Immobilization biocatalysis is a potential technology to improve the activity and stability of biocatalysts in nonaqueous systems for efficient industrial production.Alginate-chitosan(AC)microcapsules were prepared as...Immobilization biocatalysis is a potential technology to improve the activity and stability of biocatalysts in nonaqueous systems for efficient industrial production.Alginate-chitosan(AC)microcapsules were prepared as immobilization carriers by emulsifi cation-internal gelation and complexation reaction,and their contribution on facilitating the growth and metabolism of yeast cells were testifi ed successfully in culture medium-solvent biphasic systems.The cell growth in AC microcapsules is superior to that in alginate beads,and the cells in both immobilization carriers maintain much higher activity than free cells,which demonstrates AC microcapsules can confer yeast cells the ability to resist the adverse effect of solvent.Moreover,the performance of AC microcapsules in biphasic systems could be improved by adjusting the formation of outer polyelectrolyte complex(PEC)membrane to promote the cell growth and metabolic ability under the balance of resisting solvent toxicity and permitting substrate diffusion.Therefore,these findings are quite valuable for applying AC microcapsules as novel immobilization carriers to realize the biotransformation of value-added products in aqueous-solvent biphasic systems.展开更多
As the abundant biopolymer, cellulose can be used as a feedstock for chemicals and materials. Effective conversion of cellulose by simple processes is a key point. Degradation of cellulose in its homogeneous solution ...As the abundant biopolymer, cellulose can be used as a feedstock for chemicals and materials. Effective conversion of cellulose by simple processes is a key point. Degradation of cellulose in its homogeneous solution is attractive for the molecular chains are free and spread. Here,microcrystalline cellulose was first dissolved in aqueous solution of Na OH and urea, and then hydrothermal reaction was carried out at various temperature and time. Fluorescence carbon dots(CDs) were generated accompanied with six organic acids: oxalic acid, formic acid, malonic acid, lactic acid, acetic acid, and fumaric acid. The yields of all organic acids and CDs, and the fluorescence quantum yield(QY) of CDs were studied at different reaction conditions. It was found that the maximum yield of organic acids and CDs are 80.1% and 6.03%, respectively, and the highest QY of the CDs is 10.9%. Fluorescence studies reveal that the as-prepared CDs has efficient selectivity and sensitivity toward iron ions in acidic condition, indicating it is a potential fluorescent sensor to the detection of Fe3+. Importantly, it provides a panorama to summary the degradation routes of cellulose in its homogeneous aqueous solution with both organic molecules and CDs as products.展开更多
The reverse osmosis (RO) separation of aqueous organic solutions, such as alcohols, amines, aldehydes, acids, ketones, and esters etc., by PAA (polyacrylic acid)/PSF (polysulfone) composite membrane has been studied. ...The reverse osmosis (RO) separation of aqueous organic solutions, such as alcohols, amines, aldehydes, acids, ketones, and esters etc., by PAA (polyacrylic acid)/PSF (polysulfone) composite membrane has been studied. It was found that the separation results for aliphatic alcohols, amines and aldehydes are satisfactory, the solute rejection (R-a) and the volume fluxes of solutions (J(V)) for 1000 ppm ethanol, ethylamine and ethyl aldehyde are 66.2%, 61.0%, 84.0% and 0.90 x 10(-6), 0.35 x 10(-6), 0.40 X 10(-6) m(3)/m(2) . s, respectively, at 5.0 MPa and 30 degrees C. R-a increased with increasing molecular weights of alcohols, amines and aldehydes, and the R-a for n-amyl alcohol, n-butylamine and n-butyl aldehyde reached 94.3%, 88.6% and 96.0%, respectively. Satisfactory separation results (R-a > 70%) for ketones, esters, phenols and polyols have been obtained with the PAA/PSF composite membrane. The effect of operating pressure on the properties of reverse osmosis has also been investigated. Analysis of experimental data with Spiegler-Kedem's transport model has been carried out and the membrane constants such as reflection coefficient sigma, solute and hydraulic permeabilities omega and L-p for several organic solutes have been obtained.展开更多
