Remarkable photocytotoxicity in hypoxic HeLa cells by a dipyridophenazine copper(II) Schiff base thiolate

Copper(II) complexes Cu(satp)(L)] (1-3) of a Schiff base thiolate (salicylidene-2-aminothiophenol, H(2)satP) and phenanthroline bases (L), viz. 1,10-phenanthroline (phen in 1), dipyrido3,2-d:2',3'-f]quinoxaline (dpq in 2) and dipyrido3,2-a:2',3'-c]phenazine (dppz in 3), were prepared, characterized and their anaerobic DNA photocleavage activity and hypoxic photocytotoxicity studied. The redox active complexes show the Cu(II)-Cu(I) couple near -0.5 V for 1 and near 0.0 V vs. SCE (saturated calomel electrode) for 2 and 3. The one-electron paramagnetic complexes (similar to 1.85 mu(B)) are avid DNA binders giving K(b) values within 1.0 x 10(5) - 8.0 x 10(5) M(-1). Thermal melting and viscosity data along with molecular docking calculations suggest DNA groove and/or partial intercalative binding of the complexes. The complexes show anaerobic DNA cleavage activity in red light under argon via type-I pathway, while DNA photocleavage in air proceeds via hydroxyl radical pathway. The DFT (density functional theory) calculations reveal a thyil radical pathway for the anaerobic DNA photocleavage activity and suggest the possibility of generation of a transient copper(I) species due to bond breakage between the copper and sulfur to generate the thyil radical. An oxidation of the copper(I) species is likely by oxygen in an aerobic medium or by the buffer medium in an anaerobic condition. Complex 3 exhibits significant photocytotoxicity in HeLa cells (IC(50) = 8.3(+/- 1.0) mu M) in visible light, while showing lower dark toxicity (IC(50) = 17.2(+/- 1.0) mu M). A significant reduction in the dark toxicity is observed under hypoxic cellular conditions (IC(50) = 30.0(+/- 1.0) mu M in dark), while retaining its photocytotoxicity (IC(50) = 8.0(+/- 1.0) mu M). (C) 2011 Elsevier Inc. All rights reserved.

Copper, Zinc-Superoxide Dismutase from Clinically Isolated Escherichia coli: Cloning, Analysis of sodC and Its Possible Role in Pathogenicity

Superoxide dismutase has been discovered within the periplasm of several Gram-negative pathogens. We studied the Cu,Zn-SOD enzyme in Escherichia coli isolated from clinical samples (stool samples) collected from patients suffering from diarrhea. Antibiogram studies of the isolates were carried out to determine the sensitive and resistant strains. The metal co-factor present in the enzyme was confirmed by running samples in native gels and inhibiting with 2 mM potassium cyanide. A 519 bp sodC gene was amplified from resistant and sensitive strains of Escherichia coli. Cloning and sequencing of the sodC gene indicated variation in the protein and amino acid sequences of sensitive and resistant isolates. The presence of sodC in highly resistant Escherichia coli isolates from diarrheal patients indicates that sodC may play role in enhancing the pathogenicity by protecting cells from exogenous sources of superoxide, such as the oxidative burst of phagocytes. The presence of SodC could be one of the factors for bacterial virulence.

The first copper(I) complex of tris(hydroxymethyl)phosphine

The first copper(I) complex of tris(hydroxymethyl)phosphine (THP) has been synthesized from a reaction with [Cu(CH3CN)4]ClO4. The crystal structure and spectroscopic properties of this complex showing the tetrahedral coordination around copper and a deprotonated THP coordinated to Cu through P are presented.

A General Route to Nanoparticle Thin Films and Coatings

Nanoparticles thin films have wide range of applications such as nanoelectronics, magnetic storage devices, SERS substrate fabrication, optical grating and antireflective coating. Present work describes a method to prepare large area nanoparticles thin film of the order of few square centimeters. Thin film deposition has been done successfully on a wide range of conducting as well as non conducting substrates such as carbon-coated copper grid, silicon, m-plane of alumina, glass and (100) plane of NaCl single crystal. SEM, TEM and AFM studies have been done for microstructural characterization of the thin films. A basic mechanism has been proposed towards the understanding of the deposition process.

