Unveiling the binding interaction of zinc (II) complexes of homologous Schiff-base ligands on the surface of BSA protein: A combined experimental and theoretical approach

Four new zinc (II) complexes [Zn (HL¹H)Br₂] (1), [Zn (HL¹H)Cl₂] (2), [Zn₂(HL²)Br₃] (3), and [Zn (HL²)Cl] (4) have been synthesized by adopting template synthetic strategy and utilizing two homologous Schiff base ligands (H₂L¹ = 4-bromo-2-{[2-(2-hydroxyethylamino)-ethylimino]-methyl}-6-methoxyphenol, H₂L² = 4-bromo-2-{[3-(2-hydroxyethylamino)propylimino]methyl}-6-methoxyphenol), differing in one -CH₂- unit in the ligating backbone, by adopting template synthetic strategy. All the complexes have been characterized by single crystal X-ray diffraction analysis as well as by other routine physicochemical techniques. Ligand mediated structural variations have been observed and rationalized by density functional theoretical (DFT) calculations. Interaction of the complexes 1–4 with Bovine Serum Albumin protein (BSA) has been studied by different spectroscopic techniques. A complete thermodynamic profile (ΔH^o, ΔS^o and ΔG^o) was evaluated initially from the change in absorption and fluorescence spectra upon addition of BSA to the complexes. Appreciable binding constant values in the range ~ 0.94–4.51 × 10⁴ M⁻¹ indicate efficient binding tendency of the complexes to BSA with the sequence 1 ≅ 2 > 3 ≅ 4. Circular dichroism (CD), isothermal calorimetric titration experiments, molecular docking and molecular dynamics have been performed to gain deep insight into the binding regions of complex 1 to BSA. Experimental evidences suggest an interaction of zinc complexes at the surface of BSA protein and this particular binding has been exploited to determine unknown concentration of BSA protein. For this purpose complex 1 was explored as a BSA protein quantification tool.     

Chalcogen Stabilized bis-Hydridoborate Complexes of Cobalt: Analogues of Tetracyclo[4.3.0.02,4.03,5]nonane

Treatment of Li[BH₃ER] (E=Se or Te, R=Ph; E=S, R=CH₂Ph) with [Cp*CoCl]₂ led to the formation of hydridoborate complexes, [{CoCp*Ph}{Cp*Co}{μ-EPh}{μ-κ²-E,H-EBH₃}], 1a and 1 b ( 1 a : E=Se; 1 b : E=Te) and a bis-hydridoborate species [Cp*Co{μ-κ²-Se,H-SeBH₃}]₂, 2 . All the complexes, 1 a , 1 b and 2 are stabilized by β-agostic type interaction in which 1 b represents a novel bimetallic borate complex with a rare B−Te bond. QTAIM analysis furnished direct proof for the existence of a shared and dative B-chalcogen and Co-chalcogen interactions, respectively. In parallel to the formation of the hydridoborate complexes, the reactions also yielded tetracyclic species, [Cp*Co{κ³-E,H,H-E(BH₂)₂-C₅Me₅H₃}], 3 a and 3 b ( 3 a : E=Se and 3 b : E=S), wherein the bridgehead boron atoms are surrounded by one chalcogen, one cobalt and two carbon atoms of a cyclopentane ring. Molecules 3 a and 3 b are best described as the structural mimic of tetracyclo[4.3.0.0^2,4.0^3,5]nonane having identical structure and similar valence electron counts.     

Effect of temperature on the validity of the einstein relation in heavily doped semiconductors

An analytical expression of the modified form of the Einstein relation in heavily doped semiconductors in which Gaussian band tails are formed near the lower limit of heavy doping is derived for studying the temperature dependence of the diffusivity-mobility ratio of the carriers in such semiconductors. It is found that, with increasing temperature from relatively low values, the ratio first increases in a nonlinear manner and then decreases till, at high temperatures, it approaches its value corresponding to the non-degenerate condition resulting in a peak over a narrow range of temperatures.     

Lag and anticipatory synchronization based parameter estimation scheme in modulated time-delayed systems

In this article, we have shown that using delay dynamical systems as base, one can use the modulation of the various parameters, to transmit multiple signals through a single chaotic time series. It is shown that under certain conditions the original signals and parameters of the driving signals can be recovered with the help of an adaptive demodulator. An important aspect of the present method is that the communication is possible between two time-delayed systems with parameter mismatch using lag and anticipatory synchronization. The whole idea is presented on the basis of Mackey–Glass system, with variable time delay.     

