N-substitution in isatin thiosemicarbazones decides nuclearity of Cu(II) complexes - Spectroscopic, molecular docking and cytotoxic studies.

The mono- (1) and bi-nuclear (2) copper(II) complexes containing N-substituted isatin thiosemicarbazone(s) were synthesized, and characterized by analytical and spectroscopic (UV-Visible, FT-IR and EPR) techniques. Bimetallic nature of complex 2 was confirmed by single crystal X-ray crystallography. The structures predicted by spectroscopic and crystallographic methods were validated by computational studies. From the spectroscopic, crystallographic and computational data, the structures were found to be distorted square planar for 1 and distorted square pyramidal for 2. Molecular docking studies showed hydrogen bonding and hydrophobic interactions of the complexes with tyrosinase kinase receptors. Complex 1 exhibited promising cytotoxic activity against Jurkat (leukemia) cell line, and complex 2 displayed more activity against HeLa S3 (cervical) and Jurkat cell lines with the IC50 values of 3.53 and 3.70 µM, respectively. Cytotoxicity of 1 (Jurkat) and 2 (Jurkat and HeLa S3) was better than that of cisplatin. Morphological changes in A549 (lung), HeLa S3 and Jurkat cell lines were examined in presence of the active complexes with the co-staining of Hoechst, AO (acridine orange) and EB (ethidium bromide) by fluorescence microscope.

Synthesis, Characterization and Biological Activity of Novel Cu(II) Complexes of 6-Methyl-2-Oxo-1,2-Dihydroquinoline-3-Carbaldehyde-4n-Substituted Thiosemicarbazones.

Three new 6-methyl-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-thiosemicarbazones-N-4-substituted pro-ligands and their Cu(II) complexes (1, -NH2; 2, -NHMe; 3, -NHEt) have been prepared and characterized. In both the X-ray structures of 1 and 3, two crystallographically independent complex molecules were found that differ either in the nature of weakly metal-binding species (water in 1a and nitrate in 1b) or in the co-ligand (water in 3a and methanol in 3b). Electron Paramagnetic Resonance (EPR) measurements carried out on complexes 1 and 3 confirmed the presence of such different species in the solution. The electrochemical behavior of the pro-ligands and of the complexes was investigated, as well as their biological activity. Complexes 2 and 3 exhibited a high cytotoxicity against human tumor cells and 3D spheroids derived from solid tumors, related to the high cellular uptake. Complexes 2 and 3 also showed a high selectivity towards cancerous cell lines with respect to non-cancerous cell lines and were able to circumvent cisplatin resistance. Via the Transmission Electron Microscopy (TEM) imaging technique, preliminary insights into the biological activity of copper complexes were obtained.

Bis(µ-chloro) bridged 1D CuI and CuII coordination polymer complex and mononuclear CuII complex: Synthesis, crystal structure and biological properties.

A novel one-dimensional coordination polymer containing Cu(I)Cu(II) core with chloro bridge on Cu(I) and ligand bridge on Cu(II) ions (1) and a mononuclear Cu(II) complex (2) have been synthesized from the reactions of 3- and 4-methoxy-3-quinolin-3-ylimino-methyl-2-phenol with [CuCl2(PPh3)2]. The ligands and the complexes have been characterized by spectral and analytical methods. In addition, the structures of both the ligands and the copper complexes were confirmed by single crystal X-ray diffraction studies. In both complexes, the phenolic oxygen and azomethine nitrogen atom of the ligand coordinate to the copper ions in a monobasic bidentate manner resulting in an approximately square planar geometry around the copper ion. In the polymeric complex, the N atom of the quinoline ring is coordinated to Cu(I) in addition to the phenolic oxygen and azomethine nitrogen atom coordinating to Cu(II) ion, thus bridging Cu(I) and Cu(II) ions in the complex. The interactions of the compounds with calf thymus DNA (CT-DNA) have been followed by absorption and emission titration methods, which revealed that the compounds interact with CT-DNA through intercalation. Further, the interactions of the compounds with bovine serum albumin (BSA) were also investigated using UV-visible, fluorescence spectroscopic methods. The results indicated that complex 1 exhibited a stronger binding to CT-DNA and BSA than the free ligands and complex 2. In addition, the in vitro cytotoxicity experiment showed that complexes 1 and 2 exhibit potent cytotoxic properties against PANC-1and Hela cells. Moreover, while complex 1 showed prominent cytotoxic activity against both PANC-1 and Hela cells with IC50 of 17.91 and 11.67 µM, complex 2 showed moderate cytotoxic activities with IC50 of 25.13 and 16.41 µM in PANC-1 and Hela cells. Further, apoptosis was confirmed by fluorescence image using EB/AO reagent.

