19 research outputs found
Osmium-Nitrosyl Oxalato-Bridged Lanthanide-Centered Pentanuclear Complexes - Synthesis, Crystal Structures and Magnetic Properties
International audienceA series of pentanuclear heterometallic coordination compounds of the general formula (Bu 4 N) 5 [Ln{Os(NO)(Ό-ox)-Cl 3 } 4 (H 2 O) n ] [Ln = Y (for 2) and Dy (for 3) when n = 0; Ln = Dy (for 3), Tb (for 4), and Gd (for 5) when n = 1] were synthesized by the reaction of the precursor (Bu 4 N) 2 [Os(NO)(ox)-Cl 3 ] (1) with the respective lanthanide(III) (Gd, Tb, Dy) or yttrium(III) chloride. For the five new complexes, the coordination numbers eight or nine are found for the central metal ion. The compounds were fully characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction analysis, magnetic susceptibility measurements, and ESI mass spectrometry. In addition, compound 1 was studied by UV/Vis spectroscopy and cyclic voltammetry. The X-ray dif-fraction analyses revealed that the anionic complexes consist of a lanthanide or yttrium core bridged through oxalato li-gands to four octahedral osmium-nitrosyl moieties. This picture , in which the central ion is eight-coordinate, holds fo
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{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
Complexes osmium nitrosyle avec des ligands bioactifs : synthÚse, structure, réactivité et activité antiproliférative in vitro
The PhD thesis was dedicated to the synthesis and bio-physic-chemical characterization of osmium nitrosyl complexes which could release nitric oxide (NO) in tumor cells to combine the anticancer properties of the platinum group complexes and the nitric oxide cytotoxicity. The first chapter presents the state of the art in the field of anticancer compounds and the role of nitric oxide in the apoptosis. The second chapter concerns the synthesis and characterization of azole complexes with the general formulae (C)[Os(NO)Cl4(A)] (C = Bu4N+, Na+, HA+; A = indazole, pyrazole, benzimidazole, imidazole), where the most cytotoxic is H2ind[cis-Os(NO)Cl4(indazole)]. The third chapter focuses on the kinetic and thermodynamic study of the trans â cis isomerisation of (Bu4N)[Os(NO)Cl4(indazole)] complex by NMR, which highlights a dissociative isomerisation process. The fourth chapter concerns the synthesis and the characterization of amino acids complexes with the general formulae (Bu4N)[Os(NO)Cl4(L)] (L = gly, picolinate, L-, D-pro) of whose antiproliferative activity is very low. The last chapter is dedicated to the synthesis and characterization of heterometallic clusters with the general formulae [{Os(NO)Cl3(Ox)}4Ln] (Ln = Gd, Tb, Dy, Y ; Ox = oxalate), where the coordination number 8 or 9 depends on its ionic radius. The precursor {Os(NO)Cl3(Ox)} has the highest antiproliferative activity among of all osmium nitrosyl known so farNotre travail de thĂšse a Ă©tĂ© dĂ©diĂ© Ă la synthĂšse et Ă la caractĂ©risation bio-physicochimique de complexes osmium nitrosyle, qui pourraient relarguer lâoxyde nitrique (NO) au sein des cellules tumorales pour conjuguer les propriĂ©tĂ©s anticancĂ©reuses souvent associĂ©s aux complexes du groupe du platine avec la toxicitĂ© de lâoxyde nitrique. Le premier chapitre de notre mĂ©moire de thĂšse prĂ©sente lâĂ©tat de lâart dans le domaine des composĂ©s anticancĂ©reux et le rĂŽle de lâoxyde nitrique dans lâapoptose cellulaire. Le deuxiĂšme chapitre concerne la synthĂšse et la caractĂ©risation de complexes dâazole (C)[Os(NO)Cl4(A)] (C = Bu4N+, Na+, HA+; A = indazole, pyrazole, benzimidazole, imidazole), oĂč le plus cytotoxique est H2ind[cis-Os(NO)Cl4(indazole)]. Le troisiĂšme