Entropy of Alloy Phases: A Macroscopic Perspective

This study presents a comprehensive analysis of the entropy of condensed phases, its temperature, pressure, and composition dependence on a macroscopic correlative platform. Two principal contributions to total nonconfiguration entropy (S_T) are outlined. They are: (i) the pure thermal (S_th) contribution arising from the isochoric temperature dependence of Gibbs energy (G_T) and (ii) the elastic contribution (S_el) representing the dilatational volume effects. It is then argued that entropy variation among a group of alloy phases can be exclusively related to molar volume, only when both thermal pressure (p_th) and thermal entropy terms assume common values for all members. This argument is extended to establish a linear relationship between transformation entropy (ΔS_tr) and transformation-induced volumetric strain (ΔV_tr/V). The temperature and pressure dependencies of entropy have been discussed in terms of the complementing roles of S_th and S_el and simple approximations to these effects are suggested. A macroscopic power law relation for systematizing the standard entropy variation using a composite scaling parameter (MV^2/3/T_m) has been proposed, and its validity is demonstrated for both solid and liquid metals. This power law correlation has been exploited to deduce the following outcome: (i) a simple approximation for the initial slope (dp/dT_m) of p–T_m melting curve, (ii) self-consistent correlation of entropy with specific heat and Debye temperature, (iii) estimation of entropy of metastable phases, and (iv) correlating dilute solution entropy with volume effects of alloying.

     

Dielectric spectroscopic studies on polypyrrole glucose oxidase films

An investigation was made into the dielectric spectroscopic characteristics of p-toluene sulfonate (PTS) doped polypyrrole (PPY) films in the presence and absence of immobilized glucose oxidase (GOX) in three different configurations: Al-PTS-PPY-Al-PTS-PPY/GOX-Al, and Al-PTS-PPY/GOX/β-D -glucose-Al, respectively. Measurement of dielectric loss and capacitance yielded valuable information about the dielectric properties of GOX immobilized in PTS doped PPY films. The effect of both the temperature and varying βD -glucose concentrations on the mobility of the charge carriers in these films was also systematically studied. © 1996 John Wiley & Sons, Inc.     

Self-Assembly and Neurotoxicity of β-Amyloid (21–40) Peptide Fragment: The Regulatory Role of GxxxG Motifs

The three GxxxG repeating motifs from the C-terminal region of β-amyloid (Aβ) peptide play a significant role in regulating the aggregation kinetics of the peptide. Mutation of these glycine residues to leucine greatly accelerates the fibrillation process but generates a varied toxicity profile. Using an array of biophysical techniques, we demonstrated the uniqueness of the composite glycine residues in these structural repeats. We used solvent relaxation NMR spectroscopy to investigate the role played by the surrounding water molecules in determining the corresponding aggregation pathway. Notably, the conformational changes induced by Gly³³ and Gly³⁷ mutations result in significantly decreased toxicity in a neuronal cell line. Our results indicate that G³³xxxG³⁷ is the primary motif responsible for Aβ neurotoxicity, hence providing a direct structure–function correlation. Targeting this motif, therefore, can be a promising strategy to prevent neuronal cell death associated with Alzheimer's and other related diseases, such as type II diabetes and Parkinson's.     

Effect of water deficit on yield and protein content in pearl millet grains

Seventy-two pearl millet genotypes were water stressed at panicle development and grain filling stages. Neither grain yields, yield components, protein percent nor total protein per unit area were affected by water deficit during panicle development but protein content per grain was increased. When plants were water stressed during grain filling, grain yield, grains per unit area and 1000 grain weight were reduced, but grain protein percentage increased. Total protein per unit area was reduced primarily due to lower grain yield. The protein content per grain was unaffected by stress, suggesting that the apparent increase in protein percentage is due to reduced carbohydrate accumulation under stress.     

Long‐term impact of nitrogen and potassium fertilizers on yield,soil nutrients and biochemical parameters of tea

A field experiment was conducted with tea cultivar UPASI‐9 over a period of 9 years to evaluate the long‐term effects of nitrogen (N) and potassium (K) fertilizers on yield, biochemical parameters, soil and leaf nutrient status. The yield increase was as high as 66% over the control for N application of 450 kg ha^?1 year^?1. Polyphenol and amino acid contents increased with increase in K application rate. Positive and significant correlation was found between nitrate reductase activity and the amino acid content of the tea shoots. While ammoniacal nitrogen in the soil was not affected by the application of fertilizer, ammonium acetate extractable K increased. The failure to apply fertilizer resulted in depletion of the organic matter status of the soil. Although increased rate of nitrogen application increased the overall yield of made tea (kg ha^?1 year^?1), the specific yield (kg kg^?1 N) declined. The soil tended to become acidic from frequent application of high doses of nitrogenous fertilizer. The leaf NK status was significantly influenced by the various treatments. Copyright © 2004 Society of Chemical Industry     

Effect of carbon monoxide packaging and lactate enhancement on the color stability of beef steaks stored at 1°C for 9 days

Our objective was to assess the effects of lactate enhancement in combination with different packaging systems on beef longissimus lumborum and psoas major steak color. Strip loins and tenderloins (n = 16) were assigned to one of four injection treatments (non-injected control, water-injected control, 1.25%, and 2.5% lactate in the finished product). Steaks were individually packaged in either vacuum, high-oxygen (80% O₂/20% CO₂), or 0.4% CO (30% CO₂/69.6% N₂) and stored for either 0, 5, or 9 days at 1 °C. The L^∗ and a^∗ values of both the longissimus and psoas responded similarly to lactate, which at 2.5% darkened steaks (P < 0.05) packaged in all atmospheres and improved (P < 0.05) the redness of steaks packaged in high-oxygen. Packaging steaks in CO did not counteract the darkening effects of lactate. Nevertheless, CO improved (P < 0.05) color stability compared with high-oxygen packaging.     

