Cationic triiron complexes resulting from the conjugation of the ferrocenyl skeleton(Fc)with a diiron bis-cyclopentadienyl core through a variable vinyliminium linker,[Fe2Cp2(CO)(μ-CO){μ–η^(1):η^(3)-C(Fc)CHCN(R)(...Cationic triiron complexes resulting from the conjugation of the ferrocenyl skeleton(Fc)with a diiron bis-cyclopentadienyl core through a variable vinyliminium linker,[Fe2Cp2(CO)(μ-CO){μ–η^(1):η^(3)-C(Fc)CHCN(R)(R′)}]CF_(3)SO_(3)([2a–i]CF_(3)SO_(3),Cp=η^(5)-C5H5,R,R′=alkyl,aryl),were synthesised in 70–94%yield,and the homologous nitrate salt was also prepared in one case([2h]NO_(3)).The neutral derivatives[Fe2Cp2(CO)(μ-CO){μ–η^(1):η^(3)-C(Fc)CHC(CN)NMe2}],3,and[FeCp(CO){CN(Me)(Xyl)CHC(Fc)C([double bond,length as m-dash]O)}],4(Xyl=2,6-C6H3Me2),were obtained in ca.70%yield by reactions of the respective precursors[2h]CF_(3)SO_(3) and[2i]CF_(3)SO_(3) with NBu4CN and pyrrolidine,respectively.All products were purified by alumina chromatography and fully characterised by analytical and spectroscopic methods,and by single crystal X-ray diffraction in the cases of[2a]CF_(3)SO_(3) and 3.The cytotoxicity of the complexes was assessed on A2780,A2780cisR and BxPC-3 cancer cell lines,and the nontumoral Balb/3T3 clone A31.Most of the cationic complexes display IC50 values in the low micromolar/nanomolar range concerning the cancer cell lines,and up to 35 times higher values on the nontumoral cells.In order to shed light on the mode of action,selected complexes were further characterised by cyclic voltammetry and spectroelectrochemical experiments,and assessed for their potential to trigger ROS production and to interact with a range of biomolecules,i.e.a synthetic dodecapeptide as a simplified model for thioredoxin reductase(TrxR-pept),some model proteins(cytochrome c,hen egg-white lysozyme,ubiquitin,bovine serum albumin,superoxide dismutase and human carbonic anhydrase)and one single-stranded oligonucleotide(ODN2).展开更多
Correction for‘Synthesis and studies of aqueous-stable diruthenium aminocarbyne complexes uncovered an N-indolyl derivative as a prospective anticancer agent’by Matteo Fiaschi et al.,Inorg.Chem.Front.,2024,11,2841-2...Correction for‘Synthesis and studies of aqueous-stable diruthenium aminocarbyne complexes uncovered an N-indolyl derivative as a prospective anticancer agent’by Matteo Fiaschi et al.,Inorg.Chem.Front.,2024,11,2841-2862,https://doi.org/10.1039/D4QI00096J.展开更多
The first examples of(arene)Os(II)curcuminoid derivatives have been prepared and characterized.The neutral complexes[(p-cym)Os(curc)Cl](1)and[(p-cym)Os(bdcurc)Cl](2),together with the cationic derivatives[(p-cym)Os(cu...The first examples of(arene)Os(II)curcuminoid derivatives have been prepared and characterized.The neutral complexes[(p-cym)Os(curc)Cl](1)and[(p-cym)Os(bdcurc)Cl](2),together with the cationic derivatives[(p-cym)Os(curc)(PTA)][SO_(3)CF_(3)](3)and[(p-cym)Os(bdcurc)(PTA)][SO_(3)CF_(3)](4)(PTA=1,3,5-triaza-7-phosphaadamantane)were characterized by NMR spectroscopy and ESI mass spectrometry,and the crystal structure of 1 was determined by X-ray diffraction analysis.The cytotoxicity of the complexes was evaluated in vitro against human ovarian carcinoma cells(A2780 and A2780cisR),as well as against non-tumorous Human Embryonic Kidney cells(HEK293).Binding of the complexes to potential pharmacological targets and serum carriers was also explored.展开更多
基金the University of Pisa for financial support(PRA_2020_39).
文摘Cationic triiron complexes resulting from the conjugation of the ferrocenyl skeleton(Fc)with a diiron bis-cyclopentadienyl core through a variable vinyliminium linker,[Fe2Cp2(CO)(μ-CO){μ–η^(1):η^(3)-C(Fc)CHCN(R)(R′)}]CF_(3)SO_(3)([2a–i]CF_(3)SO_(3),Cp=η^(5)-C5H5,R,R′=alkyl,aryl),were synthesised in 70–94%yield,and the homologous nitrate salt was also prepared in one case([2h]NO_(3)).The neutral derivatives[Fe2Cp2(CO)(μ-CO){μ–η^(1):η^(3)-C(Fc)CHC(CN)NMe2}],3,and[FeCp(CO){CN(Me)(Xyl)CHC(Fc)C([double bond,length as m-dash]O)}],4(Xyl=2,6-C6H3Me2),were obtained in ca.70%yield by reactions of the respective precursors[2h]CF_(3)SO_(3) and[2i]CF_(3)SO_(3) with NBu4CN and pyrrolidine,respectively.All products were purified by alumina chromatography and fully characterised by analytical and spectroscopic methods,and by single crystal X-ray diffraction in the cases of[2a]CF_(3)SO_(3) and 3.The cytotoxicity of the complexes was assessed on A2780,A2780cisR and BxPC-3 cancer cell lines,and the nontumoral Balb/3T3 clone A31.Most of the cationic complexes display IC50 values in the low micromolar/nanomolar range concerning the cancer cell lines,and up to 35 times higher values on the nontumoral cells.In order to shed light on the mode of action,selected complexes were further characterised by cyclic voltammetry and spectroelectrochemical experiments,and assessed for their potential to trigger ROS production and to interact with a range of biomolecules,i.e.a synthetic dodecapeptide as a simplified model for thioredoxin reductase(TrxR-pept),some model proteins(cytochrome c,hen egg-white lysozyme,ubiquitin,bovine serum albumin,superoxide dismutase and human carbonic anhydrase)and one single-stranded oligonucleotide(ODN2).
文摘Correction for‘Synthesis and studies of aqueous-stable diruthenium aminocarbyne complexes uncovered an N-indolyl derivative as a prospective anticancer agent’by Matteo Fiaschi et al.,Inorg.Chem.Front.,2024,11,2841-2862,https://doi.org/10.1039/D4QI00096J.
基金supported by the University of Camerino(Fondo di Ateneo per la Ricerca 2018).
文摘The first examples of(arene)Os(II)curcuminoid derivatives have been prepared and characterized.The neutral complexes[(p-cym)Os(curc)Cl](1)and[(p-cym)Os(bdcurc)Cl](2),together with the cationic derivatives[(p-cym)Os(curc)(PTA)][SO_(3)CF_(3)](3)and[(p-cym)Os(bdcurc)(PTA)][SO_(3)CF_(3)](4)(PTA=1,3,5-triaza-7-phosphaadamantane)were characterized by NMR spectroscopy and ESI mass spectrometry,and the crystal structure of 1 was determined by X-ray diffraction analysis.The cytotoxicity of the complexes was evaluated in vitro against human ovarian carcinoma cells(A2780 and A2780cisR),as well as against non-tumorous Human Embryonic Kidney cells(HEK293).Binding of the complexes to potential pharmacological targets and serum carriers was also explored.
