Department of Chemistry, The Ohio State University, Columbus, OH 43210, USA.
J Inorg Biochem. 2013 Apr;121:77-87. doi: 10.1016/j.jinorgbio.2012.12.003. Epub 2012 Dec 16.
The complex cis-Ru(phpy)(phen)(CH3CN)2 (phpy=2-phenylpyridine, phen=1,10-phenanthroline) was investigated as a potential photodynamic therapy (PDT) agent. This complex presents desirable photochemical characteristics including a low energy absorption tail extending into the PDT window (600-850nm) and photoinduced exchange of the CH3CN ligands, generating a species analogous to the chemotherapy drug cisplatin. Furthermore, photochemical reactivity can be controlled through selective irradiation into the Ru-phen singlet metal-to-ligand charge transfer ((1)MLCT) band (λirr=500 nm) of Ru(phpy)(phen)(CH3CN)2 in the presence of excess t-butylammonium chloride (TBACl) resulting in efficient photoinduced production of [Ru(phpy)(phen)(CH3CN)Cl] (Φ=0.25). This lower energy irradiation resulted in greater quantum yield of photosubstitution when compared to direct irradiation into the Ru-phpy (1)MLCT peak (λirr=450 nm; Φ=0.08) in CH2Cl2. It was found that the lower quantum yield observed for irradiation into the Ru→phpy(-)(1)MLCT band results from significant orbital mixing of the phpy(-) ligand with the t2g-type filled set in the metal, giving this state significant ligand-centered character. Lastly, this complex produced a decrease in the mobility of linearized ds-DNA when irradiated with λirr≥420nm, indicative of covalent binding by the transition metal complex similar to that observed for cisplatin. No change in mobility was found for the same samples kept in the dark indicating, unlike cisplatin, DNA binding of cis-Ru(phpy)(phen)(CH3CN)2 only occurs with the activation of light. These observations support the use of cis-Ru(phpy)(phen)(CH3CN)2 as a potential PDT agent by the photoinduced generation of a cisplatin analog.
顺式-Ru(phpy)(phen)(CH3CN)2(phpy=2-苯基吡啶,phen=1,10-菲啰啉)被研究作为一种潜在的光动力治疗(PDT)试剂。该配合物具有理想的光化学特性,包括延伸到 PDT 窗口(600-850nm)的低能量吸收尾部和 CH3CN 配体的光诱导交换,生成类似于化疗药物顺铂的物种。此外,光化学反应性可以通过在存在过量的叔丁基氯化铵(TBACl)的情况下选择性地照射到Ru(phpy)(phen)(CH3CN)2的 Ru-phen 单重态金属-配体电荷转移((1)MLCT)带(λirr=500nm)来控制,导致 [Ru(phpy)(phen)(CH3CN)Cl]的有效光诱导生成(Φ=0.25)。与直接照射到 Ru-phpy(1)MLCT 峰(λirr=450nm;Φ=0.08)相比,这种较低能量的照射导致 CH2Cl2 中光取代的量子产率更高。结果表明,观察到的照射到 Ru→phpy(-)(1)MLCT 带的量子产率较低是由于 phpy(-)配体与金属中的 t2g 型充满轨道的显著轨道混合,使该状态具有显著的配体中心特征。最后,当用 λirr≥420nm 照射时,该配合物导致线性 ds-DNA 的迁移率降低,表明过渡金属配合物的共价结合类似于顺铂观察到的情况。对于保持在黑暗中的相同样品,没有发现迁移率的变化,这表明与顺铂不同,cis-Ru(phpy)(phen)(CH3CN)2的 DNA 结合仅在光的激活下发生。这些观察结果支持使用顺式-Ru(phpy)(phen)(CH3CN)2作为光动力治疗剂,通过光诱导生成顺铂类似物。