Electrochemical, phosphate hydrolysis, DNA binding and DNA cleavage properties of new polyaza macrobicyclic dinickel(II) complexes

A new class of macrobicyclic dinickel(II) complexes Ni2L1,2 B](ClO4)(4) (1-6), where L-1,L-2 are polyaza macrobicyclic binucleating ligands, and B is a N,N-donor heterocyclic base (viz. 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)) are synthesized and characterized. The redox, catalytic, DNA binding and DNA cleavage properties were studied. They exhibit two irreversible waves in the cathodic region around E-pc = -0.95 V and E-pa = -0.85 V vs. Ag/Ag+ in CH3CN-0.1 M TBAP, respectively. The first order rate constants for the hydrolysis of 4-nitrophenylphosphate to 4-nitrophenolate by the dinickel(II) complexes 1-6 are in the range from 3.36 x 10(-5) to 10.83 x 10(-5) Ms-1. The complexes 3 and 6 show good binding propensity to calf thymus DNA giving binding constant values (K-b) in the range from 3.08 x 10(5) to 5.37 x 10(5) M-1. The binding site sizes and viscosity data suggest the DNA intercalative and/or groove binding nature of the complexes. The complexes display significant hydrolytic cleavage of supercoiled pBR322DNA at pH 7.2 and 37 degrees C. The hydrolytic cleavage of DNA by the complexes is supported by the evidence from free radical quenching and T4 ligase ligation. The pseudo Michaelis-Menten kinetic parameters k(cat) = 5.44 x 10(-2) h(-1) and K-M = 6.23 x 10(-3) M for complex 3 were obtained. Complex 3 also shows an enormous enhancement of the cleavage rate, of 1.5 x 10(6), in comparison to the uncatalysed hydrolysis rate (k = 3.6 x 10(-8) h(-1)) of ds-DNA.

Comparison of rhodamine B degradation under UV irradiation by two phases of titania nano-photocatalyst

Titania (TiO2) nano-photocatalysts, with different phases, prepared using a modified sol-gel process were employed in the degradation of rhodamine at 10 mg L-1 concentration. The degradation efficiency of these nano-photocatalysts was compared to that of commercial Degussa P25 titania. It was found that the nanocatalysts calcined at 450 degrees C and the Degussa P25 titania had similar photoreactivity profiles. The commercial Degussa P25 nanocatalysts had an overall high apparent rate constant of (K-app) of 0.023 min(-1). The other nanocatalyst had the following rate constants: 0.017, 0.0089, 0.003 and 0.0024 min(-1) for 450, 500, 550 and 600 degrees C calcined catalysts, respectively. This could be attributed to the phase of the titania as the anatase phase is highly photoactive than the other phases. Furthermore, characterisation by differential scanning calorimetry showed the transformation of titania from amorphous to anatase and finally to rutile phase. SEM and TEM characterisations were used to study the surface morphology and internal structure of the nanoparticles. BET results show that as the temperature of calcinations was raised, the surface area reduced marginally. X-ray diffraction was used to confirm the different phases of titania. This study has led to a conclusion that the anatase phase of the titania is the most photoactive nanocatalyst. It also had the highest apparent rate constant of 0.017 min(-1), which is similar to that of the commercial titania.

Comparative study on optical properties of Se-Zn-In and Se-Zn-Te-In chalcogenide glasses

In contemporary world optoelectronics materials are used in daily life owing to its verity of applications. Utility of these materials makes them attractive for investigations. Specifically study regarding optical properties of recent developed materials is worth for technical uses. Therefore, this work demonstrates a comparative study of extinction coefficient (K), real dielectric (epsilon') and imaginary dielectric (epsilon `') constants, refractive index (n) and optical energy band gap (E-g) with structural unit < r > for Se98-xZn2Inx (0 <= X-In <= 10) and Se93-yZn2Te5Iny (0 <= Y-In <= 10) chalcogenide glasses. Fixed amount of Te with increasing In concentration as cost of Se is largely influence the optical parameters of the materials. Values of optical parameters are obtained higher and lower respectively at thresholds structural units values. This comparative study demonstrates that enhanced values of optical parameters have been obtained for Te containing Se-Zn-In glasses.

