Assignment of fundamental vibrations of. ,N'-dimethylthiourea,

The infrared spectra of symmetric N,N′-dimethylthiourea (s-DMTU) and its N-deuterated (s-DMTU-d2) species have been measured. The fundamental frequencies have been assigned by comparison with the assignments in structurally related molecules and the infrared band shifts on N-deuteration, S-methylation, available Raman data and with the aid of theoretical band assignments from normal coordinate treatments for s-DMTU-d0 and -d2. A force field is derived for s-DMTU by transferring the force constants chiefly from N-methylthiourea and the subsequent refinement of the force constants by a least squares procedure.

Electrophysiological correlates of hanseniasis

Sensory nerve action potentials (SNAPs) and compound nerve action potentials (CNAPs) were recorded from 25 normal subjects and 21 hanseniasis patients following electrical stimulation of the median nerve at the wrist. The various nerve conduction parameters from the affected nerves of the patients were compared with those from the clinically normal nerves of patients as well as data from healthy individuals. Analysis of the data and clinical correlation studies indicate the suitability of amplitudes of the SNAPs and CNAPs rather than the nerve conduction velocities in better characterizing the neuropathy of the patients. Significantly reduced amplitudes of responses from clinically unaffected nerves of patients indicate an early stage of neuropathy, thus being of predictive value. Further, a discriminant classifier, trained on data from clinically affected nerves of patients, classified most of the data from clinically unaffected nerves of patients as abnormal. This indicates that clinical neurophysiological studies can reveal leprous neuropathy much before it becomes clinically evident by means of sensory or motor loss. A discriminant score involving only the parameters of motor threshold, amplitude of digit potential and palm nerve conduction velocity is able to classify almost all of the normal and abnormal responses. The authors hope that further confirmative studies might ultimately lead to the use of the study of distal sensory conduction in the upper limbs in possible screening of a population exposed to Mycobacterium leprae. On the other hand, misclassification of a normal person occurred and suggests that further refinement of the methods is necessary in order to facilitate wider use of the methods under held conditions.

A new framework for solution of multidimensional population balance equations

A new framework is proposed in this work to solve multidimensional population balance equations (PBEs) using the method of discretization. A continuous PBE is considered as a statement of evolution of one evolving property of particles and conservation of their n internal attributes. Discretization must therefore preserve n + I properties of particles. Continuously distributed population is represented on discrete fixed pivots as in the fixed pivot technique of Kumar and Ramkrishna [1996a. On the solution of population balance equation by discretization-I A fixed pivot technique. Chemical Engineering Science 51(8), 1311-1332] for 1-d PBEs, but instead of the earlier extensions of this technique proposed in the literature which preserve 2(n) properties of non-pivot particles, the new framework requires n + I properties to be preserved. This opens up the use of triangular and tetrahedral elements to solve 2-d and 3-d PBEs, instead of the rectangles and cuboids that are suggested in the literature. Capabilities of computational fluid dynamics and other packages available for generating complex meshes can also be harnessed. The numerical results obtained indeed show the effectiveness of the new framework. It also brings out the hitherto unknown role of directionality of the grid in controlling the accuracy of the numerical solution of multidimensional PBEs. The numerical results obtained show that the quality of the numerical solution can be improved significantly just by altering the directionality of the grid, which does not require any increase in the number of points, or any refinement of the grid, or even redistribution of pivots in space. Directionality of a grid can be altered simply by regrouping of pivots.

Optimization of friction stir welding parameters for dissimilar aluminum alloys

Assembly consisting of cast and wrought aluminum alloys has wide spread application in defense and aero space industries. For the efficacious use of the transition joints, the weld should have adequate strength and formability. In the present investigation, A356 and 6061 aluminum alloys were friction stir welded under tool rotational speed of 1000-1400 rpm and traversing speed of 80-240 mm/min, keeping other parameters same. The variable process window is responsible for the change in total heat input and cooling rate during welding. Structural characterization of the bonded assemblies exhibits recovery-recrystallization in the stirring zone and breaking of coarse eutectic network of Al-Si. Dispersion of fine Si rich particles, refinement of 6061 grain size, low residual stress level and high defect density within weld nugget contribute towards the improvement in bond strength. Lower will be the tool rotational and traversing speed, more dominant will be the above phenomena. Therefore, the joint fabricated using lowest tool traversing and rotational speed, exhibits substantial improvement in bond strength (similar to 98% of that of 6061 alloy), which is also maximum with respect to others. (C) 2010 Elsevier Ltd. All rights reserved.

