Selective propylene epoxidation to propylene oxide(PO) with hydrogen peroxide(H_2O_2) was carried out in a catalytic semi-batch reactor.High propylene epoxidation activity(44 h^(-1)) was observed over Nb based mesopor...Selective propylene epoxidation to propylene oxide(PO) with hydrogen peroxide(H_2O_2) was carried out in a catalytic semi-batch reactor.High propylene epoxidation activity(44 h^(-1)) was observed over Nb based mesoporous silicate materials Nb-TUD-1 under mild operating conditions.The physical and chemical properties of the Nb based silicates characterized using BET,FTIR,TPD,TEM and UV–Vis revealed that the site isolation and surface acidity are crucial for PO production.Catalyst synthesis methods were investigated for their effects on PO productivity,PO selectivity and H_2O_2 utilization efficiency.It is found that Nb-TUD-1 material synthesized by the sol–gel method is more active and selective than impregnated materials for liquid phase propylene epoxidation.Surface characterization confirms that thus synthesized Nb-TUD-1 catalysts have more Lewis acidity and less Bronsted acidity compared to the catalysts by impregnation.展开更多
A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of c...A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.展开更多
Ethylene oxide(EO) and propylene oxide(PO) random copolyethers were synthesized by the sequential addition of the mixture of ethylene oxide and propylene oxide to propylene glycol (initiator) in the presence of potass...Ethylene oxide(EO) and propylene oxide(PO) random copolyethers were synthesized by the sequential addition of the mixture of ethylene oxide and propylene oxide to propylene glycol (initiator) in the presence of potassium hydroxide(KOH), and characterized with infrared spectrum(FTIR) and nuclear magnetism resonance(NMR). The effects of catalyst concentration, reaction temperature, charging rate and EO/PO mixture ratio on the polymerization reaction were investigated. It was revealed that the optimal reaction condition is the ratio of 2.5∶1 000(KOH mass vs. product mass), at 114.6℃ and pressure below 0.4 MPa. The residual KOH was neutralized by phosphoric acid(H 3PO 4). Then the crude copolyether was refined with adsorbents, and the refined copolyether, which contains less than 0.7 μg/ml K+, was obtained as colorless, viscous liquid.展开更多
In this work, the surface activity of block copolymer nonionic surfactants (RPE) has been determined, i.e., critical micelle concentration (CMC), surface excess concentration (Γ), surface area demand per molecule (A)...In this work, the surface activity of block copolymer nonionic surfactants (RPE) has been determined, i.e., critical micelle concentration (CMC), surface excess concentration (Γ), surface area demand per molecule (A), surface tension at CMC (γCMC). A linear decrease of ln[CMC] vs number of oxypropylene units in copolymer molecule was observed. The change in the work of cohesion per oxypropylene group when passing from molecular into micellar state, calculated from the Shinoda equation, was 0.43kT for the studied compounds.展开更多
A white rot fungus strain, Trichoderma sp.AH, was isolated from rotten wood in Fushun and used to study the mechanism of lignite bio-solubilization.The results showed that nitric acid pretreated Fushun lignite was sol...A white rot fungus strain, Trichoderma sp.AH, was isolated from rotten wood in Fushun and used to study the mechanism of lignite bio-solubilization.The results showed that nitric acid pretreated Fushun lignite was solubilized by T.sp.AH and that extracellular proteins from T.sp.AH were correlated with the lignite bio-solubilization results.In the presence of Fushun lignite the extracellular protein concentration from T.sp.AH was 4.5 g/L while the concentration was 3 g/L in the absence of Fushun lignite.Sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE) of the extracellular proteins detected at least four new protein bands after the T.sp.AH had solubilized the lignite.Enzyme color reactions showed that extracellular proteins from T.sp.AH mainly consisted of phenol-oxidases, but that lignin decomposition enzymes such as laccase, peroxidase and manganese peroxidases were not present.展开更多
