otsuki J., Tsujino M., Iizaki T., et al., Redox-Responsive Molecular Switch for Intramolecular Energy Transfer, J. Am. Chem. Soc.,1997,119(33):7895.
[26]Cola L.D., Belser P., Photoinduced energy and electron transfer processes in rigidly bridged dinuclear Ru/Os complexes, Coord. Chem. Rev. 1998,177: 301.
[27]宋宇飞，杨频，韩广业，四吡啶[3，2-a：2＇，3＇-c：3”，2”-h：2”~*，3”~*-j]吩嗪的钴、镍双核配合物的合成、表征及光谱学性质研究，无机化学学报，2001 ，17(1)：89．
[28]李红，巢晖，计亮年等，双核钌配合物中金属间相互作用的电化学研究，电化学，2001，7(2)：167．
[29]E.J. Corey, Nobuyuki Imai, Zhang Hong-Yue, Designed catalyst for enantioselective Diels-Alder addition from a C2-symmetric chiral bis(oxazoline)-iron(Ⅲ) complex, J. Am. Chem. Soc.,1991,113(2):728.
[30]肖小明，熊士荣，曾跃等，2，6-二(苯并咪唑-2)吡啶钌配合物的~(13)C-NMR与电子转移作用，化学物理学报，1998，11(2)：134．
[31]计亮年，张黔玲，巢晖，多吡啶配合物在大分子DNA中的功能及其应用前景，科学通报，2001，46(6) 451．
[32]Pyle A.M., Barton J.K., Probing nucleic acids with transition metal complexes, Prog. Inorg. Chem., 1990,38: 413.
[33]吴建中，陈胜，计亮年，咪唑并邻菲咯啉类配体的钌配合物的光谱研究，分析测试学报，1999，18(2)：17．
[34]Barton J. K., Dannenberg J. J., Raphael A. L., Enantiomeric selectivity in binding tris(phenanthroline)zinc(Ⅱ) to DNA, J. Am. Chem. Soc., 1982,104: 4967.
[35]Fleisher M. B., et al, Light-induced cleavage of DNA by metal complexes, Inorg. Chem., 1986, 25: 3549.
[36]Barton J.K., Danishefsky A.T., Goldberg J.M. Tris (phenanthroline) ruthenium(Ⅱ): Stereoselectivity in binding to DNA, J. Am. Chem. Soc., 1984,106: 2172.
[37]Hiort C., Lincoln P., Norden B. DNA-binding of △- and ∧-[Ru(phen)_2DPPZ]~(2+), J. Am. Chem. Soc., 1993, 115: 3448.
[38]Holmlin R.E.,Stemp E.D.A.,Barton J.K.,[Ru(phen)_2DPPZ]~(2+) luminescence: dependence on DNA sequences and groove-binding agents, Inorg. Chem.,1998,37:29.
[39]Jin Lan, Yang Pin, Synthesis and DNA binding studies of Co~(Ⅲ) mixed-ligand complex containing dipyrido[3,2-a;2',3'-c]phenazine and phen, Polyhedron, 1997,16:3395.
[40]Frederick C. A., et al., Structural comparison of anticancer drug-DNA complexes : adriamycin and daunomycin, Biochemistry, 1990,29:2538.
[41]宋宇飞，杨频，对DNA具有识别和断裂功能的金属插入剂的研究，化学进展，2001，13(9)：368．
[42]Jacquet L., et al. photoaddition of Ru(tap)_2(bpy)~2+ to DNA : a new mode of covalent attachment of metal complexes to duplex DNA, J. Am. Chem. Soc., 1997,119: 11763.
[43]Fitzsimons M.P., Barton J. K.. Design of a synthetic nuclease: DNA hydrolysis by a zinc-binding peptide tethered to arhodium intercalator. J. Am. Chem. Soc., 1997,119:3379.
[44]Eriksson M., Leijion M., Norden B., et al.. Minor groove binding of [Ru(phen)_3]~(2+) to d(GCGATCGCG)_2 evidenced by two-dimensional nuclear magnetic resonance spectroscopy. J. Am. Chem. Soc. 1992,114: 4933.
