Nitrogen-Mediated Graphene Oxide Enables Highly Efficient Proton Transfer

Two-dimensional (2D) graphene and graphene oxide (GO) offer great potential as a new type of cost-efficient proton-exchange membranes (PEM) for electrochemical devices. However, fundamental issues of proton transfer mechanism via 2D membranes are unclear and the transfer barrier for perfect graphene are too high for practical application. Using ab initio molecular dynamic simulations, we screened the proton transfer barrier for different un-doped and nitrogen doped GO membranes, and clarified the corresponding transfer mechanisms. More significantly, we further identify that N-mediated GO can be built into a highly efficient PEM with a proton transfer rate of seven orders of magnitude higher than an un-doped case via. a proton relay mechanism between a ketone-like oxygen and a pyridine-like nitrogen across the vacancy site. The N-doped 2D GO is also impermeable to small molecules, and hence a highly efficient PEM for practical applications

Nanometric size effect on Ge diffusion in polycrystalline Si

The nanosize effect on Ge diffusion (850 \u3c = T \u3c = 1000 degrees C) in polycrystalline Si layers is investigated. The Ge diffusion coefficients in microcrystalline and nanocrystalline Si layers made of 30 mu m and 40 nm wide grains, respectively, are measured and compared. In the microcrystalline Si layer, the Ge diffusion coefficient in micrograin boundaries is measured using a conventional analytical solution of Fick\u27s equations corresponding to the Fisher model. In the nanocrystalline Si layer, the Ge diffusion coefficients in nanograins and in nanograin boundaries are measured via a method based on two-dimensional simulations using the Fisher model geometry. The diffusivities in nanograins and nanograin boundaries are one order of magnitude higher than in micrograins and micrograin boundaries, respectively. However, the nanosize effect appears to be different in grains and grain boundaries; despite that the activation energy for diffusion in 40 nm wide grains is at least 1 eV lower than in Si bulk. The activation energy in nanograin boundaries is about the same as in micrograin boundaries

Mass transport phenomena between bubbles and dissolved gases in liquids under reduced gravity conditions

The experimental and analytical work that was done to establish justification and feasibility for a shuttle middeck experiment involving mass transfer between a gas bubble and a liquid is described. The experiment involves the observation and measurement of the dissolution of an isolated immobile gas bubble of specified size and composition in a thermostatted solvent liquid of known concentration in the reduced gravity environment of earth orbit. Methods to generate and deploy the bubble were successful both in normal gravity using mutually buoyant fluids and under reduced gravity conditions in the NASA Lear Jet. Initialization of the experiment with a bubble of a prescribed size and composition in a liquid of known concentration was accomplished using the concept of unstable equilibrium. Subsequent bubble dissolution or growth is obtained by a step increase or decrease in the liquid pressure. A numerical model was developed which simulates the bubble dynamics and can be used to determine molecular parameters by comparison with the experimental data. The primary objective of the experiment is the elimination of convective effects that occur in normal gravity

Pion-nucleus optical potential valid up to the DELTA-resonance region

We present in this article an optical potential for the $\pi$-nucleus interaction that can be used in various studies involving $\pi$-nucleus channels. Based on earlier treatments of the low energy $\pi$-nucleus optical potential, we have derived a potential expression applicable from threshold up to the $\Delta$-resonance region. We extracted the impulse approximation form for this potential from the $\pi-N$ scattering amplitude and then added to it kinematical and physical corrections. The kinematic corrections arise from transforming the impulse approximation expression from the $\pi-N$ center of mass frame to the $\pi$-nucleus center of mass frame, while the physical corrections arise mostly from the many-body nature of the $\pi$-nucleus interaction. By taking advantage of the experimental progress in our knowledge of the $\pi-N$ process, we have updated earlier treatments with parameters calculated from state-of-the-art experimental measurements.Comment: 23 pages, 12 figures. Accepted for publication in Physical Review

Pore-scale direct numerical simulation of particle transport in porous media

A computational platform for direct numerical simulation of fluid-particle two-phase flow in porous media is presented in this study. In the proposed platform, the Navier-Stokes equations are used to describe the motion of the continuous phase, while the discrete element method (DEM) is employed to evaluate particle-particle and particle-wall interactions, with a fictitious domain method being adopted to evaluate particle-fluid interactions. Particle-wall contact states are detected by the ERIGID scheme. Moreover, a new scheme, namely, base point-increment method is developed to improve the accuracy of particle tracking in porous media. In order to improve computationally efficiency, a time splitting strategy is applied to couple the fluid and DEM solvers, allowing different time steps to be used which are adaptively determined according to the stability conditions of each solver. The proposed platform is applied to particle transport in a porous medium with its pore structure being reconstructed from micro-CT scans from a real rock. By incorporating the effect of pore structure which has a comparable size to the particles, numerical results reveal a number of distinct microscopic flow mechanisms and the corresponding macroscopic characteristics. The time evolution of the inlet to outlet pressure-difference consists of large-scale spikes and small-scale fluctuations. Apart from the influence through direct contacts between particles, the motion of a particle can also be affected by particles without contact through blocking a nearby passage for fluid flow. Particle size has a profound influence on the macroscopic motion behavior of particles. Small particles are easier to move along the main stream and less dispersive in the direction perpendicular to the flow than large particles

In-situ electrochemical modification of pre-intercalated vanadium bronze cathodes for aqueous zinc-ion batteries

