Cationic ring opening polymerization of octamethylcyclotetrasiloxane (Da) initiated by acid treated bentonite was investigated. The experimental conditions were chosen on the basis of preliminary experiments.Higher ...Cationic ring opening polymerization of octamethylcyclotetrasiloxane (Da) initiated by acid treated bentonite was investigated. The experimental conditions were chosen on the basis of preliminary experiments.Higher temperature was found beneficial for the reaction process while stirring intensity beyond a certain level showed no obvious effect on the reaction rate. Polymers were characterized by Fourier transform infrared, proton nuclear magnetic resonance (IH-NMR) and gel perneation chromotography. The width of molecular mass distribution was found ranging between 1.2 and 1.4, which is extraordinarlly narrow compared with that of cationic polymerizations reported elsewhere (〉 1.9). The results were believed due to the absence of free proton and counter ion which simplifies the polymerization process and the huge steric hindrance provided by bentonite particles which keeps the propagation of polysiloxane onto the surface of bentonite particles in a much more regular way. A feasible mechanism is proposed and seems to be supported well by experiments. Additionally, from the results of α, ω-dihydrogen terminated polysiloxanes prepared, the possibility of applying this potential environmentally friendly heterogeneous catalyst in industrial polymerization of cyclosiloxanes is anticipated.展开更多
The combination of a zinc phthalocyanine(ZnPc)catalyst and a stoichiometric amount of dimethyl formamide(DMF)provided a simple route to formamide derivatives from amines,CO2,and hydrosilanes under mild conditions.We d...The combination of a zinc phthalocyanine(ZnPc)catalyst and a stoichiometric amount of dimethyl formamide(DMF)provided a simple route to formamide derivatives from amines,CO2,and hydrosilanes under mild conditions.We deduced that formation of an active zinc‐hydrogen(Zn‐H)species promoted hydride transfer from the hydrosilane to CO2.The cooperative activation of the Lewis acidic ZnPc by strongly polar DMF,led to formation of activated amines and hydrosilanes,which promoted the chemical reduction of CO2.Consequently,the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity,representing a simple and sustainable pathway for the reductive transformation of CO2into valuable chemicals as an alternative to conventional halogen‐containing process.展开更多
A new kind of silicon-based biological lubricating base oil with good viscosity-temperature behavior,viscosity index,thermostability,oxidation stability and wear resistance performance was synthesized as a derivative ...A new kind of silicon-based biological lubricating base oil with good viscosity-temperature behavior,viscosity index,thermostability,oxidation stability and wear resistance performance was synthesized as a derivative of methyl oleate.Trimethylsilylation reaction was introduced to further improve methyl oleate oxidation stability and lubricity after epoxidation and open-ring reactions.The order of effectiveness of acid binding agent was N,N-diisopropylethylamine(DIEA) > pyridine > diethylamine > triethylamine,and the effects of various parameters on the trimethylsilylation reaction as well as on the silicon-oxygen bond stability and reaction yield were studied.A maximum yield of 34.54%was achieved at hydroxyl/trimethyl chlorosilane/DIEA molar ratio of1:1.25:1,reaction temperature 40℃,reaction time 1.5 h.展开更多
Chemical vapor deposition(CVD) of SiC from methyltrichlorosilane(MTS) was studied at two different molar ratios of H2 to MTS(n(H2) /n(MTS) ) . The total pressure was kept as 100 kPa and the temperature was varied from...Chemical vapor deposition(CVD) of SiC from methyltrichlorosilane(MTS) was studied at two different molar ratios of H2 to MTS(n(H2) /n(MTS) ) . The total pressure was kept as 100 kPa and the temperature was varied from 850 to 1 100 ℃ at a total residence time of 1 s. Steady-state deposition rates as functions of reactor length and of temperature,investigated at different n(H2) /n(MTS) values,show that hydrogen exhibits strongly influences on the deposition rate. Especially,the deposition of Si co-deposit can be obtained in broader substrate length and at higher temperatures with increasing hydrogen partial pressure. Influence of hydrogen on the deposition process was also studied using gas phase composition and deposit composition analysis at various n(H2) /n(MTS) . SEM micrographs directly show the variation of surface morphologies at various n(H2) /n(MTS) . It can be found that the crystal grain of the deposit at 1 100 ℃ is better developed and the crystallization is also improved with increasing n(H2) /n(MTS) .展开更多
