Multifunctional catalytic sites regulation of atomic-scale iridium on orthorhombic-CoSe_(2)for high efficiency dual-functional alkaline hydrogen evolution and organic degradation

The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporating iridium(Ir)ions on the atomic scale into orthorhombic-CoSe2(Ir-CoSe_(2))was reported.Outstanding hydrogen evolution activity in alkaline media such as a low overpotential of 48.7 mV at a current density of 10 mA cm^(-2)and better performance than commercial Pt/C catalysts at high current densities were found in the Ir-CoSe_(2) samples.In the experiments and theoretical calculations,it was revealed that Ir enabled CoSe_(2)to form multifunctional sites to synergistically catalyze alkaline HER by promoting the adsorption and dissociation of H_(2)O(Ir sites)and optimizing the binding energy for H^(*)on Co sites.It was noticeable that the electrolytic system comprising the Ir-CoSe_(2)electrode not only produced hydrogen efficiently via HER,but also degraded organic pollutants(Methylene blue).The cell voltage of the dual-function electrolytic system was 1.58 V at the benchmark current density of 50 mA cm^(-2),which was significantly lower than the conventional water splitting voltage.It was indicated that this method was a novel strategy for designing advanced HER electrocatalysts by constructing multifunctional catalytic sites for hydrogen production and organic degradation.

Proposal of a Deuterium-Deuterium Fusion Reactor Intended for a Large Power Plant

This article looks for the necessary conditions to use Deuterium-Deuterium (D-D) fusion for a large power plant. At the moment, for nearly all the projects (JET, ITER…) only the Deuterium-Tritium (D-T) fuel is considered for a power plant. However, as shown in this article, even if a D-D reactor would be necessarily much bigger than a D-T reactor due to the much weaker fusion reactivity of the D-D fusion compared to the D-T fusion, a D-D reactor size would remain under an acceptable size. Indeed, a D-D power plant would be necessarily large and powerful, i.e. the net electric power would be equal to a minimum of 1.2 GWe and preferably above 10 GWe. A D-D reactor would be less complex than a D-T reactor as it is not necessary to obtain Tritium from the reactor itself. It is proposed the same type of reactor yet proposed by the author in a previous article, i.e. a Stellarator “racetrack” magnetic loop. The working of this reactor is continuous. It is reminded that the Deuterium is relatively abundant on the sea water, and so it constitutes an almost inexhaustible source of energy. Thanks to secondary fusions (D-T and D-He3) which both occur at an appreciable level above 100 keV, plasma can stabilize around such high equilibrium energy (i.e. between 100 and 150 keV). The mechanical gain (Q) of such reactor increases with the internal pipe radius, up to 4.5 m. A radius of 4.5 m permits a mechanical gain (Q) of about 17 which thanks to a modern thermo-dynamical conversion would lead to convert about 21% of the thermal power issued from the D-D reactor in a net electric power of 20 GWe. The goal of the article is to create a physical model of the D-D reactor so as to estimate this one without the need of a simulator and finally to estimate the dimensions, power and yield of such D-D reactor for different net electrical powers. The difficulties of the modeling of such reactor are listed in this article and would certainly be applicable to a future D-He3 reactor, if any.

Diverse O-methyltransferases catalyze the biosynthesis of floral benzenoids that repel aphids from the flowers of waterlily Nymphaea prolifera

