Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

Studies on interaction of colloidal Ag nanoparticles with Bovine Serum Albumin (BSA)

Biofunctionalization of noble metal nanoparticles like Ag, Au is essential to obtain biocompatibility for specific biomedical applications. Silver nanciparticles are being increasingly used in bio-sensing applications owing to excellent optoelectronic properties. Among the serum albumins, the most abundant proteins in plasma, a wide range of physiological functions of Bovine Serum Albumin (BSA) has made it a model system for biofunctionalization. In absence of adequate prior reports, this study aims to investigate the interaction between silver nanoparticles and BSA. The interaction of BSA [0.05-0.85% concentrations] with Ag nanoparticles [50 ppm concentration] in aqueous dispersion was Studied through UV-vis spectral changes, morphological and surface structural changes. At pH 7, which is More than the isoelectric point of BSA, a decrease in absorbance at plasmon peak of uninteracted nanciparticles (425 mn) was noted till 0.45% BSA, beyond that a blue shift towards 410 urn was observed. The blue shift may be attributed to enhanced electron density on the particle surfaces. Increasing pH to 12 enhanced the blue shift further to 400 rim. The conformational changes in BSA at alkaline pH ranges and consequent hydrophobic interactions also played an important role. The equilibrium adsorption data fitted better to Freundlich isotherm compared to Langmuir Curve. The X-ray diffraction study revealed complete coverage of Ag nanoparticles by BSA. The scanning electron microscopic study of the interacted nanoparticles was also carried Out to decipher morphological changes. This study established that tailoring the concentration of BSA and pH of the interaction it was possible to reduce aggregation of nanoparticles. Biofunctionalized Ag nanoparticles with reduced aggregation will be more amenable towards bio-sensing applications. (C) 2009 Elsevier B.V. All rights reserved.

Mechanism of glycine uptake by the silk glands of the silkworm Bombyx mori L.

The transport of glycine in vitro into the silk glands of the silkworm has been studied. Glycine accumulates inside the tissue to a concentration higher than that present outside, indicating an active transport mechanism. The kinetics of uptake show a biphasic curve and two apparent Km values for accumulation, 0.33 mM and 5.00 mM. The effect of inhibitors on the energy metabolism of glycine transport is inconclusive. Exchange studies indicate the existence of two pools inside the gland, one that is easily removed by exchange and osmotic shock, and the other which is not. The results obtained conform with the carrier model of Britten and McClure concerning the amino-acid pool in E. coli.

Kinetics of two-stage crystallization in Metglas 2826A

Crystallization kinetics of MSI and MSII stages in Metglas 2826A has been investigated by quantitative transmission electron microscopy. The volume fraction of crystallization against time curve has been found to show a plateau in the lower temperature region of annealing. It has been found that the glass transition temperature, T g, has no effect on the sequence reversal of the crystallization reaction. It has been shown that the sequence reversal of transformation stages occurs due to the large difference in the activation energy of crystallization of MSI and MSII. In addition, the change in the morphology of the crystals obtained by annealing the amorphous alloy below and above the glass transition temperature, T g, is reported.

Epitaxial growth of Co3O4 films by low temperature, low pressure chemical vapour deposition

The growth of strongly oriented or epitaxial thin films of metal oxides generally requires relatively high growth temperatures or infusion of energy to the growth surface through means such as ion bombardment. We have grown high quality epitaxial thin films of Co3O4 on different substrates at a temperature as low as 400 degreesC by low-pressure metalorganic chemical vapour deposition (MOCVD) using cobalt(II) acetylacetonate as the precursor. With oxygen as the reactant gas, polycrystalline Co3O4 films are formed on glass and Si (100) in the temperature range 400-550 degreesC. Under similar conditions of growth. highly oriented films of Co3O4 are formed on SrTiO3 (100) and LaAlO3 (100). The activation energy for the growth of polycrystalline films on glass is significantly higher than that for epitaxial growth on SrTiO3 (100). The film on LaAlO3 (100) grown at 450 degreesC shows a rocking curve FWHM of 1.61 degrees, which reduces to 1.32 degrees when it is annealed in oxygen at 725 degreesC. The film on SrTiO3 (100) has a FWHM of 0.33 degrees (as deposited) and 0.29 (after annealing at 725 degreesC). The phi -scan analysis shows cube-on-cube epitaxy on both these substrates. The quality of epitaxy on SrTiO3 (100) is comparable to the best of the perovskite-based oxide thin films grown at significantly higher temperatures. A plausible mechanism is proposed for the observed low temperature epitaxy. (C) 2001 Published by Elsevier Science B.V.