Cystine peptides Antiparallel β-sheet conformation of the cyclic biscystine peptide [Boc-Cys-Ala-Cys-NHCH3]2

The crystal structure analysis of the cyclic biscystine peptide [Boc-Cys1-Ala2-Cys3-NHCH3]2 with two disulfide bridges confirms the antiparallel ?-sheet conformation for the molecule as proposed for the conformation in solution. The molecule has exact twofold rotation symmetry. The 22-membered ring contains two transannular NH ? OC hydrogen bonds and two additional NH ? OC bonds are formed at both ends of the molecule between the terminal (CH3)3COCO and NHCH3 groups. The antiparallel peptide strands are distorted from a regularly pleated sheet, caused mainly by the L-Ala residue in which ?=� 155° and ?= 162°. In the disulfide bridge C? (1)-C? (1)-S(1)-(3')-C?(3')-C?(3'), S�S = 2.030 Å, angles C? SS = 107° and 105°, and the torsional angles are �49, �104, +99, �81, �61°, respectively. The biscystine peptide crystallizes in space group C2 with a = 14.555(2) Ã…, b = 10.854(2) Ã…, c = 16.512(2)Ã…, and ?= 101.34(1) with one-half formula unit of C30H52N8O10S4· 2(CH3)2SO per asymmetric unit. Least-squares refinement of 1375 reflections observed with |F| > 3?(F) yielded an R factor of 7.2%.

Selection of intrusion detection system threshold bounds for effective sensor fusion

The motivation behind the fusion of Intrusion Detection Systems was the realization that with the increasing traffic and increasing complexity of attacks, none of the present day stand-alone Intrusion Detection Systems can meet the high demand for a very high detection rate and an extremely low false positive rate. Multi-sensor fusion can be used to meet these requirements by a refinement of the combined response of different Intrusion Detection Systems. In this paper, we show the design technique of sensor fusion to best utilize the useful response from multiple sensors by an appropriate adjustment of the fusion threshold. The threshold is generally chosen according to the past experiences or by an expert system. In this paper, we show that the choice of the threshold bounds according to the Chebyshev inequality principle performs better. This approach also helps to solve the problem of scalability and has the advantage of failsafe capability. This paper theoretically models the fusion of Intrusion Detection Systems for the purpose of proving the improvement in performance, supplemented with the empirical evaluation. The combination of complementary sensors is shown to detect more attacks than the individual components. Since the individual sensors chosen detect sufficiently different attacks, their result can be merged for improved performance. The combination is done in different ways like (i) taking all the alarms from each system and avoiding duplications, (ii) taking alarms from each system by fixing threshold bounds, and (iii) rule-based fusion with a priori knowledge of the individual sensor performance. A number of evaluation metrics are used, and the results indicate that there is an overall enhancement in the performance of the combined detector using sensor fusion incorporating the threshold bounds and significantly better performance using simple rule-based fusion.

Crystal structure of copper ammonium oxalate dihydrate, Cu(NH 4)2(C2O4)2.2H 2O

The crystal structure of copper ammonium oxalate dihydrate (space group P1̃) has been derived from a refinement of the two-dimensional (hk0) and (0kl) x-ray data using the atomic coordinateis of the isomorphous salt CuK 2(C2O4)2.2H2O as the starting point of the analysis. In contrast to the chromium complexes of oxalic acid the C-C bonds in both the two nonequivalent oxalate ions in the unit cell are single bonds (1.58 and 1.61 Å) consistent with the conclusion of Jeffrey and Parry that the carboxyl groups of the oxalate ion are separated by a pure a bond with little or no π conjugation across the molecule. Both the oxalate ions are slightly nonplanar. The copper ions occupy the special positions (0, 0, 0) and 0, 1/2, 0) and their coordination is of the distorted octahedral type with four nearest oxygen neighbors ( ≃ 2 Å) at the corners of a square and two more distant atoms along the octahedral bond direction. The environment of the NH4+ ions consists of eight nearest oxygen atoms at a mean distance of 3 Å.

Room-temperature equal channel angular extrusion of pure magnesium

In this paper, we demonstrate a way to impart severe plastic deformation to magnesium at room temperature to produce ultrafine grain size of similar to 250 nm through equal channel angular extrusion (ECAE). The strategy to deform magnesium at lower temperature or to achieve such grain sizes has been proposed as: (i) to obtain a suitable initial orientation with high Schmid factor for basal slip and low Schmid factor for pyramidal/prismatic slip; (ii) to take advantage of low stacking fault energy of basal and high stacking fault energies of prismatic/pyramidal planes in order to relatively work-harden the basal plane with respect to the pyramidal/prismatic plane; and (iii) to lower the temperature of deformation in steps, leading to continual refinement of grains, resulting in finer grain size. The experimental as well as simulated texture of ECAE-processed samples indicate that the deformation mechanism leading to ultrafine grain size is slip-dominated. The recrystallization mechanism during ECAE has been found to be orientation-dependent. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A hybrid electrochemical-thermal method for the preparation of large ZnO nanoparticles