[45]Wang L.,Zhou J.Y., Ji L.N. et al.. Ruthenium coordination compounds with polypyridine: Ⅲ. Stereoselectivity of tris(phenanthroline) ruthenium binding in DNA, Chinese Chemical Letters, 1995,6: 883.
[46]Sitlani A., Long E. C., Pyle A. M. et al.. DNA photocleavage by phenanthrenequinone diimine complexes of rhodium (Ⅲ): shape-selective recognition and reaction. J. Am. Chem. Soc.,1992, 114: 2303.
[47]甄启雄，叶保辉，计亮年等，钌多吡啶配合物的合成及插入配体的位阻效应对键合DNA的影响，高等学校化学学报，1999，20(11)：1661．
[48]Pyle A.M, Rehmann J.P., Meshoyrer R., et al., Mixed-ligand complexes of ruthenium (Ⅱ): factors governing binding to DNA, J. Am. Chem. Soc.,1989,111:3051.
[49]Pang D.W., Abruna H. D., Micromethod for the investigation of the interaction between DNA and redox-active molecules. Anal. Chem.,1998,70: 3162.
[50]He X. F., Wang L., Ji L. N., et al., Synthesis, characterization and DNA binding study of polypyridyl mixed-ligand complexes, Polyhedron, 1998, 17: 3161.
[51]宋玉民，康敬万，高锦章，钴(Ⅲ)配合物DNA作用的研究．无机化学学报．2000，16(1)：53．
[52]Rehmann J. P., Barton J. K., Proton NMR studies of tris (phenanthroline) metal complexes bound to oligonucleotides: characterization of binding modes, Biochemistry, 1990, 29, 1701.
[53]Dupureur C. M., Barton J. K., Structural studies of △-and ∧ - [Ru(phen)_2dppz]~2+ bound to d(GTCGAC)_2: Characerization of enantioselective intercalation, Inorg. Chem., 1997,36: 33.
[54]Carter M. T., Bard A. J., Voltammetric syudies of the interaction of tris(1, 10-phenanthroline) cobalt (Ⅲ) with
DNA,J.AM. Chem.Soc., 1989,109, 7528.
[55]刘劲刚，叶保辉，计亮年等， △-和∧-[Ru(bpy)_2(HPIP)]~2+ 两种异构体对小牛胸腺DNA不同键合速率的CD光谱证明，高等学校化学学报，1999，20(4)：523．
[56]Zou Xiaohua, Ye Baohui, Ji Liangnian, et al., Mono-and binuclear ruthenium(Ⅱ)complexes containing a new asymmetric ligand 3-(pyrazin-2-yl)-as-triazino[5,6-f] 1,10-phenanthroline: systhesis characterization and DNA-bindingproperties, J. Chem. Soc., Dalton Trans., 1999, 1423.
[57]易平贵，商志才，俞庆森，微量热法研究[Cu(phen)_2]~2+、[Cu(bpy)_2]~2+与DNA的作用，无机化学学报，2001，17(1)：77．
[58]Anthony W. Addison, et al, New Iron(Ⅱ) spin-crossover complexes with heterocyclic amine-derived Ligand and STEPS xxperiments on photogenerated metastable high-spin states J. Chem. Soc. Dalton Trans. 1987: 2621.
[59]Xiao Xiaoming, Masa-aski Haga, Takeko M., et al. , Synthesis and proton transfer-linked redox tuning of ruthenium(Ⅱ) complexes with tridentate 2,6-his (benzimidazol-2-yl)pyridine ligands, J. chem. Soc. Dalton Trans. 1993: 2477.
[60]肖小明，芳贺正明，松村竹子，2，6-二(苯并咪唑-2)吡啶及其钌配合物的~1H-NMR研究，高等学校化学学报，1991，12(12)：1672．
[61]Whiter A., Mingos D. P., The application of microwave heating to chemical syntheses, J. of Microwave Power and Electomagnetic Entery, 1994, 29 (4): 195.