A series of new-type nanometer TiO2 modified polyacrylic copolymer sizing agent were synthesized from acrylic acid, ethyl acrylate, nanometer TiO2, oleic acid etc. by orthogonal design method. Results of the studies s...A series of new-type nanometer TiO2 modified polyacrylic copolymer sizing agent were synthesized from acrylic acid, ethyl acrylate, nanometer TiO2, oleic acid etc. by orthogonal design method. Results of the studies show that the synthetic method used in this paper was a new way and had never been found in the synthesis of acrylate sizing agent, and that the properties of those new-type size-agent were be improved, which had potential for substituting PVA (polyvinyl alcohol) sizing agent. The technology for solving the problem of nano-scale powder agglomeration and dispersion were also studied. The transmission electron microscope (TEM) observation showed that nano-TiO2had good dispersion and stability in aqueous solution and in sizing agent solution.展开更多
High temperature heat-treatment of wood, which is value-added green product, is one of the altematives to chemical treatment. It has better dimensional stability, thermal insulating properties and biological resistanc...High temperature heat-treatment of wood, which is value-added green product, is one of the altematives to chemical treatment. It has better dimensional stability, thermal insulating properties and biological resistance compared to kiln dried wood. It also has dark brown color which is very important for decorative purposes. Unfortunately, this color changes during weathering. Developing a transparent and non-toxic coating for the protection of heat-treated wood against discoloration without changing its natural appearance is the main objective of this study. For this purpose, waterborne acrylic polyurethane base was chosen because of its durability against weathering and non-toxic nature. Natural antioxidants which are extracted from barks and CeO2 nano particles （alone or together with lignin stabilizer） were used as additives to develop different coatings. The protective characteristics of these coatings were compared with highly pigmented and toxic industrial coating under accelerated weathering conditions. The results showed that acrylic polyurethane coatings protected wood better compared to commercially available coating tested in this study. The chemical modifications during accelerated weathering of coated and heat-treated wood surfaces were monitored by X-ray photoelectron spectroscopy analysis. The morphological changes took place during weathering were studied by fluorescence microscope analysis.展开更多
In plants, lipoxygenases （LOXs） play a crucial role in biotic and abiotic stresses. In our previous study, five 13-LOX genes of oriental melon were regulated by abiotic stress but it is unclear whether the 9-LOX is ...In plants, lipoxygenases （LOXs） play a crucial role in biotic and abiotic stresses. In our previous study, five 13-LOX genes of oriental melon were regulated by abiotic stress but it is unclear whether the 9-LOX is involved in biotic and abiotic stresses. The promoter analysis revealed that CmLOX09 （type of 9-LOX） has hormone elements, signal substances, and stress elements. We analyzed the expression of CmLOX09 and its downstream genes--CmHPL and CmAOS-in the leaves of four-leaf stage seedlings of the oriental melon cultivar ＂Yumeiren＂ under wound, hormone, and signal substances. CmLOX09, CmHPL, and CmAOS were all induced by wounding. CmLOX09 was induced by auxin （indole acetic acid, IAA） and gibberellins （GA3）; however, CrnHPL and CmAOS showed differential responses to IAA and GA3. CmLOX09, CmHPL, and CmAOS were all induced by hydrogen peroxide （H2O2） and methyl jasmonate （MeJA）, while being inhibited by abscisic acid （ABA） and salicylic acid （SA）. CmLOX09, CmHPL, and CmAOS were all induced by the powdery mildew pathogen Podosphaera xanthii. The content of 2-hexynol and 2-hexenal in leaves after MeJA treatment was significantly higher than that in the control. After infection with P. xanthii, the diseased leaves of the oriental melon were divided into four levels-levels 1,2, 3, and 4. The content of jasmonic acid （JA） in the leaves of levels 1 and 3 was significantly higher than that in the level 0 leaves. In summary, the results suggested that CmLOX09 might play a positive role in the response to MeJA through the hydroperoxide lyase （HPL） pathway to produce C6 alcohols and aldehydes, and in the response to P. xanthiithrough the allene oxide synthase （AOS） pathway to form JA.展开更多
Iron-catalyzed direct reduction of allylic halides with benzylic alcohol was achieved,providing a new,simple,and efficient method for conducting highly regioselective hydrodehalogenation.This method not only features ...Iron-catalyzed direct reduction of allylic halides with benzylic alcohol was achieved,providing a new,simple,and efficient method for conducting highly regioselective hydrodehalogenation.This method not only features a readily available reductant,an inexpensive catalyst,simple manipulation,and good tolerance of functional groups including nitriles,nitro,esters,and methoxyl groups,it also has mild reaction conditions and shows complete regioselectivity in that only halides sited at the allylic position are reduced.Alternatively,this method can be applied in the selective transformation of benzylic alcohols to aromatic aldehydes without overoxidation to carboxylic acids.展开更多