Synthesis, characterization and cytotoxic activity of novel copper(II) complexes with aroylhydrazone derivatives of 2-Oxo-1,2-dihydrobenzo[h]quinoline-3-carbaldehyde.

Three new 2-oxo-1,2-dihydrobenzo[h]quinoline-3-carbaldehyde terminal substituted aroylhydrazone ligands (2-Oxo-1,2-dihydrobenzo[h]quinoline-3-carbaldehyde(2'-hydroxybenzoyl)hydrazine, H2L1, 1, 2-Oxo-1,2-dihydrobenzo[h]quinoline-3-carbaldehyde(2'-hydroxybenzoyl)hydrazine, H2L2, 2, 2-Oxo-1,2-dihydrobenzo[h]quinoline-3-carbaldehyde(2'-hydroxybenzoyl)hydrazine, H2L3, 3) and the corresponding novel copper(II) complexes [Cu(L)(CH3OH)(NO3)](L = HL1 (4), HL2 (5), HL3 (6-6+), have been synthesized to compare their coordination behaviour and biological activity with respect to the presence of an OH group in different positions of the phenyl ring in the hydrazone moieties. The new ligands and their copper complexes were characterized by elemental analysis and spectroscopic techniques. The molecular structures of the new complexes 4 and 6-6+ were determined by single crystal X-ray diffraction. The interactions of the free ligands and their copper complexes with calf thymus DNA were tested by absorption measurements and ethidium bromide competitive studies which revealed that all compounds may interact with calf thymus DNA through intercalation. Furthermore, a comparative analysis of the cytotoxic effect of the compounds on a panel of human cancer cell lines showed that the copper complexes exhibited in vitro antitumor activity significantly higher than that of the free ligands and also of cisplatin.

Near-Infrared-Absorbing Organometallic Diruthenium Complex Intermediates: Evidence for Bridging Anthrasemiquinone Formation and against Mixed Valency.

The new redox-active complexes [RuH(CO)(EPh3 )2 (µ-Q2- )RuH(CO)(EPh3 )2 ], E=P (1) and E=As (2) with the bis-chelate bridging ligand Q2- =1,4-dioxido-9,10-anthraquinone were prepared and characterised. The related compound [RuCl(CO)(PPh3 )2 (µ-Qx2- )RuCl(CO)(PPh3 )2 ] (4) with E=P and Qx2- =5,8-dioxido-1,4-naphthoquinone 4 revealed trans-positioned PPh3 groups. The electrogenerated one-electron oxidised states 1+ and 2+ were examined using spectroelectrochemical techniques (EPR, IR and UV/Vis/NIR). In situ EPR studies gave spectra with 31 P or 75 As hyperfine splitting of about 16 Gauss, small 99, 101 Ru coupling and small g-anisotropy in the frozen solution state. The 31 P and 75 As hyperfine values reflect axial positioning of the four Ru-E bonds relative to the plane of an anthrasemiquinone bridge. Single CO stretching bands around 1910 cm-1 of the precursors 1 and 2 shift by about 25 cm-1 to higher energies on oxidation. The direction, uniformity and the extent of the shifts confirm ligand bridge-based oxidation. Absorbance by the cations in the near infrared region is thus assigned to intra-ligand transitions of ruthenium(II)-bonded anthrasemiquinones and not to intervalence charge transfer of mixed-valent species. Ruthenium(II) stabilisation by CO and EPh3 is made responsible for the anthrasemiquinone formation instead of metal-centered oxidation.

Spectral characterization of a pteridine derivative from cyanide-utilizing bacterium Bacillus subtilis - JN989651.