Stability of a long unsupported circular tunnel in soils with seismic forces

By using the lower-bound finite element limit analysis, the stability of a long unsupported circular tunnel has been examined with an inclusion of seismic body forces. The numerical results have been presented in terms of a non-dimensional stability number (gamma H/c) which is plotted as a function of horizontal seismic earth pressure coefficient (k (h)) for different combinations of H/D and I center dot; where (1) H is the depth of the crest of the tunnel from ground surface, (2) D is the diameter of the tunnel, (3) k (h) is the earthquake acceleration coefficient and (4) gamma, c and I center dot define unit weight, cohesion and internal friction angle of soil mass, respectively. The stability numbers have been found to decrease continuously with an increase in k (h). With an inclusion of k (h), the plastic zone around the periphery of the tunnel becomes asymmetric. As compared to the results reported in the literature, the present analysis provides a little lower estimate of the stability numbers. The numerical results obtained would be useful for examining the stability of unsupported tunnel under seismic forces.

Study of dynamic behaviour of recession curves

Since Brutsaert and Neiber (1977), recession curves are widely used to analyse subsurface systems of river basins by expressing -dQ/dt as a function of Q, which typically take a power law form: -dQ/dt=kQ, where Q is the discharge at a basin outlet at time t. Traditionally recession flows are modelled by single reservoir models that assume a unique relationship between -dQ/dt and Q for a basin. However, recent observations indicate that -dQ/dt-Q relationship of a basin varies greatly across recession events, indicating the limitation of such models. In this study, the dynamic relationship between -dQ/dt and Q of a basin is investigated through the geomorphological recession flow model which models recession flows by considering the temporal evolution of its active drainage network (the part of the stream network of the basin draining water at time t). Two primary factors responsible for the dynamic relationship are identified: (i) degree of aquifer recharge (ii) spatial variation of rainfall. Degree of aquifer recharge, which is likely to be controlled by (effective) rainfall patterns, influences the power law coefficient, k. It is found that k has correlation with past average streamflow, which confirms the notion that dynamic -dQ/dt-Q relationship is caused by the degree of aquifer recharge. Spatial variation of rainfall is found to have control on both the exponent, , and the power law coefficient, k. It is noticed that that even with same and k, recession curves can be different, possibly due to their different (recession) peak values. This may also happen due to spatial variation of rainfall. Copyright (c) 2012 John Wiley & Sons, Ltd.

Nanostructured CexZn1-xO thin films: Influence of Ce doping on the structural, optical and electrical properties

Thin films of CexZn1-xO thin films were deposited on glass substrates at 400 degrees C by nebulizer spray pyrolysis technique. Ce doping concentration (x) was varied from 0 to 10%, in steps of 2.5%. X-ray diffraction reveals that all the films have polycrystalline nature with hexagonal crystal structure and high preferential orientation along (002) plane. Optical parameters such as; transmittance, band gap energy, refractive index (n), extinction coefficient (k), complex dielectric constants (epsilon(r), epsilon(i)) and optical conductivity (sigma(r), sigma(i)) have been determined and discussed with respect to Ce concentration. All the films exhibit transmittance above 80% in the wavelength range from 330 to 2500 nm. Optical transmission measurements indicate the decrease of direct band gap energy from 3.26 to 3.12 eV with the increase of Ce concentration. Photoluminescence spectra show strong near band edge emission centered similar to 398 nm and green emission centered similar to 528 nm with excitation wavelength similar to 350 nm. High resolution scanning electron micrographs indicate the formation of vertical nano-rod like structures on the film surface with average diameter similar to 41 nm. Electrical properties of the Ce doped ZnO film have been studied using ac impedance spectroscopy in the frequency range from 100 Hz-1 MHz at different temperatures. (C) 2013 Elsevier B.V. All rights reserved.

Uplift Resistance of Long Pipelines in the Presence of Seismic Forces

The vertical uplift resistance of long pipes buried in sands and subjected to pseudostatic seismic forces has been computed by using the lower-bound theorem of the limit analysis in conjunction with finite elements and nonlinear optimization. The soil mass is assumed to follow the Mohr-Coulomb failure criterion and an associated flow rule. The failure load is expressed in the form of a nondimensional uplift factor F-gamma. The variation of F-gamma is plotted as a function of the embedment ratio of the pipe, horizontal seismic acceleration coefficient (k(h)), and soil friction angle (phi). The magnitude of F-gamma is found to decrease continuously with an increase in the horizontal seismic acceleration coefficient. The reduction in the uplift resistance becomes quite significant, especially for greater values of embedment ratios and lower values of friction angle. The predicted uplift resistance was found to compare well with the existing results reported from the literature. (C) 2014 American Society of Civil Engineers.