[62]肖小明，熊士荣，混合钌配合物[Ru(bpy)_n(Hdpa)_(3-n)]~2+中中心离子与配体之间的相互作用，湖南师范大学自然科学学报，1998，21：53．
[63]Jerry F.O' Donnell, James T. A., Charles K.M., Preparation of high purity acetonitrile, Anal. Chem., 1965, 37:1161.
[64]Anthony W. Addison, Philip J. Burke, Synthesis of some imidazol-and pyrazol-derived chelating agents, J. Heterocycl. Chem., 1981, 18: 803.
[65]Takeko Matsumra-Inoue, Masahiro T. Takayoshi M. et al., Remarkably rapid synthesis of ruthenium(Ⅱ) polypyridine complexes by microwave irradiation, Chem. Letters., 1994,2443.
[66]毕先均，谢小光，王真等，微波加热技术在有机合成和材料制备等方面的应用进展，云南化工，1998，2：7．
[67]黄卡玛，唐敬贤，电磁波对化学反应作用的动力学原理，微波学报，1994(增刊)：51．
[68]Bard A.J., Faulkner L. R., Electrochemicai Methods, Wiley, New York, 1980:194.
[69]师同顺，张旭光，柳魏等，四(α-萘基)四苯并卟啉钴配合物的光谱电化学性质，高等学校化学学报，1998，19(7)：1026．
[70]Olson E. J. C., Hu D., Barton J. K., et al., (?)-ation of the Key Intermediate in the "Light -Switch" Mechanism of [Ru(phen)_2dppz]~2+ J. Am. Chem. Soc., 1997, 119(47): 11458.
[71]Friedman A.E., Chambron J.C., Sauvage J.P., et al., Molecular "light switch" for DNA: Ru(bpy)_2(dppz)~2+, J. Am. Chem. Soc., 1990, 112: 4960.
[72]L.P. Hammett, G.H. Walden, S.M. Edmonds, New indicators for oxidimetry : some phenanthroline and diphenylamine derivatives, J, Am. Chem. Soc. 1934, 56: 1093.
[73]J.E. Dickeson, L.A. Summers, Derivatives of 1.10-phen-anthroline-5,6-quinone, Aust. J. Chem., 1970, 23: 1023.
[74]Amouyal E., Homsi A., Sauvage J.P., Synthesis and study of a mixed-ligand ruthenium(Ⅱ) complex in its ground and excited states: bis(2,2-bipyridine)(dipyrido[3,2-a;2',3'-c]phenazine-N~4N~5)ruthenium(Ⅱ),J. Chem. Soc. Dalton Trans., 1990:1841.
[75]Grassini-Strazza G.,Isola S., Thin-layer chromatrographic detection of some impurities in cobalt(Ⅲ) complexes J. Chromatogr., 1978,154: 127.
[76]R.D. Gillard, R.E.E. Hill, R. Maskill, Optically active co-ordination compounds. Part XX. Reactions of 1.10-phen-anthroline co-ordination to cobalt(Ⅲ),J. Chem. Soc. (A), 1970: 1447.
[77]George E. Inglett, G. Frederick Smith, The formation of a new nitrogen heterocyclic ring system by the loss of carbon monoxide from 1.10-phenanthroline-5,6-quinone, 1950,72: 842.
[78]Thomas W. Welch, Amanda H. C., H.H. Thorp, Electrochemical determination of nucleic acid diffusion coefficients through noncovalent association of a redox-active probe, J. Phys. Chem., 1995, 99: 11757.
[79]David S. Sigman, Abhijit M., David M. Perrin, Chemical nucleases, Chem. Rev., 1993, 93: 2295.
[80]杨频，宋宇飞，金属配合物键合DNA的研究进展，化学进展，2000，12(1)：32．
[81]Holmlin R.E., Dandliker P.J.,Barton J.K., Charge transfer through the DNA base stack, Angew. Chem. Int. Ed. Eng., 1997, 36: 2714.