Vanadium bronzes have been well-demonstrated as promising cathode materials for aqueous zinc-ion batteries. However, conventional single-ion pre-intercalated V2O5 nearly reached its energy/power ceiling due to the nature of micro/electronic structures and unfavourable phase transition during Zn2+ storage processes. Here, a simple and universal in-situ anodic oxidation method of quasi-layered CaV4O9 in a tailored electrolyte was developed to introduce dual ions (Ca2+ and Zn2+) into bilayer δ-V2O5 frameworks forming crystallographic ultra-thin vanadium bronzes, Ca0.12Zn0.12V2O5·nH2O. The materials deliver transcendental maximum energy and power densities of 366 W h kg−1 (478 mA h g−1 @ 0.2 A g−1) and 6627 W kg−1 (245 mA h g−1 @ 10 A g−1), respectively, and the long cycling stability with a high specific capacity up to 205 mA h g−1 after 3000 cycles at 10 A g−1. The synergistic contributions of dual ions and Ca2+ electrolyte additives on battery performances were systematically investigated by multiple in-/ex-situ characterisations to reveal reversible structural/chemical evolutions and enhanced electrochemical kinetics, highlighting the significance of electrolyte-governed conversion reaction process. Through the computational approach, reinforced “pillar” effects, charge screening effects and regulated electronic structures derived from pre-intercalated dual ions were elucidated for contributing to boosted charge storage properties

Purification, Cloning, Characterization and Essential Amino Acid Residues Analysis of a New iota-Carrageenase from Cellulophaga sp QY3

ι-Carrageenases belong to family 82 of glycoside hydrolases that degrade sulfated galactans in the red algae known as ι-carrageenans. The catalytic mechanism and some substrate-binding residues of family GH82 have been studied but the substrate recognition and binding mechanism of this family have not been fully elucidated. We report here the purification, cloning and characterization of a new ι-carrageenase CgiA_Ce from the marine bacterium Cellulophaga sp. QY3. CgiA_Ce was the most thermostable carrageenase described so far. It was most active at 50°C and pH 7.0 and retained more than 70% of the original activity after incubation at 50°C for 1 h at pH 7.0 or at pH 5.0–10.6 for 24 h. CgiA_Ce was an endo-type ι-carrageenase; it cleaved ι-carrageenan yielding neo-ι-carrabiose and neo-ι-carratetraose as the main end products, and neo-ι-carrahexaose was the minimum substrate. Sequence analysis and structure modeling showed that CgiA_Ce is indeed a new member of family GH82. Moreover, sequence analysis of ι-carrageenases revealed that the amino acid residues at subsites −1 and +1 were more conserved than those at other subsites. Site-directed mutagenesis followed by kinetic analysis identified three strictly conserved residues at subsites −1 and +1 of ι-carrageenases, G228, Y229 and R254 in CgiA_Ce, which played important roles for substrate binding. Furthermore, our results suggested that Y229 and R254 in CgiA_Ce interacted specifically with the sulfate groups of the sugar moieties located at subsites −1 and +1, shedding light on the mechanism of ι-carrageenan recognition in the family GH82

Erosion-deposition patterns and depo-center movements in branching channels at the near-estuary reach of the Yangtze River

Channel evolution and depo-center migrations in braided reaches are significantly influenced by variations in runoff. This study examines the effect of runoff variations on the erosion-deposition patterns and depocenter movements within branching channels of the near-estuary reach of the Yangtze River. We assume that variations in annual mean duration days of runoff discharges, ebb partition ratios in branching channels, and the erosional/depositional rates of entire channels and sub-reaches are representative of variations in runoff intensity, flow dynamics in branching channels, and morphological features in the channels. Our results show that the north region of Fujiangsha Waterway, the Liuhaisha branch of Rugaosha Waterway, the west branch of Tongzhousha Waterway, and the west branch of Langshansha Waterway experience deposition or reduced erosion under low runoff intensity, and erosion or reduced deposition under high runoff intensity, with the depocenters moving upstream and downstream, respectively. Other waterway branches undergo opposite trends in erosion-deposition patterns and depo-center movements as the runoff changes. These morphological changes may be associated with trends in ebb partition ratio as the runoff discharge rises and falls. By flattening the intra-annual distribution of runoff discharge, dam construction in the Yangtze Basin has altered the ebb partition ratios in waterway branches, affecting their erosion-deposition patterns and depo-center movements. Present trends are likely to continue into the future due to the succession of large cascade dams under construction along the upper Yangtze and ongoing climate change

Regulation of the flowering time of Arabidopsis thaliana by thylakoid ascorbate peroxidase

Flowering time of higher plants is precisely controlled by various exogenous and endogenous factors. Recent researches implied that H2O2 is a potential flowering initiation factor. In order to confirm this hypothesis, thylakoid ascorbate peroxidase (tAPX) overexpressing Arabidopsis, the mutant line containing a T-DNA insertion and the wild type have been analyzed in this study, since APX was an important enzyme scavenging H2O2 in plant cells. It was found that during the vegetative growth stage there was no phenotypic difference among the three lines under common conditions, but 3,3’-diaminobenzidinetetrahydrochloride (DAB) staining showed that the endogenous H2O2 content varied: the mutant line had the highest content; the wild type took the second place, while the tAPX-overexpressing line had the lowest H2O2 content. This trend was in accordance with the bolting and flowering time during the following reproductive growth stage: the mutant bolted and flowered first, followed by the wild type, and the overexpressing line bolted and flowered last. This correlation confirmed the previous hypothesis that “H2O2 is a possible factor in flowering induction”.Keywords: Ascorbate peroxidase, Arabidopsis thaliana, flowering time, hydrogen peroxide