Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy...Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy to improve the catalytic performance of haloalkane dehalogenase DhaA in OSs based on the energetic analysis of substrate binding to the DhaA surface.Several variants with enhanced OS resistance were obtained by replacing negative charged residues on the surface with positive charged residue(Arg).Particularly,a four-substitution variant E16R/E93R/E121R/E257R exhibited the best catalytic performance(five-fold improvement in OS resistance and seven-fold half-life increase in 40%(vol)dimethylsulfoxide).As a result,the overall catalytic performance of the variant could be at least 26 times higher than the wild-type DhaA.Fluorescence spectroscopy and molecular dynamics simulation studies revealed that the residue substitution mainly enhanced OS resistance from four aspects:(a)improved the overall structural stability,(b)increased the hydrophobicity of the local microenvironment around the catalytic triad,(c)enriched the hydrophobic substrate around the enzyme molecule,and(d)lowered the contact frequency between OS molecules and the catalytic triad.Our findings validate that computationaided surface charge engineering is an effective and ingenious rational strategy for tailoring enzyme performance in OSs.展开更多
A high performance preoxidized poly(acrylonitrile)(O-PAN)nanofiber membrane with excellent solvent resistance,thermal stability and flexibility was fabricated by the preoxidation of electrospun PAN nanofiber membrane....A high performance preoxidized poly(acrylonitrile)(O-PAN)nanofiber membrane with excellent solvent resistance,thermal stability and flexibility was fabricated by the preoxidation of electrospun PAN nanofiber membrane.The performance of resultant O-PAN nanofiber membrane was optimized by altering the PAN concentration and preoxidation temperature.The results showed that the O-PAN nanofiber membrane which made from PAN concentration of 14%(mass)and preoxidation temperature of 250.0℃ have a more optimal comprehensive performance.In the long-term separation test of SiO2 particle(1 μm)in DMAc suspension,the permeate flux of O-PAN nanofiber membrane stabilized at 227.91 L·m^(-2)·h^(-1)(25℃,0.05 MPa)while the SiO2 rejection above 99.6%,which showed excellent solvent resistance and separation performance.In order to further explore the application of the O-PAN nanofiber membrane,the OPAN nanofiber membrane was treated with fluoride and used in oil/water separation process.The O-PAN nanofiber membrane after hydrophobic treatment showed excellent hydrophobicity and good oil/water separation performance with the permeate flux about 969.59 L·m^(-2)·h^(-1)while the separation efficiency above 96.1%.The O-PAN nanofiber membrane exhibited a potential application prospect in harsh environment separation.展开更多
The solution-processed method for organic light-emitting diodes(OLEDs)offers the benefits of cost-effectiveness and enhanced material utilization.In the multilayer architecture of solution-processed OLEDs(SOLEDs),the ...The solution-processed method for organic light-emitting diodes(OLEDs)offers the benefits of cost-effectiveness and enhanced material utilization.In the multilayer architecture of solution-processed OLEDs(SOLEDs),the role of hole-transport materials(HTMs)is pivotal for cascade hole injection.However,commercial HTMs such as poly-(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine)(TFB)are hampered by incompatible energy levels and redissolution with overlayer solvent,prompting the exploration of cross-linkable HTMs(X-HTMs)for better performance.In this study,we have developed two novel small-molecule X-HTMs,N^(1),N^(1)′-((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(N^(4),N^(4)-diphenyl-N^(1)-(4-vinylphenyl)benzene-1,4-diamine)(FTPA-V)and N,N′-((perfluoropropane-2,2-diyl)bis-(4,1-phenylene))bis(9-phenyl-N-(4-vinylphenyl)-9H-carbazol-3-amine)(FPCz-V),which incorporate thermally cross-linkable vinyl groups and electron-rich trifluoromethyl units.The X-HTMs enhance interfacial contact through superior film formation and solvent resistance,along with optimal energy levels.The application of X-HTMs significantly enhances the efficiencies and longevities of blue,green,and red SOLEDs.Specially,blue SOLED incorporating FPCz-V exhibits unprecedented lifetime(LT95)extending to over 150 h,setting a new record for blue SOLEDs.The electrochemistry stability,high bond dissociation energy,and triplet energy levels of X-HTMs can effectively minimize exciton annihilation and prolong the lifetime.These findings underscore the potential of X-HTM optimization to propel the development of stable solution-processed luminescent technologies.展开更多
基金funded by the National Key Research and Development Program of China(2018YFA0900702).
