Supramolecular hydrogen-bonded structures in organic amine squarates

Structures of monohydrogen squarates of methylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, N,N'-diemethylpiperazine and N,N,N,N-tetramethylguanidine have been studied in detail. The supramolecular hydrogen-bonded molecular networks are formed by the monoanion of squaric acid by itself or in association with the parent acid. Three types of hydrogen-bonded motifs are observed in these compounds, namely a liner chain, a cyclic dimer and a cyclic tetramer. These hydrogen-bonded motifs formed by the squaric acid species interact with the amine through N-H...O hydrogen-bonding and give rise to predominantly layered structures, while some of them also exhibit three-dimensional structures. Two of the monohydrogen squarate structures also exhibit pi-pi interactions between two squarate rings. The various hydrogen-bonding parameters in the amine squarates are discussed at length. (C) 2002 Elsevier Science B.V. All rights reserved.

Synthesis of LiCo1-xNixO2 from a low temperature solution combustion route and characterization

Nickel substituted lithium-cobalt oxides, LiCo1-xNixO2 (0 < x < 0.4), have been synthesized in a very short time by a solution combustion method at 350 degreesC using diformyl hydrazine as a fuel. Pure phases with hexagonal lattice structure have been obtained. These compounds facilitate reversible insertion/extraction of Li+ ions with good discharge capacity between 3.0 and 4.4 V versus Li/Li+. Results of the studies by powder X-ray diffraction, scanning electron microscopy, cyclic voltammetry, galvanostatic charge-discharge cycling and ac impedance measurements are presented. (C) 2002 Elsevier Science B.V. All rights reserved.

System Dy-Fe-O: thermodynamic properties of ternary oxides using Calvet calorimetry and solid-state electrochemical cell

The enthalpy increments and the standard molar Gibbs energies of formation-of DyFeO3(s) and Dy3Fe5O12(s) have been measured using a Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. A co-operative phase transition, related to anti-ferromagnetic to paramagnetic transformation, is apparent. from the heat capacity data for DyFeO3 at similar to 648 K. A similar type of phase transition has been observed for Dy3Fe5O12 at similar to 560 K which is related to ferrimagnetic to paramagnetic transformation. Enthalpy increment data for DyFeO3(s) and Dy3Fe5O12(s), except in the vicinity of the second-order transition, can be represented by the following polynomial expressions:{H(0)m(T) - H(0)m(298.15 K)) (Jmol(-1)) (+/-1.1%) = -52754 + 142.9 x (T (K)) + 2.48 x 10(-3) x (T (K))(2) + 2.951 x 10(6) x (T (K))(-1); (298.15 less than or equal to T (K) less than or equal to 1000) for DyFeO3(s), and {H(0)m(T) - H(0)m(298.15 K)} (Jmol(-1)) (+/-1.2%) = -191048 + 545.0 x (T - (K)) + 2.0 x 10(-5) x (T (K))(2) + 8.513 x 10(6) x (T (K))(-1); (208.15 less than or equal to T (K) less than or equal to 1000)for Dy3Fe5O12(s). The reversible emfs of the solid-state electrochemical cells: (-)Pt/{DyFeO3(s) + Dy2O3(s) + Fe(s)}/YDT/CSZ//{Fe(s) + Fe0.95O(s)}/Pt(+) and (-)Pt/{Fe(s) + Fe0.95O(s)}//CSZ//{DyFeO3(s) + Dy3Fe5O12(s) + Fe3O4(s)}/Pt(+), were measured in the temperature range from 1021 to 1250 K and 1035 to 1250 K, respectively. The standard Gibbs energies of formation of solid DyFeO3 and Dy3Fe5O12 calculated by the least squares regression analysis of the data obtained in the present study, and data for Fe0.95O and Dy2O3 from the literature, are given by Delta(f)G(0)m(DyFeO3,s)(kJmol(-1))(+/-3.2)= -1339.9 + 0.2473 x (T(K)); (1021 less than or equal to T (K) less than or equal to 1548)and D(f)G(0)m(Dy3Fe5O12,s) (kJmol(-1)) (+/-3.5) = -4850.4 + 0.9846 x (T (K)); (1035 less than or equal to T (K) less than or equal to 1250) The uncertainty estimates for Delta(f)G(0)m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams for the system Dy-Fe-O were developed at 1250 K. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Anthropogenic aerosol fraction over Afro-Asian regions inferred using Kalpana-I and MISR data