Soil and water samples were collected from various regions of SIPCOT and nearby Vanappadi Lake, Ranipet, Tamilnadu, India. Based on their colony morphology and their stability during subculturing, 72 bacteria were isolated, of which 14 isolates were actinomycetes. Preliminary selection was carried out to exploit the ability of the microorganisms to utilize sodium cyanate as nitrogen source. Those organisms that were able to utilize cyanate were subjected to secondary screening viz., utilization of sodium cyanide as the nitrogen source. The oxygenolytic cleavage of cyanide is dependent on cyanide monooxygenase which obligately requires pterin cofactor for its activity. Based on this, the organisms capable of utilizing sodium cyanide were tested for the presence of pterin. Thin layer chromatography (TLC) of the cell extracts using n-butanol: 5 N glacial acetic acid (4:1) revealed that 10 out of 12 organisms that were able to utilize cyanide had the pterin-related blue fluorescent compound in the cell extract. The cell extracts of these 10 organisms were subjected to high performance thin layer chromatography (HPTLC) for further confirmation using a pterin standard. Based on the incubation period, cell biomass yield, peak height and area, strain VPW3 was selected and was identified as Bacillus subtilis. The Rf value of the cell extract was 0.73 which was consistent with the 0.74 Rf value of the pterin standard when scanned at 254 nm. The compound was extracted and purified by preparative High Performance Liquid Chromatography (HPLC). Characterization of the compound was performed by ultraviolet spectrum, fluorescence spectrum, Electrospray Ionization-Mass Spectrometry (ESI-MS), and Nuclear Magnetic Resonance spectroscopy (NMR). The compound is proposed to be 6-propionyl pterin (2-amino-6-propionyl-3H-pteridin-4-one).

Synthesis, structure and in vitro pharmacological evaluation of a novel 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (2'-methylbenzoyl) hydrazone bridged copper(II) coordination polymer.

A novel ligand bridged copper(II) coordination polymer, [Cu(HL)(NO3)]n has been synthesized by reacting 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (2'-methylbenzoyl) hydrazone (H2L) with Cu(NO3)2·3H2O, and characterized by X-ray diffraction studies. The DNA interaction studies revealed that the compounds could interact with CT-DNA through intercalation. A gel electrophoresis assay demonstrated the ability of the complex to cleave the pBR322 plasmid DNA. The protein binding studies indicated that the complex exhibited strong binding affinities. Investigations of antioxidative properties showed that the polymeric Cu(II) complex has strong radical scavenging potencies. The cytotoxic effect of the compounds showed that the polymeric complex exhibited excellent anticancer activity against Hep G2, and A431 cells which is six to ten times better than that of well-known commercial anticancer drug, cisplatin.

Synthesis, characterization and in vitro pharmacological evaluation of new water soluble Ni(II) complexes of 4N-substituted thiosemicarbazones of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde.

Four new Ni(II) complexes of general formula [Ni(H2-Qtsc-R)2](NO3)2 (H2-Qtsc-R = 4N-substituted thiosemicarbazones of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde, where R = H (1), Me (2), Et (3), or Ph (4)) have been synthesized and characterized. The geometry of the complexes was confirmed by single crystal X-ray crystallography for one of the complexes (3). The binding affinity of the complexes with DNA and protein have been studied which indicate that they could interact with calf thymus DNA and bovine serum albumin protein. Investigations of antioxidative properties showed that all the complexes have strong radical scavenging properties. Cytotoxic studies showed that the complexes exhibited effective cytotoxic activity against a panel of human cancer cells without affecting the normal cells much.

Role of substitution at terminal nitrogen of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde thiosemicarbazones on the coordination behavior and structure and biological properties of their palladium(II) complexes.