Seismic Bearing Capacity of Shallow Embedded Foundations on a Sloping Ground Surface

By using the lower-bound theorem of the limit analysis in conjunction with finite elements and nonlinear optimization, bearing-capacity factors, N-c and N-gamma q, with an inclusion of pseudostatic horizontal seismic body forces, have been determined for a shallow embedded horizontal strip footing placed on sloping ground surface. The variation of N-c and N-gamma q with changes in slope angle (beta) for different values of seismic acceleration coefficient (k(h)) has been obtained. The analysis reveals that irrespective of ground inclination and the embedment depth of the footing, the factors N-c and N-gamma q decrease quite considerably with an increase in k(h). As compared with N-c, the factor N-gamma q is affected more extensively with changes in k(h) and beta. Unlike most of the results reported in literature for the seismic case, the present computational results take into account the shear resistance of soil mass above the footing level. An increase in the depth of the embedment leads to an increase in the magnitudes of both N-c and N-gamma q. (C) 2014 American Society of Civil Engineers.

Homogeneous Hermitian holomorphic vector bundles and the Cowen-Douglas class over bounded symmetric domains

It is known that all the vector bundles of the title can be obtained by holomorphic induction from representations of a certain parabolic group on finite-dimensional inner product spaces. The representations, and the induced bundles, have composition series with irreducible factors. We write down an equivariant constant coefficient differential operator that intertwines the bundle with the direct sum of its irreducible factors. As an application, we show that in the case of the closed unit ball in C-n all homogeneous n-tuples of Cowen-Douglas operators are similar to direct sums of certain basic n-tuples. (c) 2015 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Age and growth of Mugil cephalus (Linnaeus, 1758) (Perciformes: Mugilidae) in Bonny Estuary

The age and growth of Mugil cephalus was investigated in Bonny Estuary, Nigeria, from January, 1995 to December, 1996. Length-weight relationships were isometric with length exponents of 2.84 (males), 2.90 (females) and 2.88 (overall). Modal length at age were 12.0cm, 20.9cm, 25.0cm, 28.4cm and 30.2cm TL for ages 0+, 1+, 2+, 3+ and 4+ respectively. Corresponding total weights were 20.01g, 78.93g, 173.12g, 217.61g and 247.50g, respectively. Asymptotic length (Lo) was estimated 33.2cm TL, asymptotic weight (W sub(o)) was 484g, growth coefficient K=0.55847 super(-1) and hypothetical age at zero length To = 0.152yr. Longevity, Tmax, was 5.0yr, length and weight growth performance indices were Q super(1)=2.79 and Q = 1.44, respectively. Total mortality, natural mortality and fishing mortality were z = 1.02yr super(-1), M=0.607yr super(-1) and F=O. 3129yr super(-1), respectively. The exploitation ratio E was 0.4048 and exploitation rate U = 0.2302yr super(-1)

A quantitative investigation of the solar modulation of cosmic-ray protons and helium nuclei

The differential energy spectra of cosmic-ray protons and He nuclei have been measured at energies up to 315 MeV/nucleon using balloon- and satellite-borne instruments. These spectra are presented for solar quiet times for the years 1966 through 1970. The data analysis is verified by extensive accelerator calibrations of the detector systems and by calculations and measurements of the production of secondary protons in the atmosphere.

The spectra of protons and He nuclei in this energy range are dominated by the solar modulation of the local interstellar spectra. The transport equation governing this process includes as parameters the solar-wind velocity, V, and a diffusion coefficient, K(r,R), which is assumed to be a scalar function of heliocentric radius, r, and magnetic rigidity, R. The interstellar spectra, j_D, enter as boundary conditions on the solutions to the transport equation. Solutions to the transport equation have been calculated for a broad range of assumed values for K(r,R) and j_D and have been compared with the measured spectra.

It is found that the solutions may be characterized in terms of a dimensionless parameter, ψ(r,R) = ^∞∫_r V dr'/(K(r',R). The amount of modulation is roughly proportional to ψ. At high energies or far from the Sun, where the modulation is weak, the solution is determined primarily by the value of ψ (and the interstellar spectrum) and is not sensitive to the radial dependence of the diffusion coefficient. At low energies and for small r, where the effects of adiabatic deceleration are found to be large, the spectra are largely determined by the radial dependence of the diffusion coefficient and are not very sensitive to the magnitude of ψ or to the interstellar spectra. This lack of sensitivity to j_D implies that the shape of the spectra at Earth cannot be used to determine the interstellar intensities at low energies.

