Sorption and desorption of sulfuryl fluoride by wheat, flour and semolina

Sulfuryl fluoride (SF) has been developed as a fumigant for control of insect pests in stored grain. However, there is very limited information on the sorption behaviour of this fumigant, which can be critical to its bioactivity, application and potential for residues. We undertook a comprehensive laboratory study of the sorption and desorption of SF by wheat (bread and durum), flour and semolina at 15, 25 and 35 °C, moisture contents 12% and 15%, and concentration × time combinations at CT = 1500 mgh/L (4.167 mg/L × 360 h, 8.928 mg/L × 168 h and 31.25 mg/L × 48 h). At each dosage, sorption rate increased as commodity temperature and moisture content increased. The highest rates of sorption occurred at 35 °C and 15% m.c., and lowest rates at 15 °C and 12% m.c., and the rate was independent of initial concentration. Sorption followed first order reaction kinetics described by the exponential decay equation, Ct = C0·e−k*t, where k is the sorption rate constant. The most important factors determining the rate of sorption were commodity particle size (exposed surfaces) and temperature. Little sorption of fumigant occurred within the first 24 h whereas longer fumigation times resulted in significant sorption. Unbound SF was rapidly lost from the commodity upon aeration with no further desorption detected under any of the test conditions.

Some Studies on Hydrogen-Oxygen Diffusion Flame

The opposed-jet diffusion flame has been considered with four step reaction kinetics for hydrogenoxygen system. The studies have revealed that the flame broadening reduces and maximum temperature increases as pressure increases. The relative importance of different reaction steps have been brought out in different regions (unstable, near extinction and equilibrium). The present studies have also led to the deduction of the oveall reaction rate constants of an equivalent single step reaction using matching of a certain overall set of parameters for four step reaction scheme and equivalent single step reaction.

Characterization of the restriction enzyme-like endonuclease encoded by the Entamoeba histolytica non-long terminal repeat retrotransposon EhLINE1

The genome of the human pathogen Entamoeba histolytica, a primitive protist, contains non-long terminal repeat retrotransposable elements called EhLINEs. These encode reverse transcriptase and endonuclease required for retrotransposition. The endonuclease shows sequence similarity with bacterial restriction endonucleases. Here we report the salient enzymatic features of one such endonuclease. The kinetics of an EhLINE1-encoded endonuclease catalyzed reaction, determined under steady-state and single-turnover conditions, revealed a significant burst phase followed by a slower steady-state phase, indicating that release of product could be the slower step in this reaction. For circular supercoiled DNA the K-m was 2.6 x 10-8 m and the k(cat) was 1.6 x 10-2 sec-1. For linear E. histolytica DNA substrate the K-m and k(cat) values were 1.3 x 10-8 m and 2.2 x 10-4 sec-1 respectively. Single-turnover reaction kinetics suggested a noncooperative mode of hydrolysis. The enzyme behaved as a monomer. While Mg2+ was required for activity, 60% activity was seen with Mn2+ and none with other divalent metal ions. Substitution of PDX12-14D (a metal-binding motif) with PAX(12-14)D caused local conformational change in the protein tertiary structure, which could contribute to reduced enzyme activity in the mutated protein. The protein underwent conformational change upon the addition of DNA, which is consistent with the known behavior of restriction endonucleases. The similarities with bacterial restriction endonucleases suggest that the EhLINE1-encoded endonuclease was possibly acquired from bacteria through horizontal gene transfer. The loss of strict sequence specificity for nicking may have been subsequently selected to facilitate spread of the retrotransposon to intergenic regions of the E. histolytica genome.

Two-dimensional tin disulfide nanosheets for enhanced sodium storage

Sodium-ion batteries (SIBs) are considered as complementary alternatives to lithium-ion batteries for grid energy storage due to the abundance of sodium. However, low capacity, poor rate capability, and cycling stability of existing anodes significantly hinder the practical applications of SIBs. Herein, ultrathin two-dimensional SnS2 nanosheets (3-4 nm in thickness) are synthesized via a facile refluxing process toward enhanced sodium storage. The SnS2 nanosheets exhibit a high apparent diffusion coefficient of Na+ and fast sodiation/desodiation reaction kinetics. In half-cells, the nanosheets deliver a high reversible capacity of 733 mAh g-1 at 0.1 A g-1, which still remains up to 435 mAh g-1 at 2 A g-1. The cell has a high capacity retention of 647 mA h g-1 during the 50th cycle at 0.1 A g-1, which is by far the best for SnS2, suggesting that nanosheet morphology is beneficial to improve cycling stability in addition to rate capability. The SnS2 nanosheets also show encouraging performance in a full cell with a Na3V2(PO4)3 cathode. In addition, the sodium storage mechanism is investigated by ex situ XRD coupled with high-resolution TEM. The high specific capacity, good rate capability, and cycling durability suggest that SnS2 nanosheets have great potential working as anodes for high-performance SIBs. © 2015 American Chemical Society.