[82]Burrows C.J., Muller J.G., Oxidative nucleobase modifications leading to strand scission, Chem. Rev., 1998,98:1109.
[83]Barton J. K., Paranawithana S. R., Restriction endonuclease EcoRI alters the enantiomeric preference of chiral metallointercalators for DNA: an illustration of a proteininduced DNA conformational change Biochemistry, 1986, 25(8): 2205.
[84]Barton J. K., Adrienne L. Raphael, Photoactivated stereo-specific cleavage of double-helical DNA by cobalt(Ⅲ)
complexes, J. Am. Chem. Soc., 1984, 106(8): 2466.
[85]Carter M. T., Rodriguez M., Bard A. J., Voltammetric studies of the interaction of metal chelates with DNA. 2: Tris-chelated complexes of cobalt(Ⅲ) and iron(Ⅱ) with 1, 10-phenanthroline and 2,2 -bipyridine. J. AM. Chem. Soc., 1989, 111, 8901.
[86]Reichmann M. E., Rice S. A., Thomas C. A., et al., A Further Examination of the Molecular Weight and Size of Desoxypentose Nucleic Acid, J. Am. Chem. Soc., 1954, 76(11) : 3047.
[87]Steven A. Tysoe, Robert J. Morgan, A. David Baker, et al., Spectroscopic investigation of differential binding modes of. DELTA. - and. LAMBDA. -Ru (bpy) 2 (ppz) 2+ with calf thymus DNA, J. Phys. Chem., 1993,97(8): 1707.
[88]Holmlin R. E., Barton J. K., [Os(phen)_2 (dppz) ]~2+: A Red-Emitting DNA Probe, Inorg. Chem., 1995, 34(1): 7.
[89]吴建中，王雷，杨光等，钌多吡啶配合物的合成及结合DNA的研究，高等学校化学学报，1996，17(7)：1010．
[2]徐勇，陈克巧，国内微波化学应用研究现状及进展，上海化工，1998，23(2)：56．
[3]金钦汉，戴树珊，黄卡玛等编，《微波化学》，科学出版社(北京)，1999：118．
[4]Bose A.K., Manhas M., Gosh M., et al. Microwave-induced organic reaction enhancement chemistry. 2. Simplified techniques, J. Org. Chem.,1991, 56(25): 6968.
[5]丁金昌，杨建鸿，傅敏，微波辐射下巴比妥的N-烃基化反应，合成化学，1997，5(3)：309．
[6]Chen S., Chiou S., Wang K., Improvement of microwave oven used for reflux chemical reaction, J. Chem. Soc. Chem. Commun., 1990: 807.
[7]Cablewski T., Faux A.F., Stauss C.R., Development and Application of a Continuous Microwave Reactor for Organic Synthesis, J. Org. Chem.,1994, 59(12): 3408.
[8]张迈生，李莉，杨燕生等，MCM-41中孔分子筛的全微波辐射快速合成，中山大学学报(自然科学版)，1998，37(2)：128．
[9]戴德昌，李沅英，蔡少华等，(CeO．67TbO．33)MgA111019和BaMgA110017：Eu2~+荧光体的微波辐射合成及其发光性能，中国稀土学报，1998，16(3)：284．
[10]贾殿赠，杨立新，夏熙等，微波技术在固相配位化学反应中的应用研究(Ⅰ)--Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)配合物在微波条件下的固相合成，高等学校化学学报，1997，18(9)：1432．
[11]曹左英，赖声礼，微波辐射下壳聚糖Zn(Ⅱ)配合物的合成，现代化工，1999，19(11)：24．
[12]Xiao Xiaoming, Jun Sakamoto, Masahiro Tanabe, et al.
Microwave synthesis and electrospectrochemical study on ruthenium(Ⅱ) polypyridine complexes, J. Electroanal. Chem., 2002, 527(1): 33.
[13]Donald P. Segers, M. Keith DeArmond, Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 2. Tris complexes of ruthenium(Ⅱ), J. Phys. Chem., 1982, 86(19): 3768.