chapitre est consacrĂ© Ă lâĂ©tude cinĂ©tique et thermodynamique par RMN de lâisomĂ©risation trans â cis du complexe (Bu4N)[Os(NO)Cl4(indazole)] qui met en Ă©vidence un processus dâisomĂ©risation de type dissociatif. Le quatriĂšme chapitre concerne la synthĂšse et la caractĂ©risation de complexes dâaminoacides (Bu4N)[Os(NO)Cl4(L)] (L = gly, picolinate, L-, D-pro) qui ont une trĂšs faible activitĂ© antiprolifĂ©rative. Le dernier chapitre est consacrĂ© Ă la synthĂšse et Ă la caractĂ©risation de clusters hĂ©tĂ©romĂ©talliques [{Os(NO)Cl3(Ox)}4Ln] (Ln = Gd, Tb, Dy, Y ; Ox=oxalate) dans lesquels la coordinance 8 ou 9 du lanthanide dĂ©pend de son rayon ionique. Le prĂ©curseur {Os(NO)Cl3(Ox)} a lâactivitĂ© antiprolifĂ©rative la plus Ă©levĂ©e de tous les complexes osmium nitrosyle connu
Osmium nitrosyl complexes with bioactive ligands : synthesis, structure, reactivity and antiproliferative activity in vitro
Notre travail de thĂšse a Ă©tĂ© dĂ©diĂ© Ă la synthĂšse et Ă la caractĂ©risation bio-physicochimique de complexes osmium nitrosyle, qui pourraient relarguer lâoxyde nitrique (NO) au sein des cellules tumorales pour conjuguer les propriĂ©tĂ©s anticancĂ©reuses souvent associĂ©s aux complexes du groupe du platine avec la toxicitĂ© de lâoxyde nitrique. Le premier chapitre de notre mĂ©moire de thĂšse prĂ©sente lâĂ©tat de lâart dans le domaine des composĂ©s anticancĂ©reux et le rĂŽle de lâoxyde nitrique dans lâapoptose cellulaire. Le deuxiĂšme chapitre concerne la synthĂšse et la caractĂ©risation de complexes dâazole (C)[Os(NO)Cl4(A)] (C = Bu4N+, Na+, HA+; A = indazole, pyrazole, benzimidazole, imidazole), oĂč le plus cytotoxique est H2ind[cis-Os(NO)Cl4(indazole)]. Le troisiĂšme chapitre est consacrĂ© Ă lâĂ©tude cinĂ©tique et thermodynamique par RMN de lâisomĂ©risation trans â cis du complexe (Bu4N)[Os(NO)Cl4(indazole)] qui met en Ă©vidence un processus dâisomĂ©risation de type dissociatif. Le quatriĂšme chapitre concerne la synthĂšse et la caractĂ©risation de complexes dâaminoacides (Bu4N)[Os(NO)Cl4(L)] (L = gly, picolinate, L-, D-pro) qui ont une trĂšs faible activitĂ© antiprolifĂ©rative. Le dernier chapitre est consacrĂ© Ă la synthĂšse et Ă la caractĂ©risation de clusters hĂ©tĂ©romĂ©talliques [{Os(NO)Cl3(Ox)}4Ln] (Ln = Gd, Tb, Dy, Y ; Ox=oxalate) dans lesquels la coordinance 8 ou 9 du lanthanide dĂ©pend de son rayon ionique. Le prĂ©curseur {Os(NO)Cl3(Ox)} a lâactivitĂ© antiprolifĂ©rative la plus Ă©levĂ©e de tous les complexes osmium nitrosyle connusThe PhD thesis was dedicated to the synthesis and bio-physic-chemical characterization of osmium nitrosyl complexes which could release nitric oxide (NO) in tumor cells to combine the anticancer properties of the platinum group complexes and the nitric oxide cytotoxicity. The first chapter presents the state of the art in the field of anticancer compounds and the role of nitric oxide in the apoptosis. The second chapter concerns the synthesis and characterization of azole complexes with the general formulae (C)[Os(NO)Cl4(A)] (C = Bu4N+, Na+, HA+; A = indazole, pyrazole, benzimidazole, imidazole), where the most cytotoxic is H2ind[cis-Os(NO)Cl4(indazole)]. The third chapter focuses on the kinetic and thermodynamic study of the trans â cis isomerisation of (Bu4N)[Os(NO)Cl4(indazole)] complex by NMR, which highlights a dissociative isomerisation process. The fourth chapter concerns the synthesis and the characterization of amino acids complexes with the general formulae (Bu4N)[Os(NO)Cl4(L)] (L = gly, picolinate, L-, D-pro) of whose antiproliferative activity is very low. The last chapter is dedicated to the synthesis and characterization of heterometallic clusters with the general formulae [{Os(NO)Cl3(Ox)}4Ln] (Ln = Gd, Tb, Dy, Y ; Ox = oxalate), where the coordination number 8 or 9 depends on its ionic radius. The precursor {Os(NO)Cl3(Ox)} has the highest antiproliferative activity among of all osmium nitrosyl known so fa