A series of four new palladium(II) complexes of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde thiosemicarbazones with triphenylphosphine as coligand have been synthesized and characterized by the aid of various spectral techniques. The single-crystal X-ray diffraction studies revealed that the unsubstituted thiosemicarbazone ligand acted as monobasic tridentate (ONS(-)) in the cationic [Pd(H-Qtsc-H)(PPh(3))]Cl complex, whereas the monosubstituted thiosemicarbazone ligands acted as monobasic bidentate (NS(-)) in their respective complexes, [PdCl(H-Qtsc-R)(PPh(3))] (R = Me (2), Et (3), Ph (4)). To ascertain the potentials of the above Pd(II) complexes toward biomolecular interactions, additional experiments involving interaction with calf thymus DNA and bovine serum albumin were carried out. Moreover, all the palladium(II) complexes have been screened for their radical scavenging activity toward DPPH, O(2)(-), OH, and NO radicals. The efficiency of the complexes in arresting the growth of human cervical cancer cells (HeLa), human laryngeal epithelial carcinoma cells (HEp-2), human liver carcinoma cells (Hep G2), and human skin cancer cells (A431) has also been studied along with the cell viability test against the noncancerous NIH 3T3 mouse embryonic fibroblasts cell lines under in vitro conditions. All the in vitro pharmacological evaluation results clearly revealed the relationship between the structure and the activity of the new Pd(II) complexes.

Influence of carboxylic acid functionalities in ruthenium (II) polypyridyl complexes on DNA binding, cytotoxicity and antioxidant activity: synthesis, structure and in vitro anticancer activity.

Four new Ru(II) complexes [RuHCl(bpy)(PPh(3))(CO)] (1), [RuHCl(bpy)(AsPh(3))(CO)] (2) (bpy = 2,2'-bipyridine), [RuCl(HL)(PPh(3))(2)(CO)] (3) and [RuCl(HL)(AsPh(3))(2)(CO)] (4) (HL = 2,2'-bipyridine-4,4'-dicarboxylic acid) were synthesized and characterized. X-ray diffraction was used to characterize 3 in solid state. The interactions of these complexes with DNA were explored by different techniques which revealed that the complexes could bind to CT-DNA through non-intercalation. The in vitro cytotoxic and antioxidant activities of the complexes validated against a panel of cancer cell lines and free radicals showed that 3 and 4 possess quite high anticancer and antioxidant activities over 1, 2 and standard drugs. An apparent dependence of biological activities on incorporation of COOH in bipyridine moiety was noticed: Inclusion of COOH caused significant differences in DNA binding, cytotoxicity and antioxidant activity.

Mixed ligand palladium(II) complexes of 6-methoxy-2-oxo-1,2-dihydroquinoline-3-carbaldehyde 4N-substituted thiosemicarbazones with triphenylphosphine co-ligand: synthesis, crystal structure and biological properties.

A series of new 6-methoxy-2-oxo-1,2-dihydroquinoline-3-carbaldehyde 4N-substituted thiosemicarbazone ligands (H2L1­H2L5) and their corresponding palladium(II) complexes [Pd(L1)(PPh3)] (1), [Pd(L2)(PPh3)] (2), [Pd(HL3)(PPh3)]Cl (3), [Pd(L4)(PPh3)] (4) and [Pd(L5)(PPh3)] (5), have been synthesized in order to evaluate the effect of terminal N-substitution in thiosemicarbazone moiety on coordination behaviour and biological activity. The new ligands and their corresponding complexes were characterized by analytical and various spectral techniques. The molecular structure of the complexes 2­5 were characterized by single crystal X-ray diffraction studies which revealed that the ligands H2L2, H2L4 and H2L5 are coordinated to palladium(II) as binegative tridentate (ONS2−) by forming six and five member rings whereas, the ligand H2L3 coordinated to Pd(II) as uninegative tridentate (ONS−). The interactions of the new complexes with calf thymus DNA (CT-DNA) have been evaluated by absorption and ethidium bromide (EB) competitive studies which revealed that complexes 1­5 could interact with CT-DNA through intercalation. Further, the interactions of the complexes with bovine serum albumin (BSA) were also investigated using UV-visible, fluorescence and synchronous fluorescence spectroscopic methods, which showed that the new complexes could bind strongly with BSA. Antioxidant studies showed that all the complexes have a strong antioxidant activity against 2-2'-diphenyl-1-picrylhydrazyl (DPPH) radical and 2,2'-azino-3-ethylbenzthiazoline-6-sulfonic acid diammonium salt (ABTS) cation radical. In addition, in vitro cytotoxicity of the complexes against human lung cancer (A549) cell line was assayed which showed that 4 has higher cytotoxic activity than the rest of the complexes and cisplatin.

