52462-29-0Relevant articles and documents
A new photoactivatable ruthenium(II) complex with an asymmetric bis-thiocarbohydrazone: Chemical and biological investigations
Alinovi, Rossella,Bisceglie, Franco,Orsoni, Nicolò,Pelosi, Giorgio,Pinelli, Silvana,Pioli, Marianna,Scaccaglia, Mirco
, (2021)
The synthesis, photoactivation and biological activity of a new piano-stool Ru(II) complex is herein reported. The peculiarity of this complex is that its monodentate ligand which undergoes the photodissociation is an asymmetric bis-thiocarbohydrazone ligand that possesses a pyridine moiety binding to Ru(II) and the other moiety contains a quinoline that endows the ligand with the capacity of chelating other metal ions. In this way, upon dissociation, the ligand can be released in the form of a metal complex. In this article, the double ability of this new Ru(II) complex to photorelease the ligand and to chelate copper and nickel is explored and confirmed. The biological activity of this compound is studied in cell line A549 revealing that, after irradiation, proliferation inhibition is reached at very low half maximal inhibitory concentration (IC50) values. Further, biological assays reveal that the dinuclear complex containing Ni is internalized in cells.
Synthesis of Ruthenium Tris-Diimine Photosensitizers Substituted by Four Methylphosphonate Anchoring Groups for Dye-Sensitized Photoelectrochemical Cell Applications
Queyriaux, Nicolas,Giannoudis, Emmanouil,Lefebvre, Jean-Fran?ois,Artero, Vincent,Chavarot-Kerlidou, Murielle
, p. 2154 - 2161 (2019)
The design and synthesis of ruthenium tris-diimine photosensitizers appropriately functionalized to be (i) anchored onto transparent conductive oxides (TCO) and (ii) covalently coupled with a water-splitting catalyst represents an important target for solar fuel production in dye-sensitized photoelectrochemical cells (DS-PECs). In this study, two different synthetic routes to prepare heteroleptic [Ru(4,4′-(CH2PO3Et2)2-bpy)2(N^N)](PF6)2 complexes are evaluated, the scope and limitations of the organometallic pathway involving half-sandwich η6-arene ruthenium complexes as synthetic intermediates being especially studied. The spectroscopic and electrochemical characterization of a series of novel structures varying by the nature of the third diimine N^N ligand is reported.
Design, synthesis and in vitro bioactivity of mixed ligand Ru(II) complexes bearing the fluoroquinolone antibacterial agents
Pulipaka, Ramadevi,Dash, Soumya R.,Khanvilkar, Priyanka,Jana, Sarmita S.,Devkar, Ranjitsinh V.,Chakraborty, Debjani
, p. 721 - 735 (2019)
Mixed ligand Ru(II) phenanthroline complexes of the type [Ru(1,10-phen)2Flq]ClO4 (RPFlq-1-3) and “piano-stool”-type Ru(II) arene complexes [Ru(η6-p-cymene)Cl(Flq)] (RAFlq-1-3), where Flq = fluoroquinolone, have been synthesized, characterized and studied for their anticancer potential. DFT calculations were in line with the proposed structures, wherein the fluoroquinolones are coordinated to the metal through the ring carbonyl and one of the carboxylic oxygen?atoms in a bidentate fashion. Binding efficacies of the synthesized complexes with bovine serum albumin (BSA) and CT-DNA were studied spectroscopically, and it has been established that the arene complexes, though have moderate binding propensities to CT-DNA (Kb = 0.8–1.7 × 103?M?1), have 102–103-fold better binding efficacies toward BSA (Ka = 3.2 × 105–2.1 × 106?M?1) due to the presence of the hydrophobic arene moiety. These results further prompted a study in their in vitro cytotoxicity assay on A-549 non-small cell lung cancer and MCF7 breast cancer cell lines. Furthermore, gene expression studies on BAX and BCL-2 genes and FACS analysis confirmed apoptosis as the mode of cell death.
Microwave-assisted synthesis and DNA-binding studies of half-sandwich ruthenium(II) arene complexes containing phenanthroimidazole-triarylamine hybrids
Abhijna Krishna, Ramakrishnan,Dheepika, Ramachandran,Muralisankar, Mathiyan,Nagarajan, Samuthira
, p. 838 - 849 (2021)
A new series of half-sandwich Ru(II)-arene complexes with phenanthroimidazole-triarylamine hybrid ligands were synthesized and scrutinized for DNA binding studies. The metal complexes were prepared via microwave-assisted synthesis with high yield and purity. The interaction of Ru(II)-arene complex with calf thymus DNA was studied by spectrophotometric methods. All six complexes exhibited significant interaction with CT-DNA. Methoxyphenyl-substituted metal complex showed the highest binding efficiency with a binding constant (Kb) of 5.053 × 104 M?1 due to its electron-rich nature. The methoxyphenyl group remarkably enhanced the interaction through stabilization of π-orbital of the metal complex which resulted in the efficient coupling. Phenyl- and thiophene-substituted ligands also showed good binding constants of 4.908 × 104 M?1 and 4.509 × 104 M?1, respectively. The absorption and ethidium bromide displacement studies declare that both the intercalation and groove binding is anticipated by these complexes. These Ru(II) complexes with phenanthroimidazole-triarylamine hybrid ligands can be realized as efficient DNA binding agents.
