Steric hindrance, ligand ejection and associated photocytotoxic properties of ruthenium(II) polypyridyl complexes

IF 2.7 3区化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY

JBIC Journal of Biological Inorganic Chemistry Pub Date : 2023-04-15 DOI:10.1007/s00775-023-01998-z

Piedad Herrera-Ramírez, Sarah Alina Berger, Dana Josa, David Aguilà, Ana B. Caballero, Pere Fontova, Vanessa Soto-Cerrato, Manuel Martínez, Patrick Gamez

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引用次数: 1

Abstract

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⁺.

Abstract Image

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钌(II)多吡啶配合物的空间位阻、配体射出及相关的光细胞毒性

以{Ru(phen)2}2+基团和第三个非位阻双齿配体，即2,2′-二吡啶胺(dpa)和n-苄基-2,2′-二吡啶胺(Bndpa)，制备了两个钌(II)多吡啶配合物。因此，对配合物[Ru(phen)2(dpa)](PF6)2(1)和[Ru(phen)2(Bndpa)](PF6)2(2)进行了表征，并研究了它们在溶液(乙腈和水)中的光化学行为。与同感“母体”化合物[Ru(phen)3](PF6)2相反，化合物1和2不表现出明显扭曲的八面体配位环境，在1050 - 430nm照射数小时后，dpa和Bndpa配体经历两步光射。dna结合研究表明，化合物1和2在辐照下对生物分子的影响不同;复合体2只改变其电泳迁移率，复合体1也能切割它。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在黑暗中都没有毒性，而只有1在照射下有明显的细胞毒性，2在这些条件下无毒。图形摘要:光照射配合阳离子[Ru(phen)2(dpa)]2+会产生瞬时的Ru物质，该物质在溶液介质中存在数小时，具有显著的细胞毒性，最终产生无毒的游离dpa和[Ru(phen)(OH2)2]2+。

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来源期刊

JBIC Journal of Biological Inorganic Chemistry 化学-生化与分子生物学

CiteScore

5.90

自引率

3.30%

发文量

审稿时长

3 months

期刊介绍： Biological inorganic chemistry is a growing field of science that embraces the principles of biology and inorganic chemistry and impacts other fields ranging from medicine to the environment. JBIC (Journal of Biological Inorganic Chemistry) seeks to promote this field internationally. The Journal is primarily concerned with advances in understanding the role of metal ions within a biological matrix—be it a protein, DNA/RNA, or a cell, as well as appropriate model studies. Manuscripts describing high-quality original research on the above topics in English are invited for submission to this Journal. The Journal publishes original articles, minireviews, and commentaries on debated issues.