Evaluation of DNA binding, antioxidant and cytotoxic activity of mononuclear Co(III) complexes of 2-oxo-1,2-dihydrobenzo[h]quinoline-3-carbaldehyde thiosemicarbazones.

Four new 2-oxo-1,2-dihydrobenzo[h]quinoline-3-carbaldehyde N-substituted thiosemicarbazone ligands (H(2)-LR, where R = H, Me, Et or Ph) and their corresponding new cobalt(III) complexes have been synthesized and characterized. The structures of the complexes 2 and 3 were determined by single crystal X-ray diffraction analysis. The interactions of the new complexes with DNA were investigated by absorption, emission and viscosity studies which indicated that the complexes bind to DNA via intercalation. Antioxidant studies of the new complexes showed that the significant antioxidant activity against DPPH radical. In addition, the in vitro cytotoxicity of complexes 1-4 against A549 cell line was assayed which showed higher cytotoxic activity with lower IC(50) values indicating their efficiency in killing the cancer cells even at very low concentrations.

Copper ion mediated selective cleavage of C-S bond in ferrocenylthiosemicarbazone forming mixed geometrical [(PPh3)Cu(µ-S)2Cu(PPh3)2] having Cu2S2 core: toward a new avenue in copper-sulfur chemistry.

Unprecedented selective cleavage of the carbon-sulfur bond of the ferrocenylthiosemicarbazone moiety has been observed for the first time, resulting in the formation of mixed geometrical binuclear copper complex [(PPh(3))Cu(µ-S)(2)Cu(PPh(3))(2)]. Upon trying direct synthesis of the title complex, an unusual tetranuclear [Cu(4)(µ(3)-Cl)(4)(PPh(3))(4)] cubane resulted.

A novel water soluble ligand bridged cobalt(II) coordination polymer of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (isonicotinic) hydrazone: evaluation of the DNA binding, protein interaction, radical scavenging and anticancer activity.

A novel water soluble ligand-bridged cobalt(II) coordination polymer has been synthesized by reacting the new ligand, 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (isonicotinic) hydrazone (H(2)L) with Co(NO(3))(2)·6H(2)O and characterized by spectral, analytical and structural methods. Single crystal X-ray diffraction studies revealed that the Co(II) complex, {[Co(H(2)L)(H(2)O)(2)](NO(3))(2)·3H(2)O}(n) has a slightly distorted octahedral geometry around the central Co(II) ion; the ligand is coordinated through the ONO donor atoms to one Co(II) metal center and bridged through the pyridine nitrogen atom to another similar Co(II) center so as to form a one-dimensional polymeric unit. The interaction of the ligand and the complex with calf thymus DNA (CT-DNA) has been explored by absorption and emission titration methods, which revealed that the compounds could interact with CT-DNA through intercalation. The interactions of the compounds with bovine serum albumin (BSA) were also investigated using UV-visible, fluorescence and synchronous fluorescence spectroscopic methods. The results indicated that the complex exhibited a strong binding to BSA over the ligand. Investigation of the antioxidative properties showed that the polymeric Co(II) complex has a strong radical scavenging potency against hydroxyl radicals, 2,2-diphenyl-1-picrylhydrazyl radicals, nitric oxide and superoxide anion radicals. Further, the cytotoxic effect of the compounds examined on cancerous cell lines, such as human cervical cancer cells (HeLa), human laryngeal epithelial carcinoma cells (HEp-2), human liver carcinoma cells (Hep G2), human skin cancer cells (A431) and non-cancerous NIH 3T3 mouse embryonic fibroblasts cell lines showed that the complex exhibited substantial anticancer activity.

Structure-activity relationship study of copper(II) complexes with 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (4'-methylbenzoyl) hydrazone: synthesis, structures, DNA and protein interaction studies, antioxidative and cytotoxic activity.

