Solvation dynamics of tryptophan in water-dimethyl sulfoxide binary mixture: In search of molecular origin of composition dependent multiple anomalies

Experimental and simulation studies have uncovered at least two anomalous concentration regimes in water-dimethyl sulfoxide (DMSO) binary mixture whose precise origin has remained a subject of debate. In order to facilitate time domain experimental investigation of the dynamics of such binary mixtures, we explore strength or extent of influence of these anomalies in dipolar solvation dynamics by carrying out long molecular dynamics simulations over a wide range of DMSO concentration. The solvation time correlation function so calculated indeed displays strong composition dependent anomalies, reflected in pronounced non-exponential kinetics and non-monotonous composition dependence of the average solvation time constant. In particular, we find remarkable slow-down in the solvation dynamics around 10%-20% and 35%-50% mole percentage. We investigate microscopic origin of these two anomalies. The population distribution analyses of different structural morphology elucidate that these two slowing down are reflections of intriguing structural transformations in water-DMSO mixture. The structural transformations themselves can be explained in terms of a change in the relative coordination number of DMSO and water molecules, from 1DMSO:2H(2)O to 1H(2)O:1DMSO and 1H(2)O:2DMSO complex formation. Thus, while the emergence of first slow down (at 15% DMSO mole percentage) is due to the percolation among DMSO molecules supported by the water molecules (whose percolating network remains largely unaffected), the 2nd anomaly (centered on 40%-50%) is due to the formation of the network structure where the unit of 1DMSO:1H(2)O and 2DMSO:1H(2)O dominates to give rise to rich dynamical features. Through an analysis of partial solvation dynamics an interesting negative cross-correlation between water and DMSO is observed that makes an important contribution to relaxation at intermediate to longer times.

Polymorphic phase boundaries and enhanced piezoelectric response in extended composition range in the lead free ferroelectric BaTi1-xZrxO3

Neutron powder diffraction study of Ba(Ti1-xZrx)O-3 at close composition intervals has revealed coexistence of ferroelectric phases: orthorhombic (Amm2) + tetragonal (P4mm) for 0.02 <= x <= 0.05 and rhombohedral (R3m) + orthorhombic (Amm2) for 0.07 <= x < 0.09. These compositions exhibit relatively enhanced piezoelectric properties as compared to their single phase counterparts outside this composition region, confirming the polymorphic phase boundary nature of the phase coexistence regions. (C) 2013 AIP Publishing LLC.

Biogeochemical facsimile of the organic matter quality and trophic status of a micro-tidal tropical estuary

Seasonal studies were carried out from 21 stations, comprising of three zones, of Cochin Estuary, to assess the organic matter quality and trophic status. The hydographical parameters showed significant seasonal variations and nutrients and chlorophylls were generally higher during the monsoon season. However, chemical contamination along with the seasonal limitations of light and nitrogen imposed restrictions on the primary production and as a result, mesotrophic conditions generally prevailed in the water column. The nutrient stoichometries and delta C-13 values of surficial sediments indicated significant allochthonous contribution of organic matter. Irrespective of the higher content of total organic matter, the labile organic matter was very low. Dominance of carbohydrates over lipids and proteins indicated the lower nutritive aspect of the organic matter, and their aged and refractory nature. This, along with higher amount of phytodetritus and the low algal contribution to the biopolymeric carbon corroborated the dominance of allochthonous organic matter and the heterotrophic nature. The spatial and seasonal variations of labile organic components could effectively substantiate the observed shift in the productivity pattern. An alternative ratio, lipids to tannins and lignins, was proposed to ascertain the relative contribution of allochthonous organic matter in the estuary. This study confirmed the efficiency of an integrated biogeochemical approach to establish zones with distinct benthic trophic status associated with different degrees of natural and anthropogenic input. Nevertheless, our results also suggest that the biochemical composition alone could lead to erroneous conclusions in the case of regions that receive enormous amounts of anthropogenic inputs.

