The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol （TMPD） catalyzed by the novel carbon based acid was first carried out....The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol （TMPD） catalyzed by the novel carbon based acid was first carried out. High conversion （≥98%） and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times. Moreover. the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.展开更多
[Hmim]_3PW_(12)O_(40) was developed and used in the acetalization of carbonyl compounds in excellent yields.The ionic liquidheteropoly acid hybrid compound and reaction medium formed temperature-dependent phase-separa...[Hmim]_3PW_(12)O_(40) was developed and used in the acetalization of carbonyl compounds in excellent yields.The ionic liquidheteropoly acid hybrid compound and reaction medium formed temperature-dependent phase-separation system with the ease of product as well as catalyst separation.The catalyst was recycled more than 10 times without any apparent loss of catalytic activity.展开更多
The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-((2-sulfoethoxy) carbonyl)acrylic acid and tetraethyl orthosilicate(TEOS). The catalytic activities were investigated throug...The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-((2-sulfoethoxy) carbonyl)acrylic acid and tetraethyl orthosilicate(TEOS). The catalytic activities were investigated through the acetalization. The results showed that the novel solid acid was very efficient for the reactions with the high yields. The high acidity, high stability and reusability were the key feature of the novel solid acid. Moreover, the sulfonic and carbonyl acid groups could cooperate during the catalytic process, which improved its catalytic activities. The catalyst shows recyclability, and hold great potential for replacement of homogeneous catalysts.展开更多
A new complex (1) was prepared by mixing pyridinium polystyrylsulfonate resin and aqueous fluoboric acid, followed by being dehydrated. 1 can be used as an acidic catalyst for the acetalization of benzaldehyde with n-...A new complex (1) was prepared by mixing pyridinium polystyrylsulfonate resin and aqueous fluoboric acid, followed by being dehydrated. 1 can be used as an acidic catalyst for the acetalization of benzaldehyde with n-butanol with a highly catalytic activity. The characterization and reusability of 1 are discussed.展开更多
Acetalizatioin on the blend fibers of poly(vinyl alcohol) (PVA) and soybean protein (SP) was studied by using dialdehydes as cross-linking agents. The optimal acetalization conditions were determined by Latin square e...Acetalizatioin on the blend fibers of poly(vinyl alcohol) (PVA) and soybean protein (SP) was studied by using dialdehydes as cross-linking agents. The optimal acetalization conditions were determined by Latin square experiment, where the modified fibers with good mechanical properties can be achieved by treating in 41 g/L dialdehyde solution at 67 ℃ for 9 min. The cross-linking reactions of PVA and SP with dialdehydes were confirmed by Fourier transform infrared (FTIR) spectroscopy. Tensile test and boiling water shrinkage measurements showed that the physical properties of PVA/SP fibers crosslinked by dialdehydes were improved comparing with those formalized fibers.展开更多
A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of butyraldehyde glycol acetal catalyzed by H3P...A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of butyraldehyde glycol acetal catalyzed by H3PW12O40/MCM-48 was studied with butyraldehyde and glycol as reactants. H3PW12O40/MCM-48 was an excellent catalyst for the synthesizing butyraldehyde glycol acetal and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（butyraldehyde）： n（glycol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions had been found, that was, molar ratio of butyraldehyde to glycol was 1： 1.6, mass ratio of catalyst used to the reactants was 0.25% and reaction time was 75 min. Under these conditions, the yield of butyraldehyde glycol acetal can reach 79.74%.展开更多
The reaction of 2-formylpyrrole acetals with sodium alkoxide in alcohols at reflux temperature smoothly proceeded to generate corresponding transacetalization products in nearly quantitative yields.A plausible mechani...The reaction of 2-formylpyrrole acetals with sodium alkoxide in alcohols at reflux temperature smoothly proceeded to generate corresponding transacetalization products in nearly quantitative yields.A plausible mechanism involving the formation of a highly reactive intermediate azafulvene species was proposed to explain the observed transformation.展开更多
The acetalization of a series of carbonyl compounds with ethanediolwas performed over two self-steaxned HY zeolle catalpsts' The acetal and ketaiproducts were obtained with high ytelds Espectw, the HY zeollte with...The acetalization of a series of carbonyl compounds with ethanediolwas performed over two self-steaxned HY zeolle catalpsts' The acetal and ketaiproducts were obtained with high ytelds Espectw, the HY zeollte with highfraxnework Si/A1 ratio was proven to be suitable cataipst for the acetabotion ofunsaturated carbonyl compounds, during which the C =C double bond was notperturbed展开更多
