Arousal of negative emotions and symptom-specific reactivity in chronic low back pain patients.

Anger may have greater effects on chronic pain severity than other negative emotions and may do so by increasing muscle tension near the site of injury (symptom-specific reactivity). For patients with chronic low back pain (CLBP), relevant muscles are lower paraspinals (LP). Ninety-four CLBP patients and 79 controls underwent anger and sadness recall interviews. EMG and cardiovascular activity were recorded. Patients exhibited greater LP tension increases during anger and slower recovery than controls. Only patients showed greater LP reactivity during anger than sadness. For both groups, trapezius reactivity during anger and sadness did not differ. LP reactivity to anger correlated with everyday pain severity for patients. Anger-induced symptom-specific LP reactivity may be linked to chronic pain aggravation among CLBP patients. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Discovery of Affinity-Based Probes for Btk Occupancy Assays

Bruton's tyrosine kinase (Btk) is an attractive target for the treatment of a wide array of B-cell malignancies and autoimmune diseases. Small-molecule covalent irreversible Btk inhibitors targeting Cys481 have been developed for the treatment of such diseases. In clinical trials, probe molecules are required in occupancy studies to measure the level of engagement of the protein by these covalent irreversible inhibitors. The result of this pharmacodynamic (PD) activity provides guidance for appropriate dosage selection to optimize inhibition of the drug target and correlation of target inhibition with disease treatment efficacy. This information is crucial for successful evaluation of drug candidates in clinical trials. Based on the pyridine carboxamide scaffold of a novel solvent-accessible pocket (SAP) series of covalent irreversible Btk inhibitors, we successfully developed a potent and selective affinity-based biotinylated probe 12 (2-[(4-{4-[5-(1-{5-[(3aS,4S,6aR)-2-oxo-hexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanamido}-3,6,9,12-tetraoxapentadecan-15-amido)pentanoyl]piperazine-1-carbonyl}phenyl)amino]-6-[1-(prop-2-enoyl)piperidin-4-yl]pyridine-3-carboxamide). Compound 12 has been used in Btk occupancy assays for preclinical studies to determine the therapeutic efficacy of Btk inhibition in two mouse lupus models driven by TLR7 activation and type I interferon.     

Large-scale and uniform preparation of pure-phase wurtzite GaAs NWs on non-crystalline substrates

One of the challenges to prepare high-performance and uniform III-V semiconductor nanowires (NWs) is to control the crystal structure in large-scale. A mixed crystal phase is usually observed due to the small surface energy difference between the cubic zincblende (ZB) and hexagonal wurtzite (WZ) structures, especially on non-crystalline substrates. Here, utilizing Au film as thin as 0.1 nm as the catalyst, we successfully demonstrate the large-scale synthesis of pure-phase WZ GaAs NWs on amorphous SiO₂/Si substrates. The obtained NWs are smooth, uniform with a high aspect ratio, and have a narrow diameter distribution of 9.5 ± 1.4 nm. The WZ structure is verified by crystallographic investigations, and the corresponding electronic bandgap is also determined to be approximately 1.62 eV by the reflectance measurement. The formation mechanism of WZ NWs is mainly attributed to the ultra-small NW diameter and the very narrow diameter distribution associated, where the WZ phase is more thermodynamically stable compared to the ZB structure. After configured as NW field-effect-transistors, a high I_ON/I_OFF ratio of 10⁴ − 10⁵ is obtained, operating in the enhancement device mode. The preparation technology and good uniform performance here have illustrated a great promise for the large-scale synthesis of pure phase NWs for electronic and optical applications.     

Multifunctional Nanochemistry: Ambient,Electroless, Template-Based Synthesis and Characterization of Segmented Bimetallic Pd/Au and Pd/Pt Nanowires as High-Performance Electrocatalysts and Nanomotors

Segmented noble-metal nanowires (NWs) represent an exciting, multifunctional, one-dimensional, structural architecture with a variety of potential applications. However, the widespread use of electrodeposition in the preparation of these systems has limited their potential to be produced on a large scale, since this protocol is costly and requires complex processes and caustic reaction media. Given the inherent limitations of electrodeposition, we report, for the first time, an ambient, surfactantless, template-based approach that is not only sustainable but also efficient for the reliable production of Pd/Pt and Pd/Au segmented NWs, possessing two spatially separated, chemically distinctive, but elementally pure, axial subunits. Our simple two-step synthetic approach allows for direct and predictable control over the relative segment lengths in these nanomaterials. Moreover, thorough structural characterization of these as-prepared samples confirms that our segmented NWs maintain high-quality, crystalline, elementally pure subunits with a well-defined interface between the constituent metals. In the context of preparing segmented NWs as multifunctional nanostructures, we demonstrate that these as-prepared NWs achieve high levels of performance when employed as both electrocatalysts and nanomotors.     