文摘Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy to improve the catalytic performance of haloalkane dehalogenase DhaA in OSs based on the energetic analysis of substrate binding to the DhaA surface.Several variants with enhanced OS resistance were obtained by replacing negative charged residues on the surface with positive charged residue(Arg).Particularly,a four-substitution variant E16R/E93R/E121R/E257R exhibited the best catalytic performance(five-fold improvement in OS resistance and seven-fold half-life increase in 40%(vol)dimethylsulfoxide).As a result,the overall catalytic performance of the variant could be at least 26 times higher than the wild-type DhaA.Fluorescence spectroscopy and molecular dynamics simulation studies revealed that the residue substitution mainly enhanced OS resistance from four aspects:(a)improved the overall structural stability,(b)increased the hydrophobicity of the local microenvironment around the catalytic triad,(c)enriched the hydrophobic substrate around the enzyme molecule,and(d)lowered the contact frequency between OS molecules and the catalytic triad.Our findings validate that computationaided surface charge engineering is an effective and ingenious rational strategy for tailoring enzyme performance in OSs.
基金supported by the Science and Technology Plans of Tianjin(18PTSYJC00170)the Young Elite Scientists Sponsorship Program by China Association for Science and Technology(YESS20160168)The Analytical&Testing Center of Tiangong University was appreciated.
文摘A high performance preoxidized poly(acrylonitrile)(O-PAN)nanofiber membrane with excellent solvent resistance,thermal stability and flexibility was fabricated by the preoxidation of electrospun PAN nanofiber membrane.The performance of resultant O-PAN nanofiber membrane was optimized by altering the PAN concentration and preoxidation temperature.The results showed that the O-PAN nanofiber membrane which made from PAN concentration of 14%(mass)and preoxidation temperature of 250.0℃ have a more optimal comprehensive performance.In the long-term separation test of SiO2 particle(1 μm)in DMAc suspension,the permeate flux of O-PAN nanofiber membrane stabilized at 227.91 L·m^(-2)·h^(-1)(25℃,0.05 MPa)while the SiO2 rejection above 99.6%,which showed excellent solvent resistance and separation performance.In order to further explore the application of the O-PAN nanofiber membrane,the OPAN nanofiber membrane was treated with fluoride and used in oil/water separation process.The O-PAN nanofiber membrane after hydrophobic treatment showed excellent hydrophobicity and good oil/water separation performance with the permeate flux about 969.59 L·m^(-2)·h^(-1)while the separation efficiency above 96.1%.The O-PAN nanofiber membrane exhibited a potential application prospect in harsh environment separation.
基金supported by the National Natural Science Foundation of China(22275003)Shenzhen Fundamental Research Program(JCYJ20200109140425347)+4 种基金the Development and Reform Commission of Shenzhen Municipality(XMHT20200106002)the Key-Area Research and Development Program of Guangdong Province(2019B010924003)Guangdong Basic and Applied Basic Research Foundation(2020B1515120030)provided by Guangdong Key Laboratory of Flexible Optoelectronic Materials and DevicesGuangdong International Science and Technology Cooperation Base of Optoelectronic Materials and Device Technology。
文摘The solution-processed method for organic light-emitting diodes(OLEDs)offers the benefits of cost-effectiveness and enhanced material utilization.In the multilayer architecture of solution-processed OLEDs(SOLEDs),the role of hole-transport materials(HTMs)is pivotal for cascade hole injection.However,commercial HTMs such as poly-(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine)(TFB)are hampered by incompatible energy levels and redissolution with overlayer solvent,prompting the exploration of cross-linkable HTMs(X-HTMs)for better performance.In this study,we have developed two novel small-molecule X-HTMs,N^(1),N^(1)′-((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(N^(4),N^(4)-diphenyl-N^(1)-(4-vinylphenyl)benzene-1,4-diamine)(FTPA-V)and N,N′-((perfluoropropane-2,2-diyl)bis-(4,1-phenylene))bis(9-phenyl-N-(4-vinylphenyl)-9H-carbazol-3-amine)(FPCz-V),which incorporate thermally cross-linkable vinyl groups and electron-rich trifluoromethyl units.The X-HTMs enhance interfacial contact through superior film formation and solvent resistance,along with optimal energy levels.The application of X-HTMs significantly enhances the efficiencies and longevities of blue,green,and red SOLEDs.Specially,blue SOLED incorporating FPCz-V exhibits unprecedented lifetime(LT95)extending to over 150 h,setting a new record for blue SOLEDs.The electrochemistry stability,high bond dissociation energy,and triplet energy levels of X-HTMs can effectively minimize exciton annihilation and prolong the lifetime.These findings underscore the potential of X-HTM optimization to propel the development of stable solution-processed luminescent technologies.