Abstract Heterogeneous catalysts with convenient recyclability and reusability are vitally important to reduce the cost of catalysts as well as to avoid complex separation and recovery operations. In this regard, magn...Abstract Heterogeneous catalysts with convenient recyclability and reusability are vitally important to reduce the cost of catalysts as well as to avoid complex separation and recovery operations. In this regard, magnetic MIL-100 （Fe）@SiO2@Fe3O4 microspheres with a novel core-shell structure were fabricated by the in-situ self-assembly of a metal-organic MIL- 100（Fe） framework around pre-synthesized magnetic SiO2@Fe3O4 particles under relatively mild and environmentally benign conditions. The catalytic activity of the MIL-100（Fe）@SiO2@Fe3O4 catalyst was tested for the liquid-phase acetalization of benzaldehyde and glycol. The MIL-100（Fe）@SiO2@Fe3O4 catalyst has a significant amount of accessible Lewis acid sites and therefore exhibited good acetalization catalytic activity. Moreover, due to its superparamagnetism properties, the heterogeneous MIL-100（Fe）@SiO2@Fe3O4 catalyst can be easily isolated from the reaction system within a few seconds by simply using an external magnet. The catalyst could then be reused at least eight times without significant loss in catalytic efficiency.展开更多
Acetalization of glycol with carbonyl compounds was carded out catalyzed by cupric p-toluenesulfonate. These carbonyl compounds included cyclohexanone, propionoaldehyde, n-butyraldehyde, /so-butyraldehyde, n-valeralde...Acetalization of glycol with carbonyl compounds was carded out catalyzed by cupric p-toluenesulfonate. These carbonyl compounds included cyclohexanone, propionoaldehyde, n-butyraldehyde, /so-butyraldehyde, n-valeraldehyde, benzaldehyde and butanone. Satisfactory results were obtained： the conversions of these carbonyl compounds were more than 90%, the selectivities were higher than 99.1%, only 0.1% mole ratio of catalyst to substrate and 90 min were sufficient in most cases. The catalyst and products were separated easily by phase separation.展开更多
Hierarchical core/shell Zeolite Socony Mobil-five(ZSM-5)zeolite was hydrothermally postsythesized in the solution of NaOH and diammonium surfactant via a dissolution-reassembly strategy.The silica and alumina species ...Hierarchical core/shell Zeolite Socony Mobil-five(ZSM-5)zeolite was hydrothermally postsythesized in the solution of NaOH and diammonium surfactant via a dissolution-reassembly strategy.The silica and alumina species were firstly dissolved partially from the bulky ZSM-5 crystals and then were reassembled into the MFI-type nanosheets with the structure-directing effect of diammonium surfactant,attaching to the out-surface of ZSM-5 core crystals.The mesopores thus were generated in both the core and shell part,giving rise to a micropore/mesopore composite material.The micropore volume and the acidity of the resultant hybrid were well-preserved during this recrystallization process.Possessing the multiple mesopores and enlarged external surface area,the core/shell ZSM-5 zeolite exhibited higher activity in the ketalation and acetalization reactions involving bulky molecules in comparison to the pristine ZSM-5.展开更多
This paper reports a practical and green method for the acetalization of carbonyl compounds as pentaerythritol diacetals and diketals derivatives using cellulose sulfuric acid as a biodegradable and reusable solid aci...This paper reports a practical and green method for the acetalization of carbonyl compounds as pentaerythritol diacetals and diketals derivatives using cellulose sulfuric acid as a biodegradable and reusable solid acid catalyst under thermal solvent-free conditions.展开更多
O,O＇Diethyl acetals were prepared in high yields under mild conditions via the reaction of triethyl orthoformate with aldehydes and ketones in absolute ethanol in the presence of as low as 0.1 tool% of Yb（OTf）3. Us...O,O＇Diethyl acetals were prepared in high yields under mild conditions via the reaction of triethyl orthoformate with aldehydes and ketones in absolute ethanol in the presence of as low as 0.1 tool% of Yb（OTf）3. Using the same catalyst in THF-H2O, these O,O＇-diethyl acetals could be converted to the corresponding carbonyl compounds efficiently. This new protection-deprotection protocol presents the advantages of ease of execution, high efficiency and good chemoselectivity.展开更多
