Synthesis, X-ray structure and catalytic properties of a copper(II) Schiff base complex modeling the activity of the Cu-B site of dopamine beta-hydroxylase

The copper(II) complex [Cu(salgly) (bpy)] . 4H(2)O (1), where salgly is a tridentate glycinatosalicylaldimine Schiffbase Ligand, is prepared and structurally characterized. The complex is found to be catalytically active in the oxidation of ascorbic acid by dioxygen and the process is also effective in the presence of benzylamine giving benzaldehyde as a product, thus modeling the activity of the Cu-B site of dopamine beta-hydroxylase. (C) 2000 Elsevier Science S.A. All rights reserved.

Double diffusive unsteady free convection on two-dimensional and axisymmetric bodies in a porous medium

The unsteady laminar free convection flow of an incompressible electrically conducting fluid over two-dimensional and axisymmetric bodies embedded in a highly porous medium with an applied magnetic field has been studied. The unsteadiness in the flow field is caused by the variation of the wall temperature and concentration with time. The coupled nonlinear partial differential equations with three independent variables have been solved numerically using an implicit finite-difference scheme in combination with the quasilinearization technique. It is observed that the skin friction, heat transfer and mass transfer increase with the permeability parameter but decrease with the magnetic parameter. The results are strongly dependent on the variation of wall temperature and concentration with time. The skin friction and heat transfer increase or decrease as the buoyancy forces from species diffusion assist or oppose the thermal buoyancy force. However, the mass transfer is found to be higher for small values of the ratio of the buoyancy parameters than for large values

A Novel Construction of Complex Orthogonal Designs with Maximal Rate and Low-PAPR

Space-time block codes based on orthogonal designs are used for wireless communications with multiple transmit antennas which can achieve full transmit diversity and have low decoding complexity. However, the rate of the square real/complex orthogonal designs tends to zero with increase in number of antennas, while it is possible to have a rate-1 real orthogonal design (ROD) for any number of antennas.In case of complex orthogonal designs (CODs), rate-1 codes exist only for 1 and 2 antennas. In general, For a transmit antennas, the maximal rate of a COD is 1/2 + l/n or 1/2 + 1/n+1 for n even or odd respectively. In this paper, we present a simple construction for maximal-rate CODs for any number of antennas from square CODs which resembles the construction of rate-1 RODs from square RODs. These designs are shown to be amenable for construction of a class of generalized CODs (called Coordinate-Interleaved Scaled CODs) with low peak-to-average power ratio (PAPR) having the same parameters as the maximal-rate codes. Simulation results indicate that these codes perform better than the existing maximal rate codes under peak power constraint while performing the same under average power constraint.

Dynamics and local structure of colossal magnetoresistance manganites

We report Extended X-ray Absorption Fine Structure and anelastic spectroscopy measurements on on hole doped manganese oxides La1-xCaxMnO3 which present the colossal magnetoresistance effect. EXAFS measurements were realized both in the absence and presence of an applied magnetic field of 1.1 Tesla, in a wide temperature range (between 330 and 77 K) and at various dopings (x = 0.25 and x = 0.33). The magnetic field orders the magnetic moments so favouring the electron mobility and the reduction of Mn-O octahedra distortions. We observe the presence of four short and two long Mn-O distances (1.93 and 2.05 Angstrom respectively) above and also below the metal-insulator phase transition. The overall distortion decreases but does not completely disappear in the metallic phase suggesting the possible coexistence of metallic and insulating regions at low temperatures. The magnetic field reduces the lattice distortions showing evidence of a microscopic counterpart of the macroscopic colossal magnetoresistance. We also present preliminary anelastic relaxation spectra in a wide temperature range from 900 K to 1 K on a sample with x = 0.40, in order to study the structural phase transitions and the lattice dynamics. A double peak has been observed at the metal-insulator transition in the imaginary part of Young's modulus. This double peak indicates that the metal-insulator transition could be a more complex phenomenon than a simple second order phase transition. In particular the peak at lower temperatures can be connected with the possible presence of inhomogeneous phase structures. Another intense dissipation peak has been observed corresponding to the structural orthorhombic-trigonal transition around 750 K.

Sociolinguistic Implications of Narratology: Focalization and ‘Double Deixis’ in Conversational Storytelling

Over the last few decades, literary narratology has branched out into a wide array of ‘post-classical’ narratologies that have borrowed concepts from cognitive psychology, sociology, anthropology, history, linguistics, and other disciplines. The question arises to what extent ‘classical’ narratological concepts can also be successfully exported to other disciplines which have an interest in narrative. In this article, I apply the concept of ‘focalization’ as well as David Herman’s insights into doubly-deictic ‘you’ in second-person narratives to an interview narrative and further materials from my empirical sociolinguistic study on general practitioners’ narrative discourse on intimate partner abuse. I consider how the narrative positioning of the GP as storyteller and ‘protagonist’ of his story corresponds with his social and professional positioning with regard to his patients in the context of intimate partner violence cases and vis-à-vis the interviewer during the research interview. Focalization and double deixis are shown to become part of a narrative strategy whereby the narrator distances himself from his own personal self in the narrative and at the same time tries to align the interviewer with his viewpoint.

