类姜黄素-芳基钌配合物的合成、结构和光照激活抗癌活性

合成了3种含姜黄素衍生物(L¹~L³)和1,3,5-三氮杂-7-磷金刚烷(PTA)配体的芳基钌配合物[(η⁶-p-cymene)Ru(L)(PTA)]PF6(1~3,L=L¹~L³),通过X射线单晶衍射、核磁共振波谱、高分辨质谱、元素分析等方法表征了这些配合物的结构,并用MTT法研究了它们在λ>400 nm的光照辅助下对Hep G2人肝癌细胞的增殖抑制活性。结果表明,这3个配合物均为半三明治型结构;光辅助下,配合物抗癌活性明显提高,其中配合物3对HepG2细胞的IC50值从(60.3±1.1)μmol·L^-1降低至(45.0±6.1)μmol·L^-1。说明光照可以有效提高此类配合物的抗肿瘤活性。     

联吡啶衍生物芳基钌配合物的合成及其与DNA、蛋白质相互作用

以2种配体4,4′-dimethyl-2,2′-bipyridine(L1)和4′-methyl-(2,2′-bipyridine)-4-carbaldehyde oxime(L2),分别与芳基钌二聚体[RuCl_2(η~6-p-cymene)]2合成了2种新型单核配合物[Ru(η~6-p-cymene)(L1)Cl]Cl(1)和[Ru(η6-p-cymene)(L2)Cl]Cl(2)。应用元素分析、ESI-MS和~1H NMR对配合物的组成和结构进行表征,通过紫外光谱法和荧光光谱法研究了配合物的水解及其与CT-DNA和血清蛋白的结合性质,并且进行了细胞毒性研究。结果表明,在水溶液中配合物1比2在动力学上更稳定(k:0.383 h~(-1)(1)、1.458 h~(-1)(2));配合物均通过嵌入作用与双链DNA结合,但2有较强的结合能力(Kb:7.8×10~3L·mol~(-1)(1)、1.86×10~4L·mol~(-1)(2))。配合物均能与蛋白质发生相互作用,引起蛋白静态猝灭,但1作用较强(KA:1.04×10~5L·mol~(-1)(1)、8.62×10~4L·mol~(-1)(2))。配合物与蛋白的较强结合能力,可能是其细胞毒性不高的原因。     

Synthesis,thermochemistry, and structural characterization of organoruthenium arene and triene complexes

The synthetic, thermodynamic and structural investigations of organoruthenium complexes of the form Cp^*Ru(triene)OTf (Cp^*=n⁵-(CH₃)₅C₅; triene=anisole 1, indole 2, cycloheptatriene 3, OTf=OSO₂CF₃) are presented in this contribution. A direct entryway into the thermochemistry of these complexes is made possible by the rapid and quantitative arene/triene substitution for the three acetonitrile ligands in Cp^*Ru(CH₃CN)₃OTf. The solution calorimetric study establishes the following order of stability: cycloheptatriene < anisole < indole. This study helps clarify the enthalpic and entropic components to the thermodynamic driving forces behind the formation of ruthenium arene/triene complexes. The solid-state structures of these three complexes(1–3) were determined by X-ray single-crystal studies. Thermodynamic factors affecting the Ru-triene bond energy are compared with structural results for these three ruthenium complexes.     

Synthesis and characterization of water-soluble arene-ruthenium complexes and their application in biphasic olefin oxidation

New water-soluble complexes [(η⁶-C₆H₆)RuCl(C₅H₄N-2-CH?=?N-R)]Cl (1) (with R?=?4-hydroxymethylphenyl (a), 2,4-dichlorophenyl (b), 2-fluorophenyl (c), 3-carboxyphenyl (d)) have been synthesized by reacting [(η⁶-C₆H₆)Ru(μ-Cl)Cl]₂ with the N,N′-bidentate ligands in a 1:2 ratio. Full characterization of all complexes was accomplished using ¹H and ¹³C NMR, elemental analyses, UV-Vis spectroscopy, IR spectroscopy and single crystal X-ray crystallography for determination of the structure of 1d, as 1d·4H₂O. The single crystal structure confirmed coordination of the ligand to the ruthenium(II) center leading to a structure commonly described as a pseudo-octahedral, three-legged piano stool. The geometry around the Ru(II) center is such that the arene ring occupies the apex of the stool while the N,N′-bidentate ligand and a chloride occupy the base of the stool. The synthesized Ru(II) complexes were tested as catalysts for oxidation of styrene using NaIO₄ as a co-oxidant in a biphasic system. All complexes were active, giving good yields of benzaldehyde. Catalyst 1c was later investigated for olefin oxidation and gave high yields of the corresponding aldehydes as the major products in all cases.     

类姜黄素-芳基钌配合物的合成、结构和光照激活抗癌活性

合成了3种含姜黄素衍生物（L¹~L³）和1，3，5-三氮杂-7-磷金刚烷（PTA）配体的芳基钌配合物[（η⁶-p-cymene）Ru（L）（PTA）]PF₆（1~3，L=L¹~L³），通过X射线单晶衍射、核磁共振波谱、高分辨质谱、元素分析等方法表征了这些配合物的结构，并用MTT法研究了它们在λ>400 nm的光照辅助下对HepG2人肝癌细胞的增殖抑制活性。结果表明，这3个配合物均为半三明治型结构；光辅助下，配合物抗癌活性明显提高，其中配合物3对HepG2细胞的IC₅₀值从（60.3±1.1）μmol·L^-1降低至（45.0±6.1）μmol·L^-1。说明光照可以有效提高此类配合物的抗肿瘤活性。