Acetalization represents an appealing approach for the valorization of biobased platform molecules into valuable chemicals and fuels.Typically,it serves as both a synthesis tool for renewable cyclic acetals and a prot...Acetalization represents an appealing approach for the valorization of biobased platform molecules into valuable chemicals and fuels.Typically,it serves as both a synthesis tool for renewable cyclic acetals and a protection strategy to improve selectivity in biomass conversion.This contribution provides an overview on the application of the acetalization strategy in biomass valorization including synthesis of cyclic acetal fuel additives from the acetalization of biobased furanic compounds with biogenic ethylene glycol/glycerol and acetalization as a protection approach to improve product selectivity in biomass valorization.The latest progresses in the development of catalytic systems for the acetalization of biobased furanic compounds and biogenic ethylene glycol/glycerol are systematically summarized and discussed,with an emphasis on the reaction pathway,relationship between catalyst structures and their performance,and relevant catalytic mechanism.Moreover,the application of the acetalization strategy for protecting carbonyl groups/diol structure functionalities to improve the target products'selectivity in lignin depolymerization,5-hydroxymethylfurfural oxidation,sorbitol dehydration,and xylose hydrogenation is also highlighted.Eventually,the prospects and challenges in the synthesis of cyclic acetal fuel additives as well as applying acetalization as a protection strategy in biomass valorization are outlined.展开更多
Studies have shown that chitosan protects against neurodegenerative diseases. However, the precise mechanism remains poorly understood. In this study, we administered chitosan intragastrically to an MPTP-induced mouse...Studies have shown that chitosan protects against neurodegenerative diseases. However, the precise mechanism remains poorly understood. In this study, we administered chitosan intragastrically to an MPTP-induced mouse model of Parkinson's disease and found that it effectively reduced dopamine neuron injury, neurotransmitter dopamine release, and motor symptoms. These neuroprotective effects of chitosan were related to bacterial metabolites, specifically shortchain fatty acids, and chitosan administration altered intestinal microbial diversity and decreased short-chain fatty acid production in the gut. Furthermore, chitosan effectively reduced damage to the intestinal barrier and the blood–brain barrier. Finally, we demonstrated that chitosan improved intestinal barrier function and alleviated inflammation in both the peripheral nervous system and the central nervous system by reducing acetate levels. Based on these findings, we suggest a molecular mechanism by which chitosan decreases inflammation through reducing acetate levels and repairing the intestinal and blood–brain barriers, thereby alleviating symptoms of Parkinson's disease.展开更多
In this work,we have reported the synthesis of a series of heterogeneous catalysts,viz.,[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe,[HMIm]_(3)[PMo_(12)O_(40)]@MOF-Fe,and[HMIm]_(4)[SiW_(12)O_(40)]@MOFFe,by a simple impregnation m...In this work,we have reported the synthesis of a series of heterogeneous catalysts,viz.,[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe,[HMIm]_(3)[PMo_(12)O_(40)]@MOF-Fe,and[HMIm]_(4)[SiW_(12)O_(40)]@MOFFe,by a simple impregnation method.The catalysts were characterized by several techniques,such as FTIR,EDX,XRD,SEM,elemental mapping,and TGA.Among these materials,[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe had more acidic sites(confirmed by potentiometric titration)and high stability around 598℃(confirmed by TGA).The catalytic prospect of the materials was examined through selective acetalization of glycerol to solketal as a fuel additive under solvent-free and room-temperature conditions.[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe exhibited the highest catalytic activity among the three catalysts in terms of glycerol conversion(100%),solketal selectivity(100%),and solketal yield(100%).A recyclability study of[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe showed that the material could be reused for up to 7 cycles with insignificant loss in its catalytic performance.展开更多
A novel carbon based strong solid acid catalyst has been synthesized successfully. The catalytic activity for acetalization and ketalization was investigated. The results showed that the novel catalyst was very effici...A novel carbon based strong solid acid catalyst has been synthesized successfully. The catalytic activity for acetalization and ketalization was investigated. The results showed that the novel catalyst was very efficient with the average yield over 92%. The novel heterogeneous catalyst also has the advantages of high activity, wide applicability even to the preparation of 7 membered ring acetals and ketals, strikingly simple workup procedure, non-pollution and reusability, which will contribute to the green process greatly.展开更多