A modified solution-diffusion model was established based on Flory-Huggins thermodynamic theory and Fujita's free volume theory. This model was used for description of the mass transfer of removal benzene from dil...A modified solution-diffusion model was established based on Flory-Huggins thermodynamic theory and Fujita's free volume theory. This model was used for description of the mass transfer of removal benzene from dilute aqueous solutions through polydimethylsiloxane (PDMS) membranes. The effect of component concentration on the interaction parameter between components, that of the polymer membrane on the selectivity to benzene, and that of feed concentration and temperature on the permeation flux and separation factor of benzene/water through PDMS membranes were investigated. Calculated pervaporation fluxes of benzene and water were compared with the experimental results and were in good agreement with the experimental data.展开更多
Silicon carbide was prepared from SiCl4-CH4-H2 gaseous precursors by isothermal, isobaric chemical vapor deposition (CVD) at atmospheric pressure and temperatures ranging from 900°C to 1100°C. Kinetic studie...Silicon carbide was prepared from SiCl4-CH4-H2 gaseous precursors by isothermal, isobaric chemical vapor deposition (CVD) at atmospheric pressure and temperatures ranging from 900°C to 1100°C. Kinetic studies showed that carbosilane of SiH2Cl2, SiHCl3 and SiCl2 formed from decomposition of SiCl4 and CH4 contributed to the deposition of hexangular facet and granular pebble structured SiC. An average apparent activation energy of 152 kJ·mol-1 was determined. The overall CVD process was controlled not only by the surface reactions but also by complex gas phase reactions. The as-deposited thin film was characterized using scanning electron microscopy, X-ray diffraction and transmission electron microscopy, these analysis showed that the deposited thin film consisted of pure phase of the β-SiC, the growth morphology of β-SiC differs from hexangular facet to granular pebble struc-tures, which varied with substrate length and CVD temperature.展开更多
The pervaporation behavior of fermentation broth was investigated experimentally and compared with those started with ethanol mixtures. Ethanol was produced by Saccharomyces cerevisiae utilizing technical grade glucos...The pervaporation behavior of fermentation broth was investigated experimentally and compared with those started with ethanol mixtures. Ethanol was produced by Saccharomyces cerevisiae utilizing technical grade glucose and recovered by pervaporation using a composite polydimethylsiloxane (PDMS) membrane prepared in our laboratory. Ethanol concentration in fermentation broth decreased to a relatively low level when pervaporation was coupled with fermentation. The more active cells appeared in the fermentation broth, the better the membrane performance was.展开更多
The enantioselective esterification of racemic 1-trimethylsilylethanol with acids catalyzed by lipase in organic solvent was successfully performed. The influence of some factors on the reaction was investigated. Amon...The enantioselective esterification of racemic 1-trimethylsilylethanol with acids catalyzed by lipase in organic solvent was successfully performed. The influence of some factors on the reaction was investigated. Among the four lipases explored, Candida rugosa lipase (CRL) showed the highest activity and enantioselectivity. Octanoic acid was the best acyl donor among the eleven acids studied and n-hexane was the most suitable medium for the reaction. The optimum shaking rate and temperature were found to be 150r·min-1 and 20℃ to 30℃, respectively. The enantiomeric excess of the remaining (5)-(-)-1-trimethylsilylethanol was 93% when substrate conversion was 53% upon incubation of the reaction mixture at 30℃, 150r·min-1 for 12 h.展开更多
CO_2 is one of the most important "renewable" carbon sources.To transform CO_2 to useful organic compounds,we examined the reactivity of two model silicon-based "waste" materials,disilanes and metallic Si powder,a...CO_2 is one of the most important "renewable" carbon sources.To transform CO_2 to useful organic compounds,we examined the reactivity of two model silicon-based "waste" materials,disilanes and metallic Si powder,as reducing agents.In these reactions,fluoride salts were found to be active catalysts:CO_2 was converted to formic acid at atmospheric pressure in the presence of H_2O as a proton source and the silicon-based reducing reagents.Based on in-situ NMR and kinetics analyses,a hydrosilane and penta-coordinate Si species are proposed as the reaction intermediate and active species,respectively.展开更多
Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from it...Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation performance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40°C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g·m?2·h?1 and 26.1, respectively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.展开更多
Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental ...Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental issues,which are currently spurring the exploration of the novel nano‐catalysts in diverse fields.In order to develop the efficient nano‐catalysts,it is essential to understand their fundamental physicochemical properties,including the coordination structures of the active centers and substrate‐adsorbate interactions.Subsequently,the nano‐catalyst design with precise manipulation at the atomic level can be attained.In this account,we have summarized our extensive investigation of the factors impacting nano‐catalysis,along with the synthetic strategies developed to prepare the nano‐catalysts for applications in electrocatalysis,photocatalysis and thermocatalysis.Finally,a brief conclusion and future research directions on nano‐catalysis have also been presented.展开更多
Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with (R)-oxynitrilase from defatted Prunus Japonica seed meal for the prep...Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with (R)-oxynitrilase from defatted Prunus Japonica seed meal for the preparation of optically active (R)-2-trimethylsilyl-2-hydroxyl-propionitrile was successfully carried out for the first time. For better understanding of the reaction, various influential variables were examined with respect to the initial reaction rate, the substrate conversion and the product enantiomeric excess (e.e.). Diisopropyl ether was found to be the best organic phase for this reaction among all the organic solvents tested. The optimal concentrations of Prunus Japonica seed meal powder, acetyltrimethylsilane and acetone cyanohydrin, volume ratio of aqueous phase to organic phase, buffer pH value and the reaction temperature were 34.5g·L^-1 and 14mmol· L^-1, 28mmol· L^-1, 13% (by volume), 5.0 and 30℃, respectively, while the initial reaction rate, the substrate conversion and the product enantiomeric excess were 1.34 mmol·L^-1·h^-1, 99.0% and 99.0%, respectively. The comparative study demonstrated that silicon atom in substrate showed great effect on the reaction and acetyltrimethylsilane was a much better substrate for (R)-hydroxynitrile lyase from Prunus Japonica seed than its carbon analogue 3,3-dimethyl-2-butanone.展开更多
Mesoporous silica materials with uniform channels containing functionalized organic monolayers have been synthesized by grafting a thiol functional group, (3-Mercaptopropyl) trimethoxysilane (MPTMS). A new approac...Mesoporous silica materials with uniform channels containing functionalized organic monolayers have been synthesized by grafting a thiol functional group, (3-Mercaptopropyl) trimethoxysilane (MPTMS). A new approach to heavy metal ion adsorbents based on the covalent grafting of MPTMS groups to the framework pore walls of mesoporous silica molecular sieves has been developed and investigated with regard to hydroxyl group densities, channel dimensions, morphologies and reaction conditions. Results show that the ordered mesostructures of functionalized samples were retained after modification and the thiol functional group was immobilized mainly inside the mesopore channel. The relative surface coverage of the monolayer can be systematically varied up to 95%. The functionalized hybrid materials show exceptional selectivity and capacity for removing mercury from aqueous waste stream with distribution coefficients up to 435,000. The regenerated material show high mercury ion uptake capacity of 2.87 mmol/g (86.5%).展开更多
In the present study, free fatty acids(FFAs, including palmitic acid, stearic acid, oleic acid, linoleic acid and arachidonic acid) in rabbit plasma were determined by gas chromatography-mass spectrometry(GC-MS) after...In the present study, free fatty acids(FFAs, including palmitic acid, stearic acid, oleic acid, linoleic acid and arachidonic acid) in rabbit plasma were determined by gas chromatography-mass spectrometry(GC-MS) after trimethylsilylation derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide(BSTFA) – trimethylchlorosilane(TMCS) as derivatization reagent. The experimental conditions, including extraction and silylation reaction, were investigated. The method was experimentally validated. The linearity between fatty acids’ peak areas and their concentrations was obtained with the corelative coefficient(r2) all more than 0.999, and the recoveries were between 82% and 111%. The intra-day variations of FFAs’ in plasma samples at different concentrations were all less than 6%. FFA analysis results of 16 rabbit plasma samples showed that the method could be well applied in the determination of plasma samples in vivo. In contrast to the traditional method of FFA derivatization, the established trimethylsilylation method presented simplicity, high specificity, and completely free from the interference of the esterified fatty acid, such as triacylglyceride. The method could be applied for analyzing FFA profiles in the clinical laboratory or pharmacological research.展开更多
