The crystal structure, morphology, dissolution kinetics and mechanism of gibbsitic bauxite and pure gibbsite in Na OH solution under atmospheric pressure were systematically investigated by XRD and SEM. The results sh...The crystal structure, morphology, dissolution kinetics and mechanism of gibbsitic bauxite and pure gibbsite in Na OH solution under atmospheric pressure were systematically investigated by XRD and SEM. The results show that the size of single crystal of gibbsite in gibbsitic bauxite is smaller than that in pure gibbsite, but the interplanar distance is larger than that of pure gibbsite, which result in more defects in the crystal and less energy needed to dissolve in alkaline solution for the gibbsitic bauxite. The dissolution kinetic equations of gibbsitic bauxite and pure gibbsite were established, and the corresponding activation energies were calculated to be 99.144 and 115.149 k J/mol, respectively.展开更多
A hydrophobic surface was fabricated on a micro-arc oxidation (MAO) treated AZ31 Mg alloys via surface modification with myristic acid. The effects of modification time on the wettability of the coatings were investig...A hydrophobic surface was fabricated on a micro-arc oxidation (MAO) treated AZ31 Mg alloys via surface modification with myristic acid. The effects of modification time on the wettability of the coatings were investigated using the contact angle measuring device. The surface morphologies and structure of the coatings were evaluated using SEM, XRD and FT-IR. The corrosion resistance was investigated by potentiodynamic polarization curves and long-term immersion test. The results showed that the water contact angle (CA) increases gradually with modification time from 0 to 5 h, the highest CA reaches 138° after being modified for 5 h, and the number and size of the micro pores are decreased. The modification method hardly alters crystalline structure of the MAO coating, but improves the corrosion resistance based on the much positive potential and low current density. Moreover, the corrosion resistance and hydrophobicity can be enhanced with increasing the alkyl chain. The wetting and spreading for the alkylcarboxylate with low surface energy become easier on the micro-porous surface, and alkylcarboxylate monolayer will be formed through bidentate bonding, which changes the surface micropores to a sealing or semi-sealing structure and makes the MAO coating dense and hydrophobic. All the results demonstrate that the modification process improves the corrosion protection ability of the MAO coating on AZ31B Mg alloy.展开更多
Auxin influences a variety of developmental and physiological processes. Early reports, suggested that auxin might affect plant stress response. We have identified a number of auxin responsive genes in Arabidopsis tha...Auxin influences a variety of developmental and physiological processes. Early reports, suggested that auxin might affect plant stress response. We have identified a number of auxin responsive genes in Arabidopsis thaliana (L.) Heynh. by using cDNA an-ay and found that stress responsive genes, such as,Arabidopsis homolog of MEK kinase 1 (ATMEKK1), ReL/SpoT homolog 3 ( At-RSH3), Catalase 1 ( Cat1) and Ferritin 1 (Fer1), were down-regulated by auxin, indicating that auxin regulates ale expression of stress responsive genes. We also demonstrated that nitrilase genes, nitrilase I ( NIT]) and nitrilase 2 (NIT2) involving in indole-3-acetic acid (IAA) biosynthesis, were induced by salinity stress, suggesting that the level of IAA might increase in response to salinity stress. To dissect the signal pathway involved in the interaction, two auxin insensitive mutants, auxin resistant 2 (axr2) and auxin resistant 1-3 (axrl-3) were used. Stress responsive genes were induced by salt stress in wild type and axr2, but not in axr1-3. The result suggests that die interaction between auxin and stress responses may be linked in the ubiquitin pathway.展开更多
The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent ...The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent （Him）[trans-RuC14 （dmso-S）（im）] （NAMI-A, im=imidazole）, was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. Tile structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.展开更多
An ionic liquid system of [Bmim]X/[Bmim]OH(X Cl,BF4,and PF6,) was developed for the hydroly-sis of ethylene carbonate to ethylene glycol. The important parameters,such as the variety of ionic liquids,molar ratio of [B...An ionic liquid system of [Bmim]X/[Bmim]OH(X Cl,BF4,and PF6,) was developed for the hydroly-sis of ethylene carbonate to ethylene glycol. The important parameters,such as the variety of ionic liquids,molar ratio of [Bmim]X to [Bmim]OH,amount of ionic liquid,molar ratio of water to ethylene carbonate,reaction tem-perature,pressure and reaction time,were investigated systematically. Excellent yield(>93%) and high selectivity(99.5%) of ethylene glycol were achieved. Under the optimum reaction conditions,the ionic liquid system could be reused at least five times and the selectivity of ethylene glycol remained higher than 99.5%.展开更多
Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synt...Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synthesized noble metal-free TiO2 photocatalysts by introducing bismuth nanoparticles as modifiers of a TiO2 single crystal(Bi-SCTiO2).The Bi-SCTiO2 can make full use of the synergistic effect of a small band overlap and low charge carrier density(Bi)with a high conductivity(single crystal),significantly boosting the separation and migration of the photogenerated charge pairs.Therefore,the Bi-SCTiO2 photocatalyst exhibits a significantly enhanced degradation rate(12 times faster)of 4-nitrophenol than a TiO2 single crystal under simulated sunlight irradiation.Notably,the complete removal of phenolic contaminants is achieved in various water matrices,which not only successfully overcomes the incomplete degradation in many reported photocatalytic systems,but also manifests a significant practical potential for sewage disposal.Therefore,this work presents a new insight in designing and constructing noble metal-free decorated semiconductor single-crystal photocatalysts with excellent activity and cyclability.展开更多
