A simple model for protein thermal denaturation

Whether proteins denature in all-or-none fashion or in a continuous fashion is as yet an unresolved problem. The all-or-none process implies that while the process of denaturation is going on, only two kinds of protein molecules can exist. One is completely unchanged and the other is altered. The altered protein molecules are indistinguishable. Underlying the 'continuum' models is the assumption that all the chains in a protein globule undergo similar changes so that it is enough to consider a single chain.

Palladium(II) and platinum(II) complexes of beta-functionalized ethyl selenolates: Effect of substitution on synthesis, reactivity, spectroscopy, structures and thermal behavior

Sodium ethylselenolates with functional groups X (where X = -OH, -COOH, -COOMe and -COOEt) at beta-carbon were prepared in situ by reductive cleavage of corresponding diselenide with NaBH4 either in methanol or aqueous ammonia. Treatment of these selenolates with [M2Cl2(mu-Cl)(2)(PR'(3))(2)] (M = Pd or Pt; PR'(3) = PMePh2, PnPr(3)) in different stoichiometry yielded various bi- and tri-nuclear complexes. The homoleptic hexanuclear complexes [Pd(mu-SeCH2CH2X)(2)](6) (X = OH, COOH, COOEt), were obtained by reacting Na2PdCl4 with NaSeCH2CH2X. All these complexes have been fully characterized. Molecular structures of ethylselenolates containing hydroxyl and carboxylic acid groups revealed solid state associated structures through inter-molecular hydrogen bond interactions. Trinuclear complex, [Pd3Cl2(mu-SeCH2CH2COOH)(4)(PnPr(3))(2)] (3a), was disposed in a boat form unlike chair conformation observed for the corresponding methylester complex. The effect of beta-functionality in ethylselenolate ligands towards reactivity, structures and thermal properties of palladium and platinum complexes has been extensively Studied.

Fabrication and Phase Transformation in Crystalline Nanoparticles of PbZrO3 Derived By Sol-Gel

In this research fabrication of crystalline PbZrO3 (PZ) nanoparticles and their phase transformation behavior is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PZ, which was dried at 150 degrees C and then calcined at 300-700 degrees C for 1 h. The morphology, crystallinity and phase formation of as synthesized nanoparticles were studied by the selected-area electron diffraction (SAED), X-ray diffraction (XRD), thermal gravimetric analysis/differential scanning calorimetry (TGA-DSC), and high resolution transmission electron microscope (HRTEM). The XRD, SAED, and TGA-DSC analyses confirmed the tetragonal lead rich zirconia phase (t-Z phase) and monoclinic zirconia phase (m-Z phase) as the intermediate phases during the calcinations process followed by crystallization of single orthorhombic PZ phase at about 700 degrees C. The average PZ particle size was observed about 20 nm as confirmed by TEM study. Energy-dispersive X-ray spectroscopy (EDX) analysis demonstrated that stoichiometric PbZrO3 was formed.

Selective growth of ZnO nanoneedles by thermal oxidation of Zn microstructures

Zinc film containing hexagonal plate stack and tower-like micro structures were grown on Si substrates at high temperature by thermal evaporation. Thermal oxidation studies on these micro structures have shown that ZnO nanoneedles selectively grow from the facets of the zinc microstructure at temperature above 300 degrees C in atmosphere TEM analysis showed that single crystalline and bicrystalline nanoneedles were formed in this oxidation process and the growth direction of these nanoneedles was identified along the [1 1 (2) overbar 0]. Based on the structural studies and morphological observation, we have proposed a possible mechanism for the selective growth of ZnO nanoneedles during thermal oxidation.

CFD analysis of high frequency miniature pulse tube refrigerators for space applications with thermal non-equilibrium model

High frequency, miniature, pulse tube cryocoolers are extensively used in space applications because of their simplicity. Parametric studies of inertance type pulse tube cooler are performed with different length-to-diameter ratios of the pulse tube with the help of the FLUENT (R) package. The local thermal non-equilibrium of the gas and the matrix is taken into account for the modeling of porous zones, in addition to the wall thickness of the components. Dynamic characteristics and the actual mechanism of energy transfer in pulse are examined with the help of the pulse tube wall time constant. The heat interaction between pulse tube wall and the oscillating gas, leading to surface heat pumping, is quantified. The axial heat conduction is found to reduce the performance of the pulse tube refrigerator. The thermal non-equilibrium predicts a higher cold heat exchanger temperature compared to thermal equilibrium. The pressure drop through the porous medium has a strong non-linear effect due to the dominating influence of Forchheimer term over that of the linear Darcy term at high operating frequencies. The phase angle relationships among the pressure, temperature and the mass flow rate in the porous zones are also important in determining the performance of pulse tuberefrigerator.

