An aminophenol ligand, N,N,N'-tri(2-hydroxy-5-methylbenzyl)-l,2-ethanediamine, was prepared through the Marmich reaction, and structurally characterized by NMR, IR, MS and single-crystal X-ray diffraction. The titl...An aminophenol ligand, N,N,N'-tri(2-hydroxy-5-methylbenzyl)-l,2-ethanediamine, was prepared through the Marmich reaction, and structurally characterized by NMR, IR, MS and single-crystal X-ray diffraction. The title compound (C26H32N2O3, Mr = 420.54) belongs to the monoclinic system, space group P21/n with a = 8.6233(14), b = 10.2655(16), c = 26.017(4) A, β = 95.797(2)°, V = 2291.3(6) A^3, Z = 4, the final R = 0.0461 and wR = 0.1139 for 4267 unique reflections (Rint = 0.028) with 11691 observed ones (I〉 2a(I)).展开更多
The continuous dehydration of D-glucose into 5-hydroxymethylfurfural(HMF) was carried out under mild conditions,using SO3H-functionalized acidic ionic liquids as catalysts and H2O-4-methyl-2-pentanone(MIBK) biphas...The continuous dehydration of D-glucose into 5-hydroxymethylfurfural(HMF) was carried out under mild conditions,using SO3H-functionalized acidic ionic liquids as catalysts and H2O-4-methyl-2-pentanone(MIBK) biphasic system as solvent.High glucose conversion of 97.4% with HMF yield of 75.1%was obtained at 120 8C for 360 min,also,small amounts of levulinic acid(LA) and formic acid were generated.Generally,the dosage of catalyst and the initial content of glucose influenced the reaction significantly; the HMF selectivity decreased with the excessive elevation of temperature and prolonging of time; and water content in the system had a negative effect on the reaction.The ionic liquid catalyst could be recycled and exhibited constant activity for five successful runs.This paper provided a new strategy for HMF production from glucose.展开更多
A selective reaction of cyclohexanone oxime-blocked tolylene-2,4-diisocyanate(2,4-TDI)with amino siloxane was observed,in which amines were capable of discriminating two reactive groups in the 2,4-TDI molecule.Thus,...A selective reaction of cyclohexanone oxime-blocked tolylene-2,4-diisocyanate(2,4-TDI)with amino siloxane was observed,in which amines were capable of discriminating two reactive groups in the 2,4-TDI molecule.Thus,tolylene-2-tert-butyldimethylsilyloxyethyl carbamide-4-cyclohexanone oxime carbamate was synthesized and its precise structure was determined by single-crystal X-ray diffraction.Moreover,it was found that oxime-blocked isocyanate could react selectively with the–NH2group with the–OH group unprotected in ethanolamine.展开更多
Several new asymmetric substituted dicarbamates were synthesized with a convenient route.Firstly,tolylene-2,4-diisocyanate dimmer was obtained from monomer with tributylphosphine as catalyst.Then,the dimmer reacted wi...Several new asymmetric substituted dicarbamates were synthesized with a convenient route.Firstly,tolylene-2,4-diisocyanate dimmer was obtained from monomer with tributylphosphine as catalyst.Then,the dimmer reacted with alcohol(R^1OH) to prepare carbamate substituted uretidione.Finally,uretidione ring was opened and the released isocyanate reacted with another alcohol (R^2OH,R^1≠R^2).展开更多
The urethane reaction of o-hydroxybenzyl alcohol with phenyl isocyanate was monitored with in situ FT-IR.Dibutyltin dilaurate was used as catalyst and its amount effect was investigated.It was found that there was an ...The urethane reaction of o-hydroxybenzyl alcohol with phenyl isocyanate was monitored with in situ FT-IR.Dibutyltin dilaurate was used as catalyst and its amount effect was investigated.It was found that there was an obvious induction period before reaction began.It was interesting that the time of induction period climbed up and then declined with the increase of dibutyltin dilaurate. When the concentration of dibutyltin dilaurate reached 9.58×10^(-5) mol/L,the induction period disappeared completely and hereafter did not appear any more.Furthermore,the urethane reaction kinetics was studied.When the concentration of dibutyltin dilaurate increased,the reaction rate of phenolic group(k_1) increased sharply,but the reaction rate of alcoholic group(k_2) appeared of little change on the whole.k_1 increased about 20-fold,yet k_2 increased about 2-fold when the concentration of dibutyltin dilaurate varied from 9.58×10^(-6) mol/L to 1.92×10~4 mol/L,which made the value of k_1/k_2 enlarge.展开更多
