Kinetics of Asymmetric Reduction of Phenylglyoxylic Acid to R-(-)-Mandelic Acid by Saccharomyces Cerevisiae FD11b

The kinetics of asymmetric production of R-（-）-mandelic acid （R-MA） from phenylglyoxylic acid （PGA） catalyzed by Saccharomyces cerevisiae sp. strain FD11b was studied by fed-batch cultures. The concentrations of glucose and PGA were controlled respectively with a dual feeding system. When the electron donor glucose was supplied at the rate of 0.0833mmol·gdw^-1·h^-1, the specific production rate （qp） and the enantiomeric excess of R-MA reached the maximum 0.353mmol·gdw^-1·h^-1 and 97.1%, respectively. The apparent reduction activity of yeast FD 11 b was obviously affected by both substrate PGA and product MA. The qp value reached the maximum 0.36-0.38mmol·gdw^-1·h^-1 when the PGA concentration was controlled between 25 and 35mmol·L^-1. The obvious substrate inhibition of bioconversion was observed at the PGA concentrations higher than 40mmol·L^-1. The accumulation of product MA also caused a severe feed-back inhibition for its production when the product concentration was above 60mmol·L^-1. The kinetic model with the inhibition effect of both substrate and product was simulated by a computer-based least-square arithrnatic. The established kinetic model was in good agreement with the experimental data.

Asymmetric Bioreduction of 3,5-Bis（trifluoromethyl） Acetophenone to Its Corresponding Alcohol by Candida troplcalis

(S)-3,5-bistrifluoromethylphenyl ethanol is a key chiral intermediate for the synthesis of NK-1 receptor antagonists. Enantioselective synthesis of (S)-3,5-bistrifluoromethylphenyl ethanol was successfully performed in high enantiomeric excess (e.e.) through asymmetric reduction of 3,5-bis(trifluoromethyl) acetophenone catalyzed by Candida tropicalis 104 cells. The influence of some key reaction parameters such as substrate concentration, co-substrate and its concentration, biomass and reaction time was examined, respectively. The results showed that these factors obviously influence the yield, but the optical purity of the prepared product remains intact. The opti-mum conditions for the preparation of (S)-3,5-bistrifluoromethylphenyl ethanol were found to be as follows: sub-strate concentration 50 mmol?L?1; 50 g·L-1 of maltose as co-substrate; wet cell concentration 300 g·L-1; reaction for 30 h. Under above optimal conditions, the maximum yield for (S)-3,5-bistrifluoromethylphenyl ethanol reached 70.3% with 100% of product e.e.

Asymmetric bioreduction of γ- and δ-keto acids by native carbonyl reductases from Saccharomyces cerevisiae

Optically pure(R)-γ-and(R)-δ-lactones can be prepared by intramolecular cyclization of chiral hydroxy acids/esters reduced asymmetrically from γ-and δ-keto acids/esters using Saccharomyces cerevisiae(S.cerevisiae) as a whole-cell biocatalyst.However,some of the enzymes catalyzing these reactions in S.cerevisiae are still unknown up to date.In this report,two carbonyl reductases,OdCRl and OdCR2,were successfully discovered,and cloned from S.cerevisiae using a genome-mining approach,and overexpressed in Escherichia coli(E.coli).Compared with OdCR1,OdCR2 can reduce 4-oxodecanoic acid and 5-oxodecanoic acid asymmetrically with higher stereoselectivity,generating(R)-γ-decalactone(99% ee) and(R)-δ-decalactone(98% ee) in 85% and 92%yields,respectively.This is the first report of native enzymes from S.cerevisiae for the enzymatic synthesis of chiral γ-and δ-lactones which is of wide uses in food and cosmetic industries.

Highly efficient synthesis of(R)-1,3-butanediol via anti-Prelog reduction of 4-hydroxy-2-butanone with absolute stereoselectivity by a newly isolated Pichia kudriavzevii

(R)-1,3-butanediol is an important pharmaceutical intermediate, and the synthesis of(R)-1,3-butanediol using green biological methods has recently been of interest for industrial application. Here, a novel strain QC-1 that efficiently transforms 4-hydroxy-2-butanone to(R)-1,3-butanediol was isolated from soil samples. Based on morphological, physiological, and biochemical tests and 5.8 S-internal transcribed spacer sequencing, the strain was identified as Pichia kudriavzevii QC-1. The reaction conditions were optimized to 35 ℃, pH 8.0, rotation speed 200 rpm, and 6:5 mass ratio of glucose to 4-hydroxy-2-butanone. Evaluation of the effects of 4-hydroxy-2-butanone concentrations on yield and cell survival rate showed that 85.60 g·L^-1 product accumulated, with an enantiomeric excess of more than 99%, when 30 g·L^-14-hydroxy-2-butanone was added at 0, 10, and 30 h in a 3-L bioreactor. Thus, strain QC-1 showed excellent catalytic activity and stereoselectivity for the synthesis of(R)-1,3-butanediol from 4-hydroxy-2-butanone.