Novel 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (4'-methylbenzoyl) hydrazone (H(2)L) (1) and its two copper(II) complexes have been synthesized. Single-crystal X-ray diffraction studies revealed that the structure of the new copper(II) chloride complex, [Cu(H(2)L)Cl(2)]·2H(2)O (2), is square pyramidal and that of the copper(II) nitrate complex, [Cu(HL)NO(3)]·DMF (3), is square planar. In 2, the copper atom is coordinated by the ligand with ONO donor atoms, one chloride ion in the apical position, and the other chloride in the basal plane. In 3, the ligand coordinates as a uninegative tridentate ONO(-) species and with one nitrate ion in the basal plane. DNA binding experiments indicated that the ligand and copper(II) complexes can interact with DNA through intercalation. Bovine serum albumin binding studies revealed that the compounds strongly quench the intrinsic fluorescence of bovine serum albumin through a static quenching process. Antioxidative activity tests showed that 1 and its copper(II) complexes have significant radical scavenging activity against free radicals. Cytotoxic activities of the ligand and copper(II) complexes showed that the two copper(II) complexes exhibited more effective cytotoxic activity against HeLa and HEp-2 cells than the corresponding ligand. The entire biological activity results showed that the activity order was 1 < 2 < 3.

Synthesis, X-ray crystal structure, DNA binding, antioxidant and cytotoxicity studies of Ni(ii) and Pd(ii) thiosemicarbazone complexes.

New complexes, [Ni(HL)(PPh(3))]Cl (1), [Pd(L)(PPh(3))](2), and [Pd(L)(AsPh(3))](3), were synthesized from the reactions of 4-chloro-5-methyl-salicylaldehyde thiosemicarbazone [H(2)L] with [NiCl(2)(PPh(3))(2)], [PdCl(2)(PPh(3))(2)] and [PdCl(2)(AsPh(3))(2)]. They were characterized by IR, electronic, (1)H-NMR spectral data. Further, the structures of the complexes have been determined by single crystal X-ray diffraction. While the thiosemicarbazone coordinated as binegative tridentate (ONS) in complexes 2 and 3, it is coordinated as mono negative tridentate (ONS) in 1. The interactions of the new complexes with calf thymus DNA was examined by absorption and emission spectra, and viscosity measurements. Moreover, the antioxidant properties of the new complexes have also been tested against DPPH radical in which complex 1 exhibited better activity than that of the other two complexes 2 and 3. The in vitro cytotoxicity of complexes 1-3 against A549 and HepG2 cell lines was assayed, and the new complexes exhibited higher cytotoxic activity with lower IC(50) values indicating their efficiency in killing the cancer cells even at very low concentrations.

Synthesis, crystal structure and pharmacological evaluation of two new Cu(II) complexes of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (benzoyl) hydrazone: a comparative investigation.

Two new copper(II) complexes have been synthesized by reacting 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (benzoyl) hydrazone (H(2)L) with CuCl(2)·2H(2)O or Cu(NO(3))(2)·3H(2)O. The structures of the complexes have been determined by single crystal X-ray diffraction studies. Results obtained using spectroscopic methods strongly suggested that the ligand and its Cu(II) complexes could interact with calf thymus DNA through intercalation. In the case of protein binding, the obtained results indicated that all the three compounds could quench the intrinsic fluorescence of bovine serum albumin through static quenching process. In addition, antioxidant activity tests showed that H(2)L and its copper(II) complexes possess significant scavenging effect against free radicals. Further, the two copper(II) complexes exhibited effective cytotoxic activity against a panel of human cancer cell lines.

Ruthenium(II)/(III) complexes of 4-hydroxy-pyridine-2,6-dicarboxylic acid with PPh3/AsPh3 as co-ligand: impact of oxidation state and co-ligands on anticancer activity in vitro.

With the aim to develop more efficient, less toxic, target specific metal drugs and evaluate their anticancer properties in terms of oxidation state and co-ligand sphere, a sequence of Ru(II), Ru(III) complexes bearing 4-hydroxy-pyridine-2,6-dicarboxylic acid and PPh(3)/AsPh(3) were synthesized and structurally characterized. Biological studies such as DNA binding, antioxidant assays and cytotoxic activity were carried out and their anticancer activities were evaluated. Interactions of the complexes with calf thymus DNA revealed that the triphenylphosphine complexes could bind more strongly than the triphenylarsine complexes. The free radical scavenging ability, assessed by a series of in vitro antioxidant assays involving DPPH radical, hydroxyl radical, nitric oxide radical, superoxide anion radical, hydrogen peroxide and metal chelating assay, showed that the Ru(III) complexes possess excellent radical scavenging properties compared to those of Ru(II). Cytotoxicity studies using three cancer lines viz HeLa, HepG2, HEp-2 and a normal cell line NIH 3T3 showed that Ru(II) complexes exhibited substantial cytotoxic specificity towards cancer cells. Furthermore, the Ru(II) complexes were found to be superior to Ru(III) complexes in inhibiting the growth of cancer cells.