In this study,we fabricated a NiOx film by electrodeposition of an ethanediamine nickel complex precursor(pH=11)on a fluorine‐doped tin oxide substrate.The resulting film is robust and exhibits high catalytic activit...In this study,we fabricated a NiOx film by electrodeposition of an ethanediamine nickel complex precursor(pH=11)on a fluorine‐doped tin oxide substrate.The resulting film is robust and exhibits high catalytic activity for electrochemical water oxidation.Water oxidation is initiated with an overpotential of375mV(1mA/cm2)and a steady current density of8.5mA/cm2is maintained for at least10h at1.3V versus the normal hydrogen electrode.Kinetic analysis reveals that there is a2e?/3H+pre‐equilibrium process before the chemical rate‐determining step.The low‐cost preparation,robustness,and longevity make this catalyst competitive for applications in solar energy conversion and storage.展开更多
Steam reforming （SR） of dimethyl ether （DME） was investigated for the production of hydrogen for fuel cells. The activity of a series of solid acids for DME hydrolysis was investigated. The solid acid catalysts we...Steam reforming （SR） of dimethyl ether （DME） was investigated for the production of hydrogen for fuel cells. The activity of a series of solid acids for DME hydrolysis was investigated. The solid acid catalysts were ZSM-5 [Si/A] = 25, 38 and 50： denoted Z（Si/Al）] and acidic alumina （γ-Al2O3） with an acid strength order that was Z（25）〉Z（38）〉Z（50）〉γ-Al2O3. Stronger acidity gave higher DME hydrolysis conversion. Physical mixtures containing a CuO-ZnO-Al2O3-ZrO2 catalyst and solid acid catalyst to couple DME hydrolysis and methanol SR were used to examine the acidity effects on DME SR. DME SR activity strongly depended on the activity for DME hydrolysis. Z（25） was the best solid acid catalyst for DME, SR and gave a DME conversion〉90% IT= 240℃,n（H20）/n（DME） = 3.5, space velocity = 1179 ml.（g cat）^-1.h^-1, and P= 0.1MPa]. The influences of the reaction temperature, space velocity and feed molar ratio were studied. Hydrogen production significantly depended on temperature and space velocity. A bifunctional catalyst of CuO-ZnO-Al2O3-ZrO2 catalyst and ZSM-5 gave a high H2 production rate and CO2 selectivity.展开更多
To obtain carbon dioxide （CO2） flux between water-air interface of Taihu lake, monthly water samplers at 14 sites and the local meteorological data of the lake were collected and analyzed in 1998. Carbon dioxide par...To obtain carbon dioxide （CO2） flux between water-air interface of Taihu lake, monthly water samplers at 14 sites and the local meteorological data of the lake were collected and analyzed in 1998. Carbon dioxide partial pressures （pCO2） at air-water interface in the lake were calculated using alkalinity, pH, ionic strength, active coefficient, and water temperature. The carbon fluxes at different sublakes and areas were estimated by concentration gradient between water and air in consideration of Schmidt numbers of 600 and daily mean windspeed at 10 m above water surface. The results indicated that the mean values of pCO2 in Wuli Lake,Meiliang Bay, hydrophyte area, west littoral zone, riverine mouths, and the open lake areas were 1 807.8±1 071.4（mean±standard deviation）μatm （latm=1.013 25×10^5pa）, 416.3±217.0μatm, 576.5±758.8μatm, 304.2±9.43.5μatm, 1 933.6±1 144.7 μatm, and 448.5±202.6μatm, respectively. Maximum and minimum pCO2 values were found in the hypertrophic （4 053.7μatm） and the eutrophic （3.2 μatm） areas. The riverine mouth areas have the maximum fluxes （82.0±62.8 mmol/m^2a）. But there was no significant difference between eutrophic and mesotrophic areas in pCO2 and the flux of CO2. The hydrophyte area, however, has the minimum （--0.58±12.9mmol/m^2a）. In respect to CO2 equilibrium, input of the rivers will obviously influence inorganic carbon distribution in the riverine estuary. For example, the annual mean CO2 flux in Zhihugang River estuary was 19 times of that in Meiliang Bay, although the former is only a part of the latter. The sites in the body of the lake show a clear seasonal cycle with pCO2 higher than atmospheric equilibrium in winter, and much lower than atmospheric in summer due to CO2 consumption by photosynthesis. The CO2 amount of the net annual evasion that enters the atmosphere is 28.42×10^4 t/a, of which those from the west littoral zone and the open lake account for 53.8% and 36.7%, respectively.展开更多