Evaluation of biomolecular interactions and cytotoxic activity of organometallic binuclear Ru(II) complexes of ferrocenyl thiosemicarbazones
Khanvilkar, Priyanka,Dash, Soumya R.,Vohra, Alisagar,Devkar, Ranjitsinh,Chakraborty, Debjani
, p. 6044 - 6055 (2021)
Four new ferrocenyl substituted thiosemicarbazone ligands (L1–L4) and their corresponding binuclear ruthenium(II) arene complexes of the general type [(η6-p cym)(L)Ru(μ-im)Ru(L)(η6-p-cym)]Cl (C1–C4) and [(η6-p cym)(L)Ru(μ-azpy)Ru(L)(η6-p-cym)]Cl2 (C5–C8) (cym = cymene, im = imidazole, azpy = 4,4′-azopyridine) have been synthesized and characterized. The structures of the complexes were established through DFT calculations and geometry optimization. The interactions of the binuclear complexes with DNA were investigated by absorption, emission and viscosity studies which indicated that the complexes bind to DNA via intercalation. Meanwhile, the interaction of complexes with the protein, bovine serum albumin (BSA), has also been studied using fluorescence emission spectroscopy. The experimental results show that the binuclear complexes exhibit good binding propensities to BSA. The complexes can quench the intrinsic fluorescence of BSA remarkably through a static or dynamic quenching process. In addition, the in?vitro cytotoxicity of complexes C1–C8 against HeLa cell line was assayed which showed lower IC50 values indicating their higher cytotoxicity and potency in killing the cancer cells at low concentrations. Communicated by Ramaswamy H. Sarma.
Imidazole/4,4′-azopyridine bridging binuclear Ru(II) complexes: design, synthesis, bimolecular interactions and cytotoxicity against HeLa cell line
Chakraborty, Debjani,Dash, Soumya R.,Devkar, Ranjitsinh,Khanvilkar, Priyanka,Pulipaka, Ramadevi,Shirsath, Kavita
, p. 3313 - 3326 (2021)
Binuclear Ru(II)-arene complexes [(η6-pcym)(Flq)Ru(μ-im/μ-azpy)Ru(Flq)(η6-p-cym)]Cl (C1–C8) (cym = cymene; Flq = fluoroquinolones; im = imidazole; azpy = 4,4′azo pyridine) have been synthesized and characterized by elemental analysis, molar conductivity and various spectral techniques (ESI-MS, IR, UV-Vis and 1H-NMR). The geometry of the complexes was optimized by DFT calculations, which revealed a pseudo-octahedral coordination around each metal centre. Binding of the synthesized complexes with CT-DNA and BSA was studied spectroscopically, and it has been established that the presence of two hydrophobic planar arene moieties enhances the binding efficacies of the binuclear complexes to the macromolecules, compared to their mononuclear analogues. The results of competitive binding between C1–C8 and ethidium bromide (EB) towards DNA have shown that the complexes are able to displace EB from DNA-EB adduct and interact with DNA via intercalation. The complexes display cytotoxicity against the HeLa human cervical cancer cell lines with IC50 values in the range of 30.1–120.9 μM.
Mixed ligand ruthenium arene complexes containing N-ferrocenyl amino acids: Biomolecular interactions and cytotoxicity against MCF7 cell line
Ramadevi, Pulipaka,Singh, Rinky,Jana, Sarmita S.,Devkar, Ranjitsinh,Chakraborty, Debjani
, p. 80 - 87 (2017)
Synthesis, characterization, DNA and protein binding as well as anticancer activity of the organometallic complexes [Ru(η6-p-cym)(L)Cl] (where, p-cym?=?p-cymene MeC6H4Pri, L?=?N-ferrocenyl amino acid conjugates) RAFcA 1–4 have been described. The complexes 1–4 exhibited strong DNA/BSA binding and anticancer activity against breast cancer MCF7 cell line. Their binding with calf thymus DNA (CT DNA) and bovine serum albumin (BSA) have been examined by absorption and emission spectral studies. Strong interactions between complexes and CT-DNA have been affirmed by absorption spectral and EB displacement studies, while interaction with BSA via static quenching was explored by fluorescence titration. Cytotoxicity, apoptosis and in?vitro anticancer activity of 1–4 toward MCF7 cell line have been investigated by MTT assay. The IC50values (37.1?μM - 86.6?μM) were found to be distinctly lower than those of NAMI-A and RAPTA complexes for MCF7 cell line which was followed by gene expression studies to confirm apoptosis as the mode of cell death.