Corrosion of Magnesia-chrome Brick by Smelting Reduction Slag with Iron Bath

Effects of FeO content （0, 5%, 10%, and 15% in mass, respectively ） in lab-synthesized smelting redttc- tion slag with iron bath and test temperature （1 450, 1 500, 1550, anti 1 600 ℃ ） on corrosion am,amount and microstructure of fused rebonded magnesia - chrome brick with 26.02 massqc of Cr2O3 were researched by rotary cylinder method. The results show that ： （ 1 ） the corro- sion amolult of magnesia -chrome brick by slag without FeO is higher than that by the slag with 5% FeO, and the vorrosion amount increases when FeO content increa- ses from 5% to 15% ; （2） the test temperature is one of the important factors affecting the slag corrosion resist- ance of magnesia - chrome brick, and the corrosion of smelting reduction slag to brick increases with the temperature rising.

Phase Composition Analysis of TiN-AI_2O_3Synthesized from Aluminum-containing Dross and Rutile by Aluminothermic Reductionnitridation Method

TiN- Al2O3 composite powder was prepared by aluminothermic reduction- nitridation method with starting materials of aluminum-containing dross and rutile,and metallic aluminum in the aluminum-containing dross as reducer. The influences of synthesis temperature（600-1 400 ℃） and aluminum-containing dross addition（20% lower than theoretical value,theoretical value,20% higher than theoretical value,and 50% higher than theoretical value） on phase compositions and microstructure of the composites were investigated,and the reaction mechanism was analyzed. The results show that（1） TiN- Al2O3 composite powder can be synthesized under the experimental conditions; the main phases are TiN,α-Al2O3,a little bytownite,and MgAl2O4;（2）enhancing synthesis temperature or increasing aluminumcontaining dross addition favors the reaction of aluminothermic reduction- nitridation;（3） in the synthesized products,α-Al2O3 is platy or columnar; TiN is sub-micron granular,which reinforces and toughens the composite.

Preparation, Characterization of Solid Solution La_4BaCu_(5- x)Mn_xO_(13+λ)(x= 0—5) and ItsCatalytic Activity in the Reduction of NO by CO

A series of layered mixed oxides La 4BaCu 5-x Mn x O 13+λ ( x =0—5) was prepared, characterized and used as catalysts for NO+CO reaction. It was found that all the samples were single phase having a structure with five layered perovskite. La 4BaCu 2Mn 3O 13+λ showed the highest activity in the title reaction, this could be attributed to the synergetic effect between Cu and Mn. The results of TPR, TPD and excess oxygen investigations confirmed that the Cu ion would be the active center. The displacement of the Cu ion by Mn caused the Cu ion to be more easily reducible and more content of excess oxygen, and it was beneficial to the activity of the catalyst. The reaction mechanism was also proposed.

Studies on the Oxazaborolidine-catalyzed Enantioselective Reduction of 3-Morpholin-4-yl-1-phenyl-1-propanone with Density Functional Theory

Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-1-phenyl-1-propanone with borane catalyzed by (S)-4-benzyl-5,5- diphenyl-1,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step III exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-1-phenyl-1-propanone spontaneously, resulting in the need of 2 mol BH3 in the reaction.

Model Reduction Methods for High-Rise Buildings with Active Mass Damper Control Systems

To improve the performance of an active mass damper control system,the controller should be designed based on a reduced-order model. An improved method based on balanced truncation method was proposed to reduce the dimension of high-rise buildings,and was compared with other widely used reduction methods by using a framework with ten floors. This optimized method has improvement of reduction process and choice of the order. Based on the reduced-order model obtained by the improved method and pole-assignment algorithm,a controller was designed. Finally,a comparative analysis of structural responses,transfer functions,and poles was conducted on an actual high-rise building. The results show the effectiveness of the improved method.

Variance Reduction Technique for Estimating Value-at-Risk based on the Cross - Entropy

Value-at-Risk （VaR） estimation via Monte Carlo （MC） simulation is studied here. The variance reduction technique is proposed in order to speed up MC algorithm. The algorithm for estimating the probability of high portfolio losses （more general risk measure） based on the Cross - Entropy importance sampling is developed. This algorithm can easily be applied in any light- or heavy-tailed case without an extra adaptation. Besides, it does not loose in the performance in comparison to other known methods. A numerical study in both cases is performed and the variance reduction rate is compared with other known methods. The problem of VaR estimation using procedures for estimating the probability of high portfolio losses is also discussed.

