TY  - JOUR
AU  - Kuhn, Paul-Steffen
AU  - Cremer, Laura
AU  - Gavriluta, Anatolie
AU  - Jovanovic, Katarina K
AU  - Filipovic, Lana
AU  - Hummer, Alfred A
AU  - Buechel, Gabriel E
AU  - Dojčinović, Biljana
AU  - Meier, Samuel M
AU  - Rompel, Annette
AU  - Radulovic, Sinisa
AU  - Tommasino, Jean Bernard
AU  - Luneau, Dominique
AU  - Arion, Vladimir B
PY  - 2015
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/1680
AB  - A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d-4f) metal complexes of the general formula (nBu(4)N)(5)[Ln{RuCl3(-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)[RuCl3(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 (CNMR)-C-13 spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)](2-) are coordinated to Y-III and Dy-III, respectively, with formation of [Ln{RuCl3(-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{OsCl3(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 IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4M 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.
PB  - Wiley-V C H Verlag Gmbh, Weinheim
T2  - Chemistry-A European Journal
T1  - Heteropentanuclear Oxalato-Bridged nd-4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity
VL  - 21
IS  - 39
SP  - 13703
EP  - 13713
DO  - 10.1002/chem.201502026
ER  - 

@article{
author = "Kuhn, Paul-Steffen and Cremer, Laura and Gavriluta, Anatolie and Jovanovic, Katarina K and Filipovic, Lana and Hummer, Alfred A and Buechel, Gabriel E and Dojčinović, Biljana and Meier, Samuel M and Rompel, Annette and Radulovic, Sinisa and Tommasino, Jean Bernard and Luneau, Dominique and Arion, Vladimir B",
year = "2015",
abstract = "A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d-4f) metal complexes of the general formula (nBu(4)N)(5)[Ln{RuCl3(-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)[RuCl3(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 (CNMR)-C-13 spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)](2-) are coordinated to Y-III and Dy-III, respectively, with formation of [Ln{RuCl3(-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{OsCl3(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 IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4M 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.",
publisher = "Wiley-V C H Verlag Gmbh, Weinheim",
journal = "Chemistry-A European Journal",
title = "Heteropentanuclear Oxalato-Bridged nd-4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity",
volume = "21",
number = "39",
pages = "13703-13713",
doi = "10.1002/chem.201502026"
}

Kuhn, P., Cremer, L., Gavriluta, A., Jovanovic, K. K., Filipovic, L., Hummer, A. A., Buechel, G. E., Dojčinović, B., Meier, S. M., Rompel, A., Radulovic, S., Tommasino, J. B., Luneau, D.,& Arion, V. B.. (2015). Heteropentanuclear Oxalato-Bridged nd-4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity. in Chemistry-A European Journal
Wiley-V C H Verlag Gmbh, Weinheim., 21(39), 13703-13713.
https://doi.org/10.1002/chem.201502026

Kuhn P, Cremer L, Gavriluta A, Jovanovic KK, Filipovic L, Hummer AA, Buechel GE, Dojčinović B, Meier SM, Rompel A, Radulovic S, Tommasino JB, Luneau D, Arion VB. Heteropentanuclear Oxalato-Bridged nd-4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity. in Chemistry-A European Journal. 2015;21(39):13703-13713.
doi:10.1002/chem.201502026 .

Kuhn, Paul-Steffen, Cremer, Laura, Gavriluta, Anatolie, Jovanovic, Katarina K, Filipovic, Lana, Hummer, Alfred A, Buechel, Gabriel E, Dojčinović, Biljana, Meier, Samuel M, Rompel, Annette, Radulovic, Sinisa, 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" in Chemistry-A European Journal, 21, no. 39 (2015):13703-13713,
https://doi.org/10.1002/chem.201502026 . .