Thermal anomalies in ternary Ge42-xPbxSe58 glasses near the charge carrier reversal threshold

The carrier type reversal (CTR) from p- to n-type in semiconducting chalcogenide glasses is an important and a long standing problem in glass science. Ge-Se glasses exhibit CTR when the metallic elements Bi and Pb are added. For example, bulk Ge42-xSe58Pbx glasses exhibit CTR around 8-9 at. % of Pb. These glasses have been prepared by melt quenching method. Glass transition temperature (T-g), Specific heat change between the liquid and the glassy states (Delta C-p) at T-g and the nonreversing heat flow (Delta H-nr) measured by modulated differential scanning calorimetry exhibit anomalies at 9 at. % of Pb. These observed anomalies are interpreted on the basis of the nano scale phase separation occurring in these glasses.

Anomalous dynamical charges, phonons, and the origin of negative thermal expansion in Y2W3O12

We use a combination of classical model and first-principles density functional theory calculations to study lattice dynamics of Y2W3O12 and identify phonons responsible for its negative thermal expansion (NTE). Born dynamical charges of various atoms are found to deviate anomalously from their nominal values. We find that the phonons with energy from 4 to 10 meV are the primary contributors to its NTE. These phonons involve rotations of the YO6 octahedra and WO4 tetrahedra in mutually opposite sense and collective translational atomic displacements, reflecting a strong mixing between acoustic and optic modes.

Computation of Thermal Stress Intensity Factors for Bimaterial Interface Cracks Using Domain Integral Method

The concept of domain integral used extensively for J integral has been applied in this work for the formulation of J(2) integral for linear elastic bimaterial body containing a crack at the interface and subjected to thermal loading. It is shown that, in the presence of thermal stresses, the J(k) domain integral over a closed path, which does not enclose singularities, is a function of temperature and body force. A method is proposed to compute the stress intensity factors for bimaterial interface crack subjected to thermal loading by combining this domain integral with the J(k) integral. The proposed method is validated by solving standard problems with known solutions.

Design, Synthesis, and DNA Binding Properties of Photoisomerizable Azobenzene−Distamycin Conjugates: An Experimental and Computational Study

Here, we present the synthesis, photochemical, and DNA binding properties of three photoisomerizable azobenzene−distamycin conjugates in which two distamycin units were linked via electron-rich alkoxy or electron-withdrawing carboxamido moieties with the azobenzene core. Like parent distamycin A, these molecules also demonstrated AT-specific DNA binding. Duplex DNA binding abilities of these conjugates were found to depend upon the nature and length of the spacer, the location of protonatable residues, and the isomeric state of the conjugate. The changes in the duplex DNA binding efficiency of the individual conjugates in the dark and with their respective photoirradiated forms were examined by circular dichroism, thermal denaturation of DNA, and Hoechst displacement assay with poly[d(A-T).d(T-A)] DNA in 150 mM NaCl buffer. Computational structural analyses of the uncomplexed ligands using ab initio HF and MP2 theory and molecular docking studies involving the conjugates with duplex d[(GC(AT)10CG)]2 DNA were performed to rationalize the nature of binding of these conjugates.

Effect of compatibilization on mechanical and thermal properties of polypropylene–soy flour composites

A new biobased composite was developed by adding soy flour (SF) to polypropylene (PP). This composite shows an enhanced tensile strength and modulus but decrease in elongation at break. The compatibilizer (coupling agent) appears to have a synergistic effect on tensile strength. The presence of the compatibilizer improves the dispersion of SF in the PP matrix. The addition of glycerol plasticizer to the composite improves the processability resulting in improved performance, as compared to composites without glycerol plasticizer. The optimal compatibilizer content appears to be 6%.

Synthesis, spectral characterization, in-vitro microbiological evaluation and cytotoxic activities of novel macrocyclic bis hydrazone

A macrocyclic hydrazone Schiff base was synthesized by reacting 1,4-dicarbonyl phenyl dihydrazide with 2,6-diformyl-4-methyl phenol and a series of metal complexes with this new Schiff base were synthesized by reaction with Co(II), Ni(II) and Cu(II) metal salts. The Schiff base and its complexes have been characterized by elemental analyses, IR, H-1 NMR, UV-vis, FAB mass, ESR spectra, fluorescence, thermal, magnetic and molar conductance data. The analytical data reveal that the Co(II), Ni(II) and Cu(II) complexes possess 2:1 metal-ligand ratios. All the complexes are non-electrolytes in DMF and DMSO due to their low molar conductance values. Infrared spectral data suggest that the hydrazone Schiff base behaves as a hexadentate ligand with NON NON donor sequence towards the metal ions. The ESR spectral data shows that the metal-ligand bond has considerable covalent character. The electrochemical behavior of the copper(II) complex was investigated by cyclic voltammetry. The Schiff base and its complexes have also been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Shigella dysentery, Micrococcus, Bacillus subtilis, Bacillus cereus and Pseudomonas aeruginosa) and antifungal activities (Aspergillus niger, Penicillium and Candida albicans) by MIC method. The brine shrimp bioassay was also carried out to study their in-vitro cytotoxic properties. (C) 2009 Elsevier Masson SAS. All rights reserved.