A full account of the novel and flexible approach to hydroxylated 8-azabicyclo[3,2,1]octan-3-ones and 9-azabicyclo[3,3,1] nonan-3-ones is presented. Using keto-lactams as the starting materials, this two-step method c...A full account of the novel and flexible approach to hydroxylated 8-azabicyclo[3,2,1]octan-3-ones and 9-azabicyclo[3,3,1] nonan-3-ones is presented. Using keto-lactams as the starting materials, this two-step method consists of silyl enol ether for mation with TBDMSOTf, lactam activation with Tf20/DTBMP, and halide-promoted cyclization. Radical dechlorination of the resulting 1-halotropan-3-ones led to the corresponding hydroxylated tropan-3-ones, which can be hydrogenated to yield 3ct,613-dihydroxytropanes. Starting from optically active keto-lactams, the method has been applied to the enantioselective syntheses of (+)-(1S,3S,5R,6S)-pervilleine C (6), (+)-(1S,3R,5S,6R)-valeroidine (3), (+)-(1S,3S,5R,6S)-dibenzoyloxytropane (8) and (+)-(1S,3S,5R,6S)-merredissine (9).展开更多
We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precu...We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA (P2) was derived by desilylation of the pristine PA with trimethylethynylsilane side chains (P1). P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane (M) under the promotion of WC16-Ph4Sn catalyst. Two synthetic routes, i.e. two-steps (from P1 to P3 via precursor P2) and one-pot (from P1 to P3 without separation and purification of P2) were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2. By using the techniques such as GPC, FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized.展开更多
基金Supported by the National Natural Science Foundation of China (No.20576117)
文摘Cationic ring opening polymerization of octamethylcyclotetrasiloxane (Da) initiated by acid treated bentonite was investigated. The experimental conditions were chosen on the basis of preliminary experiments.Higher temperature was found beneficial for the reaction process while stirring intensity beyond a certain level showed no obvious effect on the reaction rate. Polymers were characterized by Fourier transform infrared, proton nuclear magnetic resonance (IH-NMR) and gel perneation chromotography. The width of molecular mass distribution was found ranging between 1.2 and 1.4, which is extraordinarlly narrow compared with that of cationic polymerizations reported elsewhere (〉 1.9). The results were believed due to the absence of free proton and counter ion which simplifies the polymerization process and the huge steric hindrance provided by bentonite particles which keeps the propagation of polysiloxane onto the surface of bentonite particles in a much more regular way. A feasible mechanism is proposed and seems to be supported well by experiments. Additionally, from the results of α, ω-dihydrogen terminated polysiloxanes prepared, the possibility of applying this potential environmentally friendly heterogeneous catalyst in industrial polymerization of cyclosiloxanes is anticipated.
基金supported by the National Natural Science Foundation of China (21676306,21425627)the National Key Research and Development Program of China (2016YFA0602900)+1 种基金the Natural Science Foundation of Guangdong Province (2016A030310211)the Characteristic Innovation Project (Natural Science) of Guangdong Colleges and Universities~~
文摘The combination of a zinc phthalocyanine(ZnPc)catalyst and a stoichiometric amount of dimethyl formamide(DMF)provided a simple route to formamide derivatives from amines,CO2,and hydrosilanes under mild conditions.We deduced that formation of an active zinc‐hydrogen(Zn‐H)species promoted hydride transfer from the hydrosilane to CO2.The cooperative activation of the Lewis acidic ZnPc by strongly polar DMF,led to formation of activated amines and hydrosilanes,which promoted the chemical reduction of CO2.Consequently,the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity,representing a simple and sustainable pathway for the reductive transformation of CO2into valuable chemicals as an alternative to conventional halogen‐containing process.