[14]樊兴君，尤进茂，谭干祖等，微波促进有机化学反应研究进展，化学讲展，1998，10(3)：285．
[15]E.G.E. Jahngen, Ronald R. Lentz, Peter S. Pesheck, et al, Hydrolysis of adenosine triphosphate by conventional or microwave heating, J. Org. Chem., 1990, 55(10):3406.
[16]胡希明，赖声礼，张华莲等，微波诱导快速磷酸锌合成研究，化学通报，1998，12：33．
[17]Stephen D.P., Gary B., Richard B., et al, The influence of microwaves on the rate of reaction of propan-1-ol with ethanoic acid, J. Org. Chem., 1991, 56(3): 1313.
[18]Wei C.S., Pamela M. G., Jessica H. J., et al, Microwave-induced hydrolysis of phospho anhydride bonds in nucleotide triphosphates, J. Org. Chem., 1988, 53(18):4414.
[19]Juris A., Balzani V., Barigelletti F., et al., Ru(Ⅱ) polypyridine complexes: photophysics, photochemistry, and electrochemistry, and chemiluminescence. Coord. Chem. Rev.,1988,84:85.
[20]De Silva A.P., Gunaratne H. Q.N.,Gunnlaudasson T., et al., Signaling recognition event switch fluorescent sensor and switches, Chem. Rev., 1997,97:151.
[21]Balzani V., Juris A., Venturi M., et al., Luminesent and redox-Active polynuclear transition metal complexes, Chem. Rev., 1996,96:759.
[22]刘劲刚，计亮年，多吡啶钌配合物作为DNA结构探针的研究，无机化学学报，2000，16(2)：195．
[23]敬炳文，吴韬，张曼华等，功能性多吡啶配体的合成，高等学校化学学报，2000，21(3)：395．
[24]Haga M., Ali M.M., Koseki S., et al., Proton-Induced Tuning of Electrochemical and Photophysical Properties in Mononuclear and Dinuclear Ruthenium Complexes Containing 2,2'-Bis(benzimidazol-2-yl)-4,4'-bipyridine: Synthesis, Molecular Structure, and Mixed-Valence State and Excited-State Properties, Inorg. Chem.,1996, 35(11):3335.
[25]Otsuki J., Tsujino M., Iizaki T., et al., Redox-Responsive Molecular Switch for Intramolecular Energy Transfer, J. Am. Chem. Soc.,1997,119(33):7895.
[26]Cola L.D., Belser P., Photoinduced energy and electron transfer processes in rigidly bridged dinuclear Ru/Os complexes, Coord. Chem. Rev. 1998,177: 301.
[27]宋宇飞，杨频，韩广业，四吡啶[3，2-a：2＇，3＇-c：3”，2”-h：2”~*，3”~*-j]吩嗪的钴、镍双核配合物的合成、表征及光谱学性质研究，无机化学学报，2001 ，17(1)：89．
[28]李红，巢晖，计亮年等，双核钌配合物中金属间相互作用的电化学研究，电化学，2001，7(2)：167．
[29]E.J. Corey, Nobuyuki Imai, Zhang Hong-Yue, Designed catalyst for enantioselective Diels-Alder addition from a C2-symmetric chiral bis(oxazoline)-iron(Ⅲ) complex, J. Am. Chem. Soc.,1991,113(2):728.
[30]肖小明，熊士荣，曾跃等，2，6-二(苯并咪唑-2)吡啶钌配合物的~(13)C-NMR与电子转移作用，化学物理学报，1998，11(2)：134．
[31]计亮年，张黔玲，巢晖，多吡啶配合物在大分子DNA中的功能及其应用前景，科学通报，2001，46(6) 451．
[32]Pyle A.M., Barton J.K., Probing nucleic acids with transition metal complexes, Prog. Inorg. Chem., 1990,38: 413.
[33]吴建中，陈胜，计亮年，咪唑并邻菲咯啉类配体的钌配合物的光谱研究，分析测试学报，1999，18(2)：17．
[34]Barton J. K., Dannenberg J. J., Raphael A. L., Enantiomeric selectivity in binding tris(phenanthroline)zinc(Ⅱ) to DNA, J. Am. Chem. Soc., 1982,104: 4967.