Simulation of Dust Loaded V-I Characteristics of a Commercial Thermal Power Plant Precipitator

A new approach based on finite difference method, is proposed for the simulation of electrical conditions in a dc energized wire-duct electrostatic precipitator with and without dust loading. Simulated voltage-curren characteristics with and without dust loading were compared with the measured characteristics for analyzing the performance of a precipitator. The simple finite difference method gives sufficiently accurate results with reduced mesh size. The results for dust free simulation were validated with published experimental data. Further measurements were conducted at a thermal power plant in India and the results compares well with the measured ones.

Electrical Properties of Thermal Evaporated Cd1−xMnxS Nanocrystalline Films

Thin films of Cd1−xMnxS (0<=x<=0.5) were deposited on glass substrates by thermal evaporation. All the films were deposited at 300 K and annealed at 373, 473, and 573 K for 1 h in a high vacuum in the range 10−4 Pa. The as-deposited and the annealed films were characterized for composition, structure, and microstructure by using energy-dispersive X-ray, X-ray diffraction, scanning electron microscopy, and atomic force microscopy (AFM). The electrical properties were studied by Hall effect measurement. Electrical conductivity was studied in the temperature range 190–450 K. AFM studies showed that all the films were in nanocrystalline form with grain size varying in the range between 36 and 82 nm. Grain size studies showed a definite increase with annealing temperature. All the films exhibited wurtzite structure of the host material. The lattice parameter varied linearly with composition, following Vegard's law in the entire composition range. Grain size, electrical conductivity, Hall mobility, carrier concentration, and activation energy varied, exhibiting either maxima or minima at x=0.3.

Electrical switching and thermal studies on Ge22Te78-xIx chalcohalide glasses: The effect of iodine on network-topology

Investigations on the electrical switching behavior and thermal studies using Alternating Differential Scanning Calorimetry have been undertaken on bulk, melt-quenched Ge22Te78-,Is (3 <= x <= 10) chalcohalide glasses. All the glasses studied have been found to exhibit memory-type electrical switching. The threshold voltages of Ge22Te78-I-x(x) glasses have been found to increase with the addition of iodine and the composition dependence of threshold voltages of Ge22Te78-xIx glasses exhibits a cusp at 5 at.% of iodine. Also, the variation with composition of the glass transition temperature (Tg) of Ge22Te78-I-x(x) glasses, exhibits a broad hump around this composition. Based on the present results, the composition x = 5 has been identified as the inverse rigidity percolation threshold at which Ge22Te78-I-x(x) glassy system exhibits a change from a stressed rigid amorphous solid to a flexible polymeric glass. Further, a sharp minimum is seen in the composition dependence of non-reversing enthalpy (Delta H-nr) of Ge22Te78-I-x(x) glasses at x = 5, which is suggestive of a thermally reversing window at this composition. (C) 2007 Elsevier Ltd. All rights reserved.

Improved procedures for static and dynamic analyses of wrinkled membranes

An analysis of large deformations of flexible membrane structures within the tension field theory is considered. A modification-of the finite element procedure by Roddeman et al. (Roddeman, D. G., Drukker J., Oomens, C. W J., Janssen, J. D., 1987, ASME J. Appl. Mech. 54, pp. 884-892) is proposed to study the wrinkling behavior of a membrane element. The state of stress in the element is determined through a modified deformation gradient corresponding to a fictive nonwrinkled surface. The new model uses a continuously modified deformation gradient to capture the location orientation of wrinkles more precisely. It is argued that the fictive nonwrinkled surface may be looked upon as an everywhere-taut surface in the limit as the minor (tensile) principal stresses over the wrinkled portions go to zero. Accordingly, the modified deformation gradient is thought of as the limit of a sequence of everywhere-differentiable tensors. Under dynamic excitations, the governing equations are weakly projected to arrive at a system of nonlinear ordinary differential equations that is solved using different integration schemes. It is concluded that, implicit integrators work much better than explicit ones in the present context.