A simple and efficient two-step hybrid electrochemical-thermal route was developed for the synthesis of large quantity of ZnO nanoparticles using aqueous sodium bicarbonate electrolyte and sacrificial Zn anode and cathode in an undivided cell under galvanostatic mode at room temperature. The bath concentration and current density were varied from 30 to 120 mmol and 0.05 to 1.5 A/dm(2). The electrochemically generated precursor was calcined for an hour at different range of temperature from 140 to 600 A degrees C. The calcined samples were characterized by XRD, SEM/EDX, TEM, TG-DTA, FT-IR, and UV-Vis spectral methods. Rietveld refinement of X-ray data indicates that the calcined compound exhibits hexagonal (Wurtzite) structure with space group of P63mc (No. 186). The crystallite sizes were in the range of 22-75 nm based on Debye-Scherrer equation. The TEM results reveal that the particle sizes were in the order of 30-40 nm. The blue shift was noticed in UV-Vis absorption spectra, the band gaps were found to be 5.40-5.11 eV. Scanning electron micrographs suggest that all the samples were randomly oriented granular morphology.

Reactions of copper(I) aryloxides with phenyl isothiocyanate: steric and ligand control in the oligomerization of [N-phenylimino(aryloxy)methanethiolato]copper(I) complexes

The preparation of five different copper(I) complexes [CuSC(=NPh)(OAr)}L(n)]m (1-5) formed by the insertion of PhNCS into the Cu-OAr bond and the crystal structure analyses of three of them have been carried out. A monomeric species 1 (OAr = 2,6-dimethylphenoxide) is formed in the presence of excess PPh3 (n = 2, m = 1) and crystallizes as triclinic crystals with a = 12.419(4) angstrom, b = 13.298(7) angstrom, c = 15.936(3) angstrom, alpha = 67.09(3)-degrees, beta = 81.63(2)-degrees, gamma = 66.54(3)-degrees, V = 2224(2) angstrom3, and Z = 2. The structure was refined by the least-squares method to final R and R(w) values of 0.038 and 0.044, respectively, for 7186 unique reflections. Copper(I) 2,5-di-tert-butyl-4-methylphenoxide results in the formation of a dimeric species 2 in the presence of P(OMe)3 (n = 1, m = 2), where the coordination around Cu is trigonal. Crystals of 2 were found to be orthorhombic with a = 15.691(2) angstrom, b = 18.216(3) angstrom, c = 39.198(5) angstrom, v = 11204(3) angstrom3, and Z = 8. Least-squares refinement gave final residuals of R = 0.05 and R(w) = 0.057 with 6866 unique reflections. A tetrameric species 3 results when PPh3 is replaced by P(OMe)3 in the coordination sphere of copper(I) 2,6-dimethylphenoxide. It crystallizes in the space group P1BAR with a = 11.681 (1) angstrom, b = 13.373(2) angstrom, c = 20.127(1) angstrom, a = 88.55(l)-degrees, beta = 89.65(l)-degrees, gamma = 69.28(1)-degrees, V = 2940(l) angstrom3, and Z = 2. Least-squares refinement of the structure gave final values of 0.043 and 0.05 for R and R(w) respectively using 12214 unique reflections. In addition, a dimeric species 4 is formed when 1 equiv of PPh3 is added to the copper(I) 4-methylphenoxide, while with an excess of PPh3 a monomeric species 5 is isolated. Some interconversions among these complexes are also reported.

Crystal structure and electrical properties of CaNaBi2Nb3O12 ceramics

Monophasic CaNaBi2Nb3O12 powders were synthesized via the conventional solid-state reaction route. Rietveld refinement of the X-ray powder diffraction (XRD) data and selected area electron diffraction (SAED) studies confirmed the phase to be a three-layer Aurivillius oxide associated with an orthorhombic B2cb space group. The dielectric properties of the ceramics have been studied in the 300-800 K temperature range at various frequencies (1 kHz to 1 MHz). A dielectric anomaly was observed at 676 K for all the frequencies corresponding to the ferroelectric to paraelectric phase transition as it was also corroborated by the high temperature X-ray diffraction studies. The incidence of the polarization-electric field (P vs. E) hysteresis loop demonstrated CaNaBi2Nb3O12 to be ferroelectric.

