Homeodomains,a 60-amino acid sequence encoded by 180 nucleotides,are highly conserved DNA-binding motifs that are present in a variety of transcription factors in species ranging from yeast to humans.The NKX proteins ...Homeodomains,a 60-amino acid sequence encoded by 180 nucleotides,are highly conserved DNA-binding motifs that are present in a variety of transcription factors in species ranging from yeast to humans.The NKX proteins belong to the homeodomain(HD)-containing transcription factor family.They play vital roles in the regulation of morphogenesis.NKX1-2 is one member of the NKX subfamily.At present,information about its nuclear localization signal(NLS)sequence is limited.We studied the NLS sequence of zebrafish Nkx1.2 by introducing sequence changes such as deletion,mutation,and truncation,and identified an NLS motif(QNRRTKWKKQ)that is localized at the C-terminus of the homeodomain.Moreover,the deletion of two amino acid residues(RR)in this NLS motif prevents Nkx1.2 from entering the nucleus,indicating that the two amino acids are essential for Nkx1.2 nuclear localization.However,the NLS motif alone is unable to target cytoplasmic protein glutathione S-transferase(GST)to the nucleus.An intact homeodomain is necessary for mediating the complete nuclear transport of cytoplasmic protein.Unlike most nuclear import proteins with short NLS sequences,a long NLS is present in zebrafish Nkx1.2.We also demonstrated that the sequences of homeodomain of NKX1.2 are well conserved among different species.This study is informative to verify the function of the NKX1.2 protein.展开更多
Thalamic hemorrhage can lead to the development of central post-stroke pain.Changes in histone acetylation levels,which are regulated by histone deacetylases,affect the excitability of neurons surrounding the hemorrha...Thalamic hemorrhage can lead to the development of central post-stroke pain.Changes in histone acetylation levels,which are regulated by histone deacetylases,affect the excitability of neurons surrounding the hemorrhagic area.However,the regulato ry mechanism of histone deacetylases in central post-stroke pain remains unclea r.Here,we show that iron overload leads to an increase in histone deacetylase 2expression in damaged ventral posterolateral nucleus neurons.Inhibiting this increase restored histone H3 acetylation in the Kcna2 promoter region of the voltage-dependent potassium(Kv)channel subunit gene in a rat model of central post-stroke pain,thereby increasing Kcna2expression and relieving central pain.However,in the absence of nerve injury,increasing histone deacetylase 2 expression decreased Kcna2expression,decreased Kv current,increased the excitability of neurons in the ventral posterolateral nucleus area,and led to neuropathic pain symptoms.Moreover,treatment with the iron chelator deferiprone effectively reduced iron overload in the ventral posterolateral nucleus after intracerebral hemorrhage,reversed histone deacetylase 2 upregulation and Kv1.2 downregulation,and alleviated mechanical hypersensitivity in central post-stroke pain rats.These results suggest that histone deacetylase 2 upregulation and Kv1.2 downregulation,mediated by iron overload,are important factors in central post-stroke pain pathogenesis and co uld se rve as new to rgets for central poststroke pain treatment.展开更多
Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most...Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most important parameter to the extractive distillation process. The article has given out the proper solvent ratios, reflux ratios, distillate ratios, and bottom product ratios of the columns. It also discusses the thermal loads of several columns. The results of simulation are consequently compared with the plant data, which shows good accordance with each other.展开更多
A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation. A detailed kinetic model of 1,3-buta...A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation. A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments. The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments, as well as the synergistic effect between 1,3- butadiene and propyne on the formation of a series of aromatic hydrocarbons. Based on the rate of production and sensitivity analyses, key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved. The synergistic effect results from the interaction between 1,3-butadiene and propyne. The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons. Besides, the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously, which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene.展开更多
We have investigated the dynamics of the F＋C4H6 reaction using the universal crossed molecular beam method. The C4H5F＋H reaction channel was observed in this experiment. Angular resolved time-of-flight spectra have ...We have investigated the dynamics of the F＋C4H6 reaction using the universal crossed molecular beam method. The C4H5F＋H reaction channel was observed in this experiment. Angular resolved time-of-flight spectra have been measured for the C4H5F product. Prod- uct angular distributions as well as kinetic energy distributions were determined for this product channel. Experimental results show that the C4H5F product is largely backward scattered with considerable forward scattering signal, relative to the F atom beam direction. This suggests that the reaction channel mainly proceeds via a long-lived complex formation mechanism, with possible contribution from a direct SN2 type mechanism.展开更多
The one-step conversion of ethanol to 1,3-butadiene has achieved a breakthrough with the development of beta zeolite supported dual metal catalysts.However,the reaction mechanism from ethanol to butadiene is complex a...The one-step conversion of ethanol to 1,3-butadiene has achieved a breakthrough with the development of beta zeolite supported dual metal catalysts.However,the reaction mechanism from ethanol to butadiene is complex and has not yet been fully elucidated,and no catalyst screening effort has been done based on central metal atoms.In this work,density functional theory(DFT)calculations were employed to study the mechanism of one-step conversion of ethanol to butadiene over ZnY/BEA catalyst.The results show that ethanol dehydrogenation prefers to proceed on Zn site with a reaction energy of 0.77 eV in the rate-determining step,and the aldol condensation to produce butadiene prefers to proceed on Y site with a reaction energy of 0.69 eV in the rate-determining step.Based on the mechanism revealed,six elements were selected to replace Y for screening superior combination of Zn-M/BEA(M=Sn,Nb,Ta,Hf,Zr,Ti;BEA:beta polymorph A)for this reaction.As a result,Zn-Y/BEA(0.69 eV)is proven to be the most preferring catalyst compared with the other six ones,and Zn-Zr/BEA(0.85 eV),Zn-Ti/BEA(0.87 eV),and Zn-Sn/BEA(0.93 eV)can be potential candidates for the conversion of ethanol to butadiene.This work not only provides mechanistic insights into one-step catalytic conversion of ethanol to butadiene over Zn-Y/BEA catalyst but also offers more promising catalyst candidates for this reaction.展开更多
A series of Ag-ZrO_(2)/SiO_(2) catalysts with different metal-support interfaces were synthesized in an effort to elucidate the roles of specific interfaces in controlling the ethanol to 1,3-butadiene conversion and s...A series of Ag-ZrO_(2)/SiO_(2) catalysts with different metal-support interfaces were synthesized in an effort to elucidate the roles of specific interfaces in controlling the ethanol to 1,3-butadiene conversion and selectivity.According to the results of detailed characterizations(e.g.CO/pyridine-DRIFTS,XPS,TEM,NH3-TPD,and ^(1)H MAS NMR),it was found that the Ag-O-Si interfaces significantly enhanced the dehydrogenation of ethanol while the presence of ZrO_(2) improved the interaction between Ag and ZrO_(2)/SiO_(2),creating more Ag^(δ+)active sites.The high dispersion of ZrO_(2) on SiO_(2) generated abundant Zr-O-Si interfaces with medium and weak Lewis acidity,promoting the condensation of acetaldehyde to crotonaldehyde.These Zr-O-Si interfaces in close interaction with Ag^(δ+)species played a critical role in the enhanced H transfer during the MPV reduction of crotonaldehyde to crotyl alcohol.The synergies among the interfaces resulted in retarded ethanol dehydration reactivity,balanced ethanol dehydrogenation and condensation reactions,and a subsequent high 1,3-butadiene yield.展开更多
With the advent of plastