Half-sandwich (eta(6)-arene)ruthenium(II) chiral Schiff base complexes: Analysis of the diastereomeric mixtures in solution by 2D-NMR spectroscopy

2D NMR spectroscopy has been used to determine the metal configuration in solution of three complexes, viz. [(eta(6)-p-cymene)Ru(L*)Cl] (1) and [(eta(6)-p-cymene)Ru(L*)(L')] (ClO4) (L' = H2O, 2; PPh3, 3), where L* is the anion of (S)-(1-phenylethyl)salicylaldimine. The complexes exist in two diastereomeric forms in solution. Both the (R-Ru,S-C)- and (S-Ru,S-C)-diastereomers display the presence of attractive, CH/pi interaction involving the phenyl group attached to the chiral carbon and the cymene ring hydrogens. This interaction restricts the rotation of the C*-N single bond and, as a result, two structural types with either the hydrogen atom attached to the chiral carbon (C*) or the methyl group attached to C* in close proximity of the cymene ring protons get stabilized. Using 2D NMR spectroscopy as a tool, the spatial interaction involving these protons are studied in order to obtain the metal configuration(s) of the diastereomeric complexes in solution. This technique has enabled us to determine the metal configuration as (R-Ru,S-C) for the major isomers of 1-3 in solution.

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.

Synthesis and DNA binding studies of Ni(II), Co(II), Cu(II) and Zn(II) metal complexes of N(1),N(5)-bis[pyridine-2-methylene]-thiocarbohydrazone Schiff-base ligand

The thiocarbohydrazone Schiff-base ligand with a nitrogen and sulphur donor was synthesized through condensation of pyridine-2-carbaldehyde and thiocarbohydrazide. Schiff-base ligands have the ability to conjugate with metal salts. A series of metal complexes with a general formula [MCl(2)(H(2)L)]center dot nH(2)O (M=Ni, Co, Cu and Zn) were synthesized by forming complexes of the N(1),N5-bis[pyridine-2-methylene]thiocarbohydrazone (H2L) Schiff-base ligand. These metal complexes and ligand were characterized by using ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FT-IR), (1)H and (13)C NMR spectroscopy and mass spectroscopy, physicochemical characterization, CHNS and conductivity. The biological activity of the synthesized ligand was investigated by using Escherichia coli DNA as target. The DNA interaction of the synthesized ligand and complexes on E. coli plasmid DNA was investigated in the aqueous medium by UV-Vis spectroscopy and the binding constant (K(b)) was calculated. The DNA binding studies showed that the metal complexes had an improved interaction due to trans-geometrical isomers of the complexes than ligand isomers in cis-positions. (C) 2011 Elsevier B.V. All rights reserved.

On the fundamentally asynchronous nature of interference in cooperative base station systems

Cooperative transmission by base stations can significantly improve the spectral efficiency of multiuser, multi-cell multiple input multiple output systems. We show that in such systems the multiuser interference is asynchronous by nature, even when perfect timing-advance mechanisms ensure that the desired signal components arrive synchronously. We establish an accurate mathematical model for the asynchronism, and use it to show that the asynchronism leads to a significant performance degradation of existing linear preceding designs that assumed synchronous interference. We consider three different previously proposed precoding designs, and show how to modify them to effectively mitigate asynchronous interference.

Localization induced base isolation in fractionally damped non linear system

In the present article we take up the study of nonlinear localization induced base isolation of a 3 degree of freedom system having cubic nonlinearities under sinusoidal base excitation. The damping forces in the system are described by functions of fractional derivative of the instantaneous displacements, typically linear and quadratic damping are considered here separately. Under the assumption of smallness of certain system parameters and nonlinear terms an approximate estimate of the response at each degree of freedom of the system is obtained by the Method of Multiple Scales approach. We then consider a similar system where the nonlinear terms and certain other parameters are no longer small. Direct numerical simulation is made use of to obtain the amplitude plot in the frequency domain for this case, which helps us to establish the efficacy of this method of base isolation for a broad class of systems. Base isolation obtained this way has no counterpart in the linear theory.

3D Image Reconstruction From Truncated Helical Cone Beam Projection Data - A Linear Prediction Approach

With the introduction of 2D flat-panel X-ray detectors, 3D image reconstruction using helical cone-beam tomography is fast replacing the conventional 2D reconstruction techniques. In 3D image reconstruction, the source orbit or scanning geometry should satisfy the data sufficiency or completeness condition for exact reconstruction. The helical scan geometry satisfies this condition and hence can give exact reconstruction. The theoretically exact helical cone-beam reconstruction algorithm proposed by Katsevich is a breakthrough and has attracted interest in the 3D reconstruction using helical cone-beam Computed Tomography.In many practical situations, the available projection data is incomplete. One such case is where the detector plane does not completely cover the full extent of the object being imaged in lateral direction resulting in truncated projections. This result in artifacts that mask small features near to the periphery of the ROI when reconstructed using the convolution back projection (CBP) method assuming that the projection data is complete. A number of techniques exist which deal with completion of missing data followed by the CBP reconstruction. In 2D, linear prediction (LP)extrapolation has been shown to be efficient for data completion, involving minimal assumptions on the nature of the data, producing smooth extensions of the missing projection data.In this paper, we propose to extend the LP approach for extrapolating helical cone beam truncated data. The projection on the multi row flat panel detectors has missing columns towards either ends in the lateral direction in truncated data situation. The available data from each detector row is modeled using a linear predictor. The available data is extrapolated and this completed projection data is backprojected using the Katsevich algorithm. Simulation results show the efficacy of the proposed method.

A Profilometric Approach to 3D Face Reconstruction and Its Application to Face Recognition

3D Face Recognition is an active area of research for past several years. For a 3D face recognition system one would like to have an accurate as well as low cost setup for constructing 3D face model. In this paper, we use Profilometry approach to obtain a 3D face model.This method gives a low cost solution to the problem of acquiring 3D data and the 3D face models generated by this method are sufficiently accurate. We also develop an algorithm that can use the 3D face model generated by the above method for the recognition purpose.

Base excision and nucleotide excision repair pathways in mycobacteria

About a third of the human population is estimated to be infected with Mycobacterium tuberculosis. The bacterium displays an excellent adaptability to survive within the host macrophages. As the reactive environment of macrophages is capable of inducing DNA damage, the ability of the pathogen to safeguard its DNA against the damage is of paramount significance for its survival within the host. Analysis of the genome sequence has provided important insights into the DNA repair machinery of the pathogen, and the studies on DNA repair in mycobacteria have gained momentum in the past few years. The studies have revealed considerable differences in the mycobacterial DNA repair machinery when compared with those of the other bacteria. This review article focuses especially on the aspects of base excision, and nucleotide excision repair pathways in mycobacteria. (C) 2011 Elsevier Ltd. All rights reserved.

Evaluation of 2D image reconstruction using fan-beam FBP algorithm with no backprojection weight from WLP completed truncated projection data

This paper presents the image reconstruction using the fan-beam filtered backprojection (FBP) algorithm with no backprojection weight from windowed linear prediction (WLP) completed truncated projection data. The image reconstruction from truncated projections aims to reconstruct the object accurately from the available limited projection data. Due to the incomplete projection data, the reconstructed image contains truncation artifacts which extends into the region of interest (ROI) making the reconstructed image unsuitable for further use. Data completion techniques have been shown to be effective in such situations. We use windowed linear prediction technique for projection completion and then use the fan-beam FBP algorithm with no backprojection weight for the 2-D image reconstruction. We evaluate the quality of the reconstructed image using fan-beam FBP algorithm with no backprojection weight after WLP completion.