Confirmation of the Dominant Defect Mechanism in Amorphous In–Zn–O Through the Application of In Situ Brouwer Analysis

The dominant point defect mechanism of amorphous (a‐) indium zinc oxide (IZO) was probed through in situ electrical characterization of sputtered a‐IZO thin films in response to changes in oxygen partial pressure (pO) at 300C. The results yielded a power law dependence of conductivity (σ) versus pO of ～?1/6. This experimental method, known as Brouwer analysis, confirms doubly‐charged oxygen vacancies as the dominant defect species in a‐IZO. The success of this study suggests that Brouwer analysis is a viable method for studying the defect mechanisms of amorphous oxides.     

ION-SELECTIVE POLYMER-SUPPORTED REAGENTS

ABSTRACT

The design and synthesis of polymer-supported reagents that can selectively complex targeted metal ions from multi-component solutions will continue to be an important area of research into the 21^st century. Environmental remediation and sensor technology are only two of a number of areas in which such polymers can be applied. This paper reviews the recent literature with an emphasis on the key ligands that have been immobilized in order to better understand where this research is heading in the near future.     

Substrate Selection Influences Molecular Recognition in a Screen for Lymphoid Tyrosine Phosphatase Inhibitors

Assay design is an important variable that influences the outcome of an inhibitor screen. Here, we have investigated the hypothesis that protein tyrosine phosphatase inhibitors with improved biological activity could be identified from a screen by using a biologically relevant peptide substrate, rather than traditional phosphotyrosine mimetic substrates. A 2000‐member library of drugs and drug‐like compounds was screened for inhibitors of lymphoid tyrosine phosphatase (LYP) by using both a peptide substrate (Ac‐ARLIEDNE‐pCAP‐TAREG‐NH₂, peptide 1) and a small‐molecule phosphotyrosine mimetic substrate (difluoromethyl umbelliferyl phosphate, DiFMUP). The results demonstrate that compounds that inhibited enzyme activity on the peptide substrate had greater biological activity than compounds that only inhibited enzyme activity on DiFMUP. Finally, epigallocatechin‐3,5‐digallate was identified as the most potent inhibitor of lymphoid tyrosine phosphatase activity to date, with an IC₅₀ of 50 nM and significant activity in T‐cells. Molecular docking simulations provided a first model for binding of this potent inhibitor to LYP; this will constitute the platform for ongoing lead optimization efforts.     

Thiuram Disulfides as Pseudo‐irreversible Inhibitors of Lymphoid Tyrosine Phosphatase

We screened a small library of thiuram disulfides for inhibition of lymphoid tyrosine phosphatase (LYP) activity. The parent thiuram disulfide, disulfiram, inhibited LYP activity in vitro and in Jurkat T cells, whereas diethyldithiocarbamate failed to inhibit LYP at the concentrations tested. Compound 13 , an N‐(2‐thioxothiazolidin‐4‐one) analogue, was found to be the most potent LYP inhibitor in this series, with an IC₅₀ value of 3 μM . Compound 13 inhibits LYP pseudo‐irreversibly, as evidenced by the time‐dependence of inhibition, with a K_i value of 1.1 μM and a k_inact value of 0.004 s^?1. The inhibition of LYP by compound 13 could not be reversed significantly by incubation with glutathione or by prolonged dialysis, but could be partially reversed by incubation with dithiothreitol. Compound 13 also inhibited LYP activity in Jurkat T cells.     

Hybrid Organic‐Inorganic Membranes on Porous Supports by Size Exclusion and Thermal Sintering of Fluorescent Polyphenylsilsesquioxane Nanoparticles

Hybrid organic–inorganic membranes were prepared by size‐exclusion deposition and thermal sintering of fluorescent polyphenylsilsesquioxane nanoparticles on a ceramic support. Fluorescent polyphenylsilsesquioxane particles were prepared by a two‐step co‐polymerization of phenyltriethoxysilane with 0.1 mol‐% N‐(triethoxysilylpropyl)dansylamide. Because they were larger than the pores in the support, the particles formed a layer on top of the ceramic support that was sintered at 300 °C into a homogeneous, non‐porous membrane. Fluorescence of the modified polyphenylsilsesquioxane provided a valuable tool to monitor particle deposition and assist in characterization of the membranes.

     

Kinetics of Isothermal Crystallization of Hydrogenated Castor Oil-in-Water Emulsions

Kinetics of isothermal crystallization of hydrogenated castor oil in water emulsions exhibiting multiple crystal morphologies have been studied experimentally by DSC and polarized light microscopy. The induction time of nucleation increases with the increase of the isothermal temperature under which crystallization occurred. Crystal growth has been observed by microscopy showing that both crystal morphologies, fibers and rosettes, grow linearly at the initial stage of crystallization and then slow down to reach a plateau value. The Avrami model, which has been widely used in kinetics studies of triacylglycerol systems, was employed to fit experimental results at different isothermal temperatures. It was found that experimental trends could be captured by introducing the volume fraction of each type of morphology into three-dimensional and one-dimensional full Avrami models.     

Alterations in Serum Polyunsaturated Fatty Acids and Eicosanoids in Patients with Mild to Moderate Chronic Obstructive Pulmonary Disease (COPD)

Smoking is a major risk factor for several diseases including chronic obstructive pulmonary disease (COPD). To better understand the systemic effects of cigarette smoke exposure and mild to moderate COPD—and to support future biomarker development—we profiled the serum lipidomes of healthy smokers, smokers with mild to moderate COPD (GOLD stages 1 and 2), former smokers, and never-smokers (n = 40 per group) (ClinicalTrials.gov registration: {"type":"clinical-trial","attrs":{"text":"NCT01780298","term_id":"NCT01780298"}}NCT01780298). Serum lipidome profiling was conducted with untargeted and targeted mass spectrometry-based lipidomics. Guided by weighted lipid co-expression network analysis, we identified three main trends comparing smokers, especially those with COPD, with non-smokers: a general increase in glycero(phospho)lipids, including triglycerols; changes in fatty acid desaturation (decrease in ω-3 polyunsaturated fatty acids, and an increase in monounsaturated fatty acids); and an imbalance in eicosanoids (increase in 11,12- and 14,15-DHETs (dihydroxyeicosatrienoic acids), and a decrease in 9- and 13-HODEs (hydroxyoctadecadienoic acids)). The lipidome profiles supported classification of study subjects as smokers or non-smokers, but were not sufficient to distinguish between smokers with and without COPD. Overall, our study yielded further insights into the complex interplay between smoke exposure, lung disease, and systemic alterations in serum lipid profiles.     

Modeling of coupled mass and heat transfer through venting membranes for automotive applications

Experimental and theoretical approaches based on a mathematical model, have been developed to study the evolution of environmental parameters (temperature, total pressure, relative humidity, and water vapor partial pressure) inside a housing of an electronic device with a window containing a macroporous membrane. The model was based on the coupling of mass and heat transfer taking into account the effects of polarization of concentration in boundary layers. Membranes have been characterized by mercury porosimetry, liquid entry pressure measurements, scanning electron microscopy, and gas permeation. Once the model was experimentally validated, it was applied to investigate the influence of membranes on heat and mass transfer and to study the impact of the boundary layers on the global mass transport. The results demonstrated the importance of the membrane choice and dimensions to get the best temperature regulation and avoid water condensation inside an automotive electronic control unit (ECU). © 2008 American Institute of Chemical Engineers AIChE J, 2009