Effect of N(4)-phenyl substitution in 2-oxo-1,2-dihydroquinoline-3-carbaldehyde semicarbazones on the structure, DNA/protein interaction, and antioxidative and cytotoxic activity of Cu(II) complexes.

A new ligand, 2-oxo-1,2-dihydroquinoline-3-carbaldehyde semicarbazone (OQsc-H) (1);, its N(4)-phenyl derivative (OQsc-Ph) (2); and their corresponding copper(II) complexes [CuCl(2)(OQsc-H)]·H(2)O·CH(3)OH (3), [CuCl(2)(OQsc-Ph)(H(2)O)]·CH(3)OH (4), and [CuNO(3)(OQsc-Ph)(H(2)O)]NO(3)·H(2)O·C(2)H(5)OH (5) have been synthesized and characterized by structural, analytical, and spectral methods, in order to investigate the influence of N(4)-phenyl substitution on structure and pharmacological properties. In all of the complexes, the ligands coordinated to the Cu(II) ion in a neutral fashion via ONO donor atoms. The single-crystal X-ray structures of neutral complex (3) and cationic complex (5) exhibit a slightly distorted square-pyramidal structure, while neutral complex (4) revealed an octahedral structure. The interaction of the compounds with calf thymus DNA (CT-DNA) has been explored by absorption and emission titration methods, which revealed that compounds 1-5 could interact with CT-DNA through intercalation. A gel electrophoresis pictogram demonstrated the ability of the complexes (3-5) to cleave the pBR322 plasmid DNA through a hydrolytic process. The interactions of the compounds with bovine serum albumin (BSA) were also investigated using UV-visible, fluorescence, and synchronous fluorescence spectroscopic methods. The results indicated that all of the compounds could quench the intrinsic fluorescence of BSA in a static quenching process. Investigations of antioxidative properties showed that all of the compounds have strong radical scavenging potencies against hydroxyl radicals, 2,2-diphenyl-1-picrylhydrazyl radicals, nitric oxide, and superoxide anion radicals. Further, the cytotoxic effect of the compounds examined on cancerous cell lines such as human cervical cancer cells (HeLa), human laryngeal epithelial carcinoma cells (HEp-2), human liver carcinoma cells (Hep G2), human skin cancer cells (A431), and noncancerous NIH 3T3 mouse embryonic fibroblasts cell lines showed that all three complexes exhibited substantial cytotoxic activity. Further, all of the pharmacological investigations support the fact that there exists a strong influence of N(4)-phenyl substitution in semicarbazone.

Biological evaluation of a novel water soluble sulphur bridged binuclear copper(II) thiosemicarbazone complex.

The reaction of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde 4(N,N)-dimethylthiosemicarbazone (HL) with copper(II) nitrate in methanol yielded water soluble [{Cu(L)(CH(3)OH)}(2)](NO(3))(2) · H(2)O. Structural analysis revealed that the complex consists of centrosymmetric binuclear entities containing square-pyramidal copper(II) ions bridged through the sulfur atoms. The spectroscopic experimental evidences strongly suggested that the ligand and complex could interact with calf thymus DNA (CT-DNA) through intercalation. A gel electrophoresis assay demonstrated the ability of the complex to cleave the pBR322 plasmid DNA. The complex also exhibited a strong binding to bovine serum albumin (BSA) over the ligand. Investigations of antioxidative properties showed that the complex has strong radical scavenging properties. Further, the cytotoxic effect of the complex was examined on HeLa, Hep G2, and HEp-2, which showed that the complex exhibited substantial cytotoxic specificity on HeLa over the other two.