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Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity
A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d–4f) metal complexes of the general formula (nBu(4)N)(5)[Ln{RuCl(3)(μ-ox)(NO)}(4)], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu(4)N)(2)[RuCl(3)(ox)(NO)] (1) with the respective lanthanide...
Autores principales: | , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
WILEY-VCH Verlag
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4583781/ https://www.ncbi.nlm.nih.gov/pubmed/26260662 http://dx.doi.org/10.1002/chem.201502026 |
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author | Kuhn, Paul-Steffen Cremer, Laura Gavriluta, Anatolie Jovanović, Katarina K Filipović, Lana Hummer, Alfred A Büchel, Gabriel E Dojčinović, Biljana P Meier, Samuel M Rompel, Annette Radulović, Siniša Tommasino, Jean Bernard Luneau, Dominique Arion, Vladimir B |
author_facet | Kuhn, Paul-Steffen Cremer, Laura Gavriluta, Anatolie Jovanović, Katarina K Filipović, Lana Hummer, Alfred A Büchel, Gabriel E Dojčinović, Biljana P Meier, Samuel M Rompel, Annette Radulović, Siniša Tommasino, Jean Bernard Luneau, Dominique Arion, Vladimir B |
author_sort | Kuhn, Paul-Steffen |
collection | PubMed |
description | A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d–4f) metal complexes of the general formula (nBu(4)N)(5)[Ln{RuCl(3)(μ-ox)(NO)}(4)], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu(4)N)(2)[RuCl(3)(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by (13)C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl(3)(ox)(NO)](2−) are coordinated to Y(III) and Dy(III), respectively, with formation of [Ln{RuCl(3)(μ-ox)(NO)}(4)](5−) (Ln=Y, Dy). While Y(III) is eight-coordinate in 2, Dy(III) is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu(4)N(+) ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2–5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d–4f) analogues (nBu(4)N)(5)[Ln{OsCl(3)(ox)(NO)}(4)] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2–5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d–4f metal complexes 6–9 in terms of IC(50) values. The highest antiproliferative activity with IC(50) values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells. |
format | Online Article Text |
id | pubmed-4583781 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | WILEY-VCH Verlag |
record_format | MEDLINE/PubMed |
spelling | pubmed-45837812015-10-01 Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity Kuhn, Paul-Steffen Cremer, Laura Gavriluta, Anatolie Jovanović, Katarina K Filipović, Lana Hummer, Alfred A Büchel, Gabriel E Dojčinović, Biljana P Meier, Samuel M Rompel, Annette Radulović, Siniša Tommasino, Jean Bernard Luneau, Dominique Arion, Vladimir B Chemistry Full Papers A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d–4f) metal complexes of the general formula (nBu(4)N)(5)[Ln{RuCl(3)(μ-ox)(NO)}(4)], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu(4)N)(2)[RuCl(3)(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by (13)C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl(3)(ox)(NO)](2−) are coordinated to Y(III) and Dy(III), respectively, with formation of [Ln{RuCl(3)(μ-ox)(NO)}(4)](5−) (Ln=Y, Dy). While Y(III) is eight-coordinate in 2, Dy(III) is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu(4)N(+) ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2–5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d–4f) analogues (nBu(4)N)(5)[Ln{OsCl(3)(ox)(NO)}(4)] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2–5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d–4f metal complexes 6–9 in terms of IC(50) values. The highest antiproliferative activity with IC(50) values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells. WILEY-VCH Verlag 2015-09-21 2015-08-10 /pmc/articles/PMC4583781/ /pubmed/26260662 http://dx.doi.org/10.1002/chem.201502026 Text en © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. https://creativecommons.org/licenses/by/4.0/ © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Full Papers Kuhn, Paul-Steffen Cremer, Laura Gavriluta, Anatolie Jovanović, Katarina K Filipović, Lana Hummer, Alfred A Büchel, Gabriel E Dojčinović, Biljana P Meier, Samuel M Rompel, Annette Radulović, Siniša Tommasino, Jean Bernard Luneau, Dominique Arion, Vladimir B Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity |
title | Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity |
title_full | Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity |
title_fullStr | Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity |
title_full_unstemmed | Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity |
title_short | Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity |
title_sort | heteropentanuclear oxalato-bridged nd–4f (n=4, 5) metal complexes with no ligand: synthesis, crystal structures, aqueous stability and antiproliferative activity |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4583781/ https://www.ncbi.nlm.nih.gov/pubmed/26260662 http://dx.doi.org/10.1002/chem.201502026 |
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