The development of metal sulfide catalysts with remarkable activity toward efficient overall photocatalytic water splitting remains challenging owing to the dominant charge recombination and deficient catalytic active...The development of metal sulfide catalysts with remarkable activity toward efficient overall photocatalytic water splitting remains challenging owing to the dominant charge recombination and deficient catalytic active sites.Moreover,in the process of water oxidation catalysis,the inhibition of severe photocorrosion is an immense task,requiring effective photogenic hole-transfer kinetics.Herein,stratified Co-MnO_(2)@CdS/CoS hollow cubes with spatially separated catalytic sites were rationally designed and fabricated as highly efficient controllable catalysts for photocatalytic overall water splitting.The unique self-templated method,including a continuous anion/cation-exchange reaction,integrates a Co-doped oxidation co-catalyst(Co-MnO_(2))and a reduction co-catalyst(CoS)on the nanocubes with uniform interface contact and ultrathin two-dimensional(2D)nanometer sheets.We demonstrate that the stratified Co-MnO_(2)@CdS/CoS hollow cubes can provide an abundance of active sites for surface redox reactions and contribute to the separation and migration of the photoionization charge carriers.In particular,CoS nanoparticles dispersed on the walls of CdS hollow cubes were identified as reduction co-catalysts accelerating hydrogen generation,while Co-MnO_(2) nanosheets attached to the inner walls of the CdS hollow cube were oxidation co-catalysts,promoting oxygen evolution dynamics.Benefiting from the desirable structural and compositional advantages,optimized stratification of Co-MnO_(2)@CdS/CoS nanocubes provided a catalytic system devoid of precious metals,which exhibited a remarkable overall photocatalytic water-splitting rate(735.4(H_(2))and 361.1(O_(2))μmol h^(−1) g^(−1)),being among the highest values reported thus far for CdS-based catalysts.Moreover,an apparent quantum efficiency(AQE)of 1.32%was achieved for hydrogen evolution at 420 nm.This study emphasizes the importance of rational design on the structure and composition of photocatalysts for overall water splitting.展开更多
Gelatin from the sea cucumber(Paracaudina chinens var.) was hydrolyzed by bromelain and the hydrolysate was found to have a high free radical scavenging activity. The hydrolysate was fractionated through an ultrafiltr...Gelatin from the sea cucumber(Paracaudina chinens var.) was hydrolyzed by bromelain and the hydrolysate was found to have a high free radical scavenging activity. The hydrolysate was fractionated through an ultrafiltration membrane with 5 kDa molecular weight cutoff(MWCO). The portion(less than 5 kDa) was further separated by Sephadex G-25. The active peak was col-lected and assayed for free radical scavenging activity. The scavenging rates for superoxide anion radicals(O2·-) and hydroxyl radi-cals(·OH) of the fraction with the highest activity were 29.02% and 75.41%,respectively. A rabbit liver mitochondrial free radical damage model was adopted to study the free radical scavenging activity of the fraction. The results showed that the sea cucumber gelatin hydrolysate can prevent the damage of rabbit liver and mitochondria.展开更多
In order to estimate the biodegradation of three polycyclic aromatic hydrocarbons (PAHs) compounds, bacterial strains were isolated from marine sediments in three heavily contaminated sites (Yuandang Lake, Dongdu Port...In order to estimate the biodegradation of three polycyclic aromatic hydrocarbons (PAHs) compounds, bacterial strains were isolated from marine sediments in three heavily contaminated sites (Yuandang Lake, Dongdu Port and Aquacultural zones in Maluan Bay) in Xiamen Western Sea. The results show three bacterial strains, which used pyrene as the sole carbon source, were identified as strains of Aureobacterium sp., Arthrobacter sp., Rhodococcus sp. The PAH-degrading bacteria isolated had a strong ability to degrade phenan-hrene, fluoranthene and pyrene at different degradation rates. The highest degradation rate was observed when three PAH compounds were mixed with an individual strain in the medium. The three PAHs were degraded after one week with a degradation rate of 89.94 % for phenanthrene and 93.4 % for both of fluoranthene and pyrene. In addition, after 25 days of incubation, the degradation rate was 99.98 % for phenanthrene and 99.97 % for both of fluoranthene and pyrene. Optical density was measured to estimate bacterial growth during the degradation of PAHs. Highest levels of bacterial growth were observed with a three PAH mixture in the culture, suggesting that the concentration of PAHs influenced bacterial growth and the highest levels of degradation for most series were detected after one week of incubation.展开更多
The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl et...The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.展开更多
Micro-scale Al-Zn-Mg/Fe composite powders (MAF) with high reactivity and good storage properties were prepared by reducing iron onto the surface of Al-Zn-Mg alloy powders. Experimental results show that MAF as advance...Micro-scale Al-Zn-Mg/Fe composite powders (MAF) with high reactivity and good storage properties were prepared by reducing iron onto the surface of Al-Zn-Mg alloy powders. Experimental results show that MAF as advanced zero-valent iron are highly effective for degradation of chlorinated organic compounds. The efficiency of degradation for carbon tetrachloride and perchloroethylene is higher than 99% within a period of 2 h. The efficiency of degradation for trichloroethylene by MAF after storing for one month is equivalent to that by freshly prepared nano-size zero-valent iron particles.展开更多
The single crystals of the title compound NH4+C4H5O6- (C4H9NO6, Mr = 167.1) were obtained from a hot aqueous solution containing L-glutamine and D,L-tartaric acid in mole ratio1:1.5. The crystal belongs to monoclinic ...The single crystals of the title compound NH4+C4H5O6- (C4H9NO6, Mr = 167.1) were obtained from a hot aqueous solution containing L-glutamine and D,L-tartaric acid in mole ratio1:1.5. The crystal belongs to monoclinic space group P21/c with a = 7.646(2), b = 7.804(2), c = 11.502(3)? ?= 102.26(2)o, V = 670.7(3)?, Z = 4, F(000) = 352, Dc = 1.655 g.cm-3, m(MoKa) = 0.16 mm-1, R = 0.035, wR = 0.094 for 1028 observed reflections (I>2s(I)). The enatiomeric anions of the tartrate with both (2S,3S)- and (2R,3R)-configuration co-exist in the unit cell. The carbon skeleton assumes a coplanar arrangement with a torsion angle of 181.5o. The three- dimensional H-bonding network exists in the crystal. While tartrate groups link each other by H-bonds between carboxyl and hydroxyl groups, the ammonium cations insert between the tartrate groups to form a sandwich-like crystal structure.展开更多