Efficient visible light induced nuclease activity of a ternary mono-1,10-phenanthroline copper(II) complex containing 2-(methylthio)ethylsalicylaidimine

Ternary Schiff base copper(II) complex [CuL(phen)](ClO4), where HL is 2-(methylthio)ethylsalicylaldimine and phen is 1,10-phenanthroline, has been prepared and structurally characterized by X-ray crystallography. The complex shows a CuN3OS coordination in a square-pyramidal (4 + 1) geometry with the sulfur as an equatorial ligand. The complex is an avid binder to double-stranded DNA in the minor groove and exhibits both photonuclease and chemical nuclease activity. When exposed to UV light of 312 nm (96 W) or visible light of 532 nm (125 W) under aerobic conditions, the complex causes significant cleavage of supercoiled pUC19 DNA in the absence of any externally added reducing agent or H2O2.

Ternary copper(II) complexes of thiosemicarbazones and heterocyclic bases showing N3OS coordination as models for the type-2 centers of copper monooxygenases

Six ternary copper(II) complexes of general formulation [CuLB] (1-6), where L is dianionic ONS-donor thiosemicarbazones derived from the condensation of salicylaldehyde with thiosemicarbazides and B is NN-donor heterocyclic bases like 2,2'-bipyridine, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, are prepared from a reaction of copper(II) acetate hydrate with the heterocyclic base (B) and the thiosemicarbazone (H2L) in MeOH, and structurally characterized by X-ray diffraction technique. Crystal structures of the complexes display a distorted square-pyramidal (4 + 1) coordination geometry having the ONS-donor thiosemicarbazone bonded at the basal plane. The chelating heterocyclic bases exhibit axial-equatorial mode of bonding. The complexes are one-electron paramagnetic and they show axial X-band EPR spectra in DMF-toluene glass at 77 K giving g(parallel to)(A(parallel to)) and g(perpendicular to) values of similar to2.2 (175 x 10(-4) cm(-1)) and similar to2.0 indicating a {d(x2-y2)}(1) ground state. The complexes show a d-d band near 570 nm and a charge transfer band near 400 nm in DMF. The complexes are redox active and exhibit a quasireversible Cu(II)-Cu(I) couple in DMF-0.1 M tetrabutylammonium perchlorate near 0.1 V vs. SCE. They are catalytically active in the oxidation of ascorbic acid in presence of dioxygen. The complexes with a CuN3OS coordination model the ascorbate oxidation property of dopamine beta-hydroxylase and peptidylglycine a-hydroxylating monooxygeanase. (C) 2003 Elsevier Science B.V. All rights reserved.

The influence of grain size on deformation of copper

It is well know that grain boundaries enhance strength at low temperatures by acting as obstacles to dislocation motion, and they retard strength at higher temperatures by processes involving grain boundary sliding. The available data on the influence of grain boundaries on deformation in copper is summarized. Equi-channel angular extrusion offers a convenient means for imposing severe plastic deformation to refine the grain size in bulk materials. Experimental data on fine grained copper produced by equi-channel angular extrusion will be described, and the implications of the data for diffusion creep and superplasticity will be discussed.

Low-temperature polaronic relaxations with variable range hopping conductivity in FeTiMO(6) (M = Ta,Nb,Sb)

Low-temperature dielectric measurements on FeTiMO(6) (M = Ta,Nb,Sb) rutile-type oxides at frequencies from 0.1 Hz to 10 MHz revealed anomalous dielectric relaxations with frequency dispersion. Unlike the high-temperature relaxor response of these materials, the low-temperature relaxations are polaronic in nature. The relationship between frequency and temperature of dielectric loss peak follows T(-1/4) behavior. The frequency dependence of ac conductivity shows the well-known universal dielectric response, while the dc conductivity follows Mott variable range hopping (VRH) behavior, confirming the polaronic origin of the observed dielectric relaxations. The frequency domain analysis of the dielectric spectra shows evidence for two relaxations, with the high-frequency relaxations following Mott VRH behavior more closely. Significantly, the Cr- and Ga-based analogs, CrTiNbO(6) and GaTiMO(6) (M = Ta,Nb), that were also studied, did not show these anomalies.

Ferrocene-Conjugated L-Tryptophan Copper(II) Complexes of Phenanthroline Bases Showing DNA Photocleavage Activity and Cytotoxicity

