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The Significant Influence of a Second Metal on the Antiproliferative Properties of the Complex [Ru(η⁶ -C₁₀ H₁₄ )(Cl₂ )(dmoPTA)].

ABSTRACT: Complexes [Ru(η⁶ -C₁₀ H₁₄ )(Cl₂ )(HdmoPTA)](OSO₂ CF₃ ) (1), [Ru(η⁶ -C₁₀ H₁₄ )(Cl₂ )(dmoPTA)] (2) and [Ru(η⁶ -C₁₀ H₁₄ )(Cl₂ )-μ-dmoPTA-1κP:2κ² N,N'-MCl₂ ] (M=Zn (3), Co (4), Ni (5), dmoPTA=3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) have been synthesized and characterized by elemental analysis and spectroscopic techniques. The crystal structures of 1, 3 and 5 were obtained by single-crystal X-ray diffraction. The antiproliferative activity of the complexes was evaluated against colon cancer cell line Caco-2/TC7 by using the MTT protocol. The monometallic ruthenium complexes 1 and 2 were found to be inactive, but the bimetallic complexes 3, 4 and 5 display an increased activity (IC₅₀ 3: 9.07±0.27, 4: 5.40±0.19, 5: 7.15±0.30 μM) compared to cisplatin (IC₅₀ =45.6±8.08 μM). Importantly, no reduction in normal cell viability was observed in the presence of the complexes. Experiments targeted to obtain information on the possible action mechanism of the complexes, such as cell cycle, ROS and gene expression studies, were performed. The results showed that the complexes display different properties and action mechanism depending on the nature of metal, M, bonded to the CH₃ N_dmoPTA atoms.

SUBMITTER: Kordestani N

PROVIDER: S-EPMC9299940 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Photochemical CO2 reduction catalysed by trans(Cl)-Ru(bpy)(CO)2Cl2 (bpy = 2,2'-bipyridine) efficiently produces carbon monoxide (CO) and formate (HCOO-) in N,N-dimethylacetamide (DMA)/water containing [Ru(bpy)3]2+ as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor. We have unexpectedly found catalyst concentration dependence of the product ratio (CO/HCOO-) in the photochemical CO2 reduction: the ratio of CO/HCOO- decreases with increasing catalyst concentration. The result has led us to propose a new mechanism in which HCOO- is selectively produced by the formation of a Ru(i)-Ru(i) dimer as the catalyst intermediate. This reaction mechanism predicts that the Ru-Ru bond dissociates in the reaction of the dimer with CO2, and that the insufficient electron supply to the catalyst results in the dominant formation of HCOO-. The proposed mechanism is supported by the result that the time-course profiles of CO and HCOO- in the photochemical CO2 reduction catalysed by [Ru(bpy)(CO)2Cl]2 (0.05 mM) are very similar to those of the reduction catalysed by trans(Cl)-Ru(bpy)(CO)2Cl2 (0.10 mM), and that HCOO- formation becomes dominant under low-intensity light. The kinetic analyses based on the proposed mechanism could excellently reproduce the unusual catalyst concentration effect on the product ratio. The catalyst concentration effect observed in the photochemical CO2 reduction using [Ru(4dmbpy)3]2+ (4dmbpy = 4,4'-dimethyl-2,2'-bipyridine) instead of [Ru(bpy)3]2+ as the photosensitizer is also explained with the kinetic analyses, reflecting the smaller quenching rate constant of excited [Ru(4dmbpy)3]2+ by BNAH than that of excited [Ru(bpy)3]2+. We have further synthesized trans(Cl)-Ru(6Mes-bpy)(CO)2Cl2 (6Mes-bpy = 6,6'-dimesityl-2,2'-bipyridine), which bears bulky substituents at the 6,6'-positions in the 2,2'-bipyridyl ligand, so that the ruthenium complex cannot form the dimer due to the steric hindrance. We have found that this ruthenium complex selectively produces CO, which strongly supports the catalytic mechanism proposed in this work.

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The Significant Influence of a Second Metal on the Antiproliferative Properties of the Complex [Ru(η⁶ -C₁₀ H₁₄ )(Cl₂ )(dmoPTA)].

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The Significant Influence of a Second Metal on the Antiproliferative Properties of the Complex [Ru(η6 -C10 H14 )(Cl2 )(dmoPTA)].

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The Significant Influence of a Second Metal on the Antiproliferative Properties of the Complex [Ru(η⁶ -C₁₀ H₁₄ )(Cl₂ )(dmoPTA)].