The asymmetric hydrolysis of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. In this work, a catalytic antibody that accelerates the rate of enantioselective hydrolysis...The asymmetric hydrolysis of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. In this work, a catalytic antibody that accelerates the rate of enantioselective hydrolysis of ibuprofen methyl ester was obtained against an immunogen consisting of tetrahedral phosphonate hapten attached to bovine serum albumin (BSA). The catalytic activity of the catalytic antibody in the water-miscible organic-solvent system composed of a buffer solution and N, N-dimethylformamide (DMF) was studied. With 6% DMF in the buffer solution (containing catalytic antibody 0.25 μmol, 0.2 mol·L-1 phosphate buffer, pH 8) at 37°C for 10 h, a good conversion (48.7%) and high enantiomeric excess (>99%) could be reached. The kinetic analysis of the cata-lytic antibody-catalyzed reaction showed that the hydrolysis in the water-miscible organic-solvent system with DMF in buffer solution followed the Michaelis-Menten kinetics. The catalytic efficiency (Kcat/Km) was enhanced to 151.91 L·mmol-1·min-1, twice as large as that for the buffer solution only.展开更多
Redox-active Mn is introduced into the B site of redox-stable perovskite niobate-titanate to improve the electrocatalytic activity of composite cathode in an oxide-ion-conducting solid oxide electrolyzer. The XRD and ...Redox-active Mn is introduced into the B site of redox-stable perovskite niobate-titanate to improve the electrocatalytic activity of composite cathode in an oxide-ion-conducting solid oxide electrolyzer. The XRD and XPS results reveal the successful partial replacement of Ti/Nb by Mn in the B site of niobate-titanate. The ionic conductivities of the Mndoped niobate-titanate are significantly improved by approximately 1 order of magnitude in reducing atmosphere and 0.5 order of magnitude in oxidizing atmosphere compared with bare niobate-titanate at 800 ℃. The current efficiency for Mn-doped niobate-titanate cathode is accordingly enhanced by ,-25% and 30% in contrast to the bare cathode with and without reducing gas flowing over the cathode under the applied voltage of 2.0 V at 800 ℃ in an oxide-ion-conducting solid oxide electrolyzer, respectively.展开更多
The mechanism of ester hydrolysis has been extensively studied; however, the precise function of active-site residues in promoting catalysis is nuclear. We describe here the structural models for the complex of a cata...The mechanism of ester hydrolysis has been extensively studied; however, the precise function of active-site residues in promoting catalysis is nuclear. We describe here the structural models for the complex of a catalytic sntibody Fv fragment with a phosphonate transition -state analogue, constructed by using gene cloning, sequencing and molecular modeling, mainly based on a known X-ray structure of a catalytic atibody. Hydrophobic and electrostatic analyses of the Fv/analog and Fv/substrate interaction suggest the hydrolysis mechanism: In L91 and Tyr H97 play important roles to stabilize the β-naphthyl group of hapten through r-stack; His H35 donates a pair of free electrons at the atom NEZ to an active water and let it to be a partial hydroxide, which attacks the carbon atom of the carbonyl group of the substrate. Both His H35 and Arg L96 can form hydrogen bonds and stabilize the Anoinc tetrahedral intermediate formed during turnover. This mechanism emphasizes that an active water bridge may be formed during hydrolysis process.展开更多
For the question of applying high-pressure water injection to increase gas extraction efficiency by increasing the permeability of water to drive gas action, an independently designed gas desorption experimental measu...For the question of applying high-pressure water injection to increase gas extraction efficiency by increasing the permeability of water to drive gas action, an independently designed gas desorption experimental measuring device was used under the condition of external solution invasion. The law of water effect on gas desorption was obtained after water invasion through experiment for the first time. The results show that water＇s later invasion not only can make the quantity of gas dcsorp- tion greatly reduced, but also can make gas desorption end early. Therefore, when evaluating the applications of high-pressure water injection to increase gas extraction efficiency, we should take water damaging effects on gas desorption into account.展开更多
基金Projects(5110404151174054+2 种基金51374065)supported by the National Natural Science Foundation of ChinaProject(N130402010)supported by the Fundamental Research Funds for the Central UniversitiesChina
文摘The crystal structure, morphology, dissolution kinetics and mechanism of gibbsitic bauxite and pure gibbsite in Na OH solution under atmospheric pressure were systematically investigated by XRD and SEM. The results show that the size of single crystal of gibbsite in gibbsitic bauxite is smaller than that in pure gibbsite, but the interplanar distance is larger than that of pure gibbsite, which result in more defects in the crystal and less energy needed to dissolve in alkaline solution for the gibbsitic bauxite. The dissolution kinetic equations of gibbsitic bauxite and pure gibbsite were established, and the corresponding activation energies were calculated to be 99.144 and 115.149 k J/mol, respectively.