Electrocatalytic Reduction of Oxygen at Perovskite (BSCF)-MWCNT Composite Electrodes

A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are prepared by the direct mixing of BSCF:MWCNT at 90:10, 80:20 and 70:30 (% w/W). These electrodes are then characterized by the x-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The XRD and SEM confirm the inclusion and the uniform dispersal of the MWCNT within BSCF, respectively. The nitrogen adsorption isotherm study shows that the porosity of the composite paste electrode has been improved by two-fold from the BSCF electrode. The EIS and CV demonstrate that the higher ratios of MWCNT in the composites are critical in improving the electronic conductivity as well as the kinetics. It is also noticeable that the electrode has increased the catalysis of oxygen in 0.1 M KOH (pH 12.0). Cyclic voltammetric studies on the oxygen reduction reaction (ORR) suggest that the incorporation of MWCNT is vital in improving the electrode (cathode) properties of a fuel cell.

Efficient electroreduction of nitrate via enriched active phases on copper-cobalt oxides

Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased catalysts are difficult to drive high-efficient NO_(3)~- removal due to the multi-electron transfer steps.Herein, we present a tandem catalyst with simple structure, Cu-Co binary metal oxides(Cu-Co-O), by engineering intermediate phases as catalytic active species for NO_(3)~- conversion. Electrochemical evaluation,X-ray photoelectron spectroscopy, and in situ Raman spectra together suggest that the newly-generated Cu-based phases was prone to NO_(3)~- to NO_(2)~- conversion, then NO_(2)~- was reduced to NH_(3) on Co-based species. At an applied potential of -1.1 V vs. saturated calomel electrode, the Cu-Co-O catalyst achieved NO_(3)~- -N removal of 90% and NH_(3) faradaic efficiency of 81% for 120 min in 100 m L of 50 mg/L NO_(3)~- -N,consuming only 0.69 k Wh/mol in a two-electrode system. This study provides a facile and efficient engineering strategy for developing high-performance catalysts for electrocatalytic nitrate conversion.

Rates of bacterial sulfate reduction and their response to experimental temperature changes in coastal sediments of Qi'ao Island, Zhujiang River Estuary in China

Subtropical sediment cores （QA09-1 and QA12-9） from the coastal zone of Qi’ao Island in the Zhujiang River Estuary were used to determine the rates of sulfate reduction and their response to experimental tempera-ture changes. The depth distribution of the sulfate reduction rates was measured from whole-core incu-bations with radioactive tracer35SO42-, and peaks of 181.19 nmol/（cm3·d） and 107.49 nmol/（cm3·d） were exhibited at stations QA09-1 and QA12-9, respectively. The profiles of the pore water methane and sulfate concentrations demonstrated that anaerobic oxidation of methane occurred in the study area, which result-ed in an increase in the sulfate reduction rate at the base of the sulfate-reducing zone. Meanwhile, the sulfate concentration was not a major limiting factor for controlling the rates of sulfate reduction. In addition, the incubation of the sediment slurries in a block with a temperature gradient showed that the optimum tem-perature for the sulfate reduction reaction was 36°C. The Arrhenius plot was linear from the lowest tempera-ture to the optimum temperature, and the activation energy was at the lower end of the range of previously reported values. The results suggested that the ambient temperature regime of marine environments prob-ably selected for the microbial population with the best-suited physiology for the respective environment.

The Reductive Addition Reaction of Substituted 2-Chloromethyl-1,3,4-oxadiazole to Aldehydes and Ketones Promoted by Samarium Diiodide

1-（β-Hydroxyalkyl）-l,3,4-oxadiazole derivatives were synthesized via reductive addition reactions of 2-chloromethyl-l,3,4-oxadiazole with carbonyl compounds under mild conditions promoted by SmI2.

A Facile and Highly Stereosclective Reductive Dcbromination of AnhydrO-6- (R)-Hydroxyethyl- 6-Bromopenicillin

Reductive debromination of anhydro-6-(R)-hydroxycthyl-6-(R) 7 by zinc in ammonium acetate gave 9 in 81% yield with high stcreosclectivity of 6-(α):6-(β)= 13: 1

FCF-LDH/BiVO_(4)with synergistic effect of physical enrichment and chemical adsorption for efficient reduction of nitrate