Thermoregulated organic biphasic system composed of triethylene glycol monomethyl ether (TGME) and n-heptane was first applied to the hydrogenation of 1-octene. Under the optimal conditions: P(H2)=5.0MPa, T=80℃,...Thermoregulated organic biphasic system composed of triethylene glycol monomethyl ether (TGME) and n-heptane was first applied to the hydrogenation of 1-octene. Under the optimal conditions: P(H2)=5.0MPa, T=80℃, t=3h, 1-octene/Ru=1000 (molar ratio), the yield of n-octane reached up to 99.6%. Furthermore, the simply decanted catalyst could be reused for 10 times without apparent loss of catalytic activity.展开更多
The purpose of this study is to determine the properties of the solvents responsible of the chromatographic phenomenon. A simple and homogeneous system of ascending chromatography on paper is described, allowing varyi...The purpose of this study is to determine the properties of the solvents responsible of the chromatographic phenomenon. A simple and homogeneous system of ascending chromatography on paper is described, allowing varying only one of the factors constituting it. This method made it possible to determine constants by means of a simple equation. The validity of the method is deduced from the good agreement between its mathematical expression and the experimental values obtained.展开更多
Asymmetric synthesis of (-)-1-trimethylsilyl-ethanol with immobilized Saccharomyces cerevisiae cells in water/organic solvent biphasic system was studied. The effects of shake speed, hydrophobicity of organic solvent,...Asymmetric synthesis of (-)-1-trimethylsilyl-ethanol with immobilized Saccharomyces cerevisiae cells in water/organic solvent biphasic system was studied. The effects of shake speed, hydrophobicity of organic solvent, volume ratio of water phase to organic phase, pH value of aqueous phase and reaction temperature on the initial reaction rate, maximum yield and enantiomeric excess (ee) of the product were systematically explored. All the above-mentioned factors had significant influence on the reaction. n-Hexane was found to be the best organic solvent for the reaction. The optimum shake speed, volume ratio of water phase to organic phase, pH value and reaction temperature were 150 r.min-1, 1/2, 8 and 30 ℃ respectively, under which the maximum yield and enantiomeric excess of the product were as high as 96.8% and 95.7%, which are 15% and 16% higher than those of the corresponding reaction performed in aqueous phase. To our best knowledge, this is the most satisfactory result obtained.展开更多
Rh nanoparticles stabilized by PEG-substituted triphenyl-phosphine(PETPP,P[C6H4-p-(OCH2CH2)nOH]3) combining double stabilization effects demonstrated high activity and good recyclability in aqueous biphasic hydrog...Rh nanoparticles stabilized by PEG-substituted triphenyl-phosphine(PETPP,P[C6H4-p-(OCH2CH2)nOH]3) combining double stabilization effects demonstrated high activity and good recyclability in aqueous biphasic hydrogenation of benzene.The value of turnover frequency(TOF) was 3333 h^-1.Furthermore,the rhodium nanoparticle catalyst could be easily recycled for five times without loss in activity.展开更多
A polystyrene(PS)/nanosilica organic-inorganic hybrid material was prepared from styrene monomer and commercial aqueous silica sol containing large amounts of Si-OH by means of emulsion polymerization. The nanosilic...A polystyrene(PS)/nanosilica organic-inorganic hybrid material was prepared from styrene monomer and commercial aqueous silica sol containing large amounts of Si-OH by means of emulsion polymerization. The nanosilica sol was modified by the addition of the reactive coupling agent methacrylexy propyltrimethoxysilane ( MPS), and the resulting latex particles were protected by surfactants such as sodium dodecyl sulphonate( SDS), hydroxypropyl methyl cellulose ( HMPC), and poly (vinylpyrrolidone) (PVP). The effects of the type of surfactant, the amount of surfactant, and the coupling agent on the shape and stability of the resulting latex particles were investigated. The TEM observation indicates that among SDS, HMPC, and PVP, SDS is the best surfactant. When the content of SDS is 0. 5% and the amount of MPS is 7% in the system, the latex with obvious core-shell structure could be obtained. The average diameters of the monodispersed particles range from 182 to 278 nm, and the average number of silica beads for each composite are 1325 and 4409, respectively. The FrIR analysis shows that PS was chemically linked to silica through MPS. The thermal gravimetric analysis shows that when there is a higher silica content, the hybrid composites have a better heat resistance.展开更多