Low-Temperature Processing of ZrB2-ZrC Composites by Reactive Hot Pressing

Dense ZrB2-ZrC and ZrB2-ZrC x∼0.67 composites have been produced by reactive hot pressing (RHP) of stoichiometric and nonstoichiometric mixtures of Zr and B4C powders at 40 MPa and temperatures up to 1600 °C for 30 minutes. The role of Ni addition on reaction kinetics and densification of the composites has been studied. Composites of ∼97 pct relative density (RD) have been produced with the stoichiometric mixture at 1600 °C, while the composite with ∼99 pct RD has been obtained with excess Zr at 1200 °C, suggesting the formation of carbon deficient ZrC x that significantly aids densification by plastic flow and vacancy diffusion mechanism. Stoichiometric and nonstoichiometric composites have a hardness of ∼20 GPa. The grain sizes of ZrB2 and ZrC x∼0.67 are ∼0.6 and 0.4 μm, respectively, which are finer than those reported in the literature.

Optimum atomic spacing for AlAs etching in GaAs epitaxial lift-off technology

With respect to GaAs epitaxial lift-off technology, we report here the optimum atomic spacing (5-10 nm) needed to etch off the AlAs release layer that is sandwiched between two GaAs epitaxial layers. The AlAs etching rate in hydrofluoric acid based solutions was monitored as a function of release layer thickness. We found a sudden quenching in the etching rate, approximately 20 times that of the peak value, at lower dimensions (similar to2.5 nm) of the AlAs epitaxial layer. Since this cannot be explained on the basis of a previous theory (inverse square root of release layer thickness), we propose a diffusion-limited mechanism to explain this reaction process. With the diffusion constant being a mean-free-path-dependent parameter, a relation between the mean free path and the width of the channel is considered. This relation is in reasonable agreement with the experimental results and gives a good physical insight to the reaction kinetics.

Methanation of CO2 over Ru?SiO2 catalyst

Using Ru - SiO2 catalyst, the kinetics of methanation of carbon dioxide has been studied. In the temperature range of 320-460-degrees-C a simple power law model is found to predict experimental results with a good agreement over the range of variables studied.

Realtime kinetic analysis of antigen-antibody interaction using solid phase binding: Transformation of hCG-monoclonal antibody complex

Kinetic constants of MAb-hCG interactions have been determined using solid phase binding of I-125[hCG] to immobilized MAb. While association has been shown to follow the expected pattern, dissociation consists of at least two reversible steps, one with a rate constant of 0.0025 min(-1), and a second with a rate constant of 0.00023 min(-1). Validity of affinity constant measurements in the light of the complex reaction kinetics is discussed, A comparison between the method of surface plasmon resonance technology (BIAcore) and solid phase binding (SPB) for determination of kinetic parameters shows that SPB provides not only a cost-effective approach for determination of realtime kinetic parameters of macromolecular ligand-ligate interaction but also a method with several advantages over the BIAcore system in investigating the mechanism of antigen-antibody interaction.

An improved-performance liquid-feed solid-polymer-electrolyte direct methanol fuel cell operating at near-ambient conditions

Results on the performance of a 25 cm(2) liquid-feed solid-polymer-electrolyte direct methanol fuel cell (SPE-DMFC), operating under near-ambient conditions, are reported. The SPE-DMFC can yield a maximum power density of c. 200 mW cm(-2) at 90 C while operating with 1 M aqueous methanol and oxygen under ambient pressure. While operating the SPE-DMFC under similar conditions with air, a maximum power density of ca. 100 mW cm(-2) is achieved. Analysis of the electrode reaction kinetics parameters on the methanol electrode suggests that the reaction mechanism for methanol oxidation remains invariant with temperature. Durability data on the SPE-DMFC at an operational current density of 100 mA cm(-2) have also been obtained.

Study of formation of silicon carbide in the Acheson process

Formation of silicon carbide in the Acheson process was studied using a mass transfer model which has been developed in this study. The century old Acheson process is still used for the mass production of silicon carbide. A heat resistance furnace is used in the Acheson process which uses sand and petroleum coke as major raw materials.: It is a highly energy intensive process. No mass transfer model is available for this process. Therefore, a mass transfer model has been developed to study the mass transfer aspects of the process along with heat transfer. The reaction kinetics of silicon carbide formation has been taken from the literature. It has been shown that reaction kinetics has a reasonable influence on the process efficiency. The effect of various parameters on the process such as total gas pressure, presence of silicon carbide in the initial charge, etc. has been studied. A graphical user interface has also been developed for the Acheson process to make the computer code user friendly.