Electrochemical Determination of Gibbs Energy of Formation of LaCrO3 Using a Composition-Graded Bielectrolyte

Presented are new measurements of the standard Gibbs free energy of formation of rhombohedral LaCrO3 from component oxides La2O3 and Cr2O3 in the temperature range from 875 to 1175K, using a bielectrolyte solid-state cell incorporating single crystal CaF2 and composition-graded solid electrolyte (LaF3)(y)(CaF2)(1-y) (y=0-0.32). The results can be represented analytically as Delta G(f(ox))(o) (+/- 2270)/Jmol(-1)=-72329+4.932 (T/K). The measurements were undertaken to resolve serious discrepancies in the data reported in the literature. A critical analysis of previous electrochemical measurements indicates several deficiencies that have been rectified in this study. The enthalpy of formation obtained in this study is consistent with calorimetric data. The standard enthalpy of formation of orthorhombic LaCrO3 from elements at 298.15K computed from the results of this study is Delta H-f(298.15)(o)/kJmol(-1)=-1536.2 (+/- 7). The standard entropy of orthorhombic LaCrO3 at 298.15K is estimated as 99.0 (+/- 4.5)J(molK)(-1).

Thermal and Sonochemical Degradation Kinetics of Poly(n-butyl methacrylate-co-alkyl acrylates): Variation of Chain Strength and Stability with Copolymer Composition

The thermal degradation of poly(n-butyl methacrylate-co-alkyl acrylate) was compared with ultrasonic degradation. For this purpose, different compositions of poly (n-butyl methacrylate-co-methyl acrylate) (PBMAMA) and a particular composition of poly(n-butyl methacrylate-co-ethyl acrylate) (PBMAEA) and poly(n-butyl methacrylate-co-butyl acrylate) (PBMABA) were synthesized and characterized. The thermal degradation of polymers shows that the poly(alkyl acrylates) degrade in a single stage by random chain scission and poly(n-butyl methacrylate) degrades in two stages. The number of stages of thermal degradation of copolymers was same as the majority component of the copolymer. The activation energy corresponding to random chain scission increased and then decreased with an increase of n-butyl methacrylate fraction in copolymer. The effect of methyl acrylate content, alkyl acrylate substituent, and solvents on the ultrasonic degradation of these copolymers was investigated. A continuous distribution kinetics model was used to determine the degradation rate coefficients. The degradation rate coefficient of PBMAMA varied nonlinearly with n-butyl methacrylate content. The degradation of poly (n-butyl methacrylate-co-alkyl acrylate) followed the order: PBMAMA < PBMAEA < PBMABA. The variation in the degradation rate constant with composition of the copolymer was discussed in relation to the competing effects of the stretching of the polymer in solution and the electron displacement in the main chain. (C) 2012 Society of Plastics Engineers

A composition-dependent ``re-entrant'' crystallographic phase transition in the substitutional metal acetylacetonate complex (Cr1-xGax)(acac)(3)

The formation of a complete solid solution between acetylacetonate (acac) complexes of chromium and gallium, (Cr1-x,Ga-x)(acac)(3) for 0.1 composition to have a congruent melting point, making it a substitutional complex. Whereas the pure complexes (i.e. the end members of the solid solution, x = 0 and x = 1) are both centro-symmetric, a composition-dependent crystallographic phase transition to a non-centrosymmetric structure is found to occur for compositions with 0.4 < x < 0.9. Such a ``re-entrant'' crystallographic transition is interpreted to be due to the drive to overcome the disorder present in certain centrosymmetric chromium-rich compositions, by going over to a non-centrosymmetric structure with a doubling of the unit cell. The substitutional complex is shown to lead to a substitutional oxide with the beta-gallate structure. (C) 2014 Elsevier Ltd. All rights reserved.

