Tunç Turgay, Koç Yasemin, Açık Leyla, Karacan Mehmet Sayım, Karacan Nurcan
Ahi Evran University, Science Faculty, Chemistry Department, Kirsehir, Turkey.
Ankara University, Science Faculty, Biology Department, Ankara, Turkey.
Spectrochim Acta A Mol Biomol Spectrosc. 2015 Feb 5;136 Pt C:1418-27. doi: 10.1016/j.saa.2014.10.030. Epub 2014 Oct 19.
New antimony(III) complexes, [Sb(2-aminopyridine)2Cl3] (1a), [Sb(2-aminopyridine)2Br3] (1b), [Sb(5-methyl-2-aminopyridine)2Cl3] (2a), [Sb(5-methyl-2-aminopyridine)2Br3] (2b), [Sb(2-aminopyrimidine)2Cl3] (3a), [Sb(2-aminopyrimidine)2Br3] (3b), [Sb(4,6-dimethoxy-2-aminopyrimidine)2Cl3] (4a), [Sb(4,6-dimethoxy-2-aminopyrimidine)2Br3] (4b), [Sb(2-amino-1,3,5-triazine)2Cl3] (5a), [Sb(2-amino-1,3,5-triazine)2Br3] (5b), [Sb(2-guanidinobenzimidazole) Cl3] (6a), [Sb(2-guanidinobenzimidazole)Br3] (6b) [Sb(2- benzyl-2-thiopseudeourea)2Cl3] (7a) and [Sb(2- benzyl-2-thiopseudeourea)2Br3] (7b) were synthesized. Their structures were characterized by elemental analysis, molecular conductivity, FT-IR, (1)H NMR, LC-MS techniques. Glutathione reductase inhibitor activity, antimicrobial activity and DNA cleavage studies of the complexes were determined. The geometrical structures of the complexes were optimized by DFT/B3LYP method with LANL2DZ as basis set. Calculation results indicated that the equilibrium geometries of all complexes have square pyramidal shape. About 350 molecular descriptors (constitutional, topological, geometrical, electrostatic and quantum chemical parameters) of the complexes were calculated by DFT/B3LYP/LANL2DZ method with CODESSA software. Calculated molecular parameters were correlated to glutathione reductase inhibitory activity values (pIC50) of all complexes by Best Multi-Linear Regression (BMLR) method. Obtained two-parameter QSAR equation shows that increase in "maximum partial charge for a H atom" and decrease in HOMO-LUMO gap would be favorable for the glutathione reductase inhibitory activity.
合成了新型锑（III）配合物，即[Sb(2-氨基吡啶)₂Cl₃]（1a）、[Sb(2-氨基吡啶)₂Br₃]（1b）、[Sb(5-甲基-2-氨基吡啶)₂Cl₃]（2a）、[Sb(5-甲基-2-氨基吡啶)₂Br₃]（2b）、[Sb(2-氨基嘧啶)₂Cl₃]（3a）、[Sb(2-氨基嘧啶)₂Br₃]（3b）、[Sb(4,6-二甲氧基-2-氨基嘧啶)₂Cl₃]（4a）、[Sb(4,6-二甲氧基-2-氨基嘧啶)₂Br₃]（4b）、[Sb(2-氨基-1,3,5-三嗪)₂Cl₃]（5a）、[Sb(2-氨基-1,3,5-三嗪)₂Br₃]（5b）、[Sb(2-胍基苯并咪唑)Cl₃]（6a）、[Sb(2-胍基苯并咪唑)Br₃]（6b）、[Sb(2-苄基-2-硫代假脲)₂Cl₃]（7a）和[Sb(2-苄基-2-硫代假脲)₂Br₃]（7b）。通过元素分析、分子电导率、傅里叶变换红外光谱（FT-IR）、核磁共振氢谱（¹H NMR）、液相色谱-质谱联用（LC-MS）技术对其结构进行了表征。测定了这些配合物的谷胱甘肽还原酶抑制活性、抗菌活性以及DNA裂解研究。采用密度泛函理论（DFT）/B3LYP方法，以LANL2DZ为基组对配合物的几何结构进行了优化。计算结果表明，所有配合物的平衡几何结构均为四方锥形状。利用CODESSA软件，通过DFT/B3LYP/LANL2DZ方法计算了配合物约350个分子描述符（组成、拓扑、几何、静电和量子化学参数）。通过最佳多元线性回归（BMLR）方法将计算得到的分子参数与所有配合物的谷胱甘肽还原酶抑制活性值（pIC50）进行了关联。得到的双参数定量构效关系（QSAR）方程表明，“H原子的最大部分电荷”增加以及最高占据分子轨道（HOMO）-最低未占据分子轨道（LUMO）能隙减小有利于谷胱甘肽还原酶抑制活性。
