Polyoxometalates functionalized by bisphosphonate ligands: synthesis, structural, magnetic, and spectroscopic characterizations and activity on tumor cell lines.

Polyoxometalates functionalized by bisphosphonate ligands: synthesis, structural, magnetic, and spectroscopic characterizations and activity on tumor cell lines.
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DOI:
10.1021/ic3010079
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发表时间:
2012-07-16
影响因子:
4.6
通讯作者:
Dolbecq A
Dolbecq A
中科院分区:
化学2区
文献类型:
--
作者:
El Moll H;Zhu W;Oldfield E;Rodriguez-Albelo LM;Mialane P;Marrot J;Vila N;Mbomekallé IM;Rivière E;Duboc C;Dolbecq A

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我们报告的合成和表征的八个新的钼,钨,或V-含聚氧乙烯(POM)双膦酸盐配合物的金属核度范围从1到6。通过用生物活性双膦酸盐H2 O3 PCR(OH)PO 3 H2(R = C3 H6 NH 2,Ale; R = CH 2S(CH 3)2,Sul和R = C4 H5 N2,Zol,其中Ale=阿仑膦酸盐,Sul=(2-羟基-2,2-双-膦酰基-乙基)-二甲基-锍和Zol=唑来膦酸盐)处理MoVI、WVI、VIV或VV前体,在水中合成化合物。Mo 6(Sul)2和Mo 6(Zol)2含有两个三核MoVI核,可以围绕中心氧代基团旋转,而Mo(Ale)2和W(Ale)2是单核物种。在V5(Ale)2和V5(Zol)2中,中心VIV离子被与双膦酸酯配体结合的两个VV二聚体包围。V6(Ale)4可以看作是一个V5(Ale)2与一个额外的VIV离子和两个Ale配体的缩合物,而V3(Zol)3是三角形VIV POM。这些新的POM双膦酸盐配合物的特征在于通过单晶X-射线衍射。通过31 P NMR光谱研究了Mo和W POM的稳定性,结果表明,除了单核Mo(Ale)2和W(Ale)2之外,所有化合物在溶液中都是稳定的。对钒衍生物进行的EPR测量证实了V离子的氧化态,并证明了它们在水溶液中的稳定性。对V5(Ale)2和V5(Zol)2的电化学研究表明VV还原为VIV,对V3(Zol)3的磁化率研究使得能够详细分析磁相互作用。唑来膦酸盐或钒的存在与对三种人肿瘤细胞系的最有效活性(IC 50 ~1-5 μM)相关。
We report the synthesis and characterization of eight new Mo, W, or V-containing polyoxometalate (POM) bisphosphonate complexes with metal nuclearities ranging from 1 to 6. The compounds were synthesized in water by treating MoVI, WVI, VIV or VV precursors with biologically active bisphosphonates H2O3PCR(OH)PO3H2 (R = C3H6NH2, Ale; R = CH2S(CH3)2, Sul and R = C4H5N2, Zol, where Ale=alendronate, Sul=(2-Hydroxy-2,2-bis-phosphono-ethyl)-dimethyl-sulfonium and Zol=zoledronate.). Mo6(Sul)2 and Mo6(Zol)2 contain two trinuclear MoVI cores which can rotate around a central oxo group while Mo(Ale)2 and W(Ale)2 are mononuclear species. In V5(Ale)2 and V5(Zol)2 a central VIV ion is surrounded by two VV dimers bound to bisphosphonate ligands. V6(Ale)4 can be viewed as the condensation of one V5(Ale)2 with one additional VIV ion and two Ale ligands, while V3(Zol)3 is a triangular VIV POM. These new POM bisphosphonates complexes were all characterized by single-crystal X-ray diffraction. The stability of the Mo and W POMs was studied by 31P NMR spectroscopy and showed that all compounds except the mononuclear Mo(Ale)2 and W(Ale)2 were stable in solution. EPR measurements performed on the vanadium derivatives confirmed the oxidation state of the V ions and evidenced their stability in aqueous solution. Electrochemical studies on V5(Ale)2 and V5(Zol)2 showed reduction of VV to VIV and magnetic susceptibility investigations on V3(Zol)3 enabled a detailed analysis of the magnetic interactions. The presence of zoledronate or vanadium correlated with the most potent activity (IC50~1–5 μM) against three human tumor cell lines.
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期刊: ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE
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