基金Supported by the National Natural Science Foundation of China(21306088)National Key Technologies R&D Program of China(2015BAD15B07)+1 种基金State Key Laboratory of Chemical Engineering(SKL-Ch E-13A01,Tsinghua University,China)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,China)
文摘A new kind of silicon-based biological lubricating base oil with good viscosity-temperature behavior,viscosity index,thermostability,oxidation stability and wear resistance performance was synthesized as a derivative of methyl oleate.Trimethylsilylation reaction was introduced to further improve methyl oleate oxidation stability and lubricity after epoxidation and open-ring reactions.The order of effectiveness of acid binding agent was N,N-diisopropylethylamine(DIEA) > pyridine > diethylamine > triethylamine,and the effects of various parameters on the trimethylsilylation reaction as well as on the silicon-oxygen bond stability and reaction yield were studied.A maximum yield of 34.54%was achieved at hydroxyl/trimethyl chlorosilane/DIEA molar ratio of1:1.25:1,reaction temperature 40℃,reaction time 1.5 h.
基金Project supported by the One Hundred Talents Program of Chinese Academy of Sciences
文摘Chemical vapor deposition(CVD) of SiC from methyltrichlorosilane(MTS) was studied at two different molar ratios of H2 to MTS(n(H2) /n(MTS) ) . The total pressure was kept as 100 kPa and the temperature was varied from 850 to 1 100 ℃ at a total residence time of 1 s. Steady-state deposition rates as functions of reactor length and of temperature,investigated at different n(H2) /n(MTS) values,show that hydrogen exhibits strongly influences on the deposition rate. Especially,the deposition of Si co-deposit can be obtained in broader substrate length and at higher temperatures with increasing hydrogen partial pressure. Influence of hydrogen on the deposition process was also studied using gas phase composition and deposit composition analysis at various n(H2) /n(MTS) . SEM micrographs directly show the variation of surface morphologies at various n(H2) /n(MTS) . It can be found that the crystal grain of the deposit at 1 100 ℃ is better developed and the crystallization is also improved with increasing n(H2) /n(MTS) .
文摘A modified solution-diffusion model was established based on Flory-Huggins thermodynamic theory and Fujita's free volume theory. This model was used for description of the mass transfer of removal benzene from dilute aqueous solutions through polydimethylsiloxane (PDMS) membranes. The effect of component concentration on the interaction parameter between components, that of the polymer membrane on the selectivity to benzene, and that of feed concentration and temperature on the permeation flux and separation factor of benzene/water through PDMS membranes were investigated. Calculated pervaporation fluxes of benzene and water were compared with the experimental results and were in good agreement with the experimental data.
基金Supported by the One Hundred Talents Program of Chinese Academy of Sciences
文摘Silicon carbide was prepared from SiCl4-CH4-H2 gaseous precursors by isothermal, isobaric chemical vapor deposition (CVD) at atmospheric pressure and temperatures ranging from 900°C to 1100°C. Kinetic studies showed that carbosilane of SiH2Cl2, SiHCl3 and SiCl2 formed from decomposition of SiCl4 and CH4 contributed to the deposition of hexangular facet and granular pebble structured SiC. An average apparent activation energy of 152 kJ·mol-1 was determined. The overall CVD process was controlled not only by the surface reactions but also by complex gas phase reactions. The as-deposited thin film was characterized using scanning electron microscopy, X-ray diffraction and transmission electron microscopy, these analysis showed that the deposited thin film consisted of pure phase of the β-SiC, the growth morphology of β-SiC differs from hexangular facet to granular pebble struc-tures, which varied with substrate length and CVD temperature.
基金the National Natural Science Foundation of China (No. 20176030, No. 20276041).
