Synthesis,Characterization, DNA Binding Studies,Photocleavage, Cytotoxicity and Docking Studies of Ruthenium(II) Light Switch Complexes

A new ligand 3-(1H-imidazo[4,5-f][1,10]phenanthrolin-2yl)phenylboronic acid and its (IPPBA) three ruthenium(II) complexes [Ru(phen)₂(IPPBA)](ClO₄)₂ (1), [Ru(bpy)₂(IPPBA)](ClO₄)₂ (2) and [Ru(dmb)₂(IPPBA)](ClO₄)₂ (3) have been synthesized and characterized by elemental analysis, UV/VIS, IR, ¹H-NMR,¹³C-NMR and mass spectra. The binding behaviors of the three complexes to calf thymus DNA were investigated by absorption spectra, emission spectroscopy, viscosity measurements, thermal denaturation and photoactivated cleavage. The DNA-binding constants for complexes 1, 2 and 3 have been determined to be 7.9?×?10⁵ M^?1, 6.7?×?10⁵ M^?1 and 2.9?×?10⁵ M^?1. The results suggest that these complexes bound to double-stranded DNA in an intercalation mode. Upon irradiation at 365 nm, three ruthenium complexes were found to promote the cleavage of plasmid pBR322 DNA from super coiled form ? to nicked form ??. Further in the presence of Co²⁺, the emission of DNA–Ru(ΙΙ) complexes can be quenched. And when EDTA was added, the emission was recovered. The experimental results show that all three complexes exhibited the “on–off–on” properties of molecular “light switch”. The highest Cytotoxicity potential of the complex1 was observed on the Human alveolar adenocarcinoma (A549) cell line. Good agreement was generally found between the spectroscopic techniques and molecular docked model which provides further evidence of groove binding.     

Two operator representations for the trivariate <Emphasis Type="Italic">q</Emphasis>-polynomials and Hahn polynomials

In this paper, we introduce a trivariate q-polynomials \(F_n(x,y,z;q)\) as a general form of Hahn polynomials \(\psi _n^{(a)}(x|q)\) and \(\psi _n^{(a)}(x,y|q)\). We represent \(F_n(x,y,z;q)\) by two operators: the homogeneous q-shift operator \(L(b\theta _{xy})\) given by Saad and Sukhi (Appl Math Comput 215:4332–4339, 2010), and the Cauchy companion operator \(E(a,b;\theta )\) given by Chen (q-Difference Operator and Basic Hypergeometric Series, 2009) to derive the generating function, symmetric property, Mehler’s formula, Rogers formula, another Roger-type formula, linearization formula, and an extended Rogers formula for the trivariate q-polynomials. Then, we give the corresponding formulas for our new definitions of Hahn polynomials \(\psi _n^{(a)}(x|q)\) and \(\psi _n^{(a)}(x,y|q)\) by representing Hahn polynomials by the operators \(L(b\theta _{xy})\) and \(E(a,b;\theta )\), and by a special substitution in the trivariate q-polynomials \(F_n(x,y,z;q)\).     

Graphene to graphite; a layer by layer experimental measurements and density function theory calculations of electric conductivity

ABSTRACT

We measured the electric conductivity of large (25?×?50?mm) graphene films as a function of number of layers in the range of 1–20 layers. We also calculated the energy gap for such samples using density function theory. Our results showed a conductivity slightly above that of ITO for monolayer graphene and an exponential decrease as the number of graphene layers increased. Both experimental and simulation results showed a convergence of graphene into graphite at as little as 18–20 layers.     

In-situ electrical characterisation of a photodiode during nano-structuring with a focussed ion beam

We study the fabrication and power conversion efficiency of GaAs photodiodes, which have been nano-structured and covered with colloidal quantum dots. A focussed ion beam is used to etch vertical channels into the photodiodes and the detrimental effects of this treatment are characterised in-situ during the fabrication process. A novel experimental configuration allows the electrical characterization of the photodiodes under laser illumination during the nano-fabrication process and reveals the gradual decrease of the photodiodes’ shunt resistance with increasing laterally revealed surface along the etched channels. This is interpreted as evidence for leakage currents through redeposited material and surface states on the lateral channel surface. After the fabrication step the channels are filled with colloidal quantum dots, which upon absorption of light transfer electronic excitations to the photodiode via resonance energy transfer. It is found that after the addition of quantum dots the nano-structured photodiodes show larger enhancements of the energy conversion efficiency under simulated solar irradiance than the pristine photodiodes. Nevertheless, the device degradation induced by the ion beam treatment itself cannot be compensated for.     

Photoconductivity derived from an exact modelling of the uncompensated one-donor model. III—problem of fitting the exact model with approximate models

Abstract

The paper is essentially devoted to a quantitative comparison of the exact (1D) model developed in Part I, with two approximate models indicated by Kittel (1D_a1) and by Van der Ziel (1D_a2). And this is made for identical values of their common parameters. This allows to show that models 1D and 1D_a1 generally present no suitable intervals for fitting. The model of Van der Ziel is more suited, for, a good fitting with the 1D model can be obtained, for relatively reduced G values, and for temperatures bounded upward by the characteristic temperature T ₀ defined previously. The role played by the sub-models, obtained after simplifying the 1D_ai model equations, is studied also.     

