Thermal stability of HfO2-on-GaAs nanopatterns

We have evaluated the effect of thermal annealing on the morphology, crystalline phase and elemental composition of high-k dielectric HfO(2)-on-GaAs nanopatterns at 500-620 °C by using atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS). While the HfO(2)-GaAs interface continues to be atomically abrupt at 620 °C, we have found a gradual shrinkage in the pattern linewidth and period with increasing temperature. Facet formation triggered by a nanoscale-modulated sequence of tensile and compressive stresses on the GaAs substrate, observed at 620 °C, has been attributed to a volumetric expansion of the HfO(2) nanostructures, caused by the tetragonal/cubic to monoclinic HfO(2) phase transformation and, to a lesser extent, by solid-state diffusion of As into HfO(2).     

A Dual Inhibitor of DYRK1A and GSK3β for β-Cell Proliferation: Aminopyrazine Derivative GNF4877

Loss of β-cell mass and function can lead to insufficient insulin levels and ultimately to hyperglycemia and diabetes mellitus. The mainstream treatment approach involves regulation of insulin levels; however, approaches intended to increase β-cell mass are less developed. Promoting β-cell proliferation with low-molecular-weight inhibitors of dual-specificity tyrosine-regulated kinase 1A (DYRK1A) offers the potential to treat diabetes with oral therapies by restoring β-cell mass, insulin content and glycemic control. GNF4877, a potent dual inhibitor of DYRK1A and glycogen synthase kinase 3β (GSK3β) was previously reported to induce primary human β-cell proliferation in vitro and in vivo. Herein, we describe the lead optimization that lead to the identification of GNF4877 from an aminopyrazine hit identified in a phenotypic high-throughput screening campaign measuring β-cell proliferation.     

Specificity studies of bacillus 1,3-1,4-beta-glucanases and application to glycosynthase-catalyzed transglycosylation

Bacillus 1,3-1,4-beta-glucanases hydrolyze 1,3-1,4-beta-gluco-oligosaccharides with a retaining mechanism. The binding-site cleft of these endoglycosidases is composed of six subsites (-4 to +2) of which subsite -3 makes the largest contribution to transition state stabilization. The specificity of this subsite is here analyzed for both glycosidase and glycosynthase activities in the wild-type and the nucleophile-less E134A mutant Bacillus licheniformis enzymes. A D-galactosyl residue on the nonreducing end of a trisaccharide substrate is accepted by the enzyme and binds at subsite -3 in the productive enzyme-substrate complex. The wild-type enzyme catalyzes the hydrolysis of the substrate Glcbeta4Glcbeta3GlcbetaMU (Glc=glucosyl, MU=4-methylumbelliferyl) with a k(cat)/K(M) value only 1.3-fold higher than for the Galbeta4Glcbeta3GlcbetaMU (Gal=galactosyl) substrate. The corresponding alpha-fluorides act as good donors for the glycosynthase condensation reaction with mono- and disaccharide acceptors catalyzed by the E134A mutant. Whereas self-condensation and elongation products are also obtained as minor compounds with the Glcbeta4Glcbeta3GlcalphaF donor, nearly quantitative yields of single condensation products are obtained with the Galbeta4Glcbeta3GlcalphaF donor, in which the axial configuration of the 4-OH group on the nonreducing end prevents self-condensation and elongation reactions.     

Effect of molecular architecture on microstructural characteristics in some polysiloxaneimide multiblock copolymers

Efforts to correlate molecular characteristics with microstructural dimensions in microphase-separated diblock and triblock copolymers have been very successful, resulting in relationships that can be utilized to design materials with a specific microstructure and, consequently, with particular thermomechanical properties. However, similar efforts in the arena of multiblock copolymers have not been nearly as extensive, despite the increasing interest and diversity of this class of materials. In the present work, energy-filtered electron microscopy (EFEM) and small-angle neutron scattering (SANS) are used in a complementary fashion to probe the phase behavior of a series of three polysiloxaneimide (PSI) multiblock copolymers with different molecular architectures. Despite their relatively short segment lengths, all three materials exhibit signs of microphase separation at ambient temperature. SANS data are obtained from chemically unaltered materials and are subsequently interpreted with the Teubner-Strey model for microemulsions. Resultant microstructural dimensions are in good agreement with those measured from EFEM micrographs. Additional insight into the intramolecular sequencing of each copolymer is obtained from scaling relationships.     

