De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper–niobium system

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu–Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200?°C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300?°C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.     

Selective Reduction of Conjugated Ethylenic Linkage in the Presence of Ion-Exchange Resin Bound Borohydride

The use of crosslinked polystyrene anion-exchange resin as a support for borohydride ions made it possible to reduce conjugated olefinic bonds selectively under very mild conditions. The isolation of the reduced products by a simple filtration and evaporation process is another interesting feature of this reaction.     

Development and validation of a rapid HPLC method for quantitation of SP‐141, a novel pyrido[b]indole anticancer agent,and an initial pharmacokinetic study in mice

There is an increasing interest in targeting the MDM2 oncogene for cancer therapy. SP‐141, a novel designed small molecule MDM2 inhibitor, exerts excellent in vitro and in vivo anticancer activity. To facilitate the preclinical development of this candidate anticancer agent, we have developed an HPLC method for the quantitative analysis of SP‐141. The method was validated to be precise, accurate, and specific, with a linear range of 16.2–32,400 ng/mL in plasma, 16.2–6480 ng/mL in homogenates of brain, heart, liver, kidneys, lungs, muscle and tumor, and 32.4–6480 ng/mL in spleen homogenates. The lower limit of quantification was 16.2 ng/mL in plasma and all the tissue homogenates, except for spleen homogenates, where it was 32.4 ng/mL. The intra‐ and inter‐assay precisions (coefficient of variation) were between 0.86 and 13.39%, and accuracies (relative errors) ranged from ?8.50 to 13.92%. The relative recoveries were 85.6–113.38%. SP‐141 was stable in mouse plasma, modestly plasma bound and metabolized by S9 microsomal enzymes. We performed an initial pharmacokinetic study in tumor‐bearing nude mice, demonstrating that SP‐141 has a short half‐life in plasma and wide tissue distribution. In summary, this HPLC method can be used in future preclinical and clinical investigations of SP‐141. Copyright © 2014 John Wiley & Sons, Ltd.     

Polar optic phonon scattering of two dimensional electron gas in a rectangular potential well

The mobility of a two-dimensional electron gas (2DEG) in a rectangular potential well formed in a AlGaAs/GaAs/AlGaAs structure scattered by polar-optic phonon is calculated by an iterative solution of Boltzmann equation. The values are significantly different from those calculated by using a relaxation time. The polar-optic mobility is found to dominate over acoustic mobility over a temperature range of 100–300 K when the well thickness is about 10 nm. The mobility values for 2DEG are, however, found to be lower than the bulk values.     

Efficient proton-templated synthesis of 18- to 38-membered tetraimino(amino)diphenol macrocyclic ligands: structural features and spectroscopic properties

A whole range of Robson-type tetraiminodiphenol macrocyclic ligands have been prepared as their perchlorate salts [H4L](ClO4)2 in high yield (ca. 90%) by a single-step [2 + 2] condensation reaction between 4-methyl(or tert-butyl)-2,6-diformyl(or diacyl)phenols and alpha,omega-diaminoalkanes (C2-C12) in the presence of acetic acid and NaClO4. The reduction of these 18- to 38-membered macrocyclic salts with NaBH4 have afforded corresponding tetraaminodiphenol macrocycles H2L'. The X-ray crystal structures of two of the tetraiminodiphenol macrocycles with the C2 and C4 lateral chains have been determined, and the optimized configurations for all of the macrocycles have been obtained by molecular mechanics calculations. The macrocycles have been characterized by elemental analysis and by IR, absorption, emission, and NMR spectroscopic study. The protonated tetraiminodiphenol macrocycles exhibit strong fluoroscence in methanol, acetonitrile, and nitromethane and undergo quenching when treated with triethylamine. The neutral macrocycles H2L, isolated by treating [H4L](ClO4)2 with excess of triethylamine, lack luminescence, as do the reduced tetraaminodiphenol macrocycles H2L'. The hydrolytic cleavage of [H4L](ClO4)2 has been studied.     