基金Project(2014RC18)supported by Talent Introduction Funds of the Sichuan University of Science and Engineering,ChinaProject(2013CL01)supported by the Opening Project of the Material Corrosion and Protection Key Laboratory of Sichuan Province,ChinaProject(2013X06)supported by the Science and Technology Planning Project of Zigong City,China
文摘A hydrophobic surface was fabricated on a micro-arc oxidation (MAO) treated AZ31 Mg alloys via surface modification with myristic acid. The effects of modification time on the wettability of the coatings were investigated using the contact angle measuring device. The surface morphologies and structure of the coatings were evaluated using SEM, XRD and FT-IR. The corrosion resistance was investigated by potentiodynamic polarization curves and long-term immersion test. The results showed that the water contact angle (CA) increases gradually with modification time from 0 to 5 h, the highest CA reaches 138° after being modified for 5 h, and the number and size of the micro pores are decreased. The modification method hardly alters crystalline structure of the MAO coating, but improves the corrosion resistance based on the much positive potential and low current density. Moreover, the corrosion resistance and hydrophobicity can be enhanced with increasing the alkyl chain. The wetting and spreading for the alkylcarboxylate with low surface energy become easier on the micro-porous surface, and alkylcarboxylate monolayer will be formed through bidentate bonding, which changes the surface micropores to a sealing or semi-sealing structure and makes the MAO coating dense and hydrophobic. All the results demonstrate that the modification process improves the corrosion protection ability of the MAO coating on AZ31B Mg alloy.
文摘Auxin influences a variety of developmental and physiological processes. Early reports, suggested that auxin might affect plant stress response. We have identified a number of auxin responsive genes in Arabidopsis thaliana (L.) Heynh. by using cDNA an-ay and found that stress responsive genes, such as,Arabidopsis homolog of MEK kinase 1 (ATMEKK1), ReL/SpoT homolog 3 ( At-RSH3), Catalase 1 ( Cat1) and Ferritin 1 (Fer1), were down-regulated by auxin, indicating that auxin regulates ale expression of stress responsive genes. We also demonstrated that nitrilase genes, nitrilase I ( NIT]) and nitrilase 2 (NIT2) involving in indole-3-acetic acid (IAA) biosynthesis, were induced by salinity stress, suggesting that the level of IAA might increase in response to salinity stress. To dissect the signal pathway involved in the interaction, two auxin insensitive mutants, auxin resistant 2 (axr2) and auxin resistant 1-3 (axrl-3) were used. Stress responsive genes were induced by salt stress in wild type and axr2, but not in axr1-3. The result suggests that die interaction between auxin and stress responses may be linked in the ubiquitin pathway.
基金This work was supported by the National Natural Science Foundation of China （No.20903027）, the Natural Science Foundation of Guangdong Province （No.9452402301001941）, and the Doctor Startup Fund of Guangdong Medical College （No.XB0802 and No.XB0804）.
文摘The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent （Him）[trans-RuC14 （dmso-S）（im）] （NAMI-A, im=imidazole）, was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. Tile structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.
基金Supported by the National High Technology Research and Development Program of China（2006AA06Z317） National Natural Science Foundation of China（20876162）+3 种基金 National Basic Research Program of China（2009CB219901） National Key Technology Research and Development Program（2008BAF33B04） National Science Fund of China（21006117） Science and Technology Project of Beijing（Y090081135）
文摘An ionic liquid system of [Bmim]X/[Bmim]OH(X Cl,BF4,and PF6,) was developed for the hydroly-sis of ethylene carbonate to ethylene glycol. The important parameters,such as the variety of ionic liquids,molar ratio of [Bmim]X to [Bmim]OH,amount of ionic liquid,molar ratio of water to ethylene carbonate,reaction tem-perature,pressure and reaction time,were investigated systematically. Excellent yield(>93%) and high selectivity(99.5%) of ethylene glycol were achieved. Under the optimum reaction conditions,the ionic liquid system could be reused at least five times and the selectivity of ethylene glycol remained higher than 99.5%.