[35]Fleisher M. B., et al, Light-induced cleavage of DNA by metal complexes, Inorg. Chem., 1986, 25: 3549.
[36]Barton J.K., Danishefsky A.T., Goldberg J.M. Tris (phenanthroline) ruthenium(Ⅱ): Stereoselectivity in binding to DNA, J. Am. Chem. Soc., 1984,106: 2172.
[37]Hiort C., Lincoln P., Norden B. DNA-binding of △- and ∧-[Ru(phen)_2DPPZ]~(2+), J. Am. Chem. Soc., 1993, 115: 3448.
[38]Holmlin R.E.,Stemp E.D.A.,Barton J.K.,[Ru(phen)_2DPPZ]~(2+) luminescence: dependence on DNA sequences and groove-binding agents, Inorg. Chem.,1998,37:29.
[39]Jin Lan, Yang Pin, Synthesis and DNA binding studies of Co~(Ⅲ) mixed-ligand complex containing dipyrido[3,2-a;2',3'-c]phenazine and phen, Polyhedron, 1997,16:3395.
[40]Frederick C. A., et al., Structural comparison of anticancer drug-DNA complexes : adriamycin and daunomycin, Biochemistry, 1990,29:2538.
[41]宋宇飞，杨频，对DNA具有识别和断裂功能的金属插入剂的研究，化学进展，2001，13(9)：368．
[42]Jacquet L., et al. photoaddition of Ru(tap)_2(bpy)~2+ to DNA : a new mode of covalent attachment of metal complexes to duplex DNA, J. Am. Chem. Soc., 1997,119: 11763.
[43]Fitzsimons M.P., Barton J. K.. Design of a synthetic nuclease: DNA hydrolysis by a zinc-binding peptide tethered to arhodium intercalator. J. Am. Chem. Soc., 1997,119:3379.
[44]Eriksson M., Leijion M., Norden B., et al.. Minor groove binding of [Ru(phen)_3]~(2+) to d(GCGATCGCG)_2 evidenced by two-dimensional nuclear magnetic resonance spectroscopy. J. Am. Chem. Soc. 1992,114: 4933.
[45]Wang L.,Zhou J.Y., Ji L.N. et al.. Ruthenium coordination compounds with polypyridine: Ⅲ. Stereoselectivity of tris(phenanthroline) ruthenium binding in DNA, Chinese Chemical Letters, 1995,6: 883.
[46]Sitlani A., Long E. C., Pyle A. M. et al.. DNA photocleavage by phenanthrenequinone diimine complexes of rhodium (Ⅲ): shape-selective recognition and reaction. J. Am. Chem. Soc.,1992, 114: 2303.
[47]甄启雄，叶保辉，计亮年等，钌多吡啶配合物的合成及插入配体的位阻效应对键合DNA的影响，高等学校化学学报，1999，20(11)：1661．
[48]Pyle A.M, Rehmann J.P., Meshoyrer R., et al., Mixed-ligand complexes of ruthenium (Ⅱ): factors governing binding to DNA, J. Am. Chem. Soc.,1989,111:3051.
[49]Pang D.W., Abruna H. D., Micromethod for the investigation of the interaction between DNA and redox-active molecules. Anal. Chem.,1998,70: 3162.
[50]He X. F., Wang L., Ji L. N., et al., Synthesis, characterization and DNA binding study of polypyridyl mixed-ligand complexes, Polyhedron, 1998, 17: 3161.
[51]宋玉民，康敬万，高锦章，钴(Ⅲ)配合物DNA作用的研究．无机化学学报．2000，16(1)：53．
[52]Rehmann J. P., Barton J. K., Proton NMR studies of tris (phenanthroline) metal complexes bound to oligonucleotides: characterization of binding modes, Biochemistry, 1990, 29, 1701.