文摘The pervaporation behavior of fermentation broth was investigated experimentally and compared with those started with ethanol mixtures. Ethanol was produced by Saccharomyces cerevisiae utilizing technical grade glucose and recovered by pervaporation using a composite polydimethylsiloxane (PDMS) membrane prepared in our laboratory. Ethanol concentration in fermentation broth decreased to a relatively low level when pervaporation was coupled with fermentation. The more active cells appeared in the fermentation broth, the better the membrane performance was.
基金Supported by the National Natural Science Foundation of China (No. 20076019) the Natural Science Foundation of Guangdong Province (No. 000444).
文摘The enantioselective esterification of racemic 1-trimethylsilylethanol with acids catalyzed by lipase in organic solvent was successfully performed. The influence of some factors on the reaction was investigated. Among the four lipases explored, Candida rugosa lipase (CRL) showed the highest activity and enantioselectivity. Octanoic acid was the best acyl donor among the eleven acids studied and n-hexane was the most suitable medium for the reaction. The optimum shaking rate and temperature were found to be 150r·min-1 and 20℃ to 30℃, respectively. The enantiomeric excess of the remaining (5)-(-)-1-trimethylsilylethanol was 93% when substrate conversion was 53% upon incubation of the reaction mixture at 30℃, 150r·min-1 for 12 h.
基金supported by JSPS KAKENHI(15H04182)JSPS Grant-in-Aid for Scientific Research on Innovative Areas "3D Active-Site Science(26105003)","Precisely Designed Catalysts with Customized Scaffolding(16H01010)"Grant for Challenging Research Award,Tokyo Institute of Technology
文摘CO_2 is one of the most important "renewable" carbon sources.To transform CO_2 to useful organic compounds,we examined the reactivity of two model silicon-based "waste" materials,disilanes and metallic Si powder,as reducing agents.In these reactions,fluoride salts were found to be active catalysts:CO_2 was converted to formic acid at atmospheric pressure in the presence of H_2O as a proton source and the silicon-based reducing reagents.Based on in-situ NMR and kinetics analyses,a hydrosilane and penta-coordinate Si species are proposed as the reaction intermediate and active species,respectively.
基金Supported by the National Basic Research Program of China(2009CB623406) the National Natural Science Foundation of China(20990222)+1 种基金 the Natural Science Foundation of Jiangsu Province(SBK200930313) the“Six Kinds of Important Talents”Program of Jiangsu Province(2007007)
文摘Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation performance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40°C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g·m?2·h?1 and 26.1, respectively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.
文摘Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental issues,which are currently spurring the exploration of the novel nano‐catalysts in diverse fields.In order to develop the efficient nano‐catalysts,it is essential to understand their fundamental physicochemical properties,including the coordination structures of the active centers and substrate‐adsorbate interactions.Subsequently,the nano‐catalyst design with precise manipulation at the atomic level can be attained.In this account,we have summarized our extensive investigation of the factors impacting nano‐catalysis,along with the synthetic strategies developed to prepare the nano‐catalysts for applications in electrocatalysis,photocatalysis and thermocatalysis.Finally,a brief conclusion and future research directions on nano‐catalysis have also been presented.
文摘Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with (R)-oxynitrilase from defatted Prunus Japonica seed meal for the preparation of optically active (R)-2-trimethylsilyl-2-hydroxyl-propionitrile was successfully carried out for the first time. For better understanding of the reaction, various influential variables were examined with respect to the initial reaction rate, the substrate conversion and the product enantiomeric excess (e.e.). Diisopropyl ether was found to be the best organic phase for this reaction among all the organic solvents tested. The optimal concentrations of Prunus Japonica seed meal powder, acetyltrimethylsilane and acetone cyanohydrin, volume ratio of aqueous phase to organic phase, buffer pH value and the reaction temperature were 34.5g·L^-1 and 14mmol· L^-1, 28mmol· L^-1, 13% (by volume), 5.0 and 30℃, respectively, while the initial reaction rate, the substrate conversion and the product enantiomeric excess were 1.34 mmol·L^-1·h^-1, 99.0% and 99.0%, respectively. The comparative study demonstrated that silicon atom in substrate showed great effect on the reaction and acetyltrimethylsilane was a much better substrate for (R)-hydroxynitrile lyase from Prunus Japonica seed than its carbon analogue 3,3-dimethyl-2-butanone.