The First Homoleptic Complex of Seven-Coordinated Osmium: Synthesis and Crystallographical Evidence of Pentagonal Bipyramidal Polyhedron of Heptacyanoosmate(IV)
The ligand exchange in (n-Bu4N)2OsIVCl6 (n-Bu4N = tetra-n-butylammonium) leads to the formation of the osmium(IV) heptacyanide, the first fully inorganic homoleptic complex of heptacoordinated osmium. The single-crystal X-ray diffraction (SC-XRD) study reveals the pentagonal bipyramidal molecular structure of the [Os(CN)7]3â anion. The latter being a diamagnetic analogue of the highly anisotropic paramagnetic synthon, [ReIV(CN)7]3â can be used for the synthesis of the model heterometallic coordination compounds for the detailed study and simulation of the magnetic properties of the low-dimensional molecular nanomagnets involving 5d metal heptacyanides
Eu III -Based Nanolayers as Highly Efficient Downshifters for CIGS Solar Cells
International audienc
Ruthenium-Nitrosyl Complexes with Glycine, L-Alanine, L-Valine, L-Proline, D-Proline, L-Serine, L-Threonine and L-Tyrosine: Synthesis, X-ray Diffraction Structures, Spectroscopic and Electrochemical Properties and Antiproliferative Activity
The reactions of [Ru(NO)Cl5]2â with glycine (Gly), L-
16 alanine (L-Ala), L-valine (L-Val), L-proline (L-Pro), D-proline (D-Pro),
17 L-serine (L-Ser), L-threonine (L-Thr), and L-tyrosine (L-Tyr) in n-
18 butanol or n-propanol afforded eight novel complexes (1â8) of the
19 general formula [RuCl3(AAâH)(NO)]â, where AA = Gly, L-Ala, L-
20 Val, L-Pro, D-Pro, L-Ser, L-Thr, and L-Tyr, respectively. The
21 compounds were characterized by elemental analysis, electrospray
22 ionization mass spectrometry (ESI-MS), 1H NMR, UVâvisible and
23 ATR IR spectroscopy, cyclic voltammetry, and X-ray crystallography.
24 X-ray crystallography studies have revealed that in all cases the same
25 isomer type (from three theoretically possible) was isolated, namely
26 mer(Cl),trans(NO,O)-[RuCl3(AAâH)(NO)], as was also recently
27 reported for osmium analogues with Gly, L-Pro, and D-Pro (see Z. Anorg. Allg. Chem. 2013, 639, 1590â1597). Compounds 1, 4,
28 5, and 8 were investigated by ESI-MS with regard to their stability in aqueous solution and reactivity toward sodium ascorbate. In
29 addition, cell culture experiments in three human cancer cell lines, namely, A549 (nonsmall cell lung carcinoma), CH1 (ovarian
30 carcinoma), and SW480 (colon carcinoma), were performed, and the results are discussed in conjunction with the lipophilicity of
31 compounds
Y-Chromosomal Haplogroup R1b Diversity in Near East is Structured by Recent Historical Events
<p>A number of Near East populations have been studied, leading to contradictory conclusions. Sampling processes, microsatellite count and recent historic events have the potential to distort the results. Standard practice for genetic sample selection is limited to validating the geographic origin of the subjectâs father or grandfather. Restricting the sampling to 10 or 11 microsatellites allows for haplotype convergence and provides insufficient analytical value for nonbiased origin identification. Roman Catholic Crusader activity in the 11thâ13th centuries introduced western European haplotypes into the Near East, complicating the sampling process. Theories of a Neolithic origin for haplogroup R1b will have to be re-evaluated.</p