High-performance MXene-based polymer nanocomposites are well-suited for various industrial applications owing to their excellent mechanical,thermal,and other properties.However,the fabrication of flame-retardant polym...High-performance MXene-based polymer nanocomposites are well-suited for various industrial applications owing to their excellent mechanical,thermal,and other properties.However,the fabrication of flame-retardant polymer/MXene nanocom-posites remains challenging owing to the limited flame-retardant properties of MXene itself.This study prepared a novel MXene@Ag@PA hybrid material via radiation modification and complexation reaction.This material was used to further enhance the key properties of ethylene-vinyl acetate(EVA),such as its mechanical properties,thermal conductivity,flame retardancy,and electromagnetic shielding.The addition of two parts of this hybrid material increased the thermal conduc-tivity of EVA by 44.2%and reduced its peak exothermic rate during combustion by 30.1%compared with pure EVA.The material also significantly reduced smoke production and increased the residue content.In the X-band,the electromagnetic shielding effectiveness of the EVA composites reached 20 dB.Moreover,the MXene@Ag@PA hybrid material could be used to further enhance the mechanical properties of EVA composites under electron-beam irradiation.Thus,this study contributes to the development of MXene-based EVA advanced materials that are fire-safe,have high strength,and exhibit good electromagnetic shielding performance for various applications.展开更多
Developing favorable bio-based polymers that replace petroleum-based plastics is an essential environmental demand.Lignin is a by-product of the chemical pulping industry.It is a natural UV protection ingredient in br...Developing favorable bio-based polymers that replace petroleum-based plastics is an essential environmental demand.Lignin is a by-product of the chemical pulping industry.It is a natural UV protection ingredient in broad-spectrum(UVA and UVB)sunscreens.It could be partially and selectively acetylated in a simple,fast,and more reliable process.In this work,a composite film was prepared with UV-resistant properties through a casting method.Bio-based cellulose acetate(CA)was employed as a major matrix while nano-acetylated kraft lignin(AL-NPs)was used as filler during synthesizing UV-shielding films loaded with various amounts(1–5 wt.%)of AL-NPs.Kraft lignin was acetylated through a simple and fast microwave-assisted process using acetic acid as a solvent and acetylating agent.The physicochemical and morphological characteristics of the prepared films were evaluated using different methods,including scanning electron microscopy(SEM),Fourier Transform Infrared Spectroscopy(FTIR),X-ray diffraction analysis(XRD),mechanical testing and contact angle measurement.The UV-Vis spectroscopy optical investigation of the prepared films revealed that AL-NPs in the CA matrix showed strong UV absorption.This feature demonstrated the effectiveness of our research in developing UV-resistant bio-based polymer films.Hence,the prepared films can be considered as successful candidates to be applied in packaging applications.展开更多
Formic and acetic acids are the most abundant gaseous organic acids and play the key role in the atmospheric chemistry.In iodine-adduct chemical ionizationmass spectrometry(CIMS),the low utilization efficiency of meth...Formic and acetic acids are the most abundant gaseous organic acids and play the key role in the atmospheric chemistry.In iodine-adduct chemical ionizationmass spectrometry(CIMS),the low utilization efficiency of methyl iodide and humidity interference are two major issues of the vacuum ultraviolet(VUV)lamp initiated CIMS for on-line gaseous formic and acetic acids analysis.In this work,we present a new CIMS based on VUV lamp,and the ion-molecular reactor is separated into photoionization and chemical ionization zones by a reducer electrode.Acetone was added to the photoionization zone,and the VUV photoionization acetone provided low-energy electrons for methyl iodide to generate I−,and the addition of acetone reduced the amount of methyl iodide by 2/3.In the chemical ionization zone,a headspace vial containing ultrapure water was added for humidity calibration,and the vial changes the sensitivity as a function of humidity from ambiguity to well linear correlation(R2>0.95).With humidity calibration,the CIMS can quantitatively measure formic and acetic acids in the humidity range of 0%-88%RH.In this mode,limits of detection of 10 and 50 pptv are obtained for formic and acetic acids,respectively.And the relative standard deviation(RSD)of quantitation stability for 6 days were less than 10.5%.This CIMS was successfully used to determine the formic and acetic acids in the underground parking and ambient environment of the Shandong University campus(Qingdao,China).In addition,we developed a simple model based formic acid concentration to assess vehicular emissions.展开更多
基金the National Key Project ofScientific and Technical SupportingPrograms Funded by the Ministry of Science & Technology of China (No.2006BAE03B06)the Shanghai International Cooperation of Science and Technology Project (No.06SR07101).
