Browsing by Author "Tripathy S.K."
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Item Cyclometallated iridium complexes inducing paraptotic cell death like natural products: Synthesis, structure and mechanistic aspects(2016) Tripathy S.K.; De U.; Dehury N.; Laha P.; Panda M.K.; Kim H.S.; Patra S.Six mononuclear Ir complexes (1-6) using polypyridyl-pyrazine based ligands (L1 and L2) and {[cp?IrCl(?-Cl)]2 and [(ppy)2Ir(?-Cl)]2} precursors have been synthesised and characterised. Complexes 1-5 have shown potent anticancer activity against various human cancer cell lines (MCF-7, LNCap, Ishikawa, DU145, PC3 and SKOV3) while complex 6 is found to be inactive. Flow cytometry studies have established that cellular accumulation of the complexes lies in the order 2 > 1 > 5 > 4 > 3 > 6 which is in accordance with their observed cytotoxicity. No changes in the expression of the proteins like PARP, caspase 9 and beclin-1, Atg12 discard apoptosis and autophagy, respectively. Overexpression of CHOP, activation of MAPKs (P38, JNK, and ERK) and massive cytoplasmic vacuolisation collectively suggest a paraptotic mode of cell death induced by proteasomal dysfunction as well as endoplasmic reticulum and mitochondrial stress. An intimate relationship between p53, ROS production and extent of cell death has also been established using p53 wild, null and mutant type cancer cells. � 2016 The Royal Society of Chemistry.Item A dinuclear [{(: P -cym)RuIICl}2(?-bpytz-)]+ complex bridged by a radical anion: Synthesis, spectroelectrochemical, EPR and theoretical investigation (bpytz = 3,6-bis(3,5-dimethylpyrazolyl)1,2,4,5-tetrazine; P -cym = p -cymene)(2016) Tripathy S.K.; Van Der Meer M.; Sahoo A.; Laha P.; Dehury N.; Plebst S.; Sarkar B.; Samanta K.; Patra S.The reaction of the chloro-bridged dimeric precursor [{(p-cym)RuIICl}(?-Cl)]2 (p-cym = p-cymene) with the bridging ligand 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine (bpytz) in ethanol results in the formation of the dinuclear complex [{(p-cym)RuIICl}2(?-bpytz-)]+, [1]+. The bridging tetrazine ligand is reduced to the anion radical (bpytz-) which connects the two RuII centres. Compound [1](PF6) has been characterised by an array of spectroscopic and electrochemical techniques. The radical anion character has been confirmed by magnetic moment (corresponding to one electron paramagnetism) measurement, EPR spectroscopic investigation (tetrazine radical anion based EPR spectrum) as well as density functional theory based calculations. Complex [1]+ displays two successive one electron oxidation processes at 0.66 and 1.56 V versus Ag/AgCl which can be attributed to [{(p-cym)RuIIC}2(?-bpytz-)]+/[{(p-cym)RuIICl}2(?-bpytz)]2+ and [{(p-cym)RuIICl}2(?-bpytz)]+/[{(p-cym)RuIIICl}2(?-bpytz)]2+ processes (couples I and II), respectively. The reduction processes (couple III-couple V), which are irreversible, likely involve the successive reduction of the bridging ligand and the metal centres together with loss of the coordinated chloride ligands. UV-Vis-NIR spectroelectrochemical investigation reveals typical tetrazine radical anion containing bands for [1]+ and a strong absorption in the visible region for the oxidized form [1]2+, which can be assigned to a RuII ? ?? (tetrazine) MLCT transition. The assignment of spectroscopic bands was confirmed by theoretical calculations. � 2016 The Royal Society of Chemistry.Item Dinuclear [{(p-cym)RuCl}2(?-phpy)](PF6)2 and heterodinuclear [(ppy)2Ir(?-phpy)Ru(p-cym)Cl](PF6)2 complexes: Synthesis, structure and anticancer activity(2014) Tripathy S.K.; De U.; Dehury N.; Pal S.; Kim H.S.; Patra S.Phpy bridged homodinuclear Ru-Ru (1) and heterodinuclear Ir-Ru complexes (2) have been developed. Complex 2 induces autophagy towards the cisplatin resistant human breast cancer (MCF7) cell line, whereas 1 is inactive. This journal is � the Partner Organisations 2014.Item Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone(2016) Dehury N.; Maity N.; Tripathy S.K.; Basset J.-M.; Patra S.Herein, we report an example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: tetrapyrazolyl dipalladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross-coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its dimetallic analogues, and it exceeds, in terms of activity and selectivity, the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate-determining step in the tandem reaction. Interestingly, while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction, resulting in biarylketone as the final product. Unlike the pyrazole-based Pd compounds, the precursor PdCl2 and the phosphine-based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis. � 2016 American Chemical Society.Item Facile tandem Suzuki coupling/transfer hydrogenation reaction with a bis-heteroscorpionate Pd-Ru complex(2014) Dehury N.; Tripathy S.K.; Sahoo A.; Maity N.; Patra S.Design and synthesis of the bis(pyrazol-1-yl)methane based bis-heteroscorpionate Pd-Ru complex results in efficient tandem Suzuki coupling/transfer hydrogenation reaction with a