Unsteady mixed convection with double diffusion over a horizontal cylinder and a sphere within a porous medium

The combined effects of the permeability of the medium, magnetic field, buoyancy forces and dissipation on the unsteady mixed convection flow over a horizontal cylinder and a sphere embedded in a porous medium have been studied. The nonlinear coupled partial differential equations with three independent variables have been solved numerically using an implicit finite-difference scheme in combination with the quasilinearization technique. The skin friction, heat transfer and mass transfer increase with the permeability of the medium, magnetic field and buoyancy parameter. The heat and mass transfer continuously decrease with the stream-wise distance, whereas the skin friction increases from zero, attains a maximum and then decreases to zero. The skin friction, heat transfer and mass transfer are significantly affected by the free stream velocity distribution. The effect of dissipation parameter is found to be more pronounced on the heat transfer than on the skin friction and mass transfer

Antibodies raised against denatured DNA bind to double-stranded DNA

Antibodies raised against denatured DNA complexed with methylated bovine serum albumin have been reported to react with ssDNA but not with dsDNA. Using a highly sensitive avidin-biotin microELISA, we report that such antibodies also bind to dsDNA. Antibodies which reacted with ssDNA and dsDNA were found to be IgG type. The antibodies did not react with tRNA and rRNA. The binding of antibodies to dsDNA was partially inhibited dy individual deoxyribonucleotides. ssDNA as well as dsDNA inhibited the binding of antibodies to dsDNA. The binding of these antibodies to supercoiled and relaxed forms of pBR322 DNA was demonstrated by gel retardation assay. The cross-reaction with ssDNA was observed even after affinity purification on native DNA-cellulose. The antibodies were also shown to bind to poly(dA-dT)·poly(dA-dT)

A kinetic study of liquid-phase catalytic oxidation of styrene to benzaldehyde with Wilkinson complex

Liquid-phase homogeneous catalytic oxidation of styrene with Wilkinson complex by molecular oxygen in toluene medium gave selectively benzaldehyde and formaldehyde as the primary products. Higher temperatures and styrene conversions eventually led to acid formation due to co-oxidation of aldehyde.A reaction induction period and an initiation period, typical of free-radical reactions, characterized the oxidation process. The effects of temperature and catalyst and styrene concentrations on the conversion of styrene to benzaldehyde and acid formation have been studied. The optimum reaction parameters have been determined as a styrene-to-solvent mole ratio of 0.5, a catalyst-to-styrene mole ratio of 5.0 X lo4, and a reaction temperature of 75 "C. A reaction scheme based upon free-radical mechanism yielded a pseudo-first-order model which agreed well with the observed kinetic data in the absence of co-oxidation of aldehyde. A second-order model was found to fit the experimental data better in the case of aldehyde conversion to acid.

Real-Time PCR : A Molecular Approach to Investigate the Role of Intestinal Microbiota in the Pathophysiology of Irritable Bowel Syndrome

Irritable bowel syndrome (IBS) is a common multifactorial functional intestinal disorder, the pathogenesis of which is not completely understood. Increasing scientific evidence suggests that microbes are involved in the onset and maintenance of IBS symptoms. The microbiota of the human gastrointestinal (GI) tract constitutes a massive and complex ecosystem consisting mainly of obligate anaerobic microorganisms making the use of culture-based methods demanding and prone to misinterpretation. To overcome these drawbacks, an extensive panel of species- and group-specific assays for an accurate quantification of bacteria from fecal samples with real-time PCR was developed, optimized, and validated. As a result, the target bacteria were detectable at a minimum concentration range of approximately 10 000 bacterial genomes per gram of fecal sample, which corresponds to the sensitivity to detect 0.000001% subpopulations of the total fecal microbiota. The real-time PCR panel covering both commensal and pathogenic microorganisms was assessed to compare the intestinal microbiota of patients suffering from IBS with a healthy control group devoid of GI symptoms. Both the IBS and control groups showed considerable individual variation in gut microbiota composition. Sorting of the IBS patients according to the symptom subtypes (diarrhea, constipation, and alternating predominant type) revealed that lower amounts of Lactobacillus spp. were present in the samples of diarrhea predominant IBS patients, whereas constipation predominant IBS patients carried increased amounts of Veillonella spp. In the screening of intestinal pathogens, 17% of IBS samples tested positive for Staphylococcus aureus, whereas no positive cases were discovered among healthy controls. Furthermore, the methodology was applied to monitor the effects of a multispecies probiotic supplementation on GI microbiota of IBS sufferers. In the placebo-controlled double-blind probiotic intervention trial of IBS patients, each supplemented probiotic strain was detected in fecal samples. Intestinal microbiota remained stable during the trial, except for Bifidobacterium spp., which increased in the placebo group and decreased in the probiotic group. The combination of assays developed and applied in this thesis has an overall coverage of 300-400 known bacterial species, along with the number of yet unknown phylotypes. Hence, it provides good means for studying the intestinal microbiota, irrespective of the intestinal condition and health status. In particular, it allows screening and identification of microbes putatively associated with IBS. The alterations in the gut microbiota discovered here support the hypothesis that microbes are likely to contribute to the pathophysiology of IBS. The central question is whether the microbiota changes described represent the cause for, rather than the effect of, disturbed gut physiology. Therefore, more studies are needed to determine the role and importance of individual microbial species or groups in IBS. In addition, it is essential that the microbial alterations observed in this study will be confirmed using a larger set of IBS samples of different subtypes, preferably from various geographical locations.