Nymphaea is a key genus of the ANA grade(Amborellales,Nymphaeales,and Austrobaileyales)of basal flowering plants,which serve as a key model to study the early evolution of floral traits.In this study,we comprehensively investigated the emission,biosynthesis,and biological function of the floral scent in a night-blossoming waterlily Nymphaea prolifera.The headspace volatile collection combined with GC-MS analysis showed that the floral scent of N.prolifera is predominately comprised by methylated benzenoids including anisole,veratrole,guaiacol,and methoxyanisole.Moreover,the emission of these floral benzenoids in N.prolifera exhibited temporal and spatial pattern with circadian rhythm and tissue specificity.By creating and mining transcriptomes of N.prolifera flowers,12 oxygen methyltransferases(NpOMTs)were functionally identified.By in vitro enzymatic assay,NpOMT3,6,and 7 could produce anisole and NpOMT5,7,9,produce guaiacol,whereas NpOMT3,6,9,11 catalyzed the formation of veratrole.Methoxyanisole was identified as the universal product of all NpOMTs.Expression patterns of NpOMTs provided implication for their roles in the production of the respective benzenoids.Phylogenetic analysis of OMTs suggested a Nymphaea-specific expansion of the OMT family,indicating the evolution of lineage-specific functions.In bioassays,anisole,veratrole,and guaiacol in the floral benzenoids were revealed to play the critical role in repelling waterlily aphids.Overall,this study indicates that the basal flowering plant N.prolifera has evolved a diversity and complexity of OMT genes for the biosynthesis of methylated benzenoids that can repel insects from feeding the flowers.These findings provide new insights into the evolutional mechanism and ecological significance of the floral scent from early-diverged flowering plants.

Degradation of amyloid β-peptides catalyzed by nattokinase in vivo and in vitro

Amyloid-β 1-42(Aβ42)plays a pivotal role in Alzheimer disease(AD)pathogenesis. Peripheral clearance of Aβ42 largely affects its level in the brain and affects AD progression. Although nattokinase(NK)degrades Aβ40, the details of NK's capture of various Aβ species and reduction of plasma Aβ42/Aβ40 are uncharacterized. In this study, the Aβ42/Aβ40-degrading ability of NK was investigated using five Aβs and AD model mice. The C-terminal region of Aβ42/Aβ40(Gly29 to Val40)was primarily required for NK capture, and the integrated conformation in Aβ42/Aβ40 aggregates was a more efficient target for NK catalysis. Further, suspended Aβ42/Aβ40 oligomers were more easily captured by NK than suspended Aβ42/Aβ40 fibrils, while deposited Aβ42/Aβ40 fibrils recruited more NK than deposited Aβ42/Aβ40 oligomers. Although most NK was likely lost during NK uptake and/or entry into the blood, a small fraction of NK showed good plasma Aβ42/Aβ40-degrading efficacy after entering the blood due to NK's stability in the plasma of AD mice for at least 9 days. It was concluded that oral administration of NK is a feasible approach for peripheral Aβ42/Aβ40 clearance. This implies that NK might serve as an anti-Aβ42 agent for the treatment of Aβ42/Aβ40-related diseases such as AD.

Preparation of Conjugated Linoleic Acid of High Purity and Its Apparent Kinetic Characteristics During Formation

Conjugated linoleic acid (CLA) is a fatty acid with physiological activities and potential application prospect. This paper focuses on the method of synthesis of conjugated linoleic acid of high purity and the process line and conditions for its purification that can be used in large scale production. CLA of more than 95% purity was prepared by means of urea adduct purification and conjugation using safflower oil as material. The total recovery of the product adds up to more than 48%. The reactive kinetics about linoleic acid from sunflower oil converted into CLA was investigated, and its apparent kinetic model was also established, which can be used as a base for industrial designs.

A review of the direct oxidation of methane to methanol

This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.

A Molecular Hydrogen Production Model from Li and LiH in the Early Universe

Neutral isotopes and ions of H, He and Li define the chemistry of the early universe by collisional and radiative process, where under low temperature and radiation regime, only neutral species were essential in the cooling mass that gave origin to the first proto star structures. Nevertheless, up to now, in every kinetic model Li is permanently discarded from fundamental reactions due to its extremely low density. Contrarily to these previous models we have developed a novel kinetic model based on two consecutive reactions of Li and LiH with H, in order to generate a recursive process that fit well H2 production to temperatures as low as 200 K, according to the cosmological time at the end of the dark epoch. Our results show how Li and LiH merge as first catalyzers of the H to H2 chemical reaction and permit us to explain the expected abundance of H2 as the main coolant in the early universe as well as in cold regions of the cosmos.

