Reaction-based epoxide fluorescent probe for in vivo visualization of hydrogen sulfide.

Hydrogen sulfide (H2S) has emerged as the most important biosynthetic gasotransmitters along with nitric oxide (NO) and carbon monoxide (CO). In this study, we report the design and the synthesis of a new epoxide fluorescent probe 7-glycidyloxy-9-(2-glycidyloxycarbonylphenyl)-2-xanthone (FEPO) for use in in vivo visualization of hydrogen sulfide. The probe employs a fluorescein as a fluorophore, and is equipped with an operating epoxide unit. FEPO functions via epoxide ring opening upon nucleophilic attack of H2S. This ring opening strategy may open a new avenue for the development of various H2S fluorescent sensors. FEPO showed high selectivity and high sensitivity for H2S. FEPO's cytotoxicity was tested using MTT (2-(4,5-dimethyl-2-thiazolyl)-3,5-diphenyl-2H-tetrazolium bromide) assay. Furthermore, the use of confocal imaging of H2S and in vivo imaging in live zebra fish demonstrated FEPO's potential biological applications. We anticipate that, owing to their ideal properties, probes of this type will find great uses in exploring the role of H2S in biology.

Organometallic ruthenium(II) complexes: synthesis, structure and influence of substitution at azomethine carbon towards DNA/BSA binding, radical scavenging and cytotoxicity.

Bivalent, ruthenium organometallics containing hydrazone ligands with the composition [RuH(CO)(PPh(3))(2)(L(1-3))] (4-6) have been synthesised from the reactions of [RuH(2)(CO)(PPh(3))(3)] and benzoic acid pyridine-2-ylmethylene-hydrazide (HL(1)) (1) /benzoic acid (1-pyridin-2-yl-ethylidene)-hydrazide (HL(2)) (2)/benzoic acid (phenyl-pyridin-2-yl-methylene)-hydrazide (HL(3)) (3) and characterised by various physico-chemical techniques. The X-ray crystal structure of one of the above complexes, [RuH(CO)(PPh(3))(2)(L(3))] (6) demonstrated a distorted octahedral coordination geometry around the metal centre. Results of our investigation on the effect of substitution (H or CH(3) or C(6)H(5)) at the azomethine carbon of coordinated hydrazone in these ruthenium chelates on the potential binding with DNA/BSA, free radical scavenging and cytotoxicity is presented.

Synthesis of novel heterobimetallic copper(I) hydrazone Schiff base complexes: a comparative study on the effect of heterocyclic hydrazides towards interaction with DNA/protein, free radical scavenging and cytotoxicity.

Two new copper(I) hydrazone complexes have been synthesised from bivalent copper precursor [CuCl(2)(PPh(3))(2)] and ferrocene containing bidentate hydrazone ligands HL(1) (1) or HL(2) (2). Based on the elemental analyses and spectroscopic data, the complexes are best formulated as [CuL(1)(PPh(3))(2)] (3) and [CuL(2)(PPh(3))(2)] (4) of the monovalent copper ion. Solid state structures of ligand 2 and its corresponding complex 4 were also determined. The DNA/albumin interactions of all the synthesised compounds were investigated using absorption, emission and synchronous fluorescence studies. Further, antioxidant properties of all the compounds have also been checked against ABTS, O(2)(-) and OH radicals. Additionally, the in vitro cytotoxic activity of compounds 1-4 was assessed using tumour (HeLa, A431) and non-tumour (NIH 3T3) cell lines.

Variation in the biomolecular interactions of nickel(II) hydrazone complexes upon tuning the hydrazide fragment.

Three new bivalent nickel hydrazone complexes have been synthesised from the reactions of [NiCl(2)(PPh(3))(2)] with H(2)L {L = dianion of the hydrazones derived from the condensation of o-hydroxynaphthaldehyde with furoic acid hydrazide (H(2)L(1)) (1)/thiophene-2-acid hydrazide (H(2)L(2)) (2)/isonicotinic acid hydrazide (H(2)L(3)) (3)} and formulated as [Ni(L(1))(PPh(3))] (4), [Ni(L(2))(PPh(3))] (5) and [Ni(L(3))(PPh(3))] (6). Structural characterization of these compounds 4-6 were accomplished by using various physico-chemical techniques. Single crystal X-ray diffraction data of complexes 4 and 5 proved their distorted square planar geometry. In order to ascertain the potential of the above synthesised compounds towards biomolecular interactions, additional experiments involving interaction with calf thymus DNA (CT DNA) and bovine serum albumin (BSA) were carried out. All the ligands and corresponding nickel(ii) chelates have been screened for their scavenging effect towards O(2)(-), OH and NO radicals. The efficiency of complexes 4-6 to arrest the growth of HeLa, HepG-2 and A431 tumour cell lines has been studied along with the cell viability test against the non-cancerous NIH 3T3 cells under in vitro conditions.