Mineral dust constitutes the single largest contributor of natural aerosols over continents. The first step towards separating natural aerosol radiative impact from its anthropogenic counterparts over continents is to gather information on dust aerosols. The infrared (IR) radiance (10.5-12.5 mu m) acquired from the Kalpana-I satellite (similar to 8-km resolution) was used to retrieve regional characteristics of dust aerosols over the Afro-Asian region during the winter of 2004, coinciding with a national aerosol campaign. Here, we used aerosol-induced IR radiance depression as an index of dust load. The regional distribution of dust over various arid and semi-arid regions of India and adjacent continents has been estimated, and these data in conjunction with regional maps of column aerosol optical depth (AOD) are used to infer anthropogenic aerosol fraction. Surprisingly, even over desert locations in India and Saudi Arabia, the anthropogenic fraction was relatively high (similar to 0.3 to 0.4) and the regionally averaged anthropogenic fraction over India was 0.62 +/- 0.06.

An open-framework cobalt oxalato-squarate containing a ligated amine

A cobalt oxalato-squarate of the formula [Co-2(C4O4)(C2O4)(C3N2H4)(2)], containing a ligated amine has been synthesized hydrothermally and its structure determined by single crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group P2(1)2(1)2 with a = 18.3845(8) Angstrom, b = 5.7884(3) Angstrom, c = 7.2598(4) Angstrom, V = 772.56(7)Angstrom(3) and Z = 4. It has a layered structure where two-dimensional sheets are formed by the connectivity of the squarate and the oxalate units with the cobalt centres, with the ligating amine molecules protruding out from the layers. (C) 2003 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Role of interface states associated with transitional nanophase precipitates in the photoluminescence enhancement of SrTiO3 : Pr3+,Al3+

SrTiO3:Pr3+,Al3+ phosphor samples with varying ratios of Sr/Ti/Al were prepared by the gel-carbonate method and the mechanism of enhancement of the red photoluminescence intensity therein was investigated. The photoluminescence (PL) spectra of SrTiO3:Pr3+ show both D-1(2) --> H-3(4) and P-3(0) --> H-3(4) emission in the red and blue spectral regions, respectively, with comparable intensity. The emission intensity of D-1(2) --> H-3(4) is drastically enhanced by the incorporation of Al3+ and excess Ti4+ in the compositional range Sr(Ti,Al-y)(O3+3y/2):Pr3+ (0.2 less than or equal to y less than or equal to 0.4) and SrTi1+xAlyO3+z:Pr3+ (0.2 less than or equal to x less than or equal to 0.5; 0.05 less than or equal to y less than or equal to 0.1; z = 2x + 3y/2) with the complete disappearance of the blue band. This cannot be explained by the simple point defect model as the EPR studies do not show any evidence for the presence of electron or hole centers. TEM investigations show the presence of exsolved nanophases of SrAl12O19 and/or TiO2 in the grain boundary region as well as grain interiors as lamellae which, in turn, form the solid-state defects, namely, dislocation networks, stacking faults and crystallographic shear planes whereby the framework of corner shared TiO6 octehedra changes over to edge-sharing TiO5-AlO5 strands as indicated from the Al-27 MAS NMR studies. The presence of transitional nanophases and the associated defects modify the excitation-emission processes by way of formation of electronic sub-levels at 3.40 and 4.43 eV, leading to magnetic-dipole related red emission with enhanced intensity. This is evidenced by the fact that SrAl12O19:Pr3+,Ti4+ shows bright red emission whereas SrAl12O19:Pr3+ does not show red photoluminescence.