文摘The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol （TMPD） catalyzed by the novel carbon based acid was first carried out. High conversion （≥98%） and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times. Moreover. the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.
基金support from Nanjing University of Science and Technology
文摘[Hmim]_3PW_(12)O_(40) was developed and used in the acetalization of carbonyl compounds in excellent yields.The ionic liquidheteropoly acid hybrid compound and reaction medium formed temperature-dependent phase-separation system with the ease of product as well as catalyst separation.The catalyst was recycled more than 10 times without any apparent loss of catalytic activity.
基金Supported by the Chinese National General Administration of Quality Supervision,Inspection and Quarantine(2012IK048,2011IK041)the National Natural Science Foundation of China(21103111)
文摘The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-((2-sulfoethoxy) carbonyl)acrylic acid and tetraethyl orthosilicate(TEOS). The catalytic activities were investigated through the acetalization. The results showed that the novel solid acid was very efficient for the reactions with the high yields. The high acidity, high stability and reusability were the key feature of the novel solid acid. Moreover, the sulfonic and carbonyl acid groups could cooperate during the catalytic process, which improved its catalytic activities. The catalyst shows recyclability, and hold great potential for replacement of homogeneous catalysts.
基金Supported by the National Natural Science Foundation of China Natural Science Founclation of Tianjin
文摘A new complex (1) was prepared by mixing pyridinium polystyrylsulfonate resin and aqueous fluoboric acid, followed by being dehydrated. 1 can be used as an acidic catalyst for the acetalization of benzaldehyde with n-butanol with a highly catalytic activity. The characterization and reusability of 1 are discussed.
文摘Acetalizatioin on the blend fibers of poly(vinyl alcohol) (PVA) and soybean protein (SP) was studied by using dialdehydes as cross-linking agents. The optimal acetalization conditions were determined by Latin square experiment, where the modified fibers with good mechanical properties can be achieved by treating in 41 g/L dialdehyde solution at 67 ℃ for 9 min. The cross-linking reactions of PVA and SP with dialdehydes were confirmed by Fourier transform infrared (FTIR) spectroscopy. Tensile test and boiling water shrinkage measurements showed that the physical properties of PVA/SP fibers crosslinked by dialdehydes were improved comparing with those formalized fibers.
基金This work was financially supported by the Natural Science Foundation of Hubei Province, China （No. 2005ABA053）.
文摘A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of butyraldehyde glycol acetal catalyzed by H3PW12O40/MCM-48 was studied with butyraldehyde and glycol as reactants. H3PW12O40/MCM-48 was an excellent catalyst for the synthesizing butyraldehyde glycol acetal and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（butyraldehyde）： n（glycol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions had been found, that was, molar ratio of butyraldehyde to glycol was 1： 1.6, mass ratio of catalyst used to the reactants was 0.25% and reaction time was 75 min. Under these conditions, the yield of butyraldehyde glycol acetal can reach 79.74%.
基金The Ministry of Education of The People's Republic of ChinaDepartment of education of Jiangxi ProvinceJiangxi Provincial Natural Science Foundation for financial support
文摘The reaction of 2-formylpyrrole acetals with sodium alkoxide in alcohols at reflux temperature smoothly proceeded to generate corresponding transacetalization products in nearly quantitative yields.A plausible mechanism involving the formation of a highly reactive intermediate azafulvene species was proposed to explain the observed transformation.