Asymmetric reduction of 3,5-bistrifluoromethyl acetophenone to produce(S)-3,5-bistrifluoromethylphenyl ethanol was successfully carried out with sodium alginate immobilized Saccharomyces rhodotorula cells in an aqueou...Asymmetric reduction of 3,5-bistrifluoromethyl acetophenone to produce(S)-3,5-bistrifluoromethylphenyl ethanol was successfully carried out with sodium alginate immobilized Saccharomyces rhodotorula cells in an aqueous-organic solvent biphasic system.The possible influential factors were examined thoroughly according to their effects on conversion rate and e.e of the product.Organic solvents were rated by their biocompatibility and conversion potential.The immobilized cells [125 mg/mL in 20 mmol/L Tris-HCl buffer and 5%(j) octane at pH 8] showed the best conversion with a substrate concentration of 1.42 g/L at 30℃ with glucose as co-substrate for cofactor regeneration.Sequential 8-batch process was carried out with immobilized cells with a slow decrease in conversion and e.e.The immobilized cells showed stable catalytic activity with 50% reserved activity and are superior especially in reusability in comparison with resting cells.展开更多
Optimized calculations of 209 polychlorinated diphenyl ethers (PCDEs) and diphenyl ethers were carried out at the B3LYP/6-31G^* level with the Gaussian 98 program. Based on the theoretical linear solvation energy r...Optimized calculations of 209 polychlorinated diphenyl ethers (PCDEs) and diphenyl ethers were carried out at the B3LYP/6-31G^* level with the Gaussian 98 program. Based on the theoretical linear solvation energy relationship (TLSER) model, the obtained structural parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting aqueous solubility (-lgSw) of PCDEs. The model obtained in this work contains two variables: mean molecular polarizability (a) and the most positive partial charge on a hydrogen atom (qH^+), of which RE = 0.9606 and SD = 0.32. And the results of cross-validation test also show that the model exhibits optimum stability and better predictive power. Moreover, the predictive power of the new model is better than that of MCIs method.展开更多
基金Supported by the National Natural Science Foundation of China(No.21276033)the Open Foundation of the State Key Laboratory of Bioactive Seaweed Substances(Nos.SKL-BASS1707,SKL-BASS1711)the Liaoning Provincial BaiQianWan Talents Program(No.2017-6)
文摘Immobilization biocatalysis is a potential technology to improve the activity and stability of biocatalysts in nonaqueous systems for efficient industrial production.Alginate-chitosan(AC)microcapsules were prepared as immobilization carriers by emulsifi cation-internal gelation and complexation reaction,and their contribution on facilitating the growth and metabolism of yeast cells were testifi ed successfully in culture medium-solvent biphasic systems.The cell growth in AC microcapsules is superior to that in alginate beads,and the cells in both immobilization carriers maintain much higher activity than free cells,which demonstrates AC microcapsules can confer yeast cells the ability to resist the adverse effect of solvent.Moreover,the performance of AC microcapsules in biphasic systems could be improved by adjusting the formation of outer polyelectrolyte complex(PEC)membrane to promote the cell growth and metabolic ability under the balance of resisting solvent toxicity and permitting substrate diffusion.Therefore,these findings are quite valuable for applying AC microcapsules as novel immobilization carriers to realize the biotransformation of value-added products in aqueous-solvent biphasic systems.