Sustainable biomass production for energy in selected Asian countries

This paper presents a synthesis of assessment of sustainable biomass production potential in six Asian countries-China, India, Malaysia, Philippines, Sri Lanka and Thailand, and is based on the detailed studies carried out in these countries under the Asian Regional Research Programme in Energy, Environment and Climate (ARRPEEC). National level studies were undertaken to estimate land availability for biomass production, identify and evaluate the biomass production options in terms of yield per hectare and financial viability, estimate sustainable biomass production for energy, and estimate the energy potential of biomass production in the six Asian countries. Sustainable biomass production from plantation is estimated to be in the range of 182.5-210.5, 62-310, 0.4-1.7, 3.7-20.4, 2.0-9.9 and 11.6-106.6 Mt yr(-1) for China, India, Malaysia, Philippines, Sri Lanka and Thailand, respectively. The maximum annual electricity generation potential, using advanced technologies, from the sustainable biomass production is estimated to be about 27, 114, 4.5, 79, 254 and 195 percentage of the total electricity generation in year 2000 in China, India, Malaysia, Philippines, Sri Lanka and Thailand, respectively. Investment cost for bioenergy production varies from US$381 to 1842 ha(-1) in the countries considered in this study; investment cost for production of biomass varies from US$5.1 to 23 t(-1). (C) 2003 Elsevier Ltd. All rights reserved.

Turbulent flow computations using upwind RANS technique for a flat plate and an airfoil

Reynolds Averaged Navier Stokes (RANS) equations are solved using third order upwind biased Roe's scheme for the inviscid fluxes and second order central difference scheme for the viscous fluxes. The Baldwin & Lomax turbulence model is employed for Reynolds stresses. The governing equations are solved using finite-volume implicit scheme in body fitted curvilinear coordinate O-grid system. Computations axe reported for a flat plate apart from RAE 2822 and NACA 0012 airfoils. Results for the flat plate at M = 0.3, R-c = 4.0 x 10(6) compare favourably with the analytical solution. Results for the two airfoils are compared with experiment. There is a good agreement in C-p distribution between experiment and computation for both the airfoils. Comparison of C-f distribution with experiment for RAE 2822 airfoil is reasonable.

An investigation of carbon nanotubes obtained from the decomposition of methane over reduced Mg1− xM xAl2O4 spinel catalysts

Carbon nanotubes produced by the treatment of Mg1−xMxAl2O4 (M = Fe, Co, or Ni; x = 0.1, 0.2, 0.3, or 0.4) spinels with an H2–CH4 mixture at 1070 °C have been investigated systematically. The grains of the oxide-metal composite particles are uniformly covered by a weblike network of carbon nanotube bundles, several tens of micrometers long, made up of single-wall nanotubes with a diameter close to 4 nm. Only the smallest metal particles (<5 nm) are involved in the formation of the nanotubes. A macroscopic characterization method involving surface area measurements and chemical analysis has been developed in order to compare the different nanotube specimens. An increase in the transition metal content of the catalyst yields more carbon nanotubes (up to a metal content of 10.0 wt% or x = 0.3), but causes a decrease in carbon quality. The best compromise is to use 6.7 wt% of metal (x = 0.2) in the catalyst. Co gives superior results with respect to both the quantity and quality of the nanotubes. In the case of Fe, the quality is notably hampered by the formation of Fe3C particles.

Identification and characterization of cysteine proteinases of Trypanosoma evansi

