Photocytotoxic and anaerobic DNA cleavage activity of binuclear 3,3 '-dithiodipropionic acid cobalt(II) complexes having phenanthroline bases

Dicobalt(II) complexes [{(B)Co-11)(2)(mu-dtdp)(2)] (1-3) of 3,3'-dithiodipropionic acid (dtdp) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq in 2) and dipyrido13,2-a:2',3'-clphenazine (dppz in 3), have been prepared, characterized and their photo-induced anaerobic DNA cleavage activity studied. The elemental analysis and mass spectral data suggest binuclear formulation of the complexes. The redox inactive complexes have magnetically non-interacting dicobalt(II) core showing magnetic moment of similar to 3.9 p per cobalt(II) center. The complexes show good binding propensity to calf thymus DNA giving K-b values within 4.3 x 10(5)-4.0 x 10(6) M-1. Thermal melting and viscosity data predict DNA groove binding and/or partial intercalative nature of the complexes. The complexes show significant anaerobic DNA cleavage activity in green light under argon atmosphere possibly involving radical species generated from the disulfide moiety in a type-I pathway. The DNA cleavage reaction under aerobic medium in green light is found to involve hydroxyl radical species. The dppz complex 3 exhibits significant photocytotoxicity in HeLa cervical cancer cells with an IC50 value of 2.31 mu M in UV-A light of 365 nm, while it is essentially non-toxic in dark giving an IC50 value of >200 mu M. A significant reduction of the dark toxicity of the organic dppz base (IC50 = 8.3 mu M in dark) is observed on binding to the cobalt(II) center while essentially retaining its photocytotoxicity in UV-A light (IC50 = 0.4 mu M). (C) 2010 Elsevier Ltd. All rights reserved.

A numerical study of laminar axisymmetric plumes due to the combined buoyancy of heat and mass diffusion

This paper presents the results of a computational study of laminar axisymmetric plumes generated by the simultaneous diffusion of thermal energy and chemical species. Species concentrations are assumed small. The plume is treated as a boundary layer. Boussinesq approximations are incorporated and the governing conservation equations of mass, momentum, energy and species are suitably non-dimensionalised. These equations are solved using one time-step-forward explicit finite-difference method. Upwind differencing is employed for convective terms. The results thus obtained are explained in terms of the basic physical mechanisms that govern these flows. They show many interesting aspects of the complex interaction of the two buoyant mechanisms.

Natural Convection on a Horizontal Cone in a Porous Medium with Non-Uniform Wall Temperature/Concentration or Heat/Mass Flux and Suction/Injection

The steady natural convection flow on a horizontal cone embedded in a saturated porous medium with non-uniform wall temperature/concentration or heat/mass flux and suction/injection has been investigated. Non-similar solutions have been obtained. The nonlinear couple differential equations under boundary layer approximations governing the flow have been numerically solved. The Nusselt and Sherwood numbers are found to depend on the buoyancy forces, suction/injection rates, variation of wall temperature/concentration or heat/mass flux, Lewis number and the non-Darcy parameter.

Evolution of polyandry by reduction in progeny number variance in structured populations

When there is a variation in the quality of males in a population, multiple mating can lead to an increase in the genetic fitness of a female by reducing the variance of the progeny number. The extent of selective advantage obtainable by this process is investigated for a population subdivided into structured demes. It is seen that for a wide range of model parameters (deme size, distribution of male quality, local resource level), multiple mating leads to a considerable increase in the fitness. Frequency-dependent selection or a stable coexistence between polyandry and monandry can also result when the possible costs involved in multiple mating are taken into account.

NO reduction, CO and hydrocarbon oxidation over combustion synthesized Ag/CeO2 catalyst

The combustion technique produces ionically dispersed Ag on a nano-crystalline CeO2 surface. The catalysts thus produced were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Catalytic properties towards NO reduction, CO and hydrocarbon oxidation have been investigated using the temperature programmed reaction technique in a packed bed tubular reactor. These results are compared with alpha-Al2O3 supported finely divided Ag metal particles synthesized by the same method. Both oxidation and reduction reactions over Ag/CeO2 have been observed to occur at lower temperatures compared to Ag/Al2O3. The rate and turnover frequency of the NO+CO reaction over 1% Ag/CeO2 are 56.3 mu mol g(-1) s(-1) and 0.97 s(-1) at 225 degrees C respectively. Activation energy (E-a) values are 71 and 67 kJ mol(-1) for CO+O-2 and NO+CO reactions, respectively, over 1% Ag/CeO2 catalyst.

