...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, carbohydrate- and DNA-binding studies of cationic 2,2′:6′,2′′-terpyridineplatinum(ii) complexes containing N- and S-donor boronic acid ligands
【24h】

Synthesis, carbohydrate- and DNA-binding studies of cationic 2,2′:6′,2′′-terpyridineplatinum(ii) complexes containing N- and S-donor boronic acid ligands

机译：含N-和S-供体硼酸配体的阳离子2,2'：6'，2''-吡啶吡啶（ii）配合物的合成，碳水化合物和DNA结合研究

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

A series of platinum(ii) complexes of the type [Pt(trpy)L](NO _3)_n (L = 3- or 4-pyridineboronic acid (3- or 4-pyB, respectively), n = 2; HL = 4-mercaptophenylboronic acid (HmpB), n = 1; trpy = 2,2′:6′,2′′-terpyridine) and [{Pt(trpy)} _2(μ-pzB)](NO_3)_3 (HpzB = 4-pyrazoleboronic acid) were synthesized and fully characterized by means of multinuclear (~1H, ~(13)C, ~(11)B, and ~(195)Pt) 1D- and 2D-NMR spectroscopy and elemental analysis. The triflate derivatives [Pt(trpy)(4-pyB)](OTf)_2 and [{Pt(trpy)}_2(μ-pzB)](OTf) _3 were also prepared, and their molecular structures were confirmed by X-ray crystallography. Variable pH ~1H NMR spectroscopy showed that hydroxylation of the boronic acid group occurs in aqueous solution at pH > 5 and the pK_a values for the complexes were determined. In buffered aqueous solution (pH 7.4), the complexes bind strongly to simple diols such as catechol and monosaccharides including d-fructose, d-ribose, d-sorbitol and d-mannitol, as determined by isothermal titration calorimetry (ITC). The equilibrium binding constants for these reactions were determined and were found to exceed those of organic boronic acids such as phenylboronic acid by an order of magnitude or greater, an effect that can be directly attributed to the cationic charge of the complexes. 2D-NMR methods (HSQC and HMBC) were used to elucidate the structures of the carbohydrate adducts [Pt(trpy)(3-pyB)]·d- fructose·NO3 and [Pt(trpy)(4-pyB)]·d- fructose·NO_3 in aqueous solution. DNA-binding experiments with calf-thymus DNA (CT-DNA) indicate an avid DNA-binding interaction by the mononuclear complexes, as determined using thermal melting methods and ITC, but the behaviour of the dinuclear species [{Pt(trpy)}_2(μ-pzB)] (NO_3)_3 is complicated and could not be modeled adequately; higher ionic strength solutions and lower temperatures resulted in a similar DNA binding interaction to the mononuclear complexes. The presence of excess d-fructose did not significantly affect the binding of the platinum(ii)-trpy complexes to CT-DNA.
机译：[Pt（trpy）L]（NO _3）_n类型的一系列铂（ii）配合物（L = 3-或4-吡啶硼酸（分别为3-或4-pyB），n = 2; HL = 4-巯基苯基硼酸（HmpB），n = 1; trpy = 2,2'：6'，2''-叔吡啶）和[{Pt（trpy）} _2（μ-pzB）]（NO_3）_3（HpzB =合成了4-吡唑硼酸），并通过多核（〜1H，〜（13）C，〜（11）B和〜（195）Pt）1D和2D-NMR光谱和元素分析对其进行了全面表征。还制备了三氟甲磺酸衍生物[Pt（trpy）（4-pyB）]（OTf）_2和[{Pt（trpy）} _ 2（μ-pzB）]（OTf）_3，并通过X-证实了其分子结构射线晶体学。可变的pH〜1H NMR光谱表明，在pH> 5的水溶液中发生了硼酸基团的羟基化，并确定了配合物的pK_a值。在缓冲水溶液（pH 7.4）中，通过等温滴定量热（ITC）测定，络合物与简单的二醇（例如儿茶酚）和单糖（包括d-果糖，d-核糖，d-山梨糖醇和d-甘露糖醇）牢固结合。确定了这些反应的平衡结合常数，发现该常数超过有机硼酸例如苯基硼酸的数量级或更大，这种效应可以直接归因于配合物的阳离子电荷。使用2D-NMR方法（HSQC和HMBC）阐明了碳水化合物加合物[Pt（trpy）（3-pyB）]·d-果糖·NO3和[Pt（trpy）（4-pyB）]·d的结构-水溶液中的果糖·NO_3。用小胸腺胸腺DNA（CT-DNA）进行的DNA结合实验表明，单核复合物具有强烈的DNA结合相互作用，如使用热熔方法和ITC所确定的，但双核物种的行为[{Pt（trpy）} _ 2 （μ-pzB）]（NO_3）_3很复杂，无法充分建模;较高的离子强度溶液和较低的温度导致与单核复合物相似的DNA结合相互作用。过量的d-果糖的存在并不显着影响铂（ii）-trpy配合物与CT-DNA的结合。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号