Validation of the MEDFICTS dietary questionnaire: A clinical tool to assess adherence to American Heart Association dietary fat intake guidelines

Background  

Dietary assessment tools are often too long, difficult to quantify, expensive to process, and largely used for research purposes. A rapid and accurate assessment of dietary fat intake is critically important in clinical decision-making regarding dietary advice for coronary risk reduction. We assessed the validity of the MEDFICTS (MF) questionnaire, a brief instrument developed to assess fat intake according to the American Heart Association (AHA) dietary "steps".     

Scaling Effects in Perovskite Ferroelectrics: Fundamental Limits and Process‐Structure‐Property Relations

Ferroelectric materials are well‐suited for a variety of applications because they can offer a combination of high performance and scaled integration. Examples of note include piezoelectrics to transform between electrical and mechanical energies, capacitors used to store charge, electro‐optic devices, and nonvolatile memory storage. Accordingly, they are widely used as sensors, actuators, energy storage, and memory components, ultrasonic devices, and in consumer electronics products. Because these functional properties arise from a noncentrosymmetric crystal structure with spontaneous strain and a permanent electric dipole, the properties depend upon physical and electrical boundary conditions, and consequently, physical dimension. The change in properties with decreasing physical dimension is commonly referred to as a size effect. In thin films, size effects are widely observed, whereas in bulk ceramics, changes in properties from the values of large‐grained specimens is most notable in samples with grain sizes below several micrometers. It is important to note that ferroelectricity typically persists to length scales of about 10 nm, but below this point is often absent. Despite the stability of ferroelectricity for dimensions greater than ~10 nm, the dielectric and piezoelectric coefficients of scaled ferroelectrics are suppressed relative to their bulk counterparts, in some cases by changes up to 80%. The loss of extrinsic contributions (domain and phase boundary motion) to the electromechanical response accounts for much of this suppression. In this article, the current understanding of the underlying mechanisms for this behavior in perovskite ferroelectrics is reviewed. We focus on the intrinsic limits of ferroelectric response, the roles of electrical and mechanical boundary conditions, grain size and thickness effects, and extraneous effects related to processing. In many cases, multiple mechanisms combine to produce the observed scaling effects.     

Morphological development of impact polypropylene produced in gas phase with a TiCl4/MgCl2 catalyst

This article reports on a comprehensive study of the reaction kinetics, particle morphology development, and polymer properties of impact polypropylene produced in gas phase with a TiCl₄/MgCl₂ catalyst. Experiments were conducted over a range of copolymerization times, temperatures, monomer compositions, and hydrogen levels. The catalyst was found to exhibit a decay-type reaction rate for ethylene and propylene, but the presence of both monomers together caused an activation of the catalyst. Copolymer composition was constant over reaction time. Hydrogen was found to reversibly enhance the rate of propylene polymerization but to have no effect on ethylene. Microscopy provided evidence that the copolymer phase segregates from the homopolymer during polymerization. As copolymer content increased, product bulk density decreased because of the presence of sticky material on the particle surface. However, even at 70 wt % copolymer, enough pores were present in the particle to prevent monomer diffusion limitations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3085–3106, 2001     

Phage‐mediated transfer of virulence genes

Bacteriophages as accessory genetic elements play a crucial role in the dissemination of genes and the promotion of genetic diversity within bacterial populations. Such horizontal transfer of DNA is critical in the emergence of new pathogenic organisms, through the dissemination of genes encoding virulence factors such as toxins, adhesins and agressins. Phages can transfer genes that are not necessary for bacteriophage persistence and are generally recognised by their ability to convert their host bacteria to new phenotypes. This phenomenon is known as phage conversion. If such converting genes encode for virulence factors, the consequences of phage infection may include increased virulence of the host bacteria, and the conversion of a non‐pathogenic strain to a potentially dangerous pathogen. A number of virulence factors in bacteria causing diseases in plants, animals and humans are encoded by converting phages, the vast majority of which are temperate as opposed to lytic in nature. © 2001 Society of Chemical Industry     

Strain-Free Total Resonant Sextet Benzenoid Hydrocarbons

The importance of strain-free (total) resonant sextet benzenoid hydrocarbons is pointed out. The first computer-aided generation and enumeration of such systems is reported, and the data represent substantial supplements to the previous numbers of strain-free resonant sextet benzenoid isomers. Supplementary depictions of some forms of the systems in question are also provided. Constant-isomer series are delineated for the resonant sextet benzenoids. The numbers associated with these series are found to match exactly the known numbers for corresponding constant-isomer series of strictly pericondensed benzenoids.