Photoelectrochemical NO_(3)^(-)reduction(PEC NITRR)not only provides a promising solution for promoting the global nitrogen cycle,but also converts NO_(3)^(-)to the important chemicals(NH_(3)).However,it is still a great challenge to prepare catalysts with excellent NO_(3)^(-)adsorption/activation capacity to achieve high NITRR.Herein,we designed a novel Fe^(2+)~Cu^(2+)Fe^(3+)LDH/BiVO_(4)(FCF-LDH/BVO)catalyst with synergistic effect of chemical adsorption and physical enrichment.Fe^(2+)in FCF-LDH/BVO provides the rich Lewis acid sites for the adsorption of NO_(3)^(-),and the appropriate layer spacing of FCF-LDH further promotes the physical enrichment of NO_(3)^(-)in its interior,thus realizing the effective contact between NO_(3)^(-)and active sites(Fe^(2+)).FCF-LDH/BVO showed excellent NH_(3)production performance(FE_(NH_(3))=66.1%,r_(NH_(3))=13.8μg h^(-1)cm^(-2))and selectivity(FE_(NO_(2)^(-))=2.5%,r_(NO_(2)^(-))=4.9μg h^(-1)cm^(-2))in 0.5 mol L^(-1)Na_(2)SO_(4)electrolyte.In addition,FCF-LDH/BVO maintains the desirable PEC stability for six cycle experiments,showing great potential for practical application.The^(14)NO_(3)^(-)and^(15)NO_(3)^(-)isotope test provides strong evidence for further verification of the origin of N in the generated NH_(3).This LDH catalyst has a great potential in PEC removal of NO_(3)^(-)from groundwater.

桩-液化土相互作用p-y关系分析

基于多工况的桩-液化土体动力相互作用振动台试验,研究地震荷载作用下液化土层中桩土间侧向相互作用力p与桩身和土体间侧向相对位移y之间的关系。将试验得到的实际p-y曲线与采用拟静力法和以API规范为基础的折减系数法计算出的p-y曲线进行对比,结果表明:(1)液化土层中试验得到的桩真实p-y响应及由拟静力法和折减系数法得到的结果都呈非线性变化,三者极限状态有接近一致的趋势,但变化过程差异明显;(2)采用拟静力法和折减系数法都会使液化土层桩基础侧向反力迅速增长,很快达到屈服极限,远远超过实际情况,会导致相当保守的结果;(3)液化进程中控制桩p-y响应的是土体位移而非惯性力,因而拟静力法和折减系数法的原理不适合桩-液化土体动力相互作用分析,不能用于液化土层中桩基础地震响应的计算。

零价铁还原降解活性艳红X-3B的动力学研究

研究了不同表面积的零价铁还原降解活性艳红X-3B的动力学,结果表明零价铁对活性艳红X-3B的脱色反应符合准一级动力学过程,且随着铁粉的表面积增大及溶液的pH降低,反应动力学常数增大.

Recent advances and challenges of nitrogen/nitrate electro catalytic reduction to ammonia synthesis

The Haber-Bosch process is the most widely used synthetic ammonia technology at present.Since its invention,it has provided an important guarantee for global food security.However,the traditional Haber-Bosch ammonia synthesis process consumes a lot of energy and causes serious environmental pollution.Under the serious pressure of energy and environment,a green,clean,and sustainable ammonia synthesis route is urgently needed.Electrochemical synthesis of ammonia is a green and mild new method for preparing ammonia,which can directly convert nitrogen or nitrate into ammonia using electricity driven by solar,wind,or water energy,without greenhouse gas and toxic gas emissions.Herein,the basic mechanism of the nitrogen reduction reaction(NRR)to ammonia and nitrate reduction reaction(NO_(3)^(-))to ammonia were discussed.The representative approaches and major technologies,such as lithium mediated electrolysis and solid oxide electrolysis cell(SOEC)electrolysis for NRR,high activity catalyst and advanced electrochemical device fabrication for(NO_(3)^(-))RR and electrochemical ammonia synthesis were summarized.Based on the above discussion and analysis,the main challenges and development directions for electrochemical ammonia synthesis were further proposed.

Solar‑Driven Sustainability:Ⅲ–ⅤSemiconductor for Green Energy Production Technologies

Long-term societal prosperity depends on addressing the world’s energy and environmental problems,and photocatalysis has emerged as a viable remedy.Improving the efficiency of photocatalytic processes is fundamentally achieved by optimizing the effective utilization of solar energy and enhancing the efficient separation of photogenerated charges.It has been demonstrated that the fabrication ofⅢ–Ⅴsemiconductor-based photocatalysts is effective in increasing solar light absorption,long-term stability,large-scale production and promoting charge transfer.This focused review explores on the current developments inⅢ–Ⅴsemiconductor materials for solar-powered photocatalytic systems.The review explores on various subjects,including the advancement ofⅢ–Ⅴsemiconductors,photocatalytic mechanisms,and their uses in H2 conversion,CO_(2)reduction,environmental remediation,and photocatalytic oxidation and reduction reactions.In order to design heterostructures,the review delves into basic concepts including solar light absorption and effective charge separation.It also highlights significant advancements in green energy systems for water splitting,emphasizing the significance of establishing eco-friendly systems for CO_(2)reduction and hydrogen production.The main purpose is to produce hydrogen through sustainable and ecologically friendly energy conversion.The review intends to foster the development of greener and more sustainable energy source by encouraging researchers and developers to focus on practical applications and advancements in solar-powered photocatalysis.