Trypanosoma evansi is a causative agent of `surra', a common haemoprotozoan disease of livestock in India causing high morbidity and mortality in disease endemic areas. The proteinases released by live and dead trypanosomes entail immunosuppression in the infected host, which immensely contribute in disease pathogenesis. Cysteine proteinases are identified in the infectious cycle of trypanosomes such as cruzain from Trypanosoma cruzi, rhodesain or brucipain from Trypanosoma brucei rhodesiense and congopain from Trypanosoma congelense. These enzymes localised in lysosome-like organelles, flagellar pocket and on cell surface, which play a critical role in the life cycle of protozoan parasites, viz. in host invasion, nutrition and alteration of the host immune response. The paper describes the identification of cysteine proteinases of T. evansi lysate, activity profile at different pH optima and inhibition pattern using a specific inhibitor, besides the polypeptide profile of an antigen. Eight proteinases of T. evansi were identified in the molecular weight (MW) ranges of 28-170 kDa using gelatin substrate-polyacrylamide gel electrophoresis (GS-PAGE), and of these proteinases, six were cysteine proteinases, as they were inhibited by L-3-carboxy-2,3-transepoxypropionyl-lecuylamido (4-guanidino)-butane (E-64), a specific inhibitor. These proteolytic enzymes were most reactive in acidic pH between 3.0 and 5.5 in the presence of dithiothreitol and completely inactive at alkaline pH 10.0. Similarly, the GS-PAGE profile of the serum samples of rats infected with T. evansi revealed strong proteolytic activity only at the 28-kDa zone at pH 5.5, while no proteolytic activity was observed in serum samples of uninfected rats. Further, the other zones of clearance, which were evident in T. evansi antigen zymogram, could not be observed in the serum samples of rats infected with T. evansi. The polypeptide pattern of the whole cell lysate antigen revealed 12-15 polypeptide bands ranging from 28 to 81 kDa along with five predominant polypeptides bands (MW of 81, 66, 62, 55 and 45 kDa), which were immunoreactive with hyperimmune serum (HIS) and serum of experimentally infected rabbits with T. evansi infection. The immunoblot recognised antibodies in experimentally infected rabbits and against HIS as well, corresponding to the zone of clearances at lower MW ranges (28-41 kDa), which may be attributed to the potential of these proteinases in the diagnosis of T. evansi infection. Since these thiol-dependent enzymes are most active in acidic pH and considering their inhibition characteristics, these data suggest that they resemble to the mammalian lysosomal cathepsin B and L.

Synthesis, Structure, Negative Thermal Expansion, and Photocatalytic Property of Mo Doped ZrV(2)O(7)

A new series of compounds identified in the phase diagram of ZrO(2)-V(2)O(8)-MoO(3) have been synthesized via the solution combustion method. Single crystals of one of the compounds in the series, ZrV(1.50)Mo(0.50)O(7.25), were grown by the melt-cool technique from the starting materials with double the MoO(3) quantity. The room temperature average crystal structure of the grown crystals was solved using the single crystal X-ray diffraction technique. The crystals belong to the cubic crystal system, space group Pa (3) over bar (No. 205) with a = 8.8969 (4) angstrom, V = 704.24 (6) angstrom(3), and Z = 4. The final R(1) value of 0.0213 was achieved for 288 independent reflections during the structure refinement. The Zr(4+) occupies the special position (4a) whereas V(5+) and Mo(6+) occupy two unique (8c) Wyckoff positions. Two fully occupied O atoms, (24d) and (4b), one partially occupied 0 atom (8c) have been identified for this molybdovanadate, which is a unique feature for these crystals. The structure is related to both ZrV(2)O(7) and cubic ZrMo(2)O(8). The temperature dependent single crystal studies show negative thermal expansion above 370 K. The compounds have been characterized by powder X-ray diffraction, solid-state UV-vis diffuse reflectance spectra, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The photocatalytic activity of these compounds has been investigated for the degradation of various dyes, and these compounds show specificity toward the degradation of non-azoic dyes.

A Scalable Low Power Issue Queue for Large Instruction Window Processors

Large instruction windows and issue queues are key to exploiting greater instruction level parallelism in out-of-order superscalar processors. However, the cycle time and energy consumption of conventional large monolithic issue queues are high. Previous efforts to reduce cycle time segment the issue queue and pipeline wakeup. Unfortunately, this results in significant IPC loss. Other proposals which address energy efficiency issues by avoiding only the unnecessary tag-comparisons do not reduce broadcasts. These schemes also increase the issue latency.To address both these issues comprehensively, we propose the Scalable Lowpower Issue Queue (SLIQ). SLIQ augments a pipelined issue queue with direct indexing to mitigate the problem of delayed wakeups while reducing the cycle time. Also, the SLIQ design naturally leads to significant energy savings by reducing both the number of tag broadcasts and comparisons required.A 2 segment SLIQ incurs an average IPC loss of 0.2% over the entire SPEC CPU2000 suite, while achieving a 25.2% reduction in issue latency when compared to a monolithic 128-entry issue queue for an 8-wide superscalar processor. An 8 segment SLIQ improves scalability by reducing the issue latency by 38.3% while incurring an IPC loss of only 2.3%. Further, the 8 segment SLIQ significantly reduces the energy consumption and energy-delay product by 48.3% and 67.4% respectively on average.