Contribution of forest fire ash and plant litter decay on stream dissolved composition in a sub-humid tropical watershed (Mule Hole, Southern India)

The current understanding of wildfire effects on water chemistry is limited by the quantification of the elemental dissolution rates from ash and element release rate from the plant litter, as well as quantification of the specific ash contribution to stream water chemistry. The main objective of the study was to provide such knowledge through combination of experimental modelling, field data and end-member mixing analysis (EMMA) of wildfire impact on a watershed scale. The study concerns watershed effects of fire in the Indian subcontinent, a region that is typically not well represented in the fire science literature. In plant litter ash, major elements are either hosted in readily-soluble phases (K, Mg) such as salts, carbonates and oxides or in less-soluble carrier-phases (Si, Ca) such as amorphous silica, quartz and calcite. Accordingly, elemental release rates, inferred from ash leaching experiments in batch reactor, indicated that the element release into solution followed the order K > Mg > Na > Si > Ca. Experiments on plant litter leaching in mixed-flow reactor indicated two dissolution regimes: rapid, over the week and slower over the month. The mean dissolution rates at steady-state (R-ss) indicated that the release of major elements from plant litter followed the order Ca > Si > Cl > Mg > K > Na. R-ss for Si and Ca for tree leaves and herbaceous species are similar to those reported for boreal and European tree species and are higher than that from the dissolution of soil clay minerals. This identifies tropical plant litters as important source of Si and Ca for tropical surface waters. In the wildfire-impacted year 2004, the EMMA indicated that the streamflow composition (Ca, K, Mg, Na, Si, Cl) was controlled by four main sources: rainwater, throughfall, ash leaching and soil solution. The influence of the ash end-member was maximal early in the rainy season (the two first storm events) and decreased later in the rainy season, when the stream was dominated by the throughfall end-member. The contribution of plant litter decay to the streamwater composition for a year not impacted by wildfire is significant with estimated solute fluxes originating from this decay greatly exceed, for most major elements, the annual elemental dissolved fluxes at the Mule Hole watershed outlet. This highlighted the importance of solute retention and vegetation back uptake processes within the soil profile. Overall, the fire increased the mobility and export of major elements from the soils to the stream. It also shifted the vegetation-related contribution to the elemental fluxes at the watershed outlet from long-term (seasonal) to short-term (daily to monthly). (C) 2014 Elsevier B.V. All rights reserved.

Modelling the effects of chorus species composition and caller density on acoustic masking interference in multispecies choruses of crickets and katydids

Natural multispecies acoustic choruses such as the dusk chorus of a tropical rain forest consist of simultaneously signalling individuals of different species whose calls travel through a common shared medium before reaching their `intended' receivers. This causes masking interference between signals and impedes signal detection, recognition and localization. The levels of acoustic overlap depend on a number of factors, including call structure, intensity, habitat-dependent signal attenuation and receiver tuning. In addition, acoustic overlaps should also depend on caller density and the species composition of choruses, including relative and absolute abundance of the different calling species. In this study, we used simulations to examine the effects of chorus species relative abundance and caller density on the levels of effective heterospecific acoustic overlap in multispecies choruses composed of the calls of five species of crickets and katydids that share the understorey of a rain forest in southern India. We found that on average species-even choruses resulted in higher levels of effective heterospecific acoustic overlap than choruses with strong dominance structures. This effect was found consistently across dominance levels ranging from 0.4 to 0.8 for larger choruses of forty individuals. For smaller choruses of twenty individuals, the effect was seen consistently for dominance levels of 0.6 and 0.8 but not 0.4. Effective acoustic overlap (EAO) increased with caller density but the manner and extent of increase depended both on the species' call structure and the acoustic context provided by the composition scenario. The Phaloria sp. experienced very low levels of EAO and was highly buffered to changes in acoustic context whereas other species experienced high FAO across contexts or were poorly buffered. These differences were not simply predictable from call structures. These simulation-based findings may have important implications for acoustic biodiversity monitoring and for the study of acoustic masking interference in natural environments. (C) 2013 Elsevier B.V. All rights reserved.