Dechlorination of carbon tetrachloride by the catalyzed Fe-Cu process

The dectrochemical reduction characteristics of carbon tetrachlofide （CT） were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders＇ iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders＇ iron. The entire CT in 350 ml aqueous solution with 320 mg/L was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with Fe/Cu ratio of 10：1 （w/w） were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were different. The degradation rate was not significantly influenced by pH in the catalyzed Fe-Cu process; in Master Builders＇ iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders＇ iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode （Cu） and anode （Fe） compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.

Multivariate Statistical Process Monitoring of an Industrial Polypropylene Catalyzer Reactor with Component Analysis and Kernel Density Estimation

Abstract Data-driven tools, such as principal component analysis （PCA） and independent component analysis （ICA） have been applied to different benchmarks as process monitoring methods. The difference between the two methods is that the components of PCA are still dependent while ICA has no orthogonality constraint and its latentvariables are independent. Process monitoring with PCA often supposes that process data or principal components is Gaussian distribution. However, this kind of constraint cannot be satisfied by several practical processes. To ex-tend the use of PCA, a nonparametric method is added to PCA to overcome the difficulty, and kernel density estimation （KDE） is rather a good choice. Though ICA is based on non-Gaussian distribution intormation, .KDE can help in the close monitoring of the data. Methods, such as PCA, ICA, PCA.with .KDE（KPCA）, and ICA with KDE,（KICA）, are demonstrated and. compared by applying them to a practical industnal Spheripol craft polypropylene catalyzer reactor instead of a laboratory emulator.

Dyes wastewater treatment by reduction-oxidation process in an electrochemical reactor packed with natural manganese mineral

A novel technology which combined electrochemical process catalyzed by manganese mineral with electro-assisted coagulation process was proposed in this study. The mineralization of organic pollutant from simulated dye wastewater containing an azo dye Acid Red B（ARB） was experimentally investigated using this method. It was found that the manganese mineral could catalyze the electrochemical process dramatically. The TOC removal percentage of electrochemical treatment catalyzed by manganese mineral was 43.6% while the TOC removal percentage of the process using the manganese mineral alone and using the electrolysis alone were 9.3% and 20.8%, respectively. Moreover, it was found that combined electroxidation with electro-assisted coagulation process could more effectively eliminate ARB. After a period of 180 min electrooxidation and 300 min electroreduction, almost 66.9% of TOC was removed, and the dissolved Mn^2＋. could be effectivly removed. The effects of the order of oxidation and reduction, the proper ratio electrooxidation/reduction time, and current density on the removal efficiency were investigated in detail. In addition, a proposed mechanism of manganese-mineral-catalyzed electrooxidation-reduction process was discussed in this paper.

Electrochemical reduction characteristics and mechanism of nitrobenzene compounds in the catalyzed Fe-Cu process

The reduction of the nitrobenzene compounds （NBCs） by the catalyzed Fe-Cu process and the relationship between the electrochemical reduction characteristics of NBCs at copper electrode and reduction rate were studied in alkaline medium（pH=11）. The catalyzed Fe-Cu process was found more effective on degradation of NBCs compared to Master Builder＇s iron. The reduction rate by the catalyzed Fe-Cu process decreased in the following order： nitrobenzene 〉4-chloro-nitrobenzene ≥m-dinitrobenzene ：〉 4-nitrophenol ≥2,4-dinitrotoluene 〉2-nitrophenol. The reduction rate by Master Builder＇s iron decreased in the following order： m-dinitrobenzene ≥4-chloro-nitrobenzene 〉4-nitrophenol 〉2,4-dinitrotoluene ≈nitrobenzene 〉2-nitrophenol. NBCs were reduced directly on the surface of copper rather than by the hydrogen produced at cathode in the catalyzed Fe-Cu process. The reduction was realized by the hydrogen produced at cathode and Fe（OH）2 in Master Builder＇s iron, It is an essential difference in reaction mechanisms between these two technologies. For this reason, the reduction by the catalyzed Fe-Cu depended greatly on NBC＇s electron withdrawing ability.

