Acid-catalyzed dehydration of naphthalene-cis-1,2-dihydrodiols: origin of impaired resonance effect of 3-substituents

Acid-catalyzed dehydrations of substituted naphthalene-cis-1,2-dihydrodiols occur with loss of the 1- or 2-OH group to form 2- and 1-naphthols, respectively. Effects of substituents MeO, Me, H, F, Br, I, and CN at 3-, 6-, and 7-positions of the naphthalene ring are consistent with rate-determining formation of β-hydroxynaphthalenium ion (carbocation) intermediates. For reaction of the 1-hydroxyl group the 3-substituents are correlated by the Yukawa-Tsuno relationship with ρ = -4.7 and r = 0.25 or by σ(p) constants with ρ = -4.25; for reaction of the 2-hydroxyl group the 3-substituents are correlated by σ(m) constants with ρ = -8.1. The correlations for the 1-hydroxyl imply a surprisingly weak resonance interaction of +M substituents (MeO, Me) with a carbocation reaction center but are consistent with the corresponding correlation for acid-catalyzed dehydration of 3-substituted benzene-cis-1,2-dihydrodiols for which ρ = -6.9 and r = 0.43. Substituents at the 6- and 7-positions of the naphthalene rings by contrast are correlated by σ(+) with ρ = -3.2 for reaction of the 1-hydroxyl group and ρ = -2.7 for reaction of the 2-hydroxyl group. The unimpaired resonance implied by these substituent effects appears to be inconsistent with a previous explanation of the weak resonance of the 3-substituents in terms of imbalance of charge development and/or nonplanarity of the benzenium ring in the transition state. An alternative possibility is that the adjacent hydroxyl group interferes sterically with conjugation of +M substituents. "Hyperaromaticity" of the arenium ion intermediates does not appear to be a factor influencing this behavior.     

Conformational studies of the robust 2-Cys peroxiredoxin Salmonella typhimurium AhpC by solution phase hydrogen/deuterium (H/D) exchange monitored by electrospray ionization mass spectrometry

This is the first comprehensive HX-MS study of a "robust" 2-Cys peroxiredoxin (Prx), namely Salmonella typhimurium AhpC (StAhpC). Prx proteins control intracellular peroxide levels and are abundant antioxidant proteins in eukaryotes, archaea and bacteria. Crystal structural analyses and structure/activity studies of several bacterial and mammalian 2-Cys Prxs have revealed that the activity of 2-Cys Prxs is regulated by redox-dependent oligmerization and a sensitivity of the active site cysteine residue to overoxidation. The propensity to overoxidation is linked to the conformational flexibility of the peroxidatic active site loop. The HX-MS results emphasize the modulation of the conformational motility of the active site loop by disulfide formation. To obtain information on the conformational impact of decamer formation on the active site loop motility, mutants with Thr77 substituted by Ile, a decamer-disrupting mutation or by Val, a decamer-stabilizing mutation, were studied. For the isoleucine mutant, enhanced mobility was observed for regions encompassing the α4 helix located in the dimer-dimer interface and regions surrounding the peroxidatic loop. In contrast, the T77V mutation resulted in an increase in conformational stability in most regions of the protein except for the active site loop and the region encompassing the resolving cysteine.     

Nanocelluloses: a new family of nature-based materials

Cellulose fibrils with widths in the nanometer range are nature-based materials with unique and potentially useful features. Most importantly, these novel nanocelluloses open up the strongly expanding fields of sustainable materials and nanocomposites, as well as medical and life-science devices, to the natural polymer cellulose. The nanodimensions of the structural elements result in a high surface area and hence the powerful interaction of these celluloses with surrounding species, such as water, organic and polymeric compounds, nanoparticles, and living cells. This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.     

Nickel based electrocatalysts for oxygen evolution in high current density, alkaline water electrolysers

A number of nickel based materials are investigated as potential oxygen evolution catalysts under conditions close to those met in modern, high current density alkaline water electrolysers. Microelectrodes are used to avoid distortion of voltammetric data by IR drop even at the high current densities employed in such water electrolysers. High surface area nickel metal oxides prepared by cathodic deposition and mixed oxides prepared by thermal methods are considered. A mixed Ni/Fe oxide is the preferred electrocatalyst. The influence of hydroxide ion concentration and temperature on the voltammetry is defined. Preliminary stability tests in a zero gap cell with an OH(-) conducting membrane show no significant increase in overpotential during 10 days operation in 4 M NaOH electrolyte at a current density of 1 A cm(-2) at 333 K.     

The Problems of the Turbulent Burning Velocity

The paper reviews the practical problems in measuring a turbulent burning velocity that gives the mass rate of burning. These largely centre on identifying an appropriate flame surface to associate with the turbulent burning velocity, u _t , and the density of the unburned mixture. Such a flame surface has been identified, in terms of the mean reaction progress variable, $\bar {c}$ , for explosive flame propagation in a fan-stirred bomb. Measurement of $\bar {c}$ makes possible an estimation of the flame surface density, ??, from the relationship ${\it \Sigma} =k\bar {c}\left( {1-\bar {c}} \right)$ . It is shown that in such explosions, mass rates of burning derived from the measured total flame surface area agreed well with those found from the measured turbulent burning velocity. Flamelet considerations identify appropriate dimensionless correlating parameters for u _t . As a result, correlations of turbulent burning velocity divided by the effective rms turbulent velocity, are plotted against the turbulent Karlovitz stretch factor, K, for different values of the Markstein number for flame strain rate, Ma_sr. These plots cover a wide range of variables, including pressure and fuels, and are indicative of different regimes of turbulent combustion. At the lower values of K, there is some evidence of increases in u _t and k due to high-frequency flame surface wrinkling arising from flame instabilities. These increase as Ma_sr becomes more negative. It is found from the developed value of the mean flame surface density throughout the flame brush that, to a first approximation, an increase in u _t for a given mixture is accompanied by a proportional increase in the volume of the brush. The analysis shows that the volume fraction of the turbulent flame brush that is reacting is quite small.     

A Differential Harnack Inequality for the Newell-Whitehead-Segel Equation

This paper will develop a Li-Yau-Hamilton type differential Harnack estimate for positive solutions to the Newell-Whitehead-Segel equation on R^n.We then use our LYH-differential Harnack inequality to prove several properties about positive solutions to the equation,including deriving a classical Harnack inequality and characterizing standing solutions and traveling wave solutions.     

Finite mixture-of-gamma distributions: estimation,inference, and model-based clustering

Advances in Data Analysis and Classification - Finite mixtures of (multivariate) Gaussian distributions have broad utility, including their usage for model-based clustering. There is increasing...     

Sizing Large Hollow Micro-Balloons with the phase doppler interferometer

A combined theoretical and experimental study has been conducted to evaluate the effectiveness of using large, hollow micro-balloons as LDV seed particles. The study has focused on the ability of phase Doppler systems to size hollow microballoons, the ability of large micro-balloons to respond to high frequency spatial and temporal flow field variations, and the overall advantages and disadvantages of using large microballoons instead of conventional LDV seed particles, such as very small water droplets or polystyrene latex (PSL) particles. This paper discusses the development of a theoretical phase Doppler response model for stratified spheres, the experimental facility, and the theoretical and experimental results.