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首页> 外文学位 >Copper complexes bearing pendant, protonatable noncoordinating groups: Synthesis, structural characterization and DNA cleavage activity.
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Copper complexes bearing pendant, protonatable noncoordinating groups: Synthesis, structural characterization and DNA cleavage activity.

机译：带有侧基，可质子化的非配位基团的铜配合物：合成，结构表征和DNA裂解活性。

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摘要

Copper proteins belong to a class of metalloproteins which possess unusual spectroscopic properties and a wide range of redox potential. Low molecular weight synthetic analogues have been used to help explain these unique properties. The pyridine-carboxaldehyde Schiff base derivatives of the parent complex (5-amino-5-methyl-3,7-diaza-1,9-nonanedioate) (chloro) copper(II) have been synthesized and characterized to serve as functional models for the electrostatic interactions in copper proteins. The changes in their spectroscopic properties and redox potential have been found to be largely dependent on the distance from the metal center and orientation of a proximate, noncoordinated positively-charged group.; Previous work in our laboratory has shown that a simple monofunctional copper(II) coordination complex, ((2S,2R)-5-amino-2,8-dibenzyl-5-methyl-3,7-diaza-{dollar}1 ,9{dollar}-nonanedioate)copper(11) (1), equipped with essential recognition elements, can effect nonrandom double-strand DNA cleavage similar to those of enediynes and bleomycins. Related copper(II) complexes have been designed and synthesized to investigate the efficiency of double-strand break (dsb) formation in duplex DNA as a function of structure.; In the course of the synthesis of the (2S,2S)- or (2R,2R)- diastereomers of 1, an intermediate has been trapped, crystallized and identified as ((2S)-5- amino-2-benzyl-6-hydroxy-5-methyl-3-azahexanoate)copper(II) or its (2R)-enantiomer. A possible reaction mechanism for the synthesis of the intermediate under the reaction condition used is proposed.; The variation in the cleavage efficiencies of 1 versus the other four complexes appears to be due to differences in binding DNA rather than differences in reactivities. The most efficient double-strand DNA cleavage agents are the two intermediate enantiomers which contains only a single hydrophobic moiety. It seems that the presence of two hydrophobic side chains sterically hinders binding and/or intercalation between DNA bases.
机译：铜蛋白属于一类金属蛋白，具有异常的光谱特性和广泛的氧化还原电位。低分子量合成类似物已被用来帮助解释这些独特的性质。母体配合物（5-氨基-5-甲基-3,7-二氮杂-1,9-壬二酸酯）（氯）铜（II）的吡啶-羧醛席夫碱衍生物已经合成，并可以用作功能模型铜蛋白中的静电相互作用。已经发现它们的光谱性质和氧化还原电势的变化很大程度上取决于距金属中心的距离和邻近的，未配位的正电荷基团的取向。我们实验室以前的工作表明，一个简单的单官能铜（II）配位化合物（（（2S，2R）-5-amino-2,8-di苄基-5-甲基-3,7-二氮杂-{dollar} 1，配备必需的识别元件的9 {dollar-nonanedioate）copper（11）（1）可以实现与烯二炔和博来霉素相似的非随机双链DNA切割。已经设计并合成了相关的铜（II）配合物，以研究双链DNA中双链断裂（dsb）形成效率与结构的关系。在1的（2S，2S）-或（2R，2R）-非对映异构体的合成过程中，中间体被捕集，结晶并鉴定为（（2S）-5-氨基-2-苄基-6-羟基-5-甲基-3-氮杂己酸酯）铜（II）或其（2R）-对映体。提出了在所用反应条件下合成中间体的可能的反应机理。 1对其他四种复合物的切割效率的变化似乎是由于结合DNA的差异而不是反应性的差异。最有效的双链DNA裂解剂是两个仅包含一个疏水部分的中间对映体。似乎两个疏水性侧链的存在在空间上阻碍了DNA碱基之间的结合和/或嵌入。

著录项

  • 作者

    Villanueva, Nydia D.;

  • 作者单位

    The University of Connecticut.;

  • 授予单位 The University of Connecticut.;
  • 学科 Chemistry Inorganic.; Chemistry Biochemistry.
  • 学位 Ph.D.
  • 年度 1998
  • 页码 137 p.
  • 总页数 137
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;生物化学;
  • 关键词

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