Effect of post-deposition annealing on composition and electrical properties of dc reactive magnetron sputtered Al2O3 thin films

We have investigated the effect of post- deposition annealing on the composition and electrical properties of alumina (Al2O3) thin films. Al2O3 were deposited on n-type Si < 100 >. substrates by dc reactive magnetron sputtering. The films were subjected to post- deposition annealing at 623, 823 and 1023 K in vacuum. X-ray photoelectron spectroscopy results revealed that the composition improved with post- deposition annealing, and the film annealed at 1023 K became stoichiometric with an O/Al atomic ratio of 1.49. Al/Al2O3/Si metal-oxide-semiconductor (MOS) structures were then fabricated, and a correlation between the dielectric constant epsilon(r) and interface charge density Q(i) with annealing conditions were studied. The dielectric constant of the Al2O3 thin films increased to 9.8 with post- deposition annealing matching the bulk value, whereas the oxide charge density decreased to 3.11 x 10(11) cm(-2.) Studies on current-voltage IV characteristics indicated ohmic and Schottky type of conduction at lower electric fields (<0.16 MV cm(-1)) and space charge limited conduction at higher electric fields.

Synthesis and Mechanism of Composition and Size Dependent Morphology Selection in Nanoparticles of Ag-Cu Alloys Processed by Laser Ablation Under Liquid Medium

We have synthesized Ag-Cu alloy nanoparticles of four different compositions by using the laser ablation technique with the target under aqueous medium. Following this, we report a morphological transition in the nanoparticles from a normal two-phase microstructure to a structure with random segregation and finally a core shell structure at small sizes as a function of Cu concentration. To illustrate the composition dependence of morphology, we report observations carried out on nanoparticles of two different sizes: similar to 5 and similar to 20 nm. The results could be rationalized through the thermodynamic modeling of free energy of phase mixing and wettability of the alloying phases.

Use of Composition-Graded Bi-Electrolyte Cells for Thermodynamic Studies on Lanthanum Aluminates

Innovative bi-electrolyte solid-state cells incorporating single crystal CaF2 and composition-graded solid electrolyte (LaF3) y (CaF2) 1-y (y = 0 to 0.32) were used for measurement of the standard Gibbs energy of formation of hexagonal La0.885Al11.782O19 and cubic LaAlO3 from component binary oxides La2O3 and alpha-Al2O3 in the temperature range from 875 to 1175 K. The cells were designed based on experimentally verified relevant phase relations in the systems La2O3-Al2O3LaF3 and CaF2-LaF3. The results can be summarized as: 5.891 alpha-Al2O3 + 0.4425 La2O3 (A-rare earth)-> La0.885Al11.782O19 (hex), Delta G(f(ox))(degrees)(+/- 2005)/Jmol(-1) = -80982 + 7.313(T/K); 1/2 La2O3 (A-rare earth) + 1/2 a-Al2O3 -> LaAlO3 (cubic), Delta G(f(ox))(degrees)(+/- 2100)/Jmol(-1) = -59810 + 4.51(T/K). Electron probe microanalysis was used to ascertain the non-stoichiometric range of the hexaaluminate phase. The results are critically analyzed in the light of earlier electrochemical measurements. Several imperfections in the electrochemical cells used by former investigators are identified. Data obtained in the study for LaAlO3 are consistent with calorimetric enthalpy of formation and entropy derived from heat capacity data. Estimated are the standard entropy and the standard enthalpy of formation from elements of hexagonal La0.885Al11.782O19 and rhombohedral LaAlO3 at 298.15 K. c 2014 The Electrochemical Society. All rights reserved.

Lactoylglutathione lyase, a critical enzyme in methylglyoxal detoxification, contributes to survival of Salmonella in the nutrient rich environment