文摘Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synthesized noble metal-free TiO2 photocatalysts by introducing bismuth nanoparticles as modifiers of a TiO2 single crystal(Bi-SCTiO2).The Bi-SCTiO2 can make full use of the synergistic effect of a small band overlap and low charge carrier density(Bi)with a high conductivity(single crystal),significantly boosting the separation and migration of the photogenerated charge pairs.Therefore,the Bi-SCTiO2 photocatalyst exhibits a significantly enhanced degradation rate(12 times faster)of 4-nitrophenol than a TiO2 single crystal under simulated sunlight irradiation.Notably,the complete removal of phenolic contaminants is achieved in various water matrices,which not only successfully overcomes the incomplete degradation in many reported photocatalytic systems,but also manifests a significant practical potential for sewage disposal.Therefore,this work presents a new insight in designing and constructing noble metal-free decorated semiconductor single-crystal photocatalysts with excellent activity and cyclability.
基金supported by the National Basic Research Program of China(973 program,2014CB239402)the National Natural Science Foundation of China(21476043)the Swedish Energy Agency and K&A Wallenberg Foundation~~
文摘In this study,we fabricated a NiOx film by electrodeposition of an ethanediamine nickel complex precursor(pH=11)on a fluorine‐doped tin oxide substrate.The resulting film is robust and exhibits high catalytic activity for electrochemical water oxidation.Water oxidation is initiated with an overpotential of375mV(1mA/cm2)and a steady current density of8.5mA/cm2is maintained for at least10h at1.3V versus the normal hydrogen electrode.Kinetic analysis reveals that there is a2e?/3H+pre‐equilibrium process before the chemical rate‐determining step.The low‐cost preparation,robustness,and longevity make this catalyst competitive for applications in solar energy conversion and storage.
基金Supported by the Ministry of Science and Technology （G1999022408） and the National Natural Science Foundation of China （20773075）.
文摘Steam reforming （SR） of dimethyl ether （DME） was investigated for the production of hydrogen for fuel cells. The activity of a series of solid acids for DME hydrolysis was investigated. The solid acid catalysts were ZSM-5 [Si/A] = 25, 38 and 50： denoted Z（Si/Al）] and acidic alumina （γ-Al2O3） with an acid strength order that was Z（25）〉Z（38）〉Z（50）〉γ-Al2O3. Stronger acidity gave higher DME hydrolysis conversion. Physical mixtures containing a CuO-ZnO-Al2O3-ZrO2 catalyst and solid acid catalyst to couple DME hydrolysis and methanol SR were used to examine the acidity effects on DME SR. DME SR activity strongly depended on the activity for DME hydrolysis. Z（25） was the best solid acid catalyst for DME, SR and gave a DME conversion〉90% IT= 240℃,n（H20）/n（DME） = 3.5, space velocity = 1179 ml.（g cat）^-1.h^-1, and P= 0.1MPa]. The influences of the reaction temperature, space velocity and feed molar ratio were studied. Hydrogen production significantly depended on temperature and space velocity. A bifunctional catalyst of CuO-ZnO-Al2O3-ZrO2 catalyst and ZSM-5 gave a high H2 production rate and CO2 selectivity.
基金This research was supported by the Knowledge Innovation Project of Chinese Academy of Sciences (KZCX1-SW-01-15) and (KZCX1- SW-12)
文摘To obtain carbon dioxide （CO2） flux between water-air interface of Taihu lake, monthly water samplers at 14 sites and the local meteorological data of the lake were collected and analyzed in 1998. Carbon dioxide partial pressures （pCO2） at air-water interface in the lake were calculated using alkalinity, pH, ionic strength, active coefficient, and water temperature. The carbon fluxes at different sublakes and areas were estimated by concentration gradient between water and air in consideration of Schmidt numbers of 600 and daily mean windspeed at 10 m above water surface. The results indicated that the mean values of pCO2 in Wuli Lake,Meiliang Bay, hydrophyte area, west littoral zone, riverine mouths, and the open lake areas were 1 807.8±1 071.4（mean±standard deviation）μatm （latm=1.013 25×10^5pa）, 416.3±217.0μatm, 576.5±758.8μatm, 304.2±9.43.5μatm, 1 933.6±1 144.7 μatm, and 448.5±202.6μatm, respectively. Maximum and minimum pCO2 values were found in the hypertrophic （4 053.7μatm） and the eutrophic （3.2 μatm） areas. The riverine mouth areas have the maximum fluxes （82.0±62.8 mmol/m^2a）. But there was no significant difference between eutrophic and mesotrophic areas in pCO2 and the flux of CO2. The hydrophyte area, however, has the minimum （--0.58±12.9mmol/m^2a）. In respect to CO2 equilibrium, input of the rivers will obviously influence inorganic carbon distribution in the riverine estuary. For example, the annual mean CO2 flux in Zhihugang River estuary was 19 times of that in Meiliang Bay, although the former is only a part of the latter. The sites in the body of the lake show a clear seasonal cycle with pCO2 higher than atmospheric equilibrium in winter, and much lower than atmospheric in summer due to CO2 consumption by photosynthesis. The CO2 amount of the net annual evasion that enters the atmosphere is 28.42×10^4 t/a, of which those from the west littoral zone and the open lake account for 53.8% and 36.7%, respectively.