基金supported by the National Natural Science Foundation of China (No. 51373162 and 51673180)
文摘As the abundant biopolymer, cellulose can be used as a feedstock for chemicals and materials. Effective conversion of cellulose by simple processes is a key point. Degradation of cellulose in its homogeneous solution is attractive for the molecular chains are free and spread. Here,microcrystalline cellulose was first dissolved in aqueous solution of Na OH and urea, and then hydrothermal reaction was carried out at various temperature and time. Fluorescence carbon dots(CDs) were generated accompanied with six organic acids: oxalic acid, formic acid, malonic acid, lactic acid, acetic acid, and fumaric acid. The yields of all organic acids and CDs, and the fluorescence quantum yield(QY) of CDs were studied at different reaction conditions. It was found that the maximum yield of organic acids and CDs are 80.1% and 6.03%, respectively, and the highest QY of the CDs is 10.9%. Fluorescence studies reveal that the as-prepared CDs has efficient selectivity and sensitivity toward iron ions in acidic condition, indicating it is a potential fluorescent sensor to the detection of Fe3+. Importantly, it provides a panorama to summary the degradation routes of cellulose in its homogeneous aqueous solution with both organic molecules and CDs as products.
文摘The reverse osmosis (RO) separation of aqueous organic solutions, such as alcohols, amines, aldehydes, acids, ketones, and esters etc., by PAA (polyacrylic acid)/PSF (polysulfone) composite membrane has been studied. It was found that the separation results for aliphatic alcohols, amines and aldehydes are satisfactory, the solute rejection (R-a) and the volume fluxes of solutions (J(V)) for 1000 ppm ethanol, ethylamine and ethyl aldehyde are 66.2%, 61.0%, 84.0% and 0.90 x 10(-6), 0.35 x 10(-6), 0.40 X 10(-6) m(3)/m(2) . s, respectively, at 5.0 MPa and 30 degrees C. R-a increased with increasing molecular weights of alcohols, amines and aldehydes, and the R-a for n-amyl alcohol, n-butylamine and n-butyl aldehyde reached 94.3%, 88.6% and 96.0%, respectively. Satisfactory separation results (R-a > 70%) for ketones, esters, phenols and polyols have been obtained with the PAA/PSF composite membrane. The effect of operating pressure on the properties of reverse osmosis has also been investigated. Analysis of experimental data with Spiegler-Kedem's transport model has been carried out and the membrane constants such as reflection coefficient sigma, solute and hydraulic permeabilities omega and L-p for several organic solutes have been obtained.
基金the financial support from the National Natural Science Foundation of China (Grant no. 20376013) the Fok Ying Tung Education Foundation (Grant no. 91071) the Doctorate Program Foundation of Higher Education (Grant no. 20020141004).
文摘Thermoregulated organic biphasic system composed of triethylene glycol monomethyl ether (TGME) and n-heptane was first applied to the hydrogenation of 1-octene. Under the optimal conditions: P(H2)=5.0MPa, T=80℃, t=3h, 1-octene/Ru=1000 (molar ratio), the yield of n-octane reached up to 99.6%. Furthermore, the simply decanted catalyst could be reused for 10 times without apparent loss of catalytic activity.
文摘The purpose of this study is to determine the properties of the solvents responsible of the chromatographic phenomenon. A simple and homogeneous system of ascending chromatography on paper is described, allowing varying only one of the factors constituting it. This method made it possible to determine constants by means of a simple equation. The validity of the method is deduced from the good agreement between its mathematical expression and the experimental values obtained.
基金Supported by the National Natural Science Foundation of China(No.20076019)the Natural Science Foundation of Guang-dong Province(No.000444).
文摘Asymmetric synthesis of (-)-1-trimethylsilyl-ethanol with immobilized Saccharomyces cerevisiae cells in water/organic solvent biphasic system was studied. The effects of shake speed, hydrophobicity of organic solvent, volume ratio of water phase to organic phase, pH value of aqueous phase and reaction temperature on the initial reaction rate, maximum yield and enantiomeric excess (ee) of the product were systematically explored. All the above-mentioned factors had significant influence on the reaction. n-Hexane was found to be the best organic solvent for the reaction. The optimum shake speed, volume ratio of water phase to organic phase, pH value and reaction temperature were 150 r.min-1, 1/2, 8 and 30 ℃ respectively, under which the maximum yield and enantiomeric excess of the product were as high as 96.8% and 95.7%, which are 15% and 16% higher than those of the corresponding reaction performed in aqueous phase. To our best knowledge, this is the most satisfactory result obtained.