Substitution of chromium for univalent copper in superconducting Pb2Sr2(Ca,Y)Cu3O8+delta

Following considerations of geometry and the similarity between chromate and carbonate groups in terms of size and charge, we have investigated the possibility of replacing the two-coordinate Cu-I in superconducting lead cuprates of the general formula Pb2Sr2(Ca, Y)CU3O8 by Cr. A high-resolution electron microscopy study coupled with energy dispersive X-ray analysis on small crystals of the title phases suggests that between 10 and 15% of the Cu-I can be replaced by Cr. While from the present structural study using HRTEM and Rietveld refinement of X-ray powder data we are unable to precisely obtain the oxidation state and oxygen coordination of Cr, we suggest in analogy with Cr substitution in other similar cuprates that in the title phases (CuO2)-O-I rods are partially replaced by tetrahedral CrO42- groups. Infrared spectroscopy supports the presence of CrO42- groups. The phases Pb1.75Sr2Ca0.2Y0.8O8+delta and Pb1.75Sr2Ca0.2Y0.8CCu2.85Cr0.15O8+delta are superconducting as-prepared, but the substitution of Cr for Cu-I results in a decrease of the Te as well as the superconducting volume fraction. (C) 1996 Academic Press, lnc.

Development of solidification microstructure in boron-modified alloy Ti-6Al-4V-0.1B

Hypoeutectic boron addition (0.1 wt.%) to Ti-6Al-4V is known to cause significant refinement of the cast microstructure. In the present investigation, it has been observed that trace boron addition to Ti-6Al-4V alloy also ensures excellent microstructural homogeneity throughout the ingot. A subdued thermal gradient, related to the basic grain refinement mechanism by constitutional undercooling, persists during solidification for the boron-containing alloy and maintains equivalent beta grain growth kinetics at different locations in the ingot. The Ti-6Al-4V alloy shows relatively strong texture with preferred components (e.g. ingot axis parallel to[0 0 0 1] or [1 0 (1) over bar 0]) over the entire ingot and gradual transition of texture components along the radius. For Ti-6Al-4V-0.1B alloy, significant weakening characterizes both the high-temperature beta and room-temperature a texture. In addition to solidification factors that are responsible for weak beta texture development, microstructural differences due to boron addition, e.g. the absence of grain boundary alpha phase and presence of TiB particles, strongly affects the mechanism of beta -> alpha phase transformation and consequently weakens the alpha phase texture. Based on the understanding developed for the boron-modified alloy, a novel mechanism has been proposed for the microstructure and texture formation during solidification and phase transformation. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A thermodynamic study of liquid Cu-Cr alloys and metastable liquid immiscibility

he thermodynamic acitivity of chromium in liquid Cu-Cr alloys is measured in the temperature range from 1473 to 1873 K using the solid state cell: Pt, W, Cr + Cr2O3 |(Y2O3) ThO2|Cu - Cr + Cr2O3, Pt The activity of copper and the Gibbs energy of mixing of the liquid alloy are derived. Activities exhibit large positive deviations from Raoult's law. The mixing properties can be represented by a pseudo-subregular solution model in which the excess entropy has the same type of functional dependence on composition as the enthalpy of mixing: ΔGE = XCr(1 - XCr)[60880 - 18750 XCr)-- T(16.25 - 7.55 XCr)]J mol-1 Pure liquid Cu and Cr are taken as the reference states. The results predict a liquid-liquid metastable miscibility gap, with TC = 1787 (±3) K and XCr = 0.436 (±0.02), lying below the liquidus. The results obtained in this study are in general agreement with experimental information reported in the literature, but provide further refinement of the thermodynamic parameters.

Progressive structure-based alignment of homologous proteins: Adopting sequence comparison strategies

Comparison of multiple protein structures has a broad range of applications in the analysis of protein structure, function and evolution. Multiple structure alignment tools (MSTAs) are necessary to obtain a simultaneous comparison of a family of related folds. In this study, we have developed a method for multiple structure comparison largely based on sequence alignment techniques. A widely used Structural Alphabet named Protein Blocks (PBs) was used to transform the information on 3D protein backbone conformation as a ID sequence string. A progressive alignment strategy similar to CLUSTALW was adopted for multiple PB sequence alignment (mulPBA). Highly similar stretches identified by the pairwise alignments are given higher weights during the alignment. The residue equivalences from PB based alignments are used to obtain a three dimensional fit of the structures followed by an iterative refinement of the structural superposition. Systematic comparisons using benchmark datasets of MSTAs underlines that the alignment quality is better than MULTIPROT, MUSTANG and the alignments in HOMSTRAD, in more than 85% of the cases. Comparison with other rigid-body and flexible MSTAs also indicate that mulPBA alignments are superior to most of the rigid-body MSTAs and highly comparable to the flexible alignment methods. (C) 2012 Elsevier Masson SAS. All rights reserved.