Water quality parameter estimation in steady-state distribution system

The maintenance of chlorine residual is needed at all the points in the distribution system supplied with chlorine as a disinfectant. The propagation and level of chlorine in a distribution system is affected by both bulk and pipe wall reactions. It is well known that the field determination of wall reaction parameter is difficult. The source strength of chlorine to maintain a specified chlorine residual at a target node is also an important parameter. The inverse model presented in the paper determines these water quality parameters, which are associated with different reaction kinetics, either in single or in groups of pipes. The weighted-least-squares method based on the Gauss-Newton minimization technique is used for the estimation of these parameters. The validation and application of the inverse model is illustrated with an example pipe distribution system under steady state. A generalized procedure to handle noisy and bad (abnormal) data is suggested, which can be used to estimate these parameters more accurately. The developed inverse model is useful for water supply agencies to calibrate their water distribution system and to improve their operational strategies to maintain water quality.

Conformational Basis for Substrate Recruitment in Protein Tyrosine Phosphatase 10D

The coordinated activity of protein tyrosine phosphatases (PTPs) is crucial for the initiation, modulation, and termination of diverse cellular processes. The catalytic activity of this protein depends on a nucleophilic cysteine at the active site that mediates the hydrolysis of the incoming phosphotyrosine substrate. While the role of conserved residues in the catalytic mechanism of PTPs has been extensively examined, the diversity in the mechanisms of substrate recognition and modulation of catalytic activity suggests that other, less conserved sequence and structural features could contribute to this process. Here we describe the crystal structures of Drosophila melanogaster PTP10D in the apo form as well as in a complex with a substrate peptide and an inhibitor. These studies reveal the role of aromatic ring stacking interactions at the boundary of the active site of PTPs in mediating substrate recruitment. We note that phenylalanine 76, of the so-called KNRY loop, is crucial for orienting the phosphotyrosine residue toward the nucleophilic cysteine. Mutation of phenylalanine 76 to leucine results in a 60-fold decrease in the catalytic efficiency of the enzyme. Fluorescence measurements with a competitive inhibitor, p-nitrocatechol sulfate, suggest that Phe76 also influences the formation of the enzyme-substrate intermediate. The structural and biochemical data for PTP10D thus highlight the role of relatively less conserved residues in PTP domains in both substrate recruitment and modulation of reaction kinetics.

Environmental remediation by photocatalysis

Photocatalysis refers to the oxidation and reduction reactions on semiconductor surfaces, mediated by the valence band holes and conduction band electrons, which are generated by the absorption of ultraviolet or visible light radiation. Photocatalysis is widely being practiced for the degradation and mineralization of hazardous organic compounds to CO2 and H2O, reduction of toxic metal ions to their non-toxic states, deactivation and destruction of water borne microorganisms, decomposition of air pollutants like volatile organic compounds, NOx, CO and NH3, degradation of waste plastics and green synthesis of industrially important chemicals. This review attempts to showcase the well established mechanism of photocatalysis, the use of photocatalysts for water and air pollution control,visible light responsive modified-TiO2 and non-TiO2 based materials for environmental and energy applications, and the importance of developing reaction kinetics for a comprehensive understanding and design of the processes.

Endurance of Nafion-composite membranes in PEFCs operating at elevated temperature under low relative-humidity

PEFCs employing Nafion-silica (Nafion-SiO2) and Nafion-mesoporous zirconium phosphate (Nafion-MZP) composite membranes are subjected to accelerated-durability test at 100 degrees C and 15% relative humidity (RH) at open-circuit voltage (OCV) for 50 h and performance compared with the PEFC employing pristine Nafion-1135 membrane. PEFCs with composite membranes sustain the operating voltage better with fluoride-ion-emission rate at least an order of magnitude lower than PEFC with pristine Nafion-1135 membrane. Reduced gas-crossover, fast fuel-cell-reaction kinetics and superior performance of the PEFCs with Nafion-SiO2 and Nafion-MZP composite membranes in relation to the PEFC with pristine Nafion-1135 membrane support the long-term operational usage of the former in PEFCs. An 8-cell PEFC stack employing Nafion-SiO2 composite membrane is also assembled and successfully operated at 60 degrees C without external humidification.

Preferential oxidation of CO on Ni/CeO2 catalysts in the presence of excess H-2 and CO2

Preferential oxidation of CO (CO-PROX) was carried out over Ni supported on CeO2 prepared by the co-precipitation method. The influence of metal loadings (2.5, 5 and 10 wt.% Ni) and the reaction conditions such as reaction temperature and feed composition on CO oxidation and oxidation selectivity were evaluated by using dry reformate gas. No other reactions like CO or CO2 methanation, coking, reverse water gas shift (RWGS) reaction is observed in the temperature range of 100-200 A degrees C on these catalysts. Hydrogen oxidation dominates over CO oxidation above the temperature of 200 A degrees C. An increase in oxygen leads to an increase in CO conversion but a simultaneous decrease in the O-2 selectivity. It has been noticed that 5 and 10 % Ni/CeO2 show better catalytic activity towards CO-PROX reaction. These catalysts were characterized by S-BET, XRD, TEM, XPS and H-2-TPR.