文摘Mesoporous silica materials with uniform channels containing functionalized organic monolayers have been synthesized by grafting a thiol functional group, (3-Mercaptopropyl) trimethoxysilane (MPTMS). A new approach to heavy metal ion adsorbents based on the covalent grafting of MPTMS groups to the framework pore walls of mesoporous silica molecular sieves has been developed and investigated with regard to hydroxyl group densities, channel dimensions, morphologies and reaction conditions. Results show that the ordered mesostructures of functionalized samples were retained after modification and the thiol functional group was immobilized mainly inside the mesopore channel. The relative surface coverage of the monolayer can be systematically varied up to 95%. The functionalized hybrid materials show exceptional selectivity and capacity for removing mercury from aqueous waste stream with distribution coefficients up to 435,000. The regenerated material show high mercury ion uptake capacity of 2.87 mmol/g (86.5%).
基金National Natural Science Foundation of China (Grant No. 31671928)Natural Science Foundation of Shanghai (Grant No. 15ZR1440800)。
文摘In the present study, free fatty acids(FFAs, including palmitic acid, stearic acid, oleic acid, linoleic acid and arachidonic acid) in rabbit plasma were determined by gas chromatography-mass spectrometry(GC-MS) after trimethylsilylation derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide(BSTFA) – trimethylchlorosilane(TMCS) as derivatization reagent. The experimental conditions, including extraction and silylation reaction, were investigated. The method was experimentally validated. The linearity between fatty acids’ peak areas and their concentrations was obtained with the corelative coefficient(r2) all more than 0.999, and the recoveries were between 82% and 111%. The intra-day variations of FFAs’ in plasma samples at different concentrations were all less than 6%. FFA analysis results of 16 rabbit plasma samples showed that the method could be well applied in the determination of plasma samples in vivo. In contrast to the traditional method of FFA derivatization, the established trimethylsilylation method presented simplicity, high specificity, and completely free from the interference of the esterified fatty acid, such as triacylglyceride. The method could be applied for analyzing FFA profiles in the clinical laboratory or pharmacological research.
基金the National Basic Research Program of China(973 Program,2010CB833200)the National Natural Science Foundation of China(21072160,21332007)the Program for Changjiang Scholars and Innovative Research Team at the University of the MOE for financial support
文摘A full account of the novel and flexible approach to hydroxylated 8-azabicyclo[3,2,1]octan-3-ones and 9-azabicyclo[3,3,1] nonan-3-ones is presented. Using keto-lactams as the starting materials, this two-step method consists of silyl enol ether for mation with TBDMSOTf, lactam activation with Tf20/DTBMP, and halide-promoted cyclization. Radical dechlorination of the resulting 1-halotropan-3-ones led to the corresponding hydroxylated tropan-3-ones, which can be hydrogenated to yield 3ct,613-dihydroxytropanes. Starting from optically active keto-lactams, the method has been applied to the enantioselective syntheses of (+)-(1S,3S,5R,6S)-pervilleine C (6), (+)-(1S,3R,5S,6R)-valeroidine (3), (+)-(1S,3S,5R,6S)-dibenzoyloxytropane (8) and (+)-(1S,3S,5R,6S)-merredissine (9).
基金partially supported by the National Natural Science Foundation of China (21074113,20634020 & 20974028)the National Basic Research Program of China (973 Program,2009CB623605)+1 种基金the Research Grants Council of Hong Kong (603509 & HKUST2/CRF/10)the University Grants Committee of Hong Kong (AoE/P-03/08)
文摘We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA (P2) was derived by desilylation of the pristine PA with trimethylethynylsilane side chains (P1). P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane (M) under the promotion of WC16-Ph4Sn catalyst. Two synthetic routes, i.e. two-steps (from P1 to P3 via precursor P2) and one-pot (from P1 to P3 without separation and purification of P2) were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2. By using the techniques such as GPC, FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized.