Piedad Herrera-Ramírez, Sarah Alina Berger, Dana Josa, David Aguilà, Ana B. Caballero, Pere Fontova, Vanessa Soto-Cerrato, Manuel Martínez, Patrick Gamez
{"title":"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","authors":"Piedad Herrera-Ramírez, Sarah Alina Berger, Dana Josa, David Aguilà, Ana B. Caballero, Pere Fontova, Vanessa Soto-Cerrato, Manuel Martínez, Patrick Gamez","doi":"10.1007/s00775-023-01998-z","DOIUrl":null,"url":null,"abstract":"<div><p>Two ruthenium(II) polypyridyl complexes were prepared with the {Ru(phen)<sub>2</sub>}<sup>2+</sup> moiety and a third sterically non-hindering bidentate ligand, namely 2,2′-dipyridylamine (dpa) and <i>N</i>-benzyl-2,2′-dipyridylamine (Bndpa). Hence, complexes [Ru(phen)<sub>2</sub>(dpa)](PF<sub>6</sub>)<sub>2</sub> (<b>1</b>) and [Ru(phen)<sub>2</sub>(Bndpa)](PF<sub>6</sub>)<sub>2</sub> (<b>2</b>) were characterized and their photochemical behaviour in solution (acetonitrile and water) was subsequently investigated. Compounds <b>1</b> and <b>2</b>, which do not exhibit notably distorted octahedral coordination environments, contrarily to the homoleptic “parent” compound [Ru(phen)<sub>3</sub>](PF<sub>6</sub>)<sub>2</sub>, experience two-step photoejection of the dpa and Bndpa ligand upon irradiation (1050–430?nm) for several hours. DNA-binding studies revealed that compounds <b>1</b> and <b>2</b> affect the biomolecule differently upon irradiation; while <b>2</b> solely modifies its electrophoretic mobility, complex <b>1</b> 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 <b>1</b> and <b>2</b> are not toxic in the dark, while only <b>1</b> is significantly cytotoxic if irradiated, <b>2</b> remaining non-toxic under these conditions.</p><h3>Graphical abstract</h3><p>Light irradiation of the complex cation [Ru(phen)<sub>2</sub>(dpa)]<sup>2+</sup> 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)(OH<sub>2</sub>)<sub>2</sub>]<sup>2+</sup>.</p>\n <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\n </div>","PeriodicalId":603,"journal":{"name":"JBIC Journal of Biological Inorganic Chemistry","volume":"28 4","pages":"403 - 420"},"PeriodicalIF":2.7000,"publicationDate":"2023-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00775-023-01998-z.pdf","citationCount":"1","resultStr":"{\"title\":\"Steric hindrance, ligand ejection and associated photocytotoxic properties of ruthenium(II) polypyridyl complexes\",\"authors\":\"Piedad Herrera-Ramírez, Sarah Alina Berger, Dana Josa, David Aguilà, Ana B. Caballero, Pere Fontova, Vanessa Soto-Cerrato, Manuel Martínez, Patrick Gamez\",\"doi\":\"10.1007/s00775-023-01998-z\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Two ruthenium(II) polypyridyl complexes were prepared with the {Ru(phen)<sub>2</sub>}<sup>2+</sup> moiety and a third sterically non-hindering bidentate ligand, namely 2,2′-dipyridylamine (dpa) and <i>N</i>-benzyl-2,2′-dipyridylamine (Bndpa). Hence, complexes [Ru(phen)<sub>2</sub>(dpa)](PF<sub>6</sub>)<sub>2</sub> (<b>1</b>) and [Ru(phen)<sub>2</sub>(Bndpa)](PF<sub>6</sub>)<sub>2</sub> (<b>2</b>) were characterized and their photochemical behaviour in solution (acetonitrile and water) was subsequently investigated. Compounds <b>1</b> and <b>2</b>, which do not exhibit notably distorted octahedral coordination environments, contrarily to the homoleptic “parent” compound [Ru(phen)<sub>3</sub>](PF<sub>6</sub>)<sub>2</sub>, experience two-step photoejection of the dpa and Bndpa ligand upon irradiation (1050–430?nm) for several hours. DNA-binding studies revealed that compounds <b>1</b> and <b>2</b> affect the biomolecule differently upon irradiation; while <b>2</b> solely modifies its electrophoretic mobility, complex <b>1</b> 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 <b>1</b> and <b>2</b> are not toxic in the dark, while only <b>1</b> is significantly cytotoxic if irradiated, <b>2</b> remaining non-toxic under these conditions.</p><h3>Graphical abstract</h3><p>Light irradiation of the complex cation [Ru(phen)<sub>2</sub>(dpa)]<sup>2+</sup> 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)(OH<sub>2</sub>)<sub>2</sub>]<sup>2+</sup>.</p>\\n <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\\n </div>\",\"PeriodicalId\":603,\"journal\":{\"name\":\"JBIC Journal of Biological Inorganic Chemistry\",\"volume\":\"28 4\",\"pages\":\"403 - 420\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2023-04-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s00775-023-01998-z.pdf\",\"citationCount\":\"1\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"JBIC Journal of Biological Inorganic Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s00775-023-01998-z\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"BIOCHEMISTRY & MOLECULAR BIOLOGY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"JBIC Journal of Biological Inorganic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://link.springer.com/article/10.1007/s00775-023-01998-z","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}
Steric hindrance, ligand ejection and associated photocytotoxic properties of ruthenium(II) polypyridyl complexes
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+.
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.
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