Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Zhejiang Normal University, Jinhua 321004, PR China.
Spectrochim Acta A Mol Biomol Spectrosc. 2013 Jun;110:100-7. doi: 10.1016/j.saa.2013.03.015. Epub 2013 Mar 13.
Three new transition metal complexes [Mn2(DCA)2(bipy)2]·5H2O (1), [M2(DCA)2(bipy)2(H2O)]·10H2O(M=Ni(II)(2);Zn(II)(3)), (DCA=demethylcantharate, 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, C8H8O5) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra and X-ray diffraction techniques. Each metal ion was six-coordinated in complexes. Complex 1 has a Mn2O2 center. Complexes 2 and 3 have asymmetric binuclear structure. Great amount of intermolecular hydrogen-bonding and π-π(*) stacking interactions were formed in these complex structures. The DNA-binding properties of complexes were investigated by electronic absorption spectra and viscosity measurements. The DNA binding constants Kb/(Lmol(-1)) were 1.71×10(4) (1), 2.62×10(4) (2) and 1.59×10(4) (3) at 298 K. The complexes could quench the intrinsic fluorescence of bovine serum albumin (BSA) strongly through static quenching. The protein binding constants Ka/(L mol(-1)) were 7.27×10(4) (1), 4.55×10(4) (2) and 7.87×10(4) L mol(-1) (3) and binding site was one. The complexes bind more tightly with DNA and BSA than with ligands. Complexes 1 and 3 had stronger inhibition ratios than Na2(DCA) against human hepatoma cells (SMMC-7721) lines and human gastric cancer cells (MGC80-3) lines in vitro. Complex 3 showed the strongest antiproliferative activity against SMMC-7721 (IC50=29.46±2.12 μmol L(-1)) and MGC80-3 (IC50=27.02±2.38 μmol L(-1)), which shows potential in anti-cancer drug development.
三种新的过渡金属配合物[Mn2(DCA)2(bipy)2]·5H2O(1)、[M2(DCA)2(bipy)2(H2O)]·10H2O(M=Ni(II)(2);Zn(II)(3))，(DCA=去甲川可待因酸，7-氧杂双环[2.2.1]庚烷-2,3-二甲酸酯，C8H8O5)，通过元素分析、摩尔电导率、红外光谱和 X 射线衍射技术进行了合成和表征。每个金属离子在配合物中都是六配位的。配合物 1 具有 Mn2O2 中心。配合物 2 和 3 具有不对称双核结构。在这些配合物结构中形成了大量的分子间氢键和π-π(*)堆积相互作用。通过电子吸收光谱和粘度测量研究了配合物的 DNA 结合性质。在 298 K 时，配合物 1 的 DNA 结合常数 Kb/(Lmol(-1))为 1.71×10(4)，配合物 2 的 DNA 结合常数 Kb/(Lmol(-1))为 2.62×10(4)，配合物 3 的 DNA 结合常数 Kb/(Lmol(-1))为 1.59×10(4)。这些配合物可以通过静态猝灭强烈猝灭牛血清白蛋白(BSA)的固有荧光。在 298 K 时，配合物 1 的蛋白质结合常数 Ka/(Lmol(-1))为 7.27×10(4)，配合物 2 的蛋白质结合常数 Ka/(Lmol(-1))为 4.55×10(4)，配合物 3 的蛋白质结合常数 Ka/(Lmol(-1))为 7.87×10(4)，结合位点均为一个。与配体相比，这些配合物与 DNA 和 BSA 的结合更为紧密。配合物 1 和 3 对人肝癌细胞(SMMC-7721)和人胃癌细胞(MGC80-3)的抑制率高于 Na2(DCA)，具有体外抑制活性。配合物 3 对 SMMC-7721(IC50=29.46±2.12 μmol L(-1))和 MGC80-3(IC50=27.02±2.38 μmol L(-1))的增殖活性最强，显示出在抗癌药物开发方面的潜力。