文摘The acetalization of a series of carbonyl compounds with ethanediolwas performed over two self-steaxned HY zeolle catalpsts' The acetal and ketaiproducts were obtained with high ytelds Espectw, the HY zeollte with highfraxnework Si/A1 ratio was proven to be suitable cataipst for the acetabotion ofunsaturated carbonyl compounds, during which the C =C double bond was notperturbed
基金Acknowledgements This work was supported by the National Natural Science Foundation of China （Grant No. 21576243） and the Public Project of Zhejiang Province of China （2016C37057）.
文摘Abstract Heterogeneous catalysts with convenient recyclability and reusability are vitally important to reduce the cost of catalysts as well as to avoid complex separation and recovery operations. In this regard, magnetic MIL-100 （Fe）@SiO2@Fe3O4 microspheres with a novel core-shell structure were fabricated by the in-situ self-assembly of a metal-organic MIL- 100（Fe） framework around pre-synthesized magnetic SiO2@Fe3O4 particles under relatively mild and environmentally benign conditions. The catalytic activity of the MIL-100（Fe）@SiO2@Fe3O4 catalyst was tested for the liquid-phase acetalization of benzaldehyde and glycol. The MIL-100（Fe）@SiO2@Fe3O4 catalyst has a significant amount of accessible Lewis acid sites and therefore exhibited good acetalization catalytic activity. Moreover, due to its superparamagnetism properties, the heterogeneous MIL-100（Fe）@SiO2@Fe3O4 catalyst can be easily isolated from the reaction system within a few seconds by simply using an external magnet. The catalyst could then be reused at least eight times without significant loss in catalytic efficiency.
基金Project supported by the National Natural Science Foundation of China （No. G2000048）.
文摘Acetalization of glycol with carbonyl compounds was carded out catalyzed by cupric p-toluenesulfonate. These carbonyl compounds included cyclohexanone, propionoaldehyde, n-butyraldehyde, /so-butyraldehyde, n-valeraldehyde, benzaldehyde and butanone. Satisfactory results were obtained： the conversions of these carbonyl compounds were more than 90%, the selectivities were higher than 99.1%, only 0.1% mole ratio of catalyst to substrate and 90 min were sufficient in most cases. The catalyst and products were separated easily by phase separation.
基金the financial support from Ministry of Science and Technology of China(Grant No.2016YFA0202804)the National Natural Science Foundation of China(Grant Nos.21872052,21533002,21571128 and 21603075).
文摘Hierarchical core/shell Zeolite Socony Mobil-five(ZSM-5)zeolite was hydrothermally postsythesized in the solution of NaOH and diammonium surfactant via a dissolution-reassembly strategy.The silica and alumina species were firstly dissolved partially from the bulky ZSM-5 crystals and then were reassembled into the MFI-type nanosheets with the structure-directing effect of diammonium surfactant,attaching to the out-surface of ZSM-5 core crystals.The mesopores thus were generated in both the core and shell part,giving rise to a micropore/mesopore composite material.The micropore volume and the acidity of the resultant hybrid were well-preserved during this recrystallization process.Possessing the multiple mesopores and enlarged external surface area,the core/shell ZSM-5 zeolite exhibited higher activity in the ketalation and acetalization reactions involving bulky molecules in comparison to the pristine ZSM-5.
文摘This paper reports a practical and green method for the acetalization of carbonyl compounds as pentaerythritol diacetals and diketals derivatives using cellulose sulfuric acid as a biodegradable and reusable solid acid catalyst under thermal solvent-free conditions.
基金Project supported by the National Natural Science Foundation of China （Nos. 20425205, 20321202） and the Shanghai Municipal Commission of Science and Technology （Nos. 04DZ 14901, 06QH 14016）.
文摘O,O＇Diethyl acetals were prepared in high yields under mild conditions via the reaction of triethyl orthoformate with aldehydes and ketones in absolute ethanol in the presence of as low as 0.1 tool% of Yb（OTf）3. Using the same catalyst in THF-H2O, these O,O＇-diethyl acetals could be converted to the corresponding carbonyl compounds efficiently. This new protection-deprotection protocol presents the advantages of ease of execution, high efficiency and good chemoselectivity.
