Marynick D S, Schaefer H F
Proc Natl Acad Sci U S A. 1975 Oct;72(10):3794-8. doi: 10.1073/pnas.72.10.3794.
Model phosphate-metal solvation complexes have been studied by ab-initio self-consistent-field techniques. The complexes studied include (RO)2PO2-(R = H or CH3) with Li+, Na+, K+, Be++, Mg++, Ca++, H2O, and Cl-. The geometries of the complexes were chosen to approximate reasonable model solvation complexes for phosphate groups in a nucleic acid environment. Calculated energies of formation vary as Be++ greater than Mg++ greater than Ca++ greater than Li+ greater than Na+ greater than K+ for all isostructural complexes, consistent with experimental binding trends. These results suggest that site binding of this type can successfully account for the relative specificities of ion binding in polynucleotides and other phosphate-containing molecules.
通过从头算自洽场技术研究了模型磷酸盐-金属溶剂化络合物。所研究的络合物包括(RO)2PO2-(R = H或CH3)与Li+、Na+、K+、Be++、Mg++、Ca++、H2O和Cl-形成的络合物。选择这些络合物的几何结构以近似核酸环境中磷酸基团合理的模型溶剂化络合物。对于所有同构络合物，计算得到的形成能变化规律为Be++大于Mg++大于Ca++大于Li+大于Na+大于K+，这与实验结合趋势一致。这些结果表明，这种类型的位点结合能够成功解释多核苷酸和其他含磷分子中离子结合的相对特异性。