Ferrocene-conjugated L-tryptophan (L-Trp) reduced Schiff base (Fc-TrpH) copper(II) complexes [Cu(Fc-Trp)(L)](ClO(4)) of phenanthroline bases (L), viz. 2,2'-bipyridine (bpy in 1), 1,10-phenanthroline (phen in 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq in 3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz in 4), were prepared and characterized and their photocytotoxicity studied. Cationic reduced Schiff base (Ph-TrpH) complexes [Cu(Ph-Trp)(L)(H(2)O)] (ClO(4)) (L = phen in 5; dppz in 6) having the ferrocenyl moiety replaced by a phenyl group and the Zn(II) analogue (7) of complex 4 were prepared and used as control species. The crystal structures of 1 and 5 with respective square-planar CuN(3)O and square-pyramidal CuN(3)O(2) coordination geometry show significantly different core structures. Complexes 1-4 exhibit a Cu(II)-Cu(I) redox couple near -0.1 V and the Fc(+)-Fc couple at similar to 0.5 V vs SCE in DMF-0.1 M [Bu(4)(n)N] (ClO(4)) (Fc = ferrocenyl moiety). The complexes display a copper(II)-based d-d band near 600 nm and a Fc-centered band at similar to 450 nm in DMF-Tris-HCl buffer. The complexes are efficient binders to calf thymus DNA. They are synthetic chemical nucleases in the presence of thiol or H(2)O(2), forming hydroxyl radicals. The photoactive complexes are cleavers of pUC19 DNA in visible light, forming hydroxyl radicals. Complexes 2-6 show photocytotoxicity in HeLa cancer cells, giving IC(50) values of 4.7, 10.2, 1.3, 4.8, and 4.3 mu M, respectively, in visible light with the appearance of apoptotic bodies. The complexes also show photocytotoxicity in MCF-7 cancer cells. Nuclear chromatin cleavage has been observed with acridine orange/ethidium bromide (AO/EB) dual staining with complex 4 in visible light. The complexes induce caspase-independent apoptosis in the HeLa cells.

Altitude variation of aerosol properties over the Himalayan range inferred from spatial measurements

Altitude variations of the mass concentration of black carbon, number concentration of composite aerosols are examined along with the columnar spectral aerosol optical depths using state of the art instruments and the Angstrom parameters are inferred from the ground based measurements at several altitude levels, en route from Manora Peak, Nainital (similar to 1950 m above mean sea level) to a low altitude station Haldwani (similar to 330 m above mean sea level) at its foothill within an aerial distance of <10,000 m. The measurements were done during the winter months (November-February) of 2005, 2006 and 2007 under fair weather conditions. The results show a rapid decrease in all the measured parameters with increase in altitude, with >60% contribution to the AOD coming from the regions below 1000 m. The Angstrom wavelength exponent remained high in the well mixed region, and decreased above. The normalized AOD gradient was used to estimate aerosol mixing height, which was found to be in the altitude range 1000-1500 m, above which the particle concentrations are slowly varying as a function of altitude. The heating rate at the surface is found to be maximum but decreases sharply with increase in altitude. Analysis of the wavelength dependence of absorption aerosol optical depth (AAOD) showed that the aerosol absorption over the site is generally due to mixed aerosols. (C) 2011 Elsevier Ltd. All rights reserved.

Texture and grain boundary character distribution during Equal Channel Angular Extrusion of some two-phase copper alloys

In the present work, a thorough investigation of evolution of microstructure and texture has been carried out to elucidate the evolution of texture and grain boundary character distribution (GBCD) during Equal Channel Angular Extrusion (ECAE) of some model two-phase materials, namely Cu-0.3Cr and Cu-40Zn. Texture of Cu-0.3Cr alloy is similar to that reported for pure copper. On the other hand, in Cu-40Zn alloy, texture evolution in α and β (B2) phases are interdependent. In Cu-0.3Cr alloy, there is a considerable decreases in volume fraction of low angle boundaries (LAGBs), only a slight increase in CSL boundaries, but increase in high angle grain boundaries (HAGBs) from 1 pass to 4 passes for both the routes. In the case of Cu-40Zn alloy, there is an appreciable increase in CSL volume fraction.

Energy-insensitive Guidance of Solid Motor Propelled Long Range Flight Vehicles Using MPSP and Dynamic Inversion

A energy-insensitive explicit guidance design is proposed in this paper by appending newlydeveloped nonlinear model predictive static programming technique with dynamic inversion, which render a closed form solution of the necessary guidance command update. The closed form nature of the proposed optimal guidance scheme suppressed the computational difficulties, and facilitate realtime solution. The guidance law is successfully verified in a solid motor propelled long range flight vehicle, for which developing an effective guidance law is more difficult as compared to a liquid engine propelled vehicle, mainly because of the absence of thrust cutoff facility. The scheme guides the vehicle appropriately so that it completes the mission within a tight error bound assuming that the starting point of the second stage to be a deterministic point beyond the atmosphere. The simulation results demonstrate its ability to intercept the target, even with an uncertainty of greater than 10% in the burnout time