Catalytic oxidation of calcium sulfite in solution/aqueous slurry

Forced oxidation of calcium sulfite aqueous slurry is a key step for the calcium-based flue gas desulfurization(FGD) residue. Experiments were conducted in a semi-batch system and a continuous flow system on lab scales. The main reactor in semi-batch system is a 1000 ml volume flask. It has five necks for continuous feeding of gas and a batch of calcium sulfite solution/aqueous slurry. In continuous flow system, the main part is a jacketed Pyrex glass reactor in which gas and solution/aqueous slurry are fed continuously. Calcium sulfite oxidation is a series of complex free-radical reactions. According to experimental results and literature data, the reactions are influenced significantly by manganese as catalyst. At low concentration of manganese and calcium sulfite, the reaction rate is dependent on 1.5 order of sulfite concentration, 0.5 order of manganese concentration, and zero order of oxygen concentration in which the oxidation is controlled by chemical kinetics. With concentrations of calcium sulfite and manganese increasing, the reactions are independent gradually on the constituents in solution but are impacted by oxygen concentration. Manganese can accelerate the free-radical reactions, and then enhances the mass transfer of oxygen from gas to liquid. The critical concentration of calcium sulfite is 0.007 mol/L, manganese is 10 -4 mol/L, and oxygen is of 0.2—0.4 atm.

Thermal decomposition of ammonium perchlorate catalyzed with CuO nanoparticles

Ammonium perchlorate(APC)is the most common oxidizer in use for solid rocket propulsion systems.However its initial thermal decomposition is an endothermic process that requires 102.5 J·g^-1.This manner involves high activation energy and could render high burning rate regime.This study reports on the sustainable fabrication of CuO nanoparticles as a novel catalyzing agent for APC oxidizer.Colloidal CuO nanoparticles with consistent product quality were fabricated by using hydrothermal processing.TEM micrographs demonstrated mono-dispersed particles of 15 nm particle size.XRD diffractogram demonstrated highly crystalline material.The synthesized colloidal CuO particles were effectively coated with APC particles via co-precipitation by using fast-crash solvent-antisolvent technique.The impact of copper oxide particles on APC thermal behavior has been investigated using DSC and TGA techniques.APC demonstrated an initial endothermic decomposition stage at 242℃ with subsequent two exothermic decomposition stages at 297,8℃ and 452.8℃ respectively.At 1 wt%,copper oxide offered decrease in initial endothermic decomposition stage by 30%.The main outcome of this study is that the two main exothermic decomposition peaks were merged into one single peak with an increase in total heat release by 53%.These novel features can inherit copper oxide particles unique catalyzing ability for advanced highly energetic systems.

A new approach to the synthesis of diacetals(diketals) pentaerythritol catalyzed by SO_3H-functionalized ionic liquids

In this article,an efficient,simple and environmentally friendly approach to the synthesis of diacetals(diketals) pentaerythritol using SOH-functionalized ionic liquids(ILs) as catalysts was reported.The ILs show high catalytic activity and reusability with good to excellent yields of the desired products.Hammett method has been used to determine the acidity order of these ionic liquids and the results are consistent with the catalytic activities observed in acetalization reaction.Maximum product yield of 93%was observed on using[PSPy][OTf]as catalyst and it can be reused at least 8 times without obvious activity loss.

A Novel Bimetallic Tetrahedron Cobalt Complex Promoting the Addition of Diethylzinc to Benzaldehyde

Our recent work found a novel bimetallic tetrahedron cobalt complex which can catalyze the addition of diethylzinc to benzaldehyde effectively.