5D non-symmetric gravity and geodesic confinement

This work focuses on an unexplored aspect of non-symmetric geometry where only the off-diagonal metric components along the extra dimension, in a 5-dimensional spacetime, are non-symmetric. We show that the energy densities of the stationary non-symmetric models are similar to that of brane models thereby mimicking the thick-brane scenario. We find that the massive test particles are confined near the location of the brane for both growing and decaying warp factors. This feature is unique to the non-symmetric nature of our model. We have also studied the dynamical models where standard 4D FLRW brane is embedded. Our analysis shows that the non-symmetric terms deconfine energy density at the early universe while automatically confine at late times.     

Controlled Markov processes on the infinite planning horizon: Weighted and overtaking cost criteria

Stochastic control problems for controlled Markov processes models with an infinite planning horizon are considered, under some non-standard cost criteria. The classical discounted and average cost criteria can be viewed as complementary, in the sense that the former captures the short-time and the latter the long-time performance of the system. Thus, we study a cost criterion obtained as weighted combinations of these criteria, extending to a general state and control space framework several recent results by Feinberg and Shwartz, and by Krass et al. In addition, a functional characterization is given for overtaking optimal policies, for problems with countable state spaces and compact control spaces; our approach is based on qualitative properties of the optimality equation for problems with an average cost criterion.Research partially supported by the Engineering Foundation under grant RI-A-93-10, in part by the National Science Foundation under grant NSF-INT 9201430, and in part by a grant from the AT&T Foundation.Research partially supported by the Air Force Office of Scientific Research under Grant F49620-92-J-0045, and in part by the National Science Foundation under Grant CDR-8803012.     

Conducting polymer based hybrid structure as transparent and flexible field electron emitter

An efficient cathode material with high transparency (93%) based on conducting polymer poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and single wall carbon nanotubes (SWCNTs) has been developed for the fabrication of highly transparent and flexible field electron emitters (FEE). This kind of material showed superior field emission (FE) performance with very high current density (10^–3A/cm²) at very low electric field. The FE performance of the hybrid materials was dramatically improved compared to either SWCNTs and PEDOT:PSS. Thus the hybrid structures of conducting polymer and SWCNTs might be a good choice for use as a cathode material to enhance the FE performance and for potential application in future portable displays. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of initial orientation on twinning in commercially pure titanium

Abstract

The effect of initial orientation on twinning micro-mechanisms during tensile deformation of commercially pure titanium has been studied using micro focus X-ray diffraction and electron back scatter diffraction (EBSD) in a scanning electron microscope. Three orientations A, B and C obtained from a rolled and annealed block of commercially pure titanium were deformed in uniaxial tension till failure and the tested specimens were characterised with regard to bulk texture, microstructure and crystal orientation mapping using EBSD. Orientation B along the transverse direction in ND-TD plane exhibits higher strength and lower strain hardening compared to orientations A and C along the rolling direction in TD-RD and ND-RD plane, respectively. This is attributed to different texture of sample B compared to samples A and C leading to dissimilar twinning micro-mechanisms and characteristic variation in nature of twinning. It is observed that limited twin nucleation and prominent lateral growth plays a dominant role in orientation B while multiple twin nucleation with significant non-Schmid behaviour is dominant for the other two orientations. It is proposed from this study that conventional factors associated with twin formation like Schmid factor play a main role in twin nucleation and propagation, however, growth or lateral thickening of the twins is explained by elastic stiffness variation across twins and their parent grains.     

On the Uniform Approximation of Laplace′s Prior by t-Priors in Location Problems

The problem of deriving robust and classically acceptable Bayesian inference on location parameters is considered in this paper. The main result of the paper allows one to obtain uniform posterior approximation starting with likelihood functions with heavy tails, e.g., t-distributions with unknown location. The approximations of the relevant Bayes quantities are obtained as Well.     

A zero sum differential game in a Hilbert space

We study a zero sum differential game of fixed duration in a separable Hilbert space. We prove a minimax principle and establish the equivalence between the dynamic programming principle and the existence of a saddle point equilibrium. We also prove sufficient conditions for optimality.