系列钒酰腙配合物的单晶合成及生物活性研究
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摘要
钒是生命体内的一种超微量金属元素，因具有与磷酸盐的化学相似性及本身的氧化还原性而与一些重要生理过程相关，其生理活性主要包括：Na~+，K~+-ATPase抑制剂、磷酰转移酶抑制剂、含钒固氮酶、钒卤过氧化物酶、拟胰岛素活性，以及与卤过氧化物酶相关的氧转移催化(硫化物的氧化)和氧化卤代反应等方面。特别是拟胰岛素活性、钒卤过氧化物酶和含钒固氮酶活性近年来引起了人们的极大关注，新颖结构含钒配合物的合成及其结构与性能的关系、生物药物活性的探讨受到了人们的广泛青睐。
(1)本课题设计、合成了系列具有特征结构的单、双酰腙化合物，并以其为配体，与多种钒原料VO(acac)_2、V_2O_5、VOSO_4、NH_4VO_3等在各种实验条件下反应以培养系列钒酰腙配合物单晶。
(2)对所得单晶进行IR、UV／vis、~1H NMR、TG等结构表征，进而测定其X射线衍射晶体结构，证明我们最终得到了邻香草醛苯甲酰腙双氧钒乙醇胺(配合物1)、邻香草醛苯甲酰腙双氧钒二乙三胺(配合物2)、邻香草醛2-呋喃甲酰腙双氧钒乙醇胺(配合物3)、邻香草醛3-羟基2-萘甲酰腙双氧钒乙醇胺(配合物4)等几种目标配合物单晶。它们的配位中心均为顺式双氧钒(cis-VO_2~+)的五配位拟四方锥构型，酰腙配体均以烯醇式的二价阴离子的形式进行三齿配位，形成的一价配阴离子间存在有机阳离子(HOCH_2CH_2N~+H_3或~+NH_3CH_2CH_2NHCH_2CH_2NH_2等)，后者起平衡电荷、形成氢键和填充空间的作用。几种配合物均为层状结构，晶胞内均存在π-π堆积和氢键作用。
(3)使用紫外光谱法和荧光光谱法分别测定了所得配合物与ct-DNA之间的相互作用，发现它们之间均存在一定强度的相互作用，推测其作用方式可能是配合物分子的酰腙配体部分插入了DNA双螺旋链的碱基对之间，产生了配合物芳香生色团与DNA碱基对之间的堆积相互作用。
(4)所得的同类型配合物中，代表性地研究了配合物1对糖尿病小鼠的血糖活性，发现该类配合物具有一定的拟胰岛素活性。
Vanadium is a metal element existing in organism with tiny concentration. Its compounds are related to some important physiological processes for their similarity with phosphates and their special redox properties. The physiological activities mainly include inhibiting Na~+,K~+-ATPases and phosphorylases, the potential as insulin-enhancing or insulin- mimetic agents, their model character for vanadate-dependent nitrogenases and haloperoxidases and, in relation to the latter, their use in oxo-transfer catalysis and oxidative halogenation. These activities are attracting increasing interests of correlating investigators.
In this work, the series of hydrazone ligands with typical structures were synthesized, their reactions with vanadium compounds (VO(acac)_2, V_2O_5, VOSO_4, NH_4VO_3 etc.) at some different conditions were performed and the single crystals of a series of complexes were obtained. They were characterized by IR, UV/vis, ~1H NMR spectra and TG. Analyses and the X-ray crystal structures were determined. These complexes are all monomeric cw-dioxovanadium(V) species, coordination centers all adopt pseud-square pyramidal coordination geometry with the hydrazone ligands in their enol form losing two hydrogens and coordinating by tridentate mode, and amines' cations act as counter ions. Moreover, the electronic absorption spectra of the complexes upon titration with calf thymus DNA showed certain interaction between them, which is confirmed by the fluorescence measurements of interactional solutions of the DNA and ethidium bromide affected by our complexes, probably by the mode of partial insertion of the moiety of the hydrazone ligands between the base pairs of the DNA which results in the stacking interaction between bases and the aromatic chromophores of the ligands. Lastly, the effect of the typical compound, complex 1, on rats with diabetes mellitus and ordinary rats was investigated. This kind of complexes obtained showed some insulin-mimetic activities.
(1)本课题设计、合成了系列具有特征结构的单、双酰腙化合物，并以其为配体，与多种钒原料VO(acac)_2、V_2O_5、VOSO_4、NH_4VO_3等在各种实验条件下反应以培养系列钒酰腙配合物单晶。
(2)对所得单晶进行IR、UV／vis、~1H NMR、TG等结构表征，进而测定其X射线衍射晶体结构，证明我们最终得到了邻香草醛苯甲酰腙双氧钒乙醇胺(配合物1)、邻香草醛苯甲酰腙双氧钒二乙三胺(配合物2)、邻香草醛2-呋喃甲酰腙双氧钒乙醇胺(配合物3)、邻香草醛3-羟基2-萘甲酰腙双氧钒乙醇胺(配合物4)等几种目标配合物单晶。它们的配位中心均为顺式双氧钒(cis-VO_2~+)的五配位拟四方锥构型，酰腙配体均以烯醇式的二价阴离子的形式进行三齿配位，形成的一价配阴离子间存在有机阳离子(HOCH_2CH_2N~+H_3或~+NH_3CH_2CH_2NHCH_2CH_2NH_2等)，后者起平衡电荷、形成氢键和填充空间的作用。几种配合物均为层状结构，晶胞内均存在π-π堆积和氢键作用。
(3)使用紫外光谱法和荧光光谱法分别测定了所得配合物与ct-DNA之间的相互作用，发现它们之间均存在一定强度的相互作用，推测其作用方式可能是配合物分子的酰腙配体部分插入了DNA双螺旋链的碱基对之间，产生了配合物芳香生色团与DNA碱基对之间的堆积相互作用。
(4)所得的同类型配合物中，代表性地研究了配合物1对糖尿病小鼠的血糖活性，发现该类配合物具有一定的拟胰岛素活性。
Vanadium is a metal element existing in organism with tiny concentration. Its compounds are related to some important physiological processes for their similarity with phosphates and their special redox properties. The physiological activities mainly include inhibiting Na~+,K~+-ATPases and phosphorylases, the potential as insulin-enhancing or insulin- mimetic agents, their model character for vanadate-dependent nitrogenases and haloperoxidases and, in relation to the latter, their use in oxo-transfer catalysis and oxidative halogenation. These activities are attracting increasing interests of correlating investigators.