基金support from the National Natural Science Foundation of China(No.20573015)the Program for New Century Excellent Talents in University(No.NCET-07-0138)the Science and Technology Project in Universities from the Education Department of Liaoning Province(No.2008T233)
文摘Rh nanoparticles stabilized by PEG-substituted triphenyl-phosphine(PETPP,P[C6H4-p-(OCH2CH2)nOH]3) combining double stabilization effects demonstrated high activity and good recyclability in aqueous biphasic hydrogenation of benzene.The value of turnover frequency(TOF) was 3333 h^-1.Furthermore,the rhodium nanoparticle catalyst could be easily recycled for five times without loss in activity.
基金Supported by the National Natural Science Foundation of China(No. 50373037)the Special Funds for Major State BasicResearch Projects ( No. 2005CB623802) Specialized Research Fund for the Doctoral Program of Higher Education ( No.20040335077).
文摘A polystyrene(PS)/nanosilica organic-inorganic hybrid material was prepared from styrene monomer and commercial aqueous silica sol containing large amounts of Si-OH by means of emulsion polymerization. The nanosilica sol was modified by the addition of the reactive coupling agent methacrylexy propyltrimethoxysilane ( MPS), and the resulting latex particles were protected by surfactants such as sodium dodecyl sulphonate( SDS), hydroxypropyl methyl cellulose ( HMPC), and poly (vinylpyrrolidone) (PVP). The effects of the type of surfactant, the amount of surfactant, and the coupling agent on the shape and stability of the resulting latex particles were investigated. The TEM observation indicates that among SDS, HMPC, and PVP, SDS is the best surfactant. When the content of SDS is 0. 5% and the amount of MPS is 7% in the system, the latex with obvious core-shell structure could be obtained. The average diameters of the monodispersed particles range from 182 to 278 nm, and the average number of silica beads for each composite are 1325 and 4409, respectively. The FrIR analysis shows that PS was chemically linked to silica through MPS. The thermal gravimetric analysis shows that when there is a higher silica content, the hybrid composites have a better heat resistance.
文摘Asymmetric reduction of 3,5-bistrifluoromethyl acetophenone to produce(S)-3,5-bistrifluoromethylphenyl ethanol was successfully carried out with sodium alginate immobilized Saccharomyces rhodotorula cells in an aqueous-organic solvent biphasic system.The possible influential factors were examined thoroughly according to their effects on conversion rate and e.e of the product.Organic solvents were rated by their biocompatibility and conversion potential.The immobilized cells [125 mg/mL in 20 mmol/L Tris-HCl buffer and 5%(j) octane at pH 8] showed the best conversion with a substrate concentration of 1.42 g/L at 30℃ with glucose as co-substrate for cofactor regeneration.Sequential 8-batch process was carried out with immobilized cells with a slow decrease in conversion and e.e.The immobilized cells showed stable catalytic activity with 50% reserved activity and are superior especially in reusability in comparison with resting cells.
基金funded by the 973 National Basic Research Program of China (2003CB415002)China Postdoctoral Science Foundation (No. 2003033486)
文摘Optimized calculations of 209 polychlorinated diphenyl ethers (PCDEs) and diphenyl ethers were carried out at the B3LYP/6-31G^* level with the Gaussian 98 program. Based on the theoretical linear solvation energy relationship (TLSER) model, the obtained structural parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting aqueous solubility (-lgSw) of PCDEs. The model obtained in this work contains two variables: mean molecular polarizability (a) and the most positive partial charge on a hydrogen atom (qH^+), of which RE = 0.9606 and SD = 0.32. And the results of cross-validation test also show that the model exhibits optimum stability and better predictive power. Moreover, the predictive power of the new model is better than that of MCIs method.