On stability and performance of highly c-oriented columnar AlPO4-5 and CoAPO-5 membranes

Continuous films comprised of highly c-oriented aluminophosphate AlPO₄-5 or cobalt-substituted AlPO₄-5 (CoAPO-5) were grown on porous supports and subjected to heat treatment in order to investigate the potential for membrane applications. A study in the early stages of in-plane crystalline intergrowth revealed a potential mechanism for flake-like crystal formation between the original oriented columnar crystals. Variations in metal substitution (AlPO₄-5, CoAPO-5), support (glass, silicon, porous alumina), and calcination method (conventional, rapid thermal processing) were chosen to examine the conditions by which structural integrity was compromised following secondary (or tertiary) growth, resulting in reduced membrane functionality. Through the use of rapid thermal processing, the structure debilitation could be partially avoided. The membrane quality was inspected through pervaporation measurements consisting of a liquid hydrocarbon feed of n-heptane and 1,3,5-triisopropylbenzene. By investigating the effect of template removal on the oriented, columnar crystalline structure, useful insight is provided into the potential for the membranes to participate in applications such as molecular separations, catalysis, or host-guest assemblies.     

Ecology and Evolution of Soil Nematode Chemotaxis

Plants influence the behavior of and modify community composition of soil-dwelling organisms through the exudation of organic molecules. Given the chemical complexity of the soil matrix, soil-dwelling organisms have evolved the ability to detect and respond to these cues for successful foraging. A key question is how specific these responses are and how they may evolve. Here, we review and discuss the ecology and evolution of chemotaxis of soil nematodes. Soil nematodes are a group of diverse functional and taxonomic types, which may reveal a variety of responses. We predicted that nematodes of different feeding guilds use host-specific cues for chemotaxis. However, the examination of a comprehensive nematode phylogeny revealed that distantly related nematodes, and nematodes from different feeding guilds, can exploit the same signals for positive orientation. Carbon dioxide (CO(2)), which is ubiquitous in soil and indicates biological activity, is widely used as such a cue. The use of the same signals by a variety of species and species groups suggests that parts of the chemo-sensory machinery have remained highly conserved during the radiation of nematodes. However, besides CO(2), many other chemical compounds, belonging to different chemical classes, have been shown to induce chemotaxis in nematodes. Plants surrounded by a complex nematode community, including beneficial entomopathogenic nematodes, plant-parasitic nematodes, as well as microbial feeders, are thus under diffuse selection for producing specific molecules in the rhizosphere that maximize their fitness. However, it is largely unknown how selection may operate and how belowground signaling may evolve. Given the paucity of data for certain groups of nematodes, future work is needed to better understand the evolutionary mechanisms of communication between plant roots and soil biota.     

Aromatic Halogenation by Using Bifunctional Flavin Reductase–Halogenase Fusion Enzymes

The remarkable site selectivity and broad substrate scope of flavin-dependent halogenases (FDHs) has led to much interest in their potential as biocatalysts. Multiple engineering efforts have demonstrated that FDHs can be tuned for non-native substrate scope and site selectivity. FDHs have also proven useful as in vivo biocatalysts and have been successfully incorporated into biosynthetic pathways to build new chlorinated aromatic compounds in several heterologous organisms. In both cases, reduced flavin cofactor, usually supplied by a separate flavin reductase (FR), is required. Herein, we report functional synthetic, fused FDH-FR proteins containing various FDHs and FRs joined by different linkers. We show that FDH-FR fusion proteins can increase product titers compared to the individual components for in vivo biocatalysis in Escherichia coli.     

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.     

Accuracy of approximations for CIELAB chroma and hue difference computation

The transformation in CIELAB from differences in the L^*, a^*, b^* coordinates to those in lightness, chroma, and hue, ΔL^*, ΔC_ab^*, ΔH_ab^*, can be approximated by a rotation in 3-space. Expressions for the error in the approximation of chroma and hue differences are developed. Significant errors are introduced if either the hue angle or chroma difference between reference and sample colors are large. A computed example illustrates the use of the analysis. © 1997 John Wiley & Sons, Inc. Col Res Appl, 22, 61–64, 1997.