[53]Dupureur C. M., Barton J. K., Structural studies of △-and ∧ - [Ru(phen)_2dppz]~2+ bound to d(GTCGAC)_2: Characerization of enantioselective intercalation, Inorg. Chem., 1997,36: 33.
[54]Carter M. T., Bard A. J., Voltammetric syudies of the interaction of tris(1, 10-phenanthroline) cobalt (Ⅲ) with
DNA,J.AM. Chem.Soc., 1989,109, 7528.
[55]刘劲刚，叶保辉，计亮年等， △-和∧-[Ru(bpy)_2(HPIP)]~2+ 两种异构体对小牛胸腺DNA不同键合速率的CD光谱证明，高等学校化学学报，1999，20(4)：523．
[56]Zou Xiaohua, Ye Baohui, Ji Liangnian, et al., Mono-and binuclear ruthenium(Ⅱ)complexes containing a new asymmetric ligand 3-(pyrazin-2-yl)-as-triazino[5,6-f] 1,10-phenanthroline: systhesis characterization and DNA-bindingproperties, J. Chem. Soc., Dalton Trans., 1999, 1423.
[57]易平贵，商志才，俞庆森，微量热法研究[Cu(phen)_2]~2+、[Cu(bpy)_2]~2+与DNA的作用，无机化学学报，2001，17(1)：77．
[58]Anthony W. Addison, et al, New Iron(Ⅱ) spin-crossover complexes with heterocyclic amine-derived Ligand and STEPS xxperiments on photogenerated metastable high-spin states J. Chem. Soc. Dalton Trans. 1987: 2621.
[59]Xiao Xiaoming, Masa-aski Haga, Takeko M., et al. , Synthesis and proton transfer-linked redox tuning of ruthenium(Ⅱ) complexes with tridentate 2,6-his (benzimidazol-2-yl)pyridine ligands, J. chem. Soc. Dalton Trans. 1993: 2477.
[60]肖小明，芳贺正明，松村竹子，2，6-二(苯并咪唑-2)吡啶及其钌配合物的~1H-NMR研究，高等学校化学学报，1991，12(12)：1672．
[61]Whiter A., Mingos D. P., The application of microwave heating to chemical syntheses, J. of Microwave Power and Electomagnetic Entery, 1994, 29 (4): 195.
[62]肖小明，熊士荣，混合钌配合物[Ru(bpy)_n(Hdpa)_(3-n)]~2+中中心离子与配体之间的相互作用，湖南师范大学自然科学学报，1998，21：53．
[63]Jerry F.O' Donnell, James T. A., Charles K.M., Preparation of high purity acetonitrile, Anal. Chem., 1965, 37:1161.
[64]Anthony W. Addison, Philip J. Burke, Synthesis of some imidazol-and pyrazol-derived chelating agents, J. Heterocycl. Chem., 1981, 18: 803.
[65]Takeko Matsumra-Inoue, Masahiro T. Takayoshi M. et al., Remarkably rapid synthesis of ruthenium(Ⅱ) polypyridine complexes by microwave irradiation, Chem. Letters., 1994,2443.
[66]毕先均，谢小光，王真等，微波加热技术在有机合成和材料制备等方面的应用进展，云南化工，1998，2：7．
[67]黄卡玛，唐敬贤，电磁波对化学反应作用的动力学原理，微波学报，1994(增刊)：51．
[68]Bard A.J., Faulkner L. R., Electrochemicai Methods, Wiley, New York, 1980:194.
[69]师同顺，张旭光，柳魏等，四(α-萘基)四苯并卟啉钴配合物的光谱电化学性质，高等学校化学学报，1998，19(7)：1026．
[70]Olson E. J. C., Hu D., Barton J. K., et al., (?)-ation of the Key Intermediate in the "Light -Switch" Mechanism of [Ru(phen)_2dppz]~2+ J. Am. Chem. Soc., 1997, 119(47): 11458.
[71]Friedman A.E., Chambron J.C., Sauvage J.P., et al., Molecular "light switch" for DNA: Ru(bpy)_2(dppz)~2+, J. Am. Chem. Soc., 1990, 112: 4960.
