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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Use of a fluorinated probe to quantitatively monitor amino acid binding preferences of ruthenium(ii) arene complexes
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Use of a fluorinated probe to quantitatively monitor amino acid binding preferences of ruthenium(ii) arene complexes

机译:使用氟化探针以定量监测钌(II)芳烃配合物的氨基酸结合偏好

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摘要

In order to address outstanding questions about ruthenium complexes in complex biological solutions, F-19 NMR spectroscopy was used to follow the binding preferences between fluorinated Ru-II((6)-arene)(bipyridine) complexes and protected amino acids and glutathione. Reporting what ruthenium compounds bind to in complex environments has so far been restricted to relatively qualitative methods, such as mass spectrometry and X-ray spectroscopic methods; however, quantitative information on the species present in the solution phase cannot be inferred from these techniques. Furthermore, using H-1 NMR, in water, to distinguish and monitor a number of different complex Ru-II((6)-arene) adducts forming is challenging. Incorporating an NMR active heteroatom into ruthenium organometallic complexes provides a quantitative, diagnostic fingerprint' to track solution-phase behaviour and allow for unambiguous assignment of any given adduct. The resulting F-19 NMR spectra show for the first time the varied, dynamic behaviour of organoruthenium compounds when exposed to simple biomolecules in complex mixtures. The rates of formation of the different observed species are dramatically influenced by the electronic properties at the metal, even in a closely related series of complexes in which only the electron-donating properties of the arene ligand are altered. Preference for cysteine binding is absolute: the first quantitative solution-phase evidence of such behaviour.
机译:为了解决复杂生物溶液中的关于钌配合物的未突出问题,使用F-19 NMR光谱遵循氟化Ru-II((6) - 丙烯)(Bimyridine)复合物和保护氨基酸和谷胱甘肽之间的结合偏好。迄今为止,报告了复杂环境中结合到复杂环境中的钌化合物的含量是什么意味着相对定性的方法,例如质谱和X射线光谱方法;然而,不能从这些技术中推断出在溶液阶段存在的物种的定量信息。此外,在水中使用H-1 NMR,区分和监测许多不同的复合物Ru-II((6) - are one)加合物形成是具有挑战性的。将NMR活性杂原子掺入钌有机金属络合物中提供定量,诊断指纹'跟踪溶液相行为并允许任何给定的加合物的明确分配。由此得到的F-19 NMR光谱显示,当暴露于复合物混合物中的简单生物分子时,第一次的F-19 NMR光谱显示有机丁烯化合物的变化。即使在密切相关的复合物中,不同观察到的物种的形成率显着影响金属的电子性质,其中仅改变芳烃配体的电子赋予芳烃配体的电子捐赠性质。对半胱氨酸结合的偏好是绝对的:这种行为的第一定量溶液阶段证据。

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