An EPDDMAC-GE polymer (hydrophilic molecule) has been synthesized based on epoxypropyl dodecyl dimethyl ammonium chloride (EPDDMAC) and gelatin. A DEEPSAC-GE polymer (hydrophobic molecule) has been synthesized b...An EPDDMAC-GE polymer (hydrophilic molecule) has been synthesized based on epoxypropyl dodecyl dimethyl ammonium chloride (EPDDMAC) and gelatin. A DEEPSAC-GE polymer (hydrophobic molecule) has been synthesized based on diethyl-2,3-epoxypropyl-[3-methyldimethoxyl] silpropyl ammonium chloride (DEEPSAC) and gelatin. Compared with initial gelatin, the gelatin modified with quaternary ammonium salts containing epoxide groups exhibits stronger antibacterial activity.展开更多
The hybridization of mechanically responsive molecular crystals with polymers has proven to be an efficient approach to fabricate smart hybrid materials that can produce multiple motions upon external stimulus actuati...The hybridization of mechanically responsive molecular crystals with polymers has proven to be an efficient approach to fabricate smart hybrid materials that can produce multiple motions upon external stimulus actuation.However,this fabrication approach occasionally displays limitations due to the solubility or poor dispersibility of molecular crystals in the polymer matrix solution.To address these challenges,we have created a facile and versatile strategy to use metal–organic frameworks(MOFs)as a protective coating against external perturbations while also improving the dispersibility of molecular crystals.As such,a series of hybrid smart materials with reversible photomechanical performance were successfully fabricated.Notably,the afforded smart materials can combine the photoresponsive properties of mechanically responsive molecular crystals with the vapor-responsive properties of certain polymers in one system,thereby obtaining dual-stimuli responsive actuators that can perform complicated motions(e.g.,crawling).These results pave the way for the fabrication of multistimuli responsive smart materials and broaden the applicable scope of MOFs.展开更多
基金supported by Shandong Province Higher Educational Science and Technology Program (J09LB03)
文摘An aminophenol ligand, N,N,N'-tri(2-hydroxy-5-methylbenzyl)-l,2-ethanediamine, was prepared through the Marmich reaction, and structurally characterized by NMR, IR, MS and single-crystal X-ray diffraction. The title compound (C26H32N2O3, Mr = 420.54) belongs to the monoclinic system, space group P21/n with a = 8.6233(14), b = 10.2655(16), c = 26.017(4) A, β = 95.797(2)°, V = 2291.3(6) A^3, Z = 4, the final R = 0.0461 and wR = 0.1139 for 4267 unique reflections (Rint = 0.028) with 11691 observed ones (I〉 2a(I)).
基金the financial support of the National Natural Science Foundation of China (No. 21276149)Shandong National Natural Science Funds (No. ZR2013BQ014)the Program for Scientific Research Innovation Team in Colleges and Universities of Shandong Province
文摘The continuous dehydration of D-glucose into 5-hydroxymethylfurfural(HMF) was carried out under mild conditions,using SO3H-functionalized acidic ionic liquids as catalysts and H2O-4-methyl-2-pentanone(MIBK) biphasic system as solvent.High glucose conversion of 97.4% with HMF yield of 75.1%was obtained at 120 8C for 360 min,also,small amounts of levulinic acid(LA) and formic acid were generated.Generally,the dosage of catalyst and the initial content of glucose influenced the reaction significantly; the HMF selectivity decreased with the excessive elevation of temperature and prolonging of time; and water content in the system had a negative effect on the reaction.The ionic liquid catalyst could be recycled and exhibited constant activity for five successful runs.This paper provided a new strategy for HMF production from glucose.