broad range of substrate reactivity. � 2014 the Partner Organisations.Item A porous trimetallic Au@Pd@Ru nanoparticle system: Synthesis, characterisation and efficient dye degradation and removal(2015) Sahoo A.; Tripathy S.K.; Dehury N.; Patra S.A facile room temperature one-pot synthesis of trimetallic porous Au@Pd@Ru nanoparticles (Au@Pd@RuNPs) has been developed. The trimetallic nanoparticles have been prepared by the successive sacrificial oxidation of cobalt nanoparticles (CoNPs). The average particle size of Au@Pd@RuNPs is 110 nm. The porous nature and the presence of Au, Pd and Ru have been confirmed via TEM, FE-SEM and EDS analyses. The trimetallic nanoparticles have shown excellent catalytic activity towards the reduction of p-nitrophenol and efficient degradation of various azo dyes. This has been further extended towards the removal of colour from waste water via the catalytic degradation of azo dyes. Moreover, the produced amine can be eliminated from the waste water via its sorption on an industrial solid waste dolochar. � The Royal Society of Chemistry 2015.Item Synthesis, characterisation and antibacterial activity of [(p-cym)RuX(L)]+/2+ (X = Cl, H2O; L = bpmo, bpms) complexes(2015) Tripathy S.K.; Taviti A.C.; Dehury N.; Sahoo A.; Pal S.; Beuria T.K.; Patra S.Mononuclear half-sandwiched complexes [(p-cym)RuCl(bpmo)](ClO4) {[1](ClO4)} and [(p-cym)RuCl(bpms)](PF6) {[2](PF6)} have been prepared by reacting heteroscorpionate ligands bpmo = 2-methoxyphenyl-bis(3,5-dimethylpyrazol-1-yl)methane and bpms = 2-methylthiophenyl-bis(3,5-dimethylpyrazol-1-yl)methane, respectively, with a dimeric precursor complex [(p-cym)RuCl(?-Cl)]2 (p-cym = 1-isopropyl-4-methylbenzene) in methanol. The corresponding aqua derivatives [(p-cym)Ru(H2O)(bpmo)](ClO4)2 {[3](ClO4)2} and [(p-cym)Ru(H2O)(bpms)](PF6)2 {[4](PF6)2} are obtained from {[1](ClO4)} and {[2](PF6)}, respectively, via Cl-/H2O exchange process in the presence of appropriate equivalents of AgClO4/AgNO3 + KPF6 in a methanol-water mixture. The molecular structures of the complexes {[1]Cl, [3](ClO4)2 and [4](PF6)(NO3)} are authenticated by their single crystal X-ray structures. The complexes show the expected piano-stool geometry with p-cym in the ?6 binding mode. The aqua complexes [3](ClO4)2 and [4](PF6)2 show significantly good antibacterial activity towards E. coli (gram negative) and B. subtilis (gram positive) strains, while chloro derivatives ({[1](ClO4)} and {[2](PF6)} are found to be virtually inactive. The order of antibacterial activity of the complexes according to their MIC values is [1](ClO4) (both 1000 ?g mL-1) < [2](PF6) (580 ?g mL-1 and 750 ?g mL-1) < [3](ClO4)2 (both 100 ?g mL-1) < [4](PF6)2 (30 ?g mL-1 and 60 ?g mL-1) for E. coli and B. subtilis strains, respectively. Further, the aqua complexes [3](ClO4)2 and [4](PF6)2 show clear zones of inhibition against kanamycin, ampicillin and chloramphenicol resistant E. coli strains. The detailed mechanistic aspects of the aforesaid active aqua complexes [3](ClO4)2 and [4](PF6)2 have been explored, and it reveals that both the complexes inhibit the number of nucleoids per cell in vivo and bind to DNA in vitro. The results indeed demonstrate that both [3](ClO4)2 and [4](PF6)2 facilitate the inhibition of bacterial growth by binding to DNA. � The Royal Society of Chemistry 2015.Item Synthesis, characterisation and biological activities of [(p-cym)RuX(pz4lut)]n+ and [{(p-cym)RuX} 2(?-pz4lut)]n+ (X = Cl, H2O and pz4lut = ?,?,??,??-tetra(pyrazol- 1-yl)-2,6-lutidine)(2013) Tripathy S.K.; Surada R.K.; Manne R.K.; Mobin S.M.; Santra M.K.; Patra S.Mononuclear [(p-cym)RuCl(pz4lut)]Cl (1) and dinuclear [{(p-cym)RuCl}2(?-pz4lut)]Cl2 (2) complexes (p-cym = 1-isopropyl-4-methylbenzene) comprising of bis(pyrazol-1-yl)methane based heteroscorpionate ligand ?,?,??,??- tetra(pyrazol-1-yl)-2,6-lutidine (pz4lut) have been synthesised from pz4lut ligand and dimeric precursor complex [(p-cym)RuCl(?-Cl)] 2 in methanol. The aqua derivatives [(p-cym)Ru(H2O) (pz4lut)](ClO4)2 (3) and [{(p-cym)Ru(H 2O)}2(?-pz4lut)](ClO4) 4 (4) are obtained from 1 and 2, respectively, via Cl/H2O exchange process in presence of appropriate equivalents of AgClO4 in methanol-water mixture. The molecular structures of dinuclear complexes, 2 and 4 are authenticated by their single crystal X-ray structures. Cyclic voltammetry reveals negligible electronic communication between the metal centres in the ligand bridged complex 2. All four complexes have been tested for their anticancer activities in human breast (MCF7), lung (A549) and colon (HCT116) cancer cell lines. The complexes show dose dependent suppression of cell viability with moderately good IC50 values ranging from 3.5-92 ?M. Experimental results have revealed that the aqua derivatives, 3 and 4 exhibit better cytotoxic effect against all those cell lines as compared to the precursor chlorido complexes, 1 and 2. Results also demonstrate that the complexes are more potent against HCT116 cells as compared to other cell lines. � 2013 The Royal Society of Chemistry.