N-Heterocyclic carbene (NHC) ligands
are widely investigated in
medicinal inorganic chemistry. Here, we report the preparation and
characterization of a series of half-sandwich [M(L)(NHC)Cl2] (M = Ru, Os, Rh, Ir; L = cym/Cp*) complexes with a N-flanking anthracenyl
moiety attached to imidazole- and benzimidazole-derived NHC ligands.
The anticancer activity of the complexes was investigated in cell
culture studies where, in comparison to a Rh derivative with an all-carbon-donor-atom-based
ligand (5a), they were found to be cytotoxic with IC50 values in the low micromolar range. The Ru derivative 1a was chosen as a representative for stability studies as
well as for biomolecule interaction experiments. It underwent partial
chlorido/aqua ligand exchange in DMSO-d
6/D2O to rapidly form an equilibrium in aqueous media.
The reactions of 1a with biomolecules proceeded quickly
and resulted in the formation of adducts with amino acids, DNA, and
protein. Hen egg white lysozyme crystals were soaked with 1a, and the crystallographic analysis revealed an interaction with
an l-aspartic acid residue (Asp119), resulting in the cleavage
of the p-cymene ligand but the retention of the NHC
moiety. Cell morphology studies for the Rh analog 3a suggested
that the cytotoxicity is exerted via mechanisms different from that
of cisplatin.
Curcumin has been shown to be pharmacologically active in the prevention and treatment of various human diseases. In this study, we developed a fluorous derivatization method for selective analysis of curcumin with liquid chromatography (LC)tandem mass spectrometry (MS/MS). Curcumin was derivatized with the thiol-containing fluorous reagent (1H,1H,2H,2Hperfluoro-1-decanethiol) under mild conditions via Michael addition reaction, and the obtained derivative was introduced to a fluorous LC column (Fluofix-II 120E, 150 × 2.0 mm i.d., 5 μm, Wako). The selectively retained fluorous-derivatized curcumin on the column was also enabled highly sensitive detection with negative electrospray ionization MS/MS. Pretreatment of human serum sample was used protein precipitation with CH 3 CN. The calibration curve obtained by the present method showed good linearity (r 2 = 0.9998) in the range of 7.4-442 ng/mL serum, and the limit of detection (S/N = 3) and limit of quantification (S/N = 10) were 1.8 ng/mL serum and 6.1 ng/mL serum, respectively. The present method was successfully applied to the analysis of curcumin in human serum sample.
Ruthenium-based complexes have attracted attention as promising anticancer candidates due to their lower general toxicity than the widely used platinum drugs. The complex [RuII(η6-p-cymene)(8-oxyquinolinato)Cl] 1 has shown significant cytotoxic activity...
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