文摘The development of metal sulfide catalysts with remarkable activity toward efficient overall photocatalytic water splitting remains challenging owing to the dominant charge recombination and deficient catalytic active sites.Moreover,in the process of water oxidation catalysis,the inhibition of severe photocorrosion is an immense task,requiring effective photogenic hole-transfer kinetics.Herein,stratified Co-MnO_(2)@CdS/CoS hollow cubes with spatially separated catalytic sites were rationally designed and fabricated as highly efficient controllable catalysts for photocatalytic overall water splitting.The unique self-templated method,including a continuous anion/cation-exchange reaction,integrates a Co-doped oxidation co-catalyst(Co-MnO_(2))and a reduction co-catalyst(CoS)on the nanocubes with uniform interface contact and ultrathin two-dimensional(2D)nanometer sheets.We demonstrate that the stratified Co-MnO_(2)@CdS/CoS hollow cubes can provide an abundance of active sites for surface redox reactions and contribute to the separation and migration of the photoionization charge carriers.In particular,CoS nanoparticles dispersed on the walls of CdS hollow cubes were identified as reduction co-catalysts accelerating hydrogen generation,while Co-MnO_(2) nanosheets attached to the inner walls of the CdS hollow cube were oxidation co-catalysts,promoting oxygen evolution dynamics.Benefiting from the desirable structural and compositional advantages,optimized stratification of Co-MnO_(2)@CdS/CoS nanocubes provided a catalytic system devoid of precious metals,which exhibited a remarkable overall photocatalytic water-splitting rate(735.4(H_(2))and 361.1(O_(2))μmol h^(−1) g^(−1)),being among the highest values reported thus far for CdS-based catalysts.Moreover,an apparent quantum efficiency(AQE)of 1.32%was achieved for hydrogen evolution at 420 nm.This study emphasizes the importance of rational design on the structure and composition of photocatalysts for overall water splitting.
文摘Gelatin from the sea cucumber(Paracaudina chinens var.) was hydrolyzed by bromelain and the hydrolysate was found to have a high free radical scavenging activity. The hydrolysate was fractionated through an ultrafiltration membrane with 5 kDa molecular weight cutoff(MWCO). The portion(less than 5 kDa) was further separated by Sephadex G-25. The active peak was col-lected and assayed for free radical scavenging activity. The scavenging rates for superoxide anion radicals(O2·-) and hydroxyl radi-cals(·OH) of the fraction with the highest activity were 29.02% and 75.41%,respectively. A rabbit liver mitochondrial free radical damage model was adopted to study the free radical scavenging activity of the fraction. The results showed that the sea cucumber gelatin hydrolysate can prevent the damage of rabbit liver and mitochondria.
基金Supported by the NSFC (No.30070157 40206015) and the Scientific Fund of Quanzhou City (No. Z200234).
文摘In order to estimate the biodegradation of three polycyclic aromatic hydrocarbons (PAHs) compounds, bacterial strains were isolated from marine sediments in three heavily contaminated sites (Yuandang Lake, Dongdu Port and Aquacultural zones in Maluan Bay) in Xiamen Western Sea. The results show three bacterial strains, which used pyrene as the sole carbon source, were identified as strains of Aureobacterium sp., Arthrobacter sp., Rhodococcus sp. The PAH-degrading bacteria isolated had a strong ability to degrade phenan-hrene, fluoranthene and pyrene at different degradation rates. The highest degradation rate was observed when three PAH compounds were mixed with an individual strain in the medium. The three PAHs were degraded after one week with a degradation rate of 89.94 % for phenanthrene and 93.4 % for both of fluoranthene and pyrene. In addition, after 25 days of incubation, the degradation rate was 99.98 % for phenanthrene and 99.97 % for both of fluoranthene and pyrene. Optical density was measured to estimate bacterial growth during the degradation of PAHs. Highest levels of bacterial growth were observed with a three PAH mixture in the culture, suggesting that the concentration of PAHs influenced bacterial growth and the highest levels of degradation for most series were detected after one week of incubation.
文摘The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.