基金financially supported by the National Natural Science Foundation of China (Nos. 21176147, 21276149 and 21204044)Program for Scientifc Research Innovation Team in Colleges and Universities of Shandong Province
文摘A selective reaction of cyclohexanone oxime-blocked tolylene-2,4-diisocyanate(2,4-TDI)with amino siloxane was observed,in which amines were capable of discriminating two reactive groups in the 2,4-TDI molecule.Thus,tolylene-2-tert-butyldimethylsilyloxyethyl carbamide-4-cyclohexanone oxime carbamate was synthesized and its precise structure was determined by single-crystal X-ray diffraction.Moreover,it was found that oxime-blocked isocyanate could react selectively with the–NH2group with the–OH group unprotected in ethanolamine.
基金the financial support from the National Natural Science Foundation of China(No. 20676074)
文摘Several new asymmetric substituted dicarbamates were synthesized with a convenient route.Firstly,tolylene-2,4-diisocyanate dimmer was obtained from monomer with tributylphosphine as catalyst.Then,the dimmer reacted with alcohol(R^1OH) to prepare carbamate substituted uretidione.Finally,uretidione ring was opened and the released isocyanate reacted with another alcohol (R^2OH,R^1≠R^2).
基金supported by the National Natural Science Foundation of China(No20676074 and No21176147)
文摘The urethane reaction of o-hydroxybenzyl alcohol with phenyl isocyanate was monitored with in situ FT-IR.Dibutyltin dilaurate was used as catalyst and its amount effect was investigated.It was found that there was an obvious induction period before reaction began.It was interesting that the time of induction period climbed up and then declined with the increase of dibutyltin dilaurate. When the concentration of dibutyltin dilaurate reached 9.58×10^(-5) mol/L,the induction period disappeared completely and hereafter did not appear any more.Furthermore,the urethane reaction kinetics was studied.When the concentration of dibutyltin dilaurate increased,the reaction rate of phenolic group(k_1) increased sharply,but the reaction rate of alcoholic group(k_2) appeared of little change on the whole.k_1 increased about 20-fold,yet k_2 increased about 2-fold when the concentration of dibutyltin dilaurate varied from 9.58×10^(-6) mol/L to 1.92×10~4 mol/L,which made the value of k_1/k_2 enlarge.
基金supported by Shandong Provincial Natural Science Foundation (Nos. Y2008B35 and ZR2010BQ002)the Star Youth Science and Technology Plans Project of Ji’nan City (No. 20110103)
文摘An EPDDMAC-GE polymer (hydrophilic molecule) has been synthesized based on epoxypropyl dodecyl dimethyl ammonium chloride (EPDDMAC) and gelatin. A DEEPSAC-GE polymer (hydrophobic molecule) has been synthesized based on diethyl-2,3-epoxypropyl-[3-methyldimethoxyl] silpropyl ammonium chloride (DEEPSAC) and gelatin. Compared with initial gelatin, the gelatin modified with quaternary ammonium salts containing epoxide groups exhibits stronger antibacterial activity.
基金The authors acknowledge the National Natural Science Foundation of China(no.21971126)111 Project(no.B12015).
文摘The hybridization of mechanically responsive molecular crystals with polymers has proven to be an efficient approach to fabricate smart hybrid materials that can produce multiple motions upon external stimulus actuation.However,this fabrication approach occasionally displays limitations due to the solubility or poor dispersibility of molecular crystals in the polymer matrix solution.To address these challenges,we have created a facile and versatile strategy to use metal–organic frameworks(MOFs)as a protective coating against external perturbations while also improving the dispersibility of molecular crystals.As such,a series of hybrid smart materials with reversible photomechanical performance were successfully fabricated.Notably,the afforded smart materials can combine the photoresponsive properties of mechanically responsive molecular crystals with the vapor-responsive properties of certain polymers in one system,thereby obtaining dual-stimuli responsive actuators that can perform complicated motions(e.g.,crawling).These results pave the way for the fabrication of multistimuli responsive smart materials and broaden the applicable scope of MOFs.