An eight-connected metal organic framework based on Cu(5) clusters: Synthesis, structure, magnetic and catalytic properties

A reaction of copper acetate, 5-nitroisophthalic acid in a water-methanol mixture under solvothermal condition results in a new metal-organic framework compound, [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, (1). The compound contains Cu5 pentameric cluster units connected by 5-nitro isophthalate (NIPA) moieties forming a CdCl(2)-like layer, which are further connected by another NIPA moiety forming the three-dimensional structure. The water molecules in (1) can be reversibly adsorbed. The removal of water accompanies a change in the colour as well as a structural re-organization. Magnetic studies suggest strong antiferromagnetie correlations between the Cu5 cluster units. The compound (1) exhibits heterogeneous Lewis acid catalysis for the cyanosilylation of imines with more than 95 % selectivity. Compound (1) has been characterized by IR, UV-vis, TGA, powder XRD studies.

Usefulness of in Situ Single Crystal to Single Crystal Transformation (SCSC) Studies in Understanding the Temperature-Dependent Dimensionality Cross-over and Structural Reorganization in Copper-Containing Metal-Organic Frameworks (MOFs)

Two copper-containing compounds [Cu(3)(mu(3)-OH)(2)-(H(2)O)(2){(SO(3))-C(6)H(3)-(COO)(2)}(CH(3)COO)] , I, and [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, II, were prepared using sulphoisophthalic and nitroisophthalic acids. The removal of the coordinated water molecules in the compounds was investigated using in situ single crystal to single crystal (SCSC) transformation studies, temperature-dependent powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). The efficacy of SCSC transformation studies were established by the observation of dimensionality cross-over from a two-dimensional (I) to a three-dimensional structure, Cu(6)(mu(3)-OH)(4){(SO(3))-C(6)H(3)-(COO)(2)}(2)(CH(3)COO)(2), Ia, during the removal of the coordinated water molecules. Compound H exhibited a structural reorganization forming Cu(5)(mu(2)-OH)(2){(NO(2))C(6)H(3)-(COO)(2))(4)], Ha, possessing trimeric (Cu(3)O(12)) and dimeric (Cu(2)O(8)) copper clusters. The PXRD studies indicate that the three-dimensional structure (Ia) is transient and unstable, reverting back to the more stable two-dimensional structure (I) on cooling to room temperature. Compound Ha appears to be more stable at room temperature. The rehydration/dehydration studies using a modified TGA setup suggest complete rehydration of the water molecules, indicating that the water molecules in both compounds are labile. A possible model for the observed changes in the structures has been proposed. Magnetic studies indicate changes in the exchanges between the copper centers in Ha, whereas no such behavior was observed in Ia.

Benzothiophene Carboxamide Derivatives as Inhibitors of Plasmodium falciparum Enoyl-ACP Reductase

Benzothiophene derivatives like benzothiophene sulphonamides, biphenyls, or carboxyls have been synthesized and have found wide pharmacological usage. Here we report, bromo-benzothiophene carboxamide derivatives as potent, slow tight binding inhibitors of Plasmodium enoyl-acyl carrier protein (ACP) reductase (PfENR). 3-Bromo-N-(4-fluorobenzyl)-benzo[b]thiophene-2-carboxamide (compound 6) is the most potent inhibitor with an IC(50) of 115 nM for purified PfENR. The inhibition constant (K(i)) of compound 6 was 18 nM with respect to the cofactor and 91 nM with respect to crotonoyl-CoA. These inhibitors showed competitive kinetics with cofactor and uncompetitive kinetics with the substrate. Thus, these compounds hold promise for the development of potent antimalarials. (C) 2011 IUBMB IUBMB Life, 63(12): 1101-1110, 2011