文摘Micro-scale Al-Zn-Mg/Fe composite powders (MAF) with high reactivity and good storage properties were prepared by reducing iron onto the surface of Al-Zn-Mg alloy powders. Experimental results show that MAF as advanced zero-valent iron are highly effective for degradation of chlorinated organic compounds. The efficiency of degradation for carbon tetrachloride and perchloroethylene is higher than 99% within a period of 2 h. The efficiency of degradation for trichloroethylene by MAF after storing for one month is equivalent to that by freshly prepared nano-size zero-valent iron particles.
文摘The single crystals of the title compound NH4+C4H5O6- (C4H9NO6, Mr = 167.1) were obtained from a hot aqueous solution containing L-glutamine and D,L-tartaric acid in mole ratio1:1.5. The crystal belongs to monoclinic space group P21/c with a = 7.646(2), b = 7.804(2), c = 11.502(3)? ?= 102.26(2)o, V = 670.7(3)?, Z = 4, F(000) = 352, Dc = 1.655 g.cm-3, m(MoKa) = 0.16 mm-1, R = 0.035, wR = 0.094 for 1028 observed reflections (I>2s(I)). The enatiomeric anions of the tartrate with both (2S,3S)- and (2R,3R)-configuration co-exist in the unit cell. The carbon skeleton assumes a coplanar arrangement with a torsion angle of 181.5o. The three- dimensional H-bonding network exists in the crystal. While tartrate groups link each other by H-bonds between carboxyl and hydroxyl groups, the ammonium cations insert between the tartrate groups to form a sandwich-like crystal structure.
基金Supported by the Natural Science Foundation of Zhejiang Province (Y404353)
文摘The asymmetric hydrolysis of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. In this work, a catalytic antibody that accelerates the rate of enantioselective hydrolysis of ibuprofen methyl ester was obtained against an immunogen consisting of tetrahedral phosphonate hapten attached to bovine serum albumin (BSA). The catalytic activity of the catalytic antibody in the water-miscible organic-solvent system composed of a buffer solution and N, N-dimethylformamide (DMF) was studied. With 6% DMF in the buffer solution (containing catalytic antibody 0.25 μmol, 0.2 mol·L-1 phosphate buffer, pH 8) at 37°C for 10 h, a good conversion (48.7%) and high enantiomeric excess (>99%) could be reached. The kinetic analysis of the cata-lytic antibody-catalyzed reaction showed that the hydrolysis in the water-miscible organic-solvent system with DMF in buffer solution followed the Michaelis-Menten kinetics. The catalytic efficiency (Kcat/Km) was enhanced to 151.91 L·mmol-1·min-1, twice as large as that for the buffer solution only.
基金V. ACKNOWLEDGEMENTS This work was supported by the National Natural Science Foundation of China （No.21303037）, China Postdoctoral Science Foundation （No.2013M53150）, and tile Fundamental Research Funds for the Central Univcrsitics （No.2012HGZY0001）.
文摘Redox-active Mn is introduced into the B site of redox-stable perovskite niobate-titanate to improve the electrocatalytic activity of composite cathode in an oxide-ion-conducting solid oxide electrolyzer. The XRD and XPS results reveal the successful partial replacement of Ti/Nb by Mn in the B site of niobate-titanate. The ionic conductivities of the Mndoped niobate-titanate are significantly improved by approximately 1 order of magnitude in reducing atmosphere and 0.5 order of magnitude in oxidizing atmosphere compared with bare niobate-titanate at 800 ℃. The current efficiency for Mn-doped niobate-titanate cathode is accordingly enhanced by ,-25% and 30% in contrast to the bare cathode with and without reducing gas flowing over the cathode under the applied voltage of 2.0 V at 800 ℃ in an oxide-ion-conducting solid oxide electrolyzer, respectively.
文摘The mechanism of ester hydrolysis has been extensively studied; however, the precise function of active-site residues in promoting catalysis is nuclear. We describe here the structural models for the complex of a catalytic sntibody Fv fragment with a phosphonate transition -state analogue, constructed by using gene cloning, sequencing and molecular modeling, mainly based on a known X-ray structure of a catalytic atibody. Hydrophobic and electrostatic analyses of the Fv/analog and Fv/substrate interaction suggest the hydrolysis mechanism: In L91 and Tyr H97 play important roles to stabilize the β-naphthyl group of hapten through r-stack; His H35 donates a pair of free electrons at the atom NEZ to an active water and let it to be a partial hydroxide, which attacks the carbon atom of the carbonyl group of the substrate. Both His H35 and Arg L96 can form hydrogen bonds and stabilize the Anoinc tetrahedral intermediate formed during turnover. This mechanism emphasizes that an active water bridge may be formed during hydrolysis process.
文摘For the question of applying high-pressure water injection to increase gas extraction efficiency by increasing the permeability of water to drive gas action, an independently designed gas desorption experimental measuring device was used under the condition of external solution invasion. The law of water effect on gas desorption was obtained after water invasion through experiment for the first time. The results show that water＇s later invasion not only can make the quantity of gas dcsorp- tion greatly reduced, but also can make gas desorption end early. Therefore, when evaluating the applications of high-pressure water injection to increase gas extraction efficiency, we should take water damaging effects on gas desorption into account.
