Lewandowski W, Kalinowska M, Lewandowska H
Department of Chemistry, Białystok Technical University, Zamenhofa 29, 15-435 Białystok, Poland.
J Inorg Biochem. 2005 Jul;99(7):1407-23. doi: 10.1016/j.jinorgbio.2005.04.010.
This paper reviews the results of the intense experimental and theoretical studies on the influence of selected metals on the electronic system of biologically important molecules such as benzoic, 2-hydroxybenzoic and 3-pyridine carboxylic acids as well as 5-carboxyuracil. The research involved following techniques: infrared (FT-IR), Raman (FT-Raman), FT-IR Ar matrix, electronic absorption spectroscopy (UV/visible), nuclear magnetic resonance ((1)H, (13)C, (15)N, (17)O NMR), X-ray and quantum mechanical calculations. The influence of metals on the electronic system was examined through comparison of the changes in so called "logical series". The exemplary series are: Li-->Na-->K-->Rb-->Cs, Na(I)-->Ca(II)-->La(III)-->Th(IV); Na(I)-->Mg(II)-->Al(III) or long series of La(III) and fourteen lanthanides La(III)-->Ce(III)-->Lu(III). The correlation between the perturbation of the electronic system of ligands and the position of metals in the periodic table was found. The influence of the carboxylic anion structure and the effect of hydration on the perturbation of the electronic system of molecule were also discussed. The partial explanation in what way metals disturb and stabilize electronic system of studied ligands was done. It is necessary to carry out the physico-chemical studies of benzoates, salicylates, 3-pyridine carboxylates and isoorotates in order to understand the nature of the interactions of these compounds with their biological targets (e.g., receptors in the cell or important cell components). The results of this study make possible to predict some properties of a molecule, such as its reactivity, durability of complex compounds, and kinship to enzymes.
本文综述了关于特定金属对生物重要分子（如苯甲酸、2-羟基苯甲酸、3-吡啶羧酸以及5-羧基尿嘧啶）电子系统影响的大量实验和理论研究结果。该研究涉及以下技术：红外（傅里叶变换红外光谱，FT-IR）、拉曼（傅里叶变换拉曼光谱，FT-Raman）、傅里叶变换红外光谱氩基质、电子吸收光谱（紫外/可见光谱）、核磁共振（（1）H、（13）C、（15）N、（17）O核磁共振）、X射线以及量子力学计算。通过比较所谓“逻辑序列”中的变化来研究金属对电子系统的影响。示例性序列有：Li→Na→K→Rb→Cs，Na（I）→Ca（II）→La（III）→Th（IV）；Na（I）→Mg（II）→Al（III）或La（III）与十四种镧系元素的长序列La（III）→Ce（III）→Lu（III）。发现了配体电子系统的扰动与金属在周期表中位置之间的相关性。还讨论了羧酸根阴离子结构的影响以及水合作用对分子电子系统扰动的影响。对金属以何种方式干扰和稳定所研究配体的电子系统进行了部分解释。有必要对苯甲酸盐、水杨酸盐、3-吡啶羧酸盐和异乳清酸盐进行物理化学研究，以了解这些化合物与其生物靶点（例如细胞中的受体或重要细胞成分）相互作用的本质。本研究结果使得预测分子的某些性质成为可能，例如其反应性、络合物的稳定性以及与酶的亲缘关系。
