Steric hindrance, ligand ejection and associated photocytotoxic properties of ruthenium(II) polypyridyl complexes,JBIC Journal of Biological Inorganic Chemistry

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Steric hindrance, ligand ejection and associated photocytotoxic properties of ruthenium(II) polypyridyl complexes
JBIC Journal of Biological Inorganic Chemistry ( IF 2.7 ) Pub Date : 2023-04-15 , DOI: 10.1007/s00775-023-01998-z
Piedad Herrera-Ramírez ₁ , Sarah Alina Berger ₁ , Dana Josa ₁ , David Aguilà _{1,

2} , Ana B Caballero _{1,

2} , Pere Fontova _{3,

4} , Vanessa Soto-Cerrato _{3,

5} , Manuel Martínez _{1,

2} , Patrick Gamez _{1,

2,

6}

Affiliation

Two ruthenium(II) polypyridyl complexes were prepared with the {Ru(phen)₂}²⁺ moiety and a third sterically non-hindering bidentate ligand, namely 2,2′-dipyridylamine (dpa) and N-benzyl-2,2′-dipyridylamine (Bndpa). Hence, complexes [Ru(phen)₂(dpa)](PF₆)₂ (1) and [Ru(phen)₂(Bndpa)](PF₆)₂ (2) were characterized and their photochemical behaviour in solution (acetonitrile and water) was subsequently investigated. Compounds 1 and 2, which do not exhibit notably distorted octahedral coordination environments, contrarily to the homoleptic “parent” compound [Ru(phen)₃](PF₆)₂, experience two-step photoejection of the dpa and Bndpa ligand upon irradiation (1050–430 nm) for several hours. DNA-binding studies revealed that compounds 1 and 2 affect the biomolecule differently upon irradiation; while 2 solely modifies its electrophoretic mobility, complex 1 is also capable of cleaving it. In vitro cytotoxicity studies with two cancer-cell lines, namely A549 (lung adenocarcinoma) and A375 (melanoma), showed that both 1 and 2 are not toxic in the dark, while only 1 is significantly cytotoxic if irradiated, 2 remaining non-toxic under these conditions.

Graphical abstract

Light irradiation of the complex cation [Ru(phen)₂(dpa)]²⁺ leads to the generation of transient Ru species that is present in the solution medium for several hours, and that is significantly cytotoxic, ultimately producing non-toxic free dpa and [Ru(phen)(OH₂)₂]²⁺.

中文翻译：

钌(II)聚吡啶配合物的空间位阻、配体喷射和相关光细胞毒性

使用 {Ru(phen) ₂ } ²⁺部分和第三个空间非位阻双齿配体（即 2,2'-二吡啶胺 (dpa) 和N-苄基-2,2'）制备了两种钌 (II) 聚吡啶配合物-二吡啶胺（Bndpa）。因此，对配合物 [Ru(phen) ₂ (dpa)](PF ₆ ) ₂ ( 1 ) 和 [Ru(phen) ₂ (Bndpa)](PF ₆ ) ₂ ( 2 ) 进行了表征，并研究了它们在溶液（乙腈）中的光化学行为。和水）随后进行了研究。与均配“母体”化合物 [Ru(phen) ₃ ](PF ₆ ) ₂相反，化合物1和2没有表现出明显扭曲的八面体配位环境，在照射下经历 dpa 和 Bndpa 配体的两步光喷射（ 1050–430 nm）几个小时。 DNA 结合研究表明，化合物1和2在照射后对生物分子的影响不同；虽然2仅改变其电泳迁移率，但复合物1也能够将其裂解。对两种癌细胞系 A549（肺腺癌）和 A375（黑色素瘤）进行的体外细胞毒性研究表明， 1和2在黑暗中均无毒性，而只有1 种在辐照后具有显着的细胞毒性， 2 种仍然无毒。在这些条件下。