Oxygen pressure acid leaching of artificial sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation

The mechanism of oxygen pressure acid leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation was investigated in this study.Artificial sphalerite was fabricated with varying amounts of iron content via the sintering of ZnS and FeS and used for the pressure acid leaching experiment.The variations in the potential of the pressure leaching system were investigated by using a self-designed potential autoclave.The results showed that compared to the non-iron sphalerite,there was a violent redox reaction between the 25.70%Fe-artificial sphalerite and dissolved oxygen during the process of pressure leaching;and the catalytic mechanism was attributed to the redox couple Fe^3+/Fe^2+,where Fe3+oxidizes the H2S gas film and the reduced Fe2+state is subsequently oxidized by the dissolved oxygen.Furthermore,the effect of temperature,H2SO4 concentration,and oxygen partial pressure on the artificial sphalerite with different iron contents was studied.The sphalerite samples with iron content were observed to dissolve more easily in sulfuric acid compared to the non-iron samples.Moreover,the activation energy of artificial sphalerite was observed to be lower in the sample with 25.70%iron content(22.26 kJ/mol)compared to that with no iron(32.31 kJ/mol);and the apparent reaction orders were obtained with respect to H2SO4 concentration(1.10 and 1.36)and oxygen partial pressure(1.29 and 1.41),respectively.A comprehensive kinetic model was developed on the basis of the experimental data and the fitted leaching ratio plot;and the kinetic equations for the leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation were determined.

WRKY72 Negatively Regulates Seed Germination Through Interfering Gibberellin Pathway in Rice

Seed germination is associated with grain yield and quality in crop production.Gibberellic acid(GA)serves as a major phytohormone in the promotion of seed germination.It is synthesized in the embryos and transmitted to the aleurone layers,where GA triggers the synthesis and secretion of a set of hydrolases,especiallyα-amylase.Subsequently,the storage nutrients such as starch in the endosperm are digested by these hydrolases and absorbed by the embryo to sustain seed germination and early seedling establishment(Kaneko et al,2002).The detailed GA biosynthesis process has been well studied and thoroughly reviewed in several literatures(Sakamoto et al,2004;Reinecke et al,2013).Briefly,geranylgeranyl diphosphate(GGDP)is turned into ent-kaurene by two terpene synthases,ent-copalyl diphosphate synthase(CPS)and ent-kaurene synthase(KS).Subsequently,the conversion of GA precursor ent-kaurene to ent-kaurenoic acid is catalyzed by ent-kaurene oxidase(KO),and that from ent-kaurenoic acid to GA12 is catalyzed by ent-kaurenoic acid oxidase(KAO).Ultimately,GA12 is converted to various GA intermediates and bioactive GAs by GA20-oxidase(GA20ox)and GA3-oxidase(GA3ox),respectively.

Precipitation of antimony from the solution of sodium thioantimonite by air oxidation in the presence of catalytic agents

The behavior of antimony oxidation in the solution of sodium thioantimonite was studied in the presence of catalytic agents. The catalytic effects of the respective addition of cupric sulfate, sodium tartrate, potassium permanganate, phenol, 1,2 dihydroxybenzene and their combination on the oxidation of sodium thioantimonite were investigated. A pilot test was carried out. The results show that the respective use of sodium tartrate, cupric sulfate, potassium permanganate, phenol and 1,2 dihydroxybenzene have little catalytic effect on the oxidation of sodium thioantimonite. However there exists obvious catalytic oxidation by the combination of 0.25 g/L 1,2 dihydroxybenzene, 0.5 g/L potassium permanganate and 1.0 g/L phenol. Moreover, high blast intensity, the increase of temperature and NaOH concentration favor the oxidation of antimony. The oxidation process of antimony has such advantages as quick reaction and low operation costs. The results of the pilot test are consistent with those of laboratory experiments.

Reductive cyclodimerization of arylmethylidenemalononitriles promoted by samarium and catalytic amount of iodine： facile synthesis of cyclopentene derivatives

Samarium and a catalytic amount of iodine were used to obtain functionalized cyclopentenes by reductive dimerization followed by intramolecular cyclization of 1， 1-dicyanoalkenes under mild conditions.

Effect of Surfactan ton the Catalyzed Oxidation of 2,6-Dimethylphenol by Rhus Vernicifera Laccase

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