Characterization of Trimmed NURBS Surface Boundaries Using Topological Criteria

This paper presents an approach based on topology for the determination of characteristics and properties of curves used in the trimming of NURBS surfaces. Through discrete subdivision and topological criteria, a method is presented to determine characteristics of the boundary; such as whether the set of trimming curves forms a set of closed loops, whether trimming curves contain singularities or self intersections, and whether the boundary is simply connected. A surface mesh partitionning the parameter space is used, formed of isoparametric lines in both parametric directions. Topological properties of the cells of this mesh and their intersections with the trimming curves allow to localize the boundary. Topological treatment of this localization allows to define the interior and exterior of the face, and to refine the boundary localization. Singularities and self intersections of the boundary as well as voids in the face are investigated through the study of topological properties of neighbors. As an application, an algorithm for point localization is presented that very rapidly allows to determine whether a given point in parameter space lies inside, on the boundary or outside of the trimmed surface.     

The Field-Dependent Magnetization of d5–d7 Metal β−Diketonate Complexes and Their Macromolecular Polymers

A vibrating sample magnetometer (VSM) has been used to study the field-dependent magnetization, M(H), of the d⁵?d⁷ metal acetates [M(OAc)₂.nH₂O], metal β?diketonate complexes [M(tba)₂(H₂O)₂] and the macromolecular polymers [M(tba)₂(4,4-bipy)]_n (where, M = Mn(II), Fe(II), and Co(II), OAc = O₂CCH₃, tba = deprotonated 3-benzoyl-1.1.1-trifluoroacetone, and 4,4-bipy = 4,4′-bipyridine). The magnetic field strength (H) was applied in the range of 0?10⁴ O_e at ambient temperature (ca. 23°C). The experimental results showed that the d⁵?d⁷ metal acetate, complexes and polymers exhibit low paramagnetic properties excepting [Fe(tba)₂(4,4-bipy)]_n polymer, which had negative magnetization M(emu/g) showing diamagnetic properties in the range 0?10⁴ O_e. The magnetization was almost equal to zero without an applied magnetic field (H(O_e)) for each d⁵?d⁷ metal acetate, complex, and polymer. The linear M(H) curve had a magnetic saturation for iron and manganese acetate species at the magnetic field strengths of 3.1 × 10³ and 4.7 × 10³ Oe, respectively. The external magnetic field reached 9.0 × 10³ O_e without any saturation magnetization for the cobalt compounds. The coordination effect of 3-benzoyl-1.1.1-trifluoroacetone (H-tba) and 4,4′-bipyridine (4,4′-bipy) ligands on the field-dependent magnetization M(H) and paramagnetic behavior of d⁵?d⁷ metal atoms is discussed. The field-dependent magnetization M(H) curves of metal β?diketonate complexes and the polymers including d⁵?d⁷ metal acetates showed a weak field octahedral geometry.     

Influence of potential function asymmetries on the performance of nonlinear energy harvesters under white noise

To improve the broadband transduction capabilities of vibratory energy harvesters (VEHs) under random and non-stationary excitations, many researchers have resorted to purposefully introducing nonlinearities into the restoring force of the harvester. While performing this task, it is often very challenging to maintain a perfectly symmetric restoring force which yields a VEH with an asymmetric potential energy function. This paper investigates the influence of potential function asymmetries on the performance of nonlinear VEHs under white noise inputs. To that end, a quadratic nonlinearity is introduced into the restoring force and its influence on the mean output power of the harvester for mono- and bi-stable quartic potentials is investigated. It is shown that, for VEHs with a mono-stable quartic potential function, the mean output power increases with the degree of potential function asymmetry. On the other hand, for energy harvesters with a bi-stable quartic potential function, asymmetries in the restoring force appear to worsen performance especially for low to moderate noise intensities. When the noise intensity becomes sufficiently large, the influence of the potential function?s asymmetry on the mean power diminishes. Results also reveal that a VEH with a symmetric bi-stable quartic potential function produces higher mean power levels than the one with the most asymmetric mono-stable potential. As such, it is concluded that a VEH with a symmetric bi-stable potential is most desirable to improve performance under white noise.     

Amplitude equation for the stochastic reaction‐diffusion equations with random Neumann boundary conditions

In this paper, we consider a quite general class of reaction‐diffusion equations with cubic nonlinearities and with random Neumann boundary conditions. We derive rigorously amplitude equations, using the natural separation of time‐scales near a change of stability and investigate whether additive degenerate noise and random boundary conditions can lead to stabilization of the solution of the stochastic partial differential equation or not. The nonlinear heat equation (Ginzburg–Landau equation) is used to illustrate our result. Copyright © 2015 John Wiley & Sons, Ltd.     

A collocation method of lines for two‐sided space‐fractional advection‐diffusion equations with variable coefficients

We present the method of lines (MOL), which is based on the spectral collocation method, to solve space‐fractional advection‐diffusion equations (SFADEs) on a finite domain with variable coefficients. We focus on the cases in which the SFADEs consist of both left‐ and right‐sided fractional derivatives. To do so, we begin by introducing a new set of basis functions with some interesting features. The MOL, together with the spectral collocation method based on the new basis functions, are successfully applied to the SFADEs. Finally, four numerical examples, including benchmark problems and a problem with discontinuous advection and diffusion coefficients, are provided to illustrate the efficiency and exponentially accuracy of the proposed method.