Copper(I) and nickel(II) complexes with 1:1 vs. 1:2 coordination of ferrocenyl hydrazone ligands: do the geometry and composition of complexes affect DNA binding/cleavage, protein binding, antioxidant and cytotoxic activities?

A new series of geometrically different complexes containing ferrocenyl hydrazone ligands were synthesised by reacting suitable precursor complex [MCl(2)(PPh(3))(2)] with the ligands HL(1) or HL(2) (where M = Cu(II) or Ni(II); HL(1) = [Cp(2)Fe(CH=N-NH-CO-C(6)H(5))] (1) and HL(2) = [Cp(2)Fe(CH=N-NH-CO-C(5)H(4)N)]) (2). The new complexes of the composition [Cu(L(1))(PPh(3))(2)], (3) [Cu(L(2))(PPh(3))(2)] (4), [Ni(L(1))(2)] (5) and [Ni(L(2))(2)] (6) were characterised by various spectral studies. Among them, complexes 3 and 5 characterised by single crystal X-ray diffraction showed a distorted tetrahedral structure for the former with 1:1 metal-ligand stoichiometry, but a distorted square planar geometry with 1:2 metal-ligand stoichiometry in the case of the latter. Systematic biological investigations like DNA binding, DNA cleavage, protein binding, free radical scavenging and cytotoxicity activities were carried out using all the synthesised compounds and the results obtained were explained on the basis of structure-activity relationships. The binding constant (K(b)) values of the synthesised compounds are found to be in the order of magnitude 10(3)-10(5) M(-1) and also they exhibit significant cleavage of supercoiled (SC) pUC19 DNA in the presence of H(2)O(2) as co-oxidant. The conformational changes of bovine serum albumin (BSA) upon binding with the above complexes were also studied. In addition, concentration dependent free radical scavenging potential of all the synthesised compounds (1-6) was also carried out under in vitro conditions. Assays on the cytotoxicity of the above complexes against HeLa and A431 tumor cells and NIH 3T3 normal cells were also carried out.

Effect of substitution and planarity of the ligand on DNA/BSA interaction, free radical scavenging and cytotoxicity of diamagnetic Ni(II) complexes: a systematic investigation.

Four new bivalent nickel hydrazone complexes have been synthesised from the reactions of [NiCl(2)(PPh(3))(2)] with H(2)L {L = dianion of the hydrazones derived from the condensation of salicylaldehyde or o-hydroxy acetophenone with p-toluic acid hydrazide (H(2)L(1)) (1), (H(2)L(2)) (2) and o-hydroxy acetophenone or o-hydroxy naphthaldehyde with benzhydrazide (H(2)L(3)) (3) and (H(2)L(4)) (4)} and formulated as [Ni(L(1))(PPh(3))] (5), [Ni(L(2))(PPh(3))] (6), [Ni(L(3))(PPh(3))] (7) and [Ni(L(4))(PPh(3))] (8). Structural characterization of complexes 5-8 were accomplished by using various physico-chemical techniques. In order to study the influence of substitution in the ligand and its planarity on the biological activity of complexes 5-8 containing them, suitable hydrazone ligands 1-4 have been selected in this study. Single crystal diffraction data of complexes 5, 7 and 8 proved the geometry of the complexes to be distorted square planar with a 1 : 1 ratio between the metal ion and the coordinated hydrazones. To provide more insight on the mode of action of complexes 5-8 under biological conditions, additional experiments involving their interaction with calf thymus DNA (CT DNA) and bovine serum albumin (BSA) were monitored by UV-visible and fluorescence titrations respectively. Further, the ligands 1-4 and corresponding nickel(ii) chelates 5-8 have been tested for their scavenging effect towards OH and O(2)(-) radicals. The effect of complexes 5-8 to arrest the growth of HeLa and Hep-2 tumour cell lines has been studied along with the cell viability against the non-cancerous NIH 3T3 cells under in vitro conditions.