Effect of plasticizers on magnesium-poly(ethyleneoxide) polymer electrolyte

Solid polymer electrolytes (SPEs) of poly(ethyleneoxide) and magnesium triflate, which are plasticized with propylene carbonate (PC), ethylene carbonate (EC) and a mixture of PC and EC, are studied for their conductivity, ac impedance of the Mg I SPE interface, cyclic voltammetry, infrared spectroscopy and differential scanning calorimetry. in the presence of plasticizers, the ionic conductivity (a) increases from a value of 1 x 10(-8) S cm(-1) to about 1 x 10(-4) S cm(-1) at ambient temperature. The a is found to follow a VTF relationship with temperature. The values of the activation energy, pre-exponential factor and equilibrium glass transition temperature are shown to depend on the concentration of plasticizer. Ac impedance studies indicate lower interfacial impedance of Mg/plasticized SPE than stainless steel/plasticized SPE. The impedance spectra are analyzed using a non-linear least square curve fitting technique and the interfacial resistance of Mg/plasticized SPE is evaluated. The cyclic voltammetric results suggest a quasireversible type of Mg/Mg2+ couple in plasticized SPE. (C) 2000 Elsevier Science B.V. All rights reserved.

On-board correction of systematic error of Earth sensors

Infrared Earth sensors are used in spacecraft for attitude sensing. Their accuracy is limited by systematic and random errors. Dominant sources of systematic errors are analyzed for a typical scanning infrared Earth sensor used in a remote-sensing satellite in a 900-km sun-synchronous orbit. The errors considered arise from 1) seasonable variation of infrared radiation, 2) oblate shape of the Earth, 3) ambient temperature of sensors, 4) changes in spin/scan period, and 5) misalignment of the axis of the sensors. Simple relations are derived using least-squares curve fitting for onboard correction of these errors. With these, it is possible to improve the accuracy of attitude determination by eight fold and achieve performance comparable to ground-based post-facto attitude computation.

Critical micelle concentration from a lattice gas model

The temperature dependence of the critical micelle concentration (CMC) and a closed-loop coexistence curve are obtained, via Monte Carlo simulations, in the water surfactant limit of a two-dimensional version of a statistical mechanical model for micro-emulsions, The CMC and the coexistence curve reproduce various experimental trends as functions of the couplings. In the oil-surfactant limit, there is a conventional coexistence cure with an upper consolute point that allows for a region of three-phase coexistence between oil-rich, water-rich and microemulsion phases.

Saturated liquid densities of cryogenic liquids and refrigerants

The saturated liquid density, varrholr, data along the liquid vapour coexistence curve published in the literature for several cryogenic liquids, hydrocarbons and halocarbon refrigerants are fitted to a generalized equation of the following form varrholr = 1 + A(1 − Tr + B(1 − Tr)β The values of β, the index in phase density differences power law, have been obtained by means of two approaches namely statistical treatment of saturated fluid phase density difference data and the existence of a maximum in T(varrho1 − varrhov) along the saturation curve. Values of the constants A and B are determined utilizing the fact that Tvarrho1 has a maximum at a characteristic temperature T. Values of A, B and β are tabulated for Ne, Ar, Kr, Xe, N2, O2, methane, ethane, propane, iso-butane, n-butane, propylene, ethylene, CO2, water, ammonia, refrigerants-11, 12, 12B1, 13, 13B1, 14, 21, 22, 23, 32, 40, 113, 114, 115, 142b, 152a, 216, 245 and azeotropes R-500, 502, 503, 504. The average error of prediction is less than 2%.

Development of a low-cost portable colorimeter for the estimation of fluoride in drinking water

People in many countries are affected by fluorosis owing to the high levels of fluoride in drinking water. An inexpensive method for estimating the concentration of the fluoride ion in drinking water would be helpful in identifying safe sources of water and also in monitoring the performance of defluoridation techniques. For this purpose, a simple, inexpensive, and portable colorimeter has been developed in the present work. It is used in conjunction with the SPADNS method, which shows a color change in the visible region on addition of water containing fluoride to a reagent solution. Groundwater samples were collected from different parts of the state of Karnataka, India and analysed for fluoride. The results obtained using the colorimeter and the double beam spectrophotometer agreed fairly well. The costs of the colorimeter and of the chemicals required per test were about Rs. 250 (US$ 5) and Rs. 2.5 (US$ 0.05), respectively. In addition, the cost of the chemicals required for constructing the calibration curve was about Rs. 15 (US$ 0.3). (C) 2010 Elsevier B.V. All rights reserved.

Field induced spin reorientation transition in epitaxial La0.5Sr0.5CoO3 films

Strained epitaxial La0.5Sr0.5CoO3 films are grown on LaAlO3 substrate. Structural, electrical,and magnetic measurements were carried out. Out of plane lattice parameter of the film undergoes compressive strain and the coercivity is enhanced. The zero field cooled (ZFC) magnetization curve for a field applied parallel to the film plane shows a jump, which suggests a spin reorientation transition (SRT), while ZFC magnetization for a field applied perpendicular to the film plane is featureless. This jump in magnetization is shifted to higher temperatures when the magnetic field is reduced. The SRT is attributed to the strain in the film. (C) 2010 Elsevier B.V. All rights reserved.