Laminar compressible boundary layer flow at a three-dimensional stagnation point with vectored mass transfer

The effect of surface mass transfer velocities having normal, principal and transverse direction components (�vectored� suction and injection) on the steady, laminar, compressible boundary layer at a three-dimensional stagnation point has been investigated both for nodal and saddle points of attachment. The similarity solutions of the boundary layer equations were obtained numerically by the method of parametric differentiation. The principal and transverse direction surface mass transfer velocities significantly affect the skin friction (both in the principal and transverse directions) and the heat transfer. Also the inadequacy of assuming a linear viscosity-temperature relation at low-wall temperatures is shown.

An assessment of the reduction potential of hydrogen plasma

Hydrogen plasma can be used for deoxidation of functional materials containing reactive metals in both bulk and thin film forms. Since the different species in the plasma are not in thermodynamic equilibrium, application of classical thermodynamics to the analysis of such a system is associated with some difficulties. While global equilibrium approaches have been tried, with and without additional approximations or constraints, there is some ambiguity in the results obtained. Presented in this article is the application of a local equilibrium concept to assess the thermodynamic limit of the reaction of each species present in the gas with oxides or oxygen dissolved in metals. Each reaction results in a different pal tial pressure of H2O. Because of the higher reactivity of the dissociated and ionized species and the larger thermodynamic driving force for reactions involving these species, they act as powerful reducing agents. It is necessary to remove the products of reaction from the plasma to prevent back reaction and gradual approach to global equilibrium. A quantitative description using the framework of the Ellingham-Richardson-Jeffes diagrams is presented.

Spin and mass content of linearized Poincaré gauge theories

A unified gauge theory of massless and massive spin-2 fields is of considerable current interest. The Poincaré gauge theories with quadratic Lagrangian are linearized, and the conditions on the parameters are found which will lead to viable linear theories with massive gauge particles. As well as the 2+ massless gravitons coming from the translational gauge potential, the rotational gauge potentials, in the linearized limit, give rise to 2+ and 2− particles of equal mass, as well as a massive pseudoscalar.

Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2.

Mass analyser optics for wide-beam ion sources in ion implantation systems

Ion implantation systems, used for producing high-current ion beams, employ wide-beam ion sources which are rotated through 90 degrees . These sources need mass analyser optics which are different from the conventional design. The authors present results of calculation of the image distance as a function of entrance and exit angles of a sector magnet mass analyser having such a source. These computations have been performed for the magnetic deflection angles 45 degrees , 60 degrees and 90 degrees . The details of the computations carried out using the computer program MODBEAM, developed for this purpose, are also discussed.

Electrochemical reduction of Cu(II)-CyDTA complex at dropping mercury electrode. An impedance approach

The electrochemical reduction of Cu(II)-CyDTA (CyDTA — trans 1,2-cyclohexanediamine N, N, N′, N′ tetraacetic acid) by impedance method reveals the unusual behaviour of complex plane polarograms owing to potential dependence of double layer capacitance. The impedance plane plots by frequency variation method indicates the quasi-reversible nature of the system. From these plots the chargetransfer resistance at various potentials was evaluated. The standard rate constant was evaluated which complements the prediction of impedance plots for the quasireversible behaviour of the system.

Electrochemical reduction of Cu(II)-EDTA complex at dropping mercury electrode. An impedance approach

The study of electrochemical reduction of Cu(II)-EDTA system by phase sensitive a.c. impedance method at dropping mercury electrode reveals several interesting features. The complex plane polarograms exhibit loop like shape in contrast to the classical zinc ion reduction where crest like shape is found. Again, the relative placement of peaks of in-phase and quadrature components, and the relative placement of portions before and after the peaks of complex plane polarograms are different from that of zinc ion reduction. The complex plane plots suggest that electrochemical reduction of Cu-EDTA is charge transfer controlled.