Mirzahosseini Arash, Noszál Béla
Department of Pharmaceutical Chemistry, Semmelweis University, Budapest, Hungary; Research Group of Drugs of Abuse and Doping Agents, Hungarian Academy of Sciences, Hungary.
Department of Pharmaceutical Chemistry, Semmelweis University, Budapest, Hungary; Research Group of Drugs of Abuse and Doping Agents, Hungarian Academy of Sciences, Hungary.
J Pharm Biomed Anal. 2014 Jul;95:184-92. doi: 10.1016/j.jpba.2014.02.023. Epub 2014 Mar 12.
Cysteamine, cysteine, homocysteine, their homodisulfides and 9 related compounds were studied by ¹H NMR-pH titrations and case-tailored evaluation methods. The resulting acid-base properties are quantified in terms of 33 macroscopic and 62 microscopic protonation constants and the concomitant 16 interactivity parameters, providing thus the first complete microspeciation of this vitally important family of biomolecules. The species- and site-specific basicities are interpreted by means of inductive and hydrogen-bonding effects through various intra- and intermolecular comparisons. The pH-dependent distribution of the microspecies is depicted. The thiolate basicities determined this way provide exclusive means for the prediction of thiolate oxidizabilities, a key parameter to understand and influence oxidative stress at the molecular level.
通过¹H NMR - pH滴定和定制的评估方法研究了半胱胺、半胱氨酸、高半胱氨酸、它们的同型二硫化物以及9种相关化合物。根据33个宏观和62个微观质子化常数以及随之而来的16个相互作用参数对所得的酸碱性质进行了量化，从而首次对这个至关重要的生物分子家族进行了完整的微观形态分析。通过各种分子内和分子间比较，借助诱导效应和氢键效应解释了物种和位点特异性碱度。描绘了微观物种的pH依赖性分布。以这种方式确定的硫醇盐碱度为预测硫醇盐氧化能力提供了独特的方法，而硫醇盐氧化能力是在分子水平上理解和影响氧化应激的关键参数。