Experimental estimation of friction force in lubricated cutting of steel

Friction force generated in lubricated cutting of steel is experimentally estimated by recording the tangential force experienced by the spherical face of a pin rubbing against a freshly cut surface. The pin and the cutting tool are both submerged in the lubricant and the pin is situated on the cut-track to record the force. The recording shows an instantaneous achievement of a peak in the force curve followed by a decline in time to a steady state value. The peak and not the steady state friction was found to be sensitive to the structure of the hydrocarbon and addition of additive to the oil. The configuration was designed and tested to demonstrate the influence of a reaction film which develops during cutting, on cutting tool friction. Given the strong correlation between the peak friction and the existence of a tribofilm in the cutting zone, the configuration is used to determine the lower limit of a cutting speed regime, which marks the initiation of lubricant starvation, in cutting of steel using an emulsion as a cutting fluid. (C) 2010 Elsevier B.V. All rights reserved.

Hormones andCuscuta development: interaction of cytokinin and indole-3-acetic acid in the growth and curvature of subapical stem segments

Cuscuta stem (vines) exhibits two modes of growth—longitudinal elongation forming free-hanging vines, or coiling growth to twine around the host. The elongation zone of free-hanging vine extended up to 160 mm from the stem apex and in vivo growth rate (during 8 h of growth) was maximal in the 20-to-40-mm region. While gibberellic acid (GA3) or fusicoccin (FC) could maintain (GA3) or enhance (FC) the growth rate of apical (10 or 25 mm) segments, indole-3-acetic acid (IAA) (10 mgrM) induced growth only in subapical (5–160 mm) segments. In vitro growth rate induced by IAA (10 mgrM) was similar to the in vivo growth rate up to 40 mm. Thereafter, up to 100 mm, IAA induced growth rate exceeded in vivo growth. p ]Subapical segments (sim13 mm) from 5- to 40-mm regions responded to a cytokinin (BA, Z, or iP) or to low IAA (0.1 mgrM) with curved growth, whereas the segments grew straight in the presence of high IAA (10 mgrM). Curvature (measured as the angle subtended at the center of the circle of which the segment formed an arc) induced by BA and low (0.1 mgrM) IAA was greater than either added separately. Besides, segments induced to curve in BA + low-IAA solution could be made to straighten out by transferring to a solution containing high IAA (10 mgrM) with or without BA. Thus in vivo patterns of straight and coiling growth could be mimicked reversibly in vitro by adjusting the relative concentrations of cytokinin and auxin; low auxin and cytokinin induced coiling growth, whereas high auxin and cytokinin induced straight growth. p ]Beyond 40 mm, BA had no growth-promoting or curvative-inducing effect.Cuscuta vine segments thus showed sequential sensitivity to applied hormones, the apical region (0–25 mm) to GA3, the subapical (5–40 mm) region to BA and IAA and the region beyond (40–160 mm) to IAA alone.

Prediction of Specimen Strain from Extensometer Deflection Measurements in a Direct Stress Fatigue Test Specimen under Static Tensile Loading

The displacement between the ridges situated outside the filleted test section of an axially loaded unnotched specimen is computed from the axial load and shape of the specimen and compared with extensometer deflection data obtained from experiments. The effect of prestrain on the extensometer deflection versus specimen strain curve has been studied experimentally and analytically. An analytical study shows that an increase in the slope of the stress-strain curve in the inelastic region increases the slope of the corresponding computed extensometer deflection versus specimen strain curve. A mathematical model has been developed which uses a modified length ¯ℓef in place of the actual length of the uniform diameter test section of the specimen. This model predicts the extensometer deflection within 5% of the corresponding experimental value. This method has been successfully used by the authors to evolve an iterative procedure for predicting the cyclic specimen strain in axial fatigue tests on unnotched specimens.

Role of external electron donor in methylene blue sensitized dichromated gelatin holograms:an experimental study

An experimental study to ascertain the role of external electron donor in methylene blue sensitized dichromated gelatin (MBDCG) holograms has been carried out. The required volume holographic transmission gratings in MBDCG have been recorded using 633-nm light from a He-Ne laser. Three well-known electron donors, namely, N, N-dimethylformamide (DMF); ethylenediaminetetraacetic acid (EDTA); triethanolamine (TEA), were used in this study. The variation of diffraction efficiency (η) as a function of light exposure (E) and concentration (C) of the electron donor under consideration was chosen as the figure of merit for judging the role of external electron donor in MBDCG holograms. A self-consistent analysis of the experimental results was carried out by recalling the various known facts about the photochemistry and the hologram formation in DSDCG and also DCG. The important findings and conclusions are as follows: (i) Each η vs E graph is a bell-shaped curve and its peak height is influenced in a characteristic manner by the external electron donor used. (ii) High diffraction efficiency/recording speed can be achieved in pure MBDCG holograms. (iii) The diffraction efficiency/recording speed achieved in electron donor sensitized MBDCG holograms did not show any significant improvement at all over that observed in pure MBDCG holograms. (iv) In electron donor sensitized MBDCG holograms, the electron donor used, depending on its type and concentration, appears to promote the process of cross-linking of gelatin molecules in a manner to either retain or deteriorate the refractive-index modulation achieved using pure MBDCG.