Competing magnetic interactions in a dinuclear Ni(II) complex: Antiferromagnetic O-H center dot center dot center dot O moiety and ferromagnetic N-3(-) ligand

Synthesis, structural characteristics, magnetic studies and DFT calculations in Ni(II) dinuclear complexes containing two bridging N-3(-) and an O-(HO)-O-... linkage reveal the existence of ferromagnetic interactions between Ni(II) centers via N-3(-) ligands and antiferromagnetic interactions through the H-bonded moiety. The overall magnetic behavior of the system depends on the delicate balance between these two competing interactions.

Effect of various factors influencing the delamination behavior of surfactant intercalated layered double hydroxides

The delamination-restacking behavior of a number of layered double hydroxides (LDHs) differing in [M-II]/[M-III] ratio, constituent metal ions and intercalated surfactant anions in different organic solvents has been studied. Colloidal dispersion due to delamination and the stability of the colloid obtained have been found to be not affected much by the nature of the constituent metal ions but increase with increase in the size of the surfactant anion. LDHs with low [M-II]/[M-III] ratio delaminate better than the ones with high [M-II]/[M-III] ratio. Delamination is best in alcohols such as 1-butanol, 1-hexanol, 1-octanol and I-decanol, while a little delamination occurs in nonpolar solvents such as hexane. In all the cases, the original layered solid could be obtained through restacking of layers from the colloidal dispersion.

An Application of 3-D Kinematical Conservation Laws: Propagation of a 3-D Wavefront

Three-dimensional (3-D) kinematical conservation laws (KCL) are equations of evolution of a propagating surface Omega(t) in three space dimensions. We start with a brief review of the 3-D KCL system and mention some of its properties relevant to this paper. The 3-D KCL, a system of six conservation laws, is an underdetermined system to which we add an energy transport equation for a small amplitude 3-D nonlinear wavefront propagating in a polytropic gas in a uniform state and at rest. We call the enlarged system of 3-D KCL with the energy transport equation equations of weakly nonlinear ray theory (WNLRT). We highlight some interesting properties of the eigenstructure of the equations of WNLRT, but the main aim of this paper is to test the numerical efficacy of this system of seven conservation laws. We take several initial shapes for a nonlinear wavefront with a suitable amplitude distribution on it and let it evolve according to the 3-D WNLRT. The 3-D WNLRT is a weakly hyperbolic 7 x 7 system that is highly nonlinear. Here we use the staggered Lax-Friedrichs and Nessyahu-Tadmor central schemes and have obtained some very interesting shapes of the wavefronts. We find the 3-D KCL to be suitable for solving many complex problems for which there presently seems to be no other method capable of giving such physically realistic features.

Interplay between multiple length and time scales in complex chemical systems

Processes in complex chemical systems, such as macromolecules, electrolytes, interfaces, micelles and enzymes, can span several orders of magnitude in length and time scales. The length and time scales of processes occurring over this broad time and space window are frequently coupled to give rise to the control necessary to ensure specificity and the uniqueness of the chemical phenomena. A combination of experimental, theoretical and computational techniques that can address a multiplicity of length and time scales is required in order to understand and predict structure and dynamics in such complex systems. This review highlights recent experimental developments that allow one to probe structure and dynamics at increasingly smaller length and time scales. The key theoretical approaches and computational strategies for integrating information across time-scales are discussed. The application of these ideas to understand phenomena in various areas, ranging from materials science to biology, is illustrated in the context of current developments in the areas of liquids and solvation, protein folding and aggregation and phase transitions, nucleation and self-assembly.

Binding of deoxyadenylate and deoxycytidylate antibodies to double-stranded DNA

Antibodies raised against deoxyadenylate and deoxycytidylate were found to react with double stranded DNA as assessed by highly sensitive avidin-biotin microELISA. The binding was specific as it was completely inhibited by the homologous hapten. The antibodies did not react with tRNA and rRNA. These antibodies were also shown to react with supercoiled and relaxed forms of pBR322 DNA as demonstrated by gel retardation assay. ssDNA, single-stranded DNA; dsDNA, double-stranded DNA; CT DNA, calf thymus DNA; AB microELISA, avidin-biotin microELISA; dpA, deoxyadenylate; dpC, deoxycytidylate; avidin-HRP, avidin-horseradish peroxidase