In this work, the series of hydrazone ligands with typical structures were synthesized, their reactions with vanadium compounds (VO(acac)_2, V_2O_5, VOSO_4, NH_4VO_3 etc.) at some different conditions were performed and the single crystals of a series of complexes were obtained. They were characterized by IR, UV/vis, ~1H NMR spectra and TG. Analyses and the X-ray crystal structures were determined. These complexes are all monomeric cw-dioxovanadium(V) species, coordination centers all adopt pseud-square pyramidal coordination geometry with the hydrazone ligands in their enol form losing two hydrogens and coordinating by tridentate mode, and amines' cations act as counter ions. Moreover, the electronic absorption spectra of the complexes upon titration with calf thymus DNA showed certain interaction between them, which is confirmed by the fluorescence measurements of interactional solutions of the DNA and ethidium bromide affected by our complexes, probably by the mode of partial insertion of the moiety of the hydrazone ligands between the base pairs of the DNA which results in the stacking interaction between bases and the aromatic chromophores of the ligands. Lastly, the effect of the typical compound, complex 1, on rats with diabetes mellitus and ordinary rats was investigated. This kind of complexes obtained showed some insulin-mimetic activities.
引文
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[2] 无机化学丛书(第八卷)，第一版，科学出版社，1987年．
[3] Luis Vilas Boas, Joao Costa Pessoa. Vanadium, Instituto Superior Tecnico, Lisbon, Portugal.
[4] 杨晓改，杨晓达，王夔．化学进展，2002，14(4)：279～286．
[5] 肖文，张华新，卢忠林，苏成勇，康北笙． 中山大学学报(自然科学版)，2001，40(1)：39～43．
[6] Nawar N., Hosny N. M. Trans. Met. Chem., 2000, 25: 1～8.
[7] 杨健国，潘富友，李钧敏．无机化学学报，2005，21(10)：1593发～1597．
[8] Ainscough E. W., Brodie A. M., Dobbs A. J. et al. Inorg. Chim. Acta., 1998, 267: 27～38.
[9] Ranford J. D., ViRal J. J., Wang Y. M. Inorg. Chem., 1998, 37: 1226～1231.
[10] Wang D. B., Chen B. H., Ma Y. X. Synth. React. Inorg. Met-Org. Chem., 1997, 27: 479～486.
[11] 陈瑞金．首都师范大学硕士学位论文，2006年．
[12] Thompson Katherine H. Biofactor, 1999, 10(1): 4351.
[13] Alan Shaver, Jesse B. Ng, David A. Hall, Barry I. Posner et al. Mol. and Cell. Biochem., 1995, 153: 5～15.
[14] A. Paul Beavan, Paul G。. Drake, Jean-Francois Yale et al. Mol. and Cell. Biochem., 1995, 153: 49～58.
[15] Mcneil J. H., Yuen V. G。, Hoyveda H. R. et al. J. Med. Chem., 1992, 35: 1489～1491.
[16] Chris Orvig, Katherine H. Thompson, Barry D. Liboiron et al. J. Inorg. Biochem., 2003, 96: 14.
[17] Storr Tim, Mitchell Devin, Buglyo Peter et al. Bioconjugate Chemistry, 2003, 14(1): 212～221.
[18] Maria Rangel, Asuka Tamura, Chihiro Fukushirna et al. J. Biol. Inorg. Chem., 2001, 6: 128～132.
[19] 谢明进，刘伟平，刘玲，陈植和．化学学报，2002，60(5)：892～896．
[20] Ryszard Grybos, Alina Samotus, Wiesaw Lasocha. Trans. Metal. Chem., 2003, 28(5): 568～571.
[21] Yasui Hiroyuki, Tamura Asuka, Takino Toshikazu et al. J. Inorg. Biochem., 2002, 91(1): 327～338.
[22] Sasagawa Takahiro, Yoshikawa Yutaka, Kawabe Kenji et al. J. Inorg. Biochem., 2002, 88(1): 108～112.
[23] Dieter Rehder, Jessica Gaetjens, Tamás Kiss. J. Inorg. Biochem., 2003, 96: 14.
[24] Hiromu Sakkurai, Hiromi Sano, Toshikazu Taino et al. J. Inorg. Biochem., 2000, 80: 99～105.
[25] Sakurai H., Taria Z., Sakai N. Inorg. Chim. Acta, 1998, 151: 85～86.
[26] H. Sakurai, H. Watanabe, H. Tamura et al. Inorg. Chim. Acta, 1998, 283: 175.
[27] Katherine H. Thompson, Chris Orvig. J. Chem. Soc. Dalton Trans., 2000, 2885～2892.
[28] Kenji Kawabe, Takahiro Sasagawa, Yutaka Yoshikawa et al. J. Biol. Inorg. Chem., 2003, 8: 893～906.
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