Glyoxalase I which is synonymously known as lactoylglutathione lyase is a critical enzyme in methylglyoxal (MG) detoxification. We assessed the STM3117 encoded lactoylglutathione lyase (Lgl) of Salmonella Typhimurium, which is known to function as a virulence factor, due in part to its ability to detoxify methylglyoxal. We found that STM3117 encoded Lgl isomerises the hemithioacetal adduct of MG and glutathione (GSH) into S-lactoylglutathione. Lgl was observed to be an outer membrane bound protein with maximum expression at the exponential growth phase. The deletion mutant of S. Typhimurium (lgl) exhibited a notable growth inhibition coupled with oxidative DNA damage and membrane disruptions, in accordance with the growth arrest phenomenon associated with typical glyoxalase I deletion. However, growth in glucose minimal medium did not result in any inhibition. Endogenous expression of recombinant Lgl in serovar Typhi led to an increased resistance and growth in presence of external MG. Being a metalloprotein, Lgl was found to get activated maximally by Co2+ ion followed by Ni2+, while Zn2+ did not activate the enzyme and this could be attributed to the geometry of the particular protein-metal complex attained in the catalytically active state. Our results offer an insight on the pivotal role of the virulence associated and horizontally acquired STM3117 gene in non-typhoidal serovars with direct correlation of its activity in lending survival advantage to Salmonella spp.

Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition

We explore the potential energy landscape of structure breaking binary mixtures (SBBM) where two constituents dislike each other, yet remain macroscopically homogeneous at intermediate to high temperatures. Interestingly, we find that the origin of strong composition dependent non-ideal behaviour lies in its phase separated inherent structure. The inherent structure (IS) of SBBM exhibits bi-continuous phase as is usually formed during spinodal decomposition. We draw analogy of this correlation between non-ideality and phase separation in IS to explain observation of non-ideality in real aqueous mixtures of small amphiphilic solutes, containing both hydrophilic and hydrophobic groups. Although we have not been able to obtain IS of these liquids, we find that even at room temperature these liquids sustain formation of fluctuating, transient bi-continuous phase, with limited lifetime (tau less than or similar to 20 ps). While in the model (A, B) binary mixture, the non-ideal composition dependence can be considered as a fluctuation from a phase separated state, a similar scenario is expected to be responsible for the unusually strong non-ideality in these aqueous binary mixtures.

Lizards of the Thar Desert - Resource partitioning and community composition

How similar species co-exist in nature is a fundamental question in community ecology. Resource partitioning has been studied in desert lizard communities across four continents, but data from South Asia is lacking. We used area-constrained visual encounter surveys to study community composition and spatial and temporal resource partitioning in a lizard community during summer in the Thar Desert, western India, addressing an important biogeographic gap in knowledge. Twelve one-hectare grids divided into 25 m x 25 m plots were placed across four habitats barren dunes, stabilized dunes, grassland, and rocky hills. We recorded 1039 sightings of 12 species during 84 sampling sessions. Lizard abundance decreased in the order stabilized dunes > grassland > barren dunes > rocky hills; richness was in roughly the opposite order. Resource partitioning was examined for the seven commonest species. Overall spatial overlap was low (<0.6) between species pairs. Overlap was higher within habitats, but species showed finer separation through use of different microhabitat categories and specific spatial resources, as well as by positioning at different distances to vegetation. Diurnal species were also separated by peak time of activity. Space appears to be an important resource dimension facilitating coexistence in this desert lizard community. (C) 2015 Elsevier Ltd. All rights reserved.

Spatial modulation of the composition of a binary liquid near a repulsive wall

When a binary liquid is confined by a strongly repulsive wall, the local density is depleted near the wall and an interface similar to that between the liquid and its vapor is formed. This analogy suggests that the composition of the binary liquid near this interface should exhibit spatial modulation similar to that near a liquid-vapor interface even if the interactions of the wall with the two components of the liquid are the same. The Guggenheim adsorption relation quantifies the concentrations of two components of a binary mixture near a liquid-vapor interface and qualitatively states that the majority (minority) component enriches the interface for negative (positive) mixing energy if the surface tensions of the two components are not very different. From molecular dynamics simulations of binary mixtures with different compositions and interactions we find that the Guggenheim relation is qualitatively satisfied at wall-induced interfaces for systems with negative mixing energy at all state points considered. For systems with positive mixing energy, this relation is found to be qualitatively valid at low densities, while it is violated at state points with high density where correlations in the liquid are strong. This observation is validated by a calculation of the density profiles of the two components of the mixture using density functional theory with the Ramakrishnan-Yussouff free-energy functional. Possible reasons for the violation of the Guggenheim relation are discussed.