Coordination chemistry of the [Pt2(μ-S)2 (PPh3)4] metalloligand with π-hydrocarbon derivatives of d6 ruthenium(II), osmium(II), rhodium(III) and iridium(III)
Audi Fong,Andy Hor,Henderson, William,Nicholson, Brian K.,Gardyne, Stephen,Devoy, Sarah M.
, p. 24 - 31 (2003)
The reactivity of [Pt2(μ-S)2 (PPh3)4] towards [RuCl2 (η6-arene)]2 (arene=C6 H6, C6Me6, p -MeC6 H4Pri = p-cymene), [OsCl2 (η6- p -cymene)]2 and [MCl2 (η5-C5Me5)]2 (M=Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type [Pt2(μ-S)2(PPh3)4 ML]2+ (L=π-hydrocarbon ligand) are observed, and a number of complexes have been prepared on the synthetic scale, isolated as their BPh4- or PF6- salts, and fully characterised. A single-crystal X-ray structure determination on the Ru p-cymene derivative confirms the presence of a pseudo-five-coordinate Ru centre. This resists addition of small donor ligands such as CO and pyridine. The reaction of [Pt2(μ-S)2 (PPh3)4] with RuClCp(PPh3) 2 (Cp=η5-C5H5) gives [Pt2(μ-S)2(PPh3) 4RuCp]+. In addition, the reaction of [Pt2(μ-S)2(PPh3)4] with the related carbonyl complex [RuCl2(CO)3] 2, monitored by electrospray mass spectrometry, gives [Pt2(μ-S)2(PPh3)4 Ru(CO)3Cl]+.
Anticancer activity of hydrogen-bond-stabilized half-sandwich Ru II complexes with heterocycles
Mitra, Raja,Das, Sangeeta,Shinde, Sridevi V.,Sinha, Sarika,Somasundaram, Kumaravel,Samuelson, Ashoka G.
, p. 12278 - 12291 (2012)
Neutral half-sandwich organometallic ruthenium(II) complexes of the type [(n6-cymene)RuCl2(L)] (H1-H10), where L represents a heterocyclic ligand, have been synthesized and characterized spectroscopically. The structures of five complexes were also established by single-crystal X-ray diffraction confirming a piano-stool geometry with n6 coordination of the arene ligand. Hydrogen bonding between the N-H group of the heterocycle and a chlorine atom attached to Ru stabilizes the metal-ligand interaction. Complexes coordinated to a mercaptobenzothiazole framework (H1) or mercaptobenzoxazole (H6) showed high cytotoxicity against several cancer cells but not against normal cells. In vitro studies have shown that the inhibition of cancer cell growth involves primarily G1-phase arrest as well as the generation of reactive oxygen species (ROS). The complexes are found to bind DNA in a non-intercalative fashion and cause unwinding of plasmid DNA in a cell-free medium. Surprisingly, the cytotoxic complexes H1 and H6 differ in their interaction with DNA, as observed by biophysical studies, they either cause a biphasic melting of the DNA or the inhibition of topoisomerase-IIα activity, respectively. Substitution of the aromatic ring of the heterocycle or adding a second hydrogen-bond donor on the heterocycle reduces the cytotoxicity. Copyright
Organometallic binuclear Ru(II) complexes: Design, synthesis, DNA/BSA binding interactions and in-vitro cytotoxicity against HeLa cell line
Khanvilkar, Priyanka,Pulipaka, Ramadevi,Shirsath, Kavita,Devkar, Ranjitsinh,Chakraborty, Debjani
, p. 134 - 140 (2019)
Synthesis, characterization, DNA/BSA binding and cytotoxicity of organometallic binuclear Ru (II) complexes [(p-cym)(Fc-AA)Ru(μ-Im)Ru(Fc-AA)(p-cym)]Cl (C1–C4; where: p-cym = p-cymene MeC6H4Pri, Fc-AA = N-ferrocenyl amino acid conjugates (Fc-tyr1, Fc-phe2, Fc-leu3, Fc-trp4) and Im = Imidazole) have been described. The complexes C1–C4 exhibited strong DNA/BSA binding affinity and cytotoxicity against human cervical cancer HeLa cell line. Their binding with calf thymus CT-DNA and bovine serum albumin BSA have been examined by absorption and emission spectral studies. Intercalative interactions between complexes and CT-DNA have been affirmed by EB displacement studies and DNA viscosity measurements, while interaction with BSA via static quenching was explored by fluorescence titration. The anti-cancer activity of C1–C4 was studied using MTT assay on HeLa cell line and the corresponding IC50 values were calculated. The IC50 value (30.0 μM–120.0 μM) obtained were further compared with the well-known ruthenium complex NAMI-A, currently under phase II clinical trials which has IC50 value 608.5 μM.