基金The authors gratefully acknowledge financial support from National Key R&D Program of China(2019YFC1905300)National Natural Science Foundation of China(No.22268019)Hunan Provincial Natural Science Foundation of China(No.2021JJ40436)。
文摘Acetalization represents an appealing approach for the valorization of biobased platform molecules into valuable chemicals and fuels.Typically,it serves as both a synthesis tool for renewable cyclic acetals and a protection strategy to improve selectivity in biomass conversion.This contribution provides an overview on the application of the acetalization strategy in biomass valorization including synthesis of cyclic acetal fuel additives from the acetalization of biobased furanic compounds with biogenic ethylene glycol/glycerol and acetalization as a protection approach to improve product selectivity in biomass valorization.The latest progresses in the development of catalytic systems for the acetalization of biobased furanic compounds and biogenic ethylene glycol/glycerol are systematically summarized and discussed,with an emphasis on the reaction pathway,relationship between catalyst structures and their performance,and relevant catalytic mechanism.Moreover,the application of the acetalization strategy for protecting carbonyl groups/diol structure functionalities to improve the target products'selectivity in lignin depolymerization,5-hydroxymethylfurfural oxidation,sorbitol dehydration,and xylose hydrogenation is also highlighted.Eventually,the prospects and challenges in the synthesis of cyclic acetal fuel additives as well as applying acetalization as a protection strategy in biomass valorization are outlined.
基金supported by the National Natural Science Foundation of China,Nos. 32260196 (to JY), 81860646 (to ZY) and 31860274 (to JY)a grant from Yunnan Department of Science and Technology,Nos. 202101AT070251 (to JY), 202201AS070084 (to ZY), 202301AY070001-239 (to JY), 202101AZ070001-012, and 2019FI016 (to ZY)。
文摘Studies have shown that chitosan protects against neurodegenerative diseases. However, the precise mechanism remains poorly understood. In this study, we administered chitosan intragastrically to an MPTP-induced mouse model of Parkinson's disease and found that it effectively reduced dopamine neuron injury, neurotransmitter dopamine release, and motor symptoms. These neuroprotective effects of chitosan were related to bacterial metabolites, specifically shortchain fatty acids, and chitosan administration altered intestinal microbial diversity and decreased short-chain fatty acid production in the gut. Furthermore, chitosan effectively reduced damage to the intestinal barrier and the blood–brain barrier. Finally, we demonstrated that chitosan improved intestinal barrier function and alleviated inflammation in both the peripheral nervous system and the central nervous system by reducing acetate levels. Based on these findings, we suggest a molecular mechanism by which chitosan decreases inflammation through reducing acetate levels and repairing the intestinal and blood–brain barriers, thereby alleviating symptoms of Parkinson's disease.
文摘In this work,we have reported the synthesis of a series of heterogeneous catalysts,viz.,[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe,[HMIm]_(3)[PMo_(12)O_(40)]@MOF-Fe,and[HMIm]_(4)[SiW_(12)O_(40)]@MOFFe,by a simple impregnation method.The catalysts were characterized by several techniques,such as FTIR,EDX,XRD,SEM,elemental mapping,and TGA.Among these materials,[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe had more acidic sites(confirmed by potentiometric titration)and high stability around 598℃(confirmed by TGA).The catalytic prospect of the materials was examined through selective acetalization of glycerol to solketal as a fuel additive under solvent-free and room-temperature conditions.[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe exhibited the highest catalytic activity among the three catalysts in terms of glycerol conversion(100%),solketal selectivity(100%),and solketal yield(100%).A recyclability study of[HMIm]_(3)[PW_(12)O_(40)]@MOF-Fe showed that the material could be reused for up to 7 cycles with insignificant loss in its catalytic performance.
文摘A novel carbon based strong solid acid catalyst has been synthesized successfully. The catalytic activity for acetalization and ketalization was investigated. The results showed that the novel catalyst was very efficient with the average yield over 92%. The novel heterogeneous catalyst also has the advantages of high activity, wide applicability even to the preparation of 7 membered ring acetals and ketals, strikingly simple workup procedure, non-pollution and reusability, which will contribute to the green process greatly.