基金Supported by the China Postdoctoral Science Foundation(2017 M612374)the Natural Science Foundation of Shandong Province(ZR2017BB007)+5 种基金the Postdoctoral Research Funding of Shandong Province(201703016)the Qingdao Postdoctoral Research Funding(BY20170210)the Fundamental Research Funding of Qingdao(17-1-1-67-jch,17-1-1-80-jch)the Fundamental Research Funds for the Central Universities(18CX02145A,17CX02017A)the New Faculty Start-up Funding from China University of Petroleum(YJ201601058)the Natural Science Foundation of China(21606254)
文摘Selective propylene epoxidation to propylene oxide(PO) with hydrogen peroxide(H_2O_2) was carried out in a catalytic semi-batch reactor.High propylene epoxidation activity(44 h^(-1)) was observed over Nb based mesoporous silicate materials Nb-TUD-1 under mild operating conditions.The physical and chemical properties of the Nb based silicates characterized using BET,FTIR,TPD,TEM and UV–Vis revealed that the site isolation and surface acidity are crucial for PO production.Catalyst synthesis methods were investigated for their effects on PO productivity,PO selectivity and H_2O_2 utilization efficiency.It is found that Nb-TUD-1 material synthesized by the sol–gel method is more active and selective than impregnated materials for liquid phase propylene epoxidation.Surface characterization confirms that thus synthesized Nb-TUD-1 catalysts have more Lewis acidity and less Bronsted acidity compared to the catalysts by impregnation.
基金Supported by the Changcheng Scholars Program of Beijing(CIT&TCD 20150316)
文摘A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.
文摘Ethylene oxide(EO) and propylene oxide(PO) random copolyethers were synthesized by the sequential addition of the mixture of ethylene oxide and propylene oxide to propylene glycol (initiator) in the presence of potassium hydroxide(KOH), and characterized with infrared spectrum(FTIR) and nuclear magnetism resonance(NMR). The effects of catalyst concentration, reaction temperature, charging rate and EO/PO mixture ratio on the polymerization reaction were investigated. It was revealed that the optimal reaction condition is the ratio of 2.5∶1 000(KOH mass vs. product mass), at 114.6℃ and pressure below 0.4 MPa. The residual KOH was neutralized by phosphoric acid(H 3PO 4). Then the crude copolyether was refined with adsorbents, and the refined copolyether, which contains less than 0.7 μg/ml K+, was obtained as colorless, viscous liquid.
基金Project (No. 2004C31058) supported by the Zhejiang ProvincialS&T Programme of China
文摘In this work, the surface activity of block copolymer nonionic surfactants (RPE) has been determined, i.e., critical micelle concentration (CMC), surface excess concentration (Γ), surface area demand per molecule (A), surface tension at CMC (γCMC). A linear decrease of ln[CMC] vs number of oxypropylene units in copolymer molecule was observed. The change in the work of cohesion per oxypropylene group when passing from molecular into micellar state, calculated from the Shinoda equation, was 0.43kT for the studied compounds.
基金Projects 50874107 and 50374068 supported by the National Natural Science Foundation of ChinaCPEUKF06-12 by the Foundation of Key Laboratory of Coal Processing & Efficient Utilization, Ministry of Education of China
文摘A white rot fungus strain, Trichoderma sp.AH, was isolated from rotten wood in Fushun and used to study the mechanism of lignite bio-solubilization.The results showed that nitric acid pretreated Fushun lignite was solubilized by T.sp.AH and that extracellular proteins from T.sp.AH were correlated with the lignite bio-solubilization results.In the presence of Fushun lignite the extracellular protein concentration from T.sp.AH was 4.5 g/L while the concentration was 3 g/L in the absence of Fushun lignite.Sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE) of the extracellular proteins detected at least four new protein bands after the T.sp.AH had solubilized the lignite.Enzyme color reactions showed that extracellular proteins from T.sp.AH mainly consisted of phenol-oxidases, but that lignin decomposition enzymes such as laccase, peroxidase and manganese peroxidases were not present.