Thermodynamics and kinetics of competing aggregation processes in a simple model system

A simple model system has been used to develop thermodynamics and kinetics for bulk and surface aggregation processes capable of competing with each other. The processes are the stepwise aggregation of monomers in a fluid medium and on an impenetrable solid surface bounding the fluid medium, besides the adsorption and desorption of the same species at the solid-fluid interface. Emphasis is on aggregation processes in the high friction limit. The theoretical model is used to compare the kinetics and thermodynamics of the processes and to infer the conditions in which one process dominates another, in the high friction limit, such as in a liquid. The motivation of this study is obtaining insight into competition between aggregation in solution and on an adjoining surface, such as a cell membrane.     

Thermodynamic studies of bovine lung surfactant extract mixing with cholesterol and its palmitate derivative

Langmuir film behavior of bovine lipid extract surfactant (BLES), mixed with cholesterol (CHOL) and cholesterol palmitate (CHOLP), has been studied by surface pressure (pi)-area (A) measurements. Associative interactions, observed for both systems, were less favored at lower BLES content. The presence of unsaturated phospholipids and surfactant proteins in BLES favored the association. Miscibility of BLES was better with CHOLP than with CHOL at all compositions, indicating more compact packing of the BLES-CHOLP than of the BLES-CHOL system. The most stable mixtures were found at 30-40 mol% CHOL and at low pi and at 20-25 mol% CHOLP but at higher pi. These results suggest that BLES-CHOL miscibility is better at low pi and low CHOL concentrations, while BLES-CHOLP miscibility is better at high pi and high CHOLP concentrations.     

Emergence of diverse dynamical responses in a fractional-order slow–fast pest–predator model

To explore the impact of pest-control strategy on integrated pest management, a three-dimensional (3D) fractional- order slow–fast prey–predator model is introduced in this article. The prey community (assumed as pest) represents fast dynamics and two predators exhibit slow dynamical variables in the three-species interacting prey–predator model. In addition, common enemies of that pest are assumed as predators of two different species. Pest community causes serious damage to the economy. Fractional-order systems can better describe the real scenarios than classical-order dynamical systems, as they show previous history-dependent properties. We establish the ability of a fractional-order model with Caputo’s fractional derivative to capture the dynamics of this prey–predator system and analyze its qualitative properties. To investigate the importance of fractional-order dynamics on the behavior of the pest, we perform the local stability analysis of possible equilibrium points, using certain assumptions for different sets of parameters and reveal that the fractional-order exponent has an impact on the stability and the existence of Hopf bifurcations in the prey–predator model. Next, we discuss the existence, uniqueness and boundedness of the fractional-order system. We also observe diverse oscillatory behavior of different amplitude modulations including mixed mode oscillations (MMOs) for the fractional-order prey–predator model. Higher amplitude pest periods are interspersed with the outbreaks of small pest concentration. With the decrease of fractional-order exponent, small pest concentration increases with decaying long pest periods. We further notice that the reduced-order model is biologically significant and sensitive to the fractional-order exponent. Additionally, the dynamics captures adaptation that occurs over multiple timescales and we find consistent differences in the characteristics of the model for various fractional exponents.

     

A decision-support model for investment decisions in new ventures

The decision to invest in new ventures is characterized by incomplete information, where some measures of firm performance are quantitative, while some others are substituted by qualitative indicators. Qualitative attributes are defined in a relative sense. We develop a decision support model for identifying successful new ventures. The model integrates quantitative and qualitative variables through the use of the Analytic Hierarchy Process (AHP). The decision model gains in predictive accuracy through the use of qualitative attributes, and AHP imparts robustness to the qualitative measures.     

Stable Isotope-Labeled Raman Imaging Reveals Dynamic Proteome Localization to Lipid Droplets in Single Fission Yeast Cells

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Highlights? Raman spectroscopy requires no dye probe but still enables molecular imaging ? Stable-isotope labeling distinguishes between existing and newly formed proteins ? Protein localization to lipid droplets has been revealed in fission yeast ? The colocalization phenomenon is associated with starvation