Evaluation of surfactant-aided degumming of vegetable oils by membrane technology

The first step in the process of vegetable oil refining is degumming, in which phospholipids and mucilaginous gums are removed that otherwise result in a low-grade oil. A membrane process is remarkably simple yet potentially offers many advantages in degumming. Studies were conducted on surfactant-aided membrane degumming with soybean and rapeseed oils in a magnetically stirred flat membrane batch cell with different types of microfiltration membranes. The reduction of phospholipids in soybean oil was in the range of 85.8–92.8% during the membrane process. The phosphorus content of membrane permeates of soybean oil was in the range of 20–58 mg/kg. Crude rapeseed oil contained higher amount of nonhydratable phospholipids and hence resulted in lower reduction in phospholipids, in the range of 66.4–83.2%. Addition of hydratable phospholipids could improve the efficiency of degumming in the membrane process without using any electrolyte, resulting in improvement of quality as well as quantity of the phospholipids.     

Processing and Properties of TiB2 with MoSi2 Sinter-additive: A First Report

The densification of non-oxide ceramics like titanium boride (TiB₂) has always been a major challenge. The use of metallic binders to obtain a high density in liquid phase-sintered borides is investigated and reported. However, a non-metallic sintering additive needs to be used to obtain dense borides for high-temperature applications. This contribution, for the first time, reports the sintering, microstructure, and properties of TiB₂ materials densified using a MoSi₂ sinter-additive. The densification experiments were carried out using a hot-pressing and pressureless sintering route. The binderless densification of monolithic TiB₂ to 98% theoretical density with 2–5 μm grain size was achieved by hot pressing at 1800°C for 1 h in vacuum. The addition of 10–20 wt% MoSi₂ enables us to achieve 97%–99%ρ_th in the composites at 1700°C under similar hot-pressing conditions. The densification mechanism is dominated by liquid-phase sintering in the presence of TiSi₂. In the pressureless sintering route, a maximum of 90%ρ_th is achieved after sintering at 1900°C for 2 h in an (Ar+H₂) atmosphere. The hot-pressed TiB₂–10 wt% MoSi₂ composites exhibit high Vickers hardness (∼26–27 GPa) and modest indentation toughness (∼4–5 MPa·m^1/2).     

Electrochemical corrosion and materials properties of reactively sputtered TiN/TiAlN multilayer coatings

TiN/TiAlN multilayers of 2 μm thickness were successfully prepared by reactive DC magnetron sputtering method. XRD pattern showed the (1 1 1) preferential orientation for both TiN and TiAlN layers. XPS characterization showed the presence of different phases like TiN, TiO₂, TiON, AlN and Al₂O₃. Cross sectional TEM indicated the columnar growth of the coatings. The average RMS roughness value of 4.8 nm was observed from AFM analysis. TiN/TiAlN coating showed lower friction coefficient and lower wear rate than single layer coatings. The results of electrochemical experiments indicated that a TiN/TiAlN multilayer coating has superior corrosion resistance in 3.5% NaCl solution.     

Atomistic insights into solvation dynamics and conformational transformation in thermo-sensitive and non-thermo-sensitive oligomers

Solvation dynamics and conformational transformation in oligomers with varying degree of temperature sensitivity is studied using molecular dynamics (MD) simulations. Conformational transformation in three model systems namely poly(N-isopropylacrylamide) (PNIPAM), poly(acrylamide) (PAA), and poly(ethylene glycol) (PEG) are compared and contrasted to understand the origin of a coil-to-globule transformations across the lower critical solution temperature (LCST) in thermo-sensitive oligomers. PNIPAM, PAA, and PEG are water-soluble oligomers. However, for the temperature range used in these simulations, PNIPAM shows an LCST whereas PAA and PEG are non-thermo-sensitive. Oligomers of PNIPAM, PAA, and PEG consisting of 30 monomer units (30-mer) each were simulated at 5 °C (278 K) and 37 °C (310 K). Conformational transformations in the oligomers are evaluated using structural and dynamical correlation functions such as radius of gyration, radial distribution function, residence time probabilities and hydrogen-bonding life-times. Our simulations suggest that the solubility, solvation dynamics, and conformation of the oligomers are dictated by two factors: (a) the local structure of proximal water and (b) the diffusion and exchange kinetics of proximal water with bulk water. In thermo-sensitive oligomer such as PNIPAM, we find that the coil-to-globule transition is closely related to the local ordering and solvation dynamics of PNIPAM. We have identified stable configurations of proximal water molecules for an oligomer undergoing conformational transition. The slow diffusional properties of proximal water molecules near PNIPAM oligomers suggests that water forms a stable network near hydrophilic groups of PNIPAM as compared to the hydrophilic groups of PAA and PEG. Thermal perturbation of this solvated structure results in significant reduction in local ordering of water, which contributes to the globular collapse and the reduced solubility of PNIPAM above its LCST. On the other hand, non-thermo-sensitive oligomers such as PAA and PEG are characterized by much faster diffusion and exchange kinetics of proximal water at the two simulated temperatures compared to PNIPAM. This faster exchange kinetics helps in maintaining higher hydration level of the oligomers and is responsible for the apparent hydrophilic character and thereby the observed solubility at the two simulated temperatures.