基金Science and Technology Bureau of Nangtong in Jiangsu Province,China(No.A5035)Depart ment of Education,Jiangsu Province,China(No.J HZD06-30)
文摘A series of new-type nanometer TiO2 modified polyacrylic copolymer sizing agent were synthesized from acrylic acid, ethyl acrylate, nanometer TiO2, oleic acid etc. by orthogonal design method. Results of the studies show that the synthetic method used in this paper was a new way and had never been found in the synthesis of acrylate sizing agent, and that the properties of those new-type size-agent were be improved, which had potential for substituting PVA (polyvinyl alcohol) sizing agent. The technology for solving the problem of nano-scale powder agglomeration and dispersion were also studied. The transmission electron microscope (TEM) observation showed that nano-TiO2had good dispersion and stability in aqueous solution and in sizing agent solution.
文摘High temperature heat-treatment of wood, which is value-added green product, is one of the altematives to chemical treatment. It has better dimensional stability, thermal insulating properties and biological resistance compared to kiln dried wood. It also has dark brown color which is very important for decorative purposes. Unfortunately, this color changes during weathering. Developing a transparent and non-toxic coating for the protection of heat-treated wood against discoloration without changing its natural appearance is the main objective of this study. For this purpose, waterborne acrylic polyurethane base was chosen because of its durability against weathering and non-toxic nature. Natural antioxidants which are extracted from barks and CeO2 nano particles （alone or together with lignin stabilizer） were used as additives to develop different coatings. The protective characteristics of these coatings were compared with highly pigmented and toxic industrial coating under accelerated weathering conditions. The results showed that acrylic polyurethane coatings protected wood better compared to commercially available coating tested in this study. The chemical modifications during accelerated weathering of coated and heat-treated wood surfaces were monitored by X-ray photoelectron spectroscopy analysis. The morphological changes took place during weathering were studied by fluorescence microscope analysis.
基金Project supported by the China Agriculture Research System(No.CARS-25)the Shenyang Science and Technology Project(No.17-143-3-00),China
文摘In plants, lipoxygenases （LOXs） play a crucial role in biotic and abiotic stresses. In our previous study, five 13-LOX genes of oriental melon were regulated by abiotic stress but it is unclear whether the 9-LOX is involved in biotic and abiotic stresses. The promoter analysis revealed that CmLOX09 （type of 9-LOX） has hormone elements, signal substances, and stress elements. We analyzed the expression of CmLOX09 and its downstream genes--CmHPL and CmAOS-in the leaves of four-leaf stage seedlings of the oriental melon cultivar ＂Yumeiren＂ under wound, hormone, and signal substances. CmLOX09, CmHPL, and CmAOS were all induced by wounding. CmLOX09 was induced by auxin （indole acetic acid, IAA） and gibberellins （GA3）; however, CrnHPL and CmAOS showed differential responses to IAA and GA3. CmLOX09, CmHPL, and CmAOS were all induced by hydrogen peroxide （H2O2） and methyl jasmonate （MeJA）, while being inhibited by abscisic acid （ABA） and salicylic acid （SA）. CmLOX09, CmHPL, and CmAOS were all induced by the powdery mildew pathogen Podosphaera xanthii. The content of 2-hexynol and 2-hexenal in leaves after MeJA treatment was significantly higher than that in the control. After infection with P. xanthii, the diseased leaves of the oriental melon were divided into four levels-levels 1,2, 3, and 4. The content of jasmonic acid （JA） in the leaves of levels 1 and 3 was significantly higher than that in the level 0 leaves. In summary, the results suggested that CmLOX09 might play a positive role in the response to MeJA through the hydroperoxide lyase （HPL） pathway to produce C6 alcohols and aldehydes, and in the response to P. xanthiithrough the allene oxide synthase （AOS） pathway to form JA.
基金the National Natural Science Foundation of China(21132002&21272038)the National Basic Research Programm of China(973 program,2009CB825300)the Shanghai Leading Academic Discipline Project(B108)for financial support
文摘Iron-catalyzed direct reduction of allylic halides with benzylic alcohol was achieved,providing a new,simple,and efficient method for conducting highly regioselective hydrodehalogenation.This method not only features a readily available reductant,an inexpensive catalyst,simple manipulation,and good tolerance of functional groups including nitriles,nitro,esters,and methoxyl groups,it also has mild reaction conditions and shows complete regioselectivity in that only halides sited at the allylic position are reduced.Alternatively,this method can be applied in the selective transformation of benzylic alcohols to aromatic aldehydes without overoxidation to carboxylic acids.
