Glucose decomposition at high temperature, mild acid, and short residence times

Glucose is an intermediate product in the conversion of biomass to liquid fuels and chemicals via H₂SO₄ hydrolysis and subsequent fermentation. Unfortunately, glucose is destroyed as well as formed in this reaction. This study of glucose decomposition kinetics can be used to more accurately determine the kinetics of glucose formation from cellulosic biomass. The results demonstrate the importance of parallel reversion reactions in explaining the higher rates of disappearance of glucose found in this study as compared to earlier studies. An heuristic set of decomposition rate constants, applicable to conditions likely to be found in a flow reactor, are presented.     

A Unified Analysis of Structured Sonar-Terrain Data Using Bayesian Functional Mixed Models

Sonar emits pulses of sound and uses the reflected echoes to gain information about target objects. It offers a low cost, complementary sensing modality for small robotic platforms. Although existing analytical approaches often assume independence across echoes, real sonar data can have more complicated structures due to device setup or experimental design. In this article, we consider sonar echo data collected from multiple terrain substrates with a dual-channel sonar head. Our goals are to identify the differential sonar responses to terrains and study the effectiveness of this dual-channel design in discriminating targets. We describe a unified analytical framework that achieves these goals rigorously, simultaneously, and automatically. The analysis was done by treating the echo envelope signals as functional responses and the terrain/channel information as covariates in a functional regression setting. We adopt functional mixed models that facilitate the estimation of terrain and channel effects while capturing the complex hierarchical structure in data. This unified analytical framework incorporates both Gaussian models and robust models. We fit the models using a full Bayesian approach, which enables us to perform multiple inferential tasks under the same modeling framework, including selecting models, estimating the effects of interest, identifying significant local regions, discriminating terrain types, and describing the discriminatory power of local regions. Our analysis of the sonar-terrain data identifies time regions that reflect differential sonar responses to terrains. The discriminant analysis suggests that a multi- or dual-channel design achieves target identification performance comparable with or better than a single-channel design. Supplementary materials for this article are available online.     

Typical intellectual engagement and personality: Reply to Rocklin (1994).

T. Rocklin (see record 1994-29650-001) examined the relations between M. Goff and P. L. Ackerman's (see record 1993-13529-001) measure of typical intellectual engagement (TIE) and a personality test measure of Openness. Rocklin's arguments are examined in the context of 3 themes: philosophical issues, TIE and Openness from a facet perspective, and the bandwidth-fidelity dilemma. Although Rocklin raised important issues about these constructs, it is demonstrated that measures of TIE and Openness, although significantly related, are theoretically and empirically distinguishable. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Polypropylene-graphite nanocomposites made by solid-state shear pulverization: Effects of significantly exfoliated, unmodified graphite content on physical, mechanical and electrical properties

Nanocomposites made from polypropylene and as-received graphite were prepared by solid-state shear pulverization (SSSP) as a function of graphite loading (0.3-8.4 wt%). X-ray diffraction indicates that SSSP employing harsh pulverization conditions yields substantial graphite exfoliation at 0.3-2.7 wt% graphite content with less exfoliation being achieved at higher graphite content. With increasing graphite content, thermal degradation temperature and non-isothermal onset crystallization temperature increase substantially (by as much as 35 and 23 °C relative to neat polypropylene) while isothermal crystallization half-time decreases dramatically. In contrast, Young’s modulus and tensile yield strength exhibit maxima (∼100% and ∼60% increases, respectively, relative to neat polypropylene) at 2.7 wt% graphite content, with all nanocomposites retaining high elongation at break values except at the highest filler loading. Electrical conductivity measurements indicate percolation of graphite at 2.7 wt% and higher graphite content, consistent with rheology measurements showing the presence of a solid-like response of melt-state shear storage modulus as a function of frequency. Significant tunability of graphite exfoliation and property enhancements is demonstrated as a function of SSSP processing.     

Advancements in the Development of non-BET Bromodomain Chemical Probes

The bromodomain and extra terminal (BET) family of bromodomain-containing proteins (BCPs) have been the subject of extensive research over the past decade, resulting in a plethora of high-quality chemical probes for their tandem bromodomains. In turn, these chemical probes have helped reveal the profound biological role of the BET bromodomains and their role in disease, ultimately leading to a number of molecules in active clinical development. However, the BET subfamily represents just 8/61 of the known human bromodomains, and attention has now expanded to the biological role of the remaining 53 non-BET bromodomains. Rapid growth of this research area has been accompanied by a greater understanding of the requirements for an effective bromodomain chemical probe and has led to a number of new non-BET bromodomain chemical probes being developed. Advances since December 2015 are discussed, highlighting the strengths/caveats of each molecule, and the value they add toward validating the non-BET bromodomains as tractable therapeutic targets.     

Charged nucleobases and their potential for RNA catalysis

Catalysis in living cells is carried out by both proteins and RNA. Protein enzymes have been known for over 200 years, but RNA enzymes, or "ribozymes", were discovered only 30 years ago. Developing insight into RNA enzyme mechanisms is invaluable for better understanding both extant biological catalysis as well as the primitive catalysis envisioned in an early RNA-catalyzed life. Natural ribozymes include large RNAs such as the group I and II introns; small RNAs such as the hepatitis delta virus and the hairpin, hammerhead, VS, and glmS ribozymes; and the RNA portion of the ribosome and spliceosome. RNA enzymes use many of the same catalytic strategies as protein enzymes, but do so with much simpler side chains. Among these strategies are metal ion, general acid-base, and electrostatic catalysis. In this Account, we examine evidence for participation of charged nucleobases in RNA catalysis. Our overall approach is to integrate direct measurements on catalytic RNAs with thermodynamic studies on oligonucleotide model systems. The charged amino acids make critical contributions to the mechanisms of nearly all protein enzymes. Ionized nucleobases should be critical for RNA catalysis as well. Indeed, charged nucleobases have been implicated in RNA catalysis as general acid-bases and oxyanion holes. We provide an overview of ribozyme studies involving nucleobase catalysis and the complications involved in developing these mechanisms. We also consider driving forces for perturbation of the pK(a) values of the bases. Mechanisms for pK(a) values shifting toward neutrality involve electrostatic stabilization and the addition of hydrogen bonding. Both mechanisms couple protonation with RNA folding, which we treat with a thermodynamic formalism and conceptual models. Furthermore, ribozyme reaction mechanisms can be multichannel, which demonstrates the versatility of ribozymes but makes analysis of experimental data challenging. We examine advances in measuring and analyzing perturbed pK(a) values in RNA. Raman crystallography and fluorescence spectroscopy have been especially important for pK(a) measurement. These methods reveal pK(a) values for the nucleobases A or C equal to or greater than neutrality, conferring potential histidine- and lysine/arginine-like behavior on them. Structural support for ionization of the nucleobases also exists: an analysis of RNA structures in the databases conducted herein suggests that charging of the bases is neither especially uncommon nor difficult to achieve under cellular conditions. Our major conclusions are that cationic and anionic charge states of the nucleobases occur in RNA enzymes and that these states make important catalytic contributions to ribozyme activity. We conclude by considering outstanding questions and possible experimental and theoretical approaches for further advances.