[72]L.P. Hammett, G.H. Walden, S.M. Edmonds, New indicators for oxidimetry : some phenanthroline and diphenylamine derivatives, J, Am. Chem. Soc. 1934, 56: 1093.
[73]J.E. Dickeson, L.A. Summers, Derivatives of 1.10-phen-anthroline-5,6-quinone, Aust. J. Chem., 1970, 23: 1023.
[74]Amouyal E., Homsi A., Sauvage J.P., Synthesis and study of a mixed-ligand ruthenium(Ⅱ) complex in its ground and excited states: bis(2,2-bipyridine)(dipyrido[3,2-a;2',3'-c]phenazine-N~4N~5)ruthenium(Ⅱ),J. Chem. Soc. Dalton Trans., 1990:1841.
[75]Grassini-Strazza G.,Isola S., Thin-layer chromatrographic detection of some impurities in cobalt(Ⅲ) complexes J. Chromatogr., 1978,154: 127.
[76]R.D. Gillard, R.E.E. Hill, R. Maskill, Optically active co-ordination compounds. Part XX. Reactions of 1.10-phen-anthroline co-ordination to cobalt(Ⅲ),J. Chem. Soc. (A), 1970: 1447.
[77]George E. Inglett, G. Frederick Smith, The formation of a new nitrogen heterocyclic ring system by the loss of carbon monoxide from 1.10-phenanthroline-5,6-quinone, 1950,72: 842.
[78]Thomas W. Welch, Amanda H. C., H.H. Thorp, Electrochemical determination of nucleic acid diffusion coefficients through noncovalent association of a redox-active probe, J. Phys. Chem., 1995, 99: 11757.
[79]David S. Sigman, Abhijit M., David M. Perrin, Chemical nucleases, Chem. Rev., 1993, 93: 2295.
[80]杨频，宋宇飞，金属配合物键合DNA的研究进展，化学进展，2000，12(1)：32．
[81]Holmlin R.E., Dandliker P.J.,Barton J.K., Charge transfer through the DNA base stack, Angew. Chem. Int. Ed. Eng., 1997, 36: 2714.
[82]Burrows C.J., Muller J.G., Oxidative nucleobase modifications leading to strand scission, Chem. Rev., 1998,98:1109.
[83]Barton J. K., Paranawithana S. R., Restriction endonuclease EcoRI alters the enantiomeric preference of chiral metallointercalators for DNA: an illustration of a proteininduced DNA conformational change Biochemistry, 1986, 25(8): 2205.
[84]Barton J. K., Adrienne L. Raphael, Photoactivated stereo-specific cleavage of double-helical DNA by cobalt(Ⅲ)
complexes, J. Am. Chem. Soc., 1984, 106(8): 2466.
[85]Carter M. T., Rodriguez M., Bard A. J., Voltammetric studies of the interaction of metal chelates with DNA. 2: Tris-chelated complexes of cobalt(Ⅲ) and iron(Ⅱ) with 1, 10-phenanthroline and 2,2 -bipyridine. J. AM. Chem. Soc., 1989, 111, 8901.
[86]Reichmann M. E., Rice S. A., Thomas C. A., et al., A Further Examination of the Molecular Weight and Size of Desoxypentose Nucleic Acid, J. Am. Chem. Soc., 1954, 76(11) : 3047.
[87]Steven A. Tysoe, Robert J. Morgan, A. David Baker, et al., Spectroscopic investigation of differential binding modes of. DELTA. - and. LAMBDA. -Ru (bpy) 2 (ppz) 2+ with calf thymus DNA, J. Phys. Chem., 1993,97(8): 1707.
[88]Holmlin R. E., Barton J. K., [Os(phen)_2 (dppz) ]~2+: A Red-Emitting DNA Probe, Inorg. Chem., 1995, 34(1): 7.
[89]吴建中，王雷，杨光等，钌多吡啶配合物的合成及结合DNA的研究，高等学校化学学报，1996，17(7)：1010．