文摘High-performance MXene-based polymer nanocomposites are well-suited for various industrial applications owing to their excellent mechanical,thermal,and other properties.However,the fabrication of flame-retardant polymer/MXene nanocom-posites remains challenging owing to the limited flame-retardant properties of MXene itself.This study prepared a novel MXene@Ag@PA hybrid material via radiation modification and complexation reaction.This material was used to further enhance the key properties of ethylene-vinyl acetate(EVA),such as its mechanical properties,thermal conductivity,flame retardancy,and electromagnetic shielding.The addition of two parts of this hybrid material increased the thermal conduc-tivity of EVA by 44.2%and reduced its peak exothermic rate during combustion by 30.1%compared with pure EVA.The material also significantly reduced smoke production and increased the residue content.In the X-band,the electromagnetic shielding effectiveness of the EVA composites reached 20 dB.Moreover,the MXene@Ag@PA hybrid material could be used to further enhance the mechanical properties of EVA composites under electron-beam irradiation.Thus,this study contributes to the development of MXene-based EVA advanced materials that are fire-safe,have high strength,and exhibit good electromagnetic shielding performance for various applications.
文摘Developing favorable bio-based polymers that replace petroleum-based plastics is an essential environmental demand.Lignin is a by-product of the chemical pulping industry.It is a natural UV protection ingredient in broad-spectrum(UVA and UVB)sunscreens.It could be partially and selectively acetylated in a simple,fast,and more reliable process.In this work,a composite film was prepared with UV-resistant properties through a casting method.Bio-based cellulose acetate(CA)was employed as a major matrix while nano-acetylated kraft lignin(AL-NPs)was used as filler during synthesizing UV-shielding films loaded with various amounts(1–5 wt.%)of AL-NPs.Kraft lignin was acetylated through a simple and fast microwave-assisted process using acetic acid as a solvent and acetylating agent.The physicochemical and morphological characteristics of the prepared films were evaluated using different methods,including scanning electron microscopy(SEM),Fourier Transform Infrared Spectroscopy(FTIR),X-ray diffraction analysis(XRD),mechanical testing and contact angle measurement.The UV-Vis spectroscopy optical investigation of the prepared films revealed that AL-NPs in the CA matrix showed strong UV absorption.This feature demonstrated the effectiveness of our research in developing UV-resistant bio-based polymer films.Hence,the prepared films can be considered as successful candidates to be applied in packaging applications.
基金supported by the National Special Fund for the Development of Major Research Equipment and Instrument(No.2020YFF01014503)the Young Taishan Scholars(No.tsqn201909039)the College 20 Project fromJi Nan Science&Technology Bureau(No.2021GXRC058).
文摘Formic and acetic acids are the most abundant gaseous organic acids and play the key role in the atmospheric chemistry.In iodine-adduct chemical ionizationmass spectrometry(CIMS),the low utilization efficiency of methyl iodide and humidity interference are two major issues of the vacuum ultraviolet(VUV)lamp initiated CIMS for on-line gaseous formic and acetic acids analysis.In this work,we present a new CIMS based on VUV lamp,and the ion-molecular reactor is separated into photoionization and chemical ionization zones by a reducer electrode.Acetone was added to the photoionization zone,and the VUV photoionization acetone provided low-energy electrons for methyl iodide to generate I−,and the addition of acetone reduced the amount of methyl iodide by 2/3.In the chemical ionization zone,a headspace vial containing ultrapure water was added for humidity calibration,and the vial changes the sensitivity as a function of humidity from ambiguity to well linear correlation(R2>0.95).With humidity calibration,the CIMS can quantitatively measure formic and acetic acids in the humidity range of 0%-88%RH.In this mode,limits of detection of 10 and 50 pptv are obtained for formic and acetic acids,respectively.And the relative standard deviation(RSD)of quantitation stability for 6 days were less than 10.5%.This CIMS was successfully used to determine the formic and acetic acids in the underground parking and ambient environment of the Shandong University campus(Qingdao,China).In addition,we developed a simple model based formic acid concentration to assess vehicular emissions.