Values of ψ determined from electron data were used to calculate the spectra of protons and He nuclei near Earth. Interstellar spectra of the form j_D α (W - 0.25m)^-2.65 for both protons and He nuclei were found to yield the best fits to the measured spectra for these values of ψ, where W is the total energy and m is the rest energy. A simple model for the diffusion coefficient was used in which the radial and rigidity dependence are separable and K is independent of radius inside a modulation region which has a boundary at a distance D. Good agreement was found between the measured and calculated spectra for the years 1965 through 1968, using typical boundary distances of 2.7 and 6.1 A.U. The proton spectra observed in 1969 and 1970 were flatter than in previous years. This flattening could be explained in part by an increase in D, but also seemed to require that a noticeable fraction of the observed protons at energies as high at 50 to 100 MeV be attributed to quiet-time solar emission. The turnup in the spectra at low energies observed in all years was also attributed to solar emission. The diffusion coefficient used to fit the 1965 spectra is in reasonable agreement with that determined from the power spectra of the interplanetary magnetic field (Jokipii and Coleman, 1968). We find a factor of roughly 3 increase in ψ from 1965 to 1970, corresponding to the roughly order of magnitude decrease in the proton intensity at 250 MeV. The change in ψ might be attributed to a decrease in the diffusion coefficient, or, if the diffusion coefficient is essentially unchanged over that period (Mathews et al., 1971), might be attributed to an increase in the boundary distance, D.

Laser-induced changes on the complex refractive indices of phase-change thin film

The refractive indices of crystalline phase-change films are usually obtained by thermal-induced crystallization. However, this is not accurate, because the crystallization of phase-change film in rewritable optical disks is laser induced. In this study, we use the initializer to crystallize the phase-change films. The dependence of the refractive index n and the extinction coefficient k of the phase-change films on the initialization conditions are studied. Remarkable changes of the refractive indices (especially k) are found when the initialization laser power density is 6.63 mW/mum(2) and the initialization velocity is 4.0 m/s. At the same time, the structure changes of the phase-change films are also studied. This dependence is explained by the structure change of the films. These results are significant in improving the accuracy of optical design and the thermal simulation of phase-change optical disks, as well as in the study of phase-change optical disks at shorter wavelengths. (C) 2003 Society of Photo-Optical Instrumentation Engineers.

Optical recording properties of metal-azo dye as recording medium with super-resolution near-field structure

A novel metallized azo dye has been synthesized. The absorption spectra of the thin film and thermal characteristic are measured. Static optical recording properties with and without the Bi mask layer super-resolution near-field structure (Super-RENS) of the metal-azo dye are investigated. The results show that the metal-azo dye film has a broad absorbance band in the region of 450-650 nm and the maximum absorbance wavelength is located at 603 nm. It is also found that the new metallized azo dye occupies excellent thermal stability, initiatory decomposition temperature is at 270 degrees C and the mass loss is about 48% in a narrow temperature region (15 degrees C). The complex refractive index N (N = n + ik) is measured. High refractive index (n = 2.45) and low extinction coefficient (k = 0.2) at the recording wavelength 650nm are attained. Static optical recording tests with and without Super-RENS are carried out using a 650nm semiconductor diode laser with recording power of 7mW and laser pulse duration of 200ns. The AFM images show that the diameter of recording mark on the dye film with the Bi mask layer is reduced about 42%, compared to that of recorded mark on the dye film without Super-RENS. It is indicated that Bi can well performed as a mask layer of the dye recording layer and the metallized azo dye can be a promising candidate for recording media with the super-resolution near-field structure.

2-氨基-6-乙氧基苯并噻唑类偶氮染料及其金属鏊合物的合成及光学热学性能研究

合成了2-（2-氨基-6-乙氧基苯并噻唑基偶氮）-5-（N,N-二乙基氨基）三氟甲基磺酰苯胺偶氮染料（EBTDATFS）及其与乙酸镍、乙酸钴、乙酸铜、乙酸锌等金属盐鏊合的金属鏊合物。通过红外光谱、紫外-可见吸收光谱和MALDI质谱等对染料及其金属鏊合物进行了结构表征;使用旋涂方法在K9玻璃和抛光的单晶硅基片上制备薄膜;研究了镍金属鏊合物的热学性能;使用椭偏仪研究了Ni和Zn鏊合物的光学常数。结果表明：4种金属鏊合物薄膜最大吸收光谱为621-629nm,且长波边吸收峰陡峭;TGA-DSC测试结果表明镍金属鏊

Optical properties of zirconia-titania-ORMOSIL films for temperature tuning distributed feedback waveguide lasers

The zirconia-titania-ORMOSIL waveguide thin films with considerable optical quality were prepared by the sol-gel process. The refractive index (n) and the extinction coefficient (k) were determined by a scanning ellipsometer. Wavelength tunable output of distributed feedback waveguide lasing was demonstrated in Rhodamine 6G doped ZrO2 TiO2-ORMOSIL thin films by varying the temperature, and about 5.5 nm wavelength tuning range was achieved around the emission wavelength of 599 nm. The thermal-optic coefficient (dn/dT) of the active ZrO2-TiO2-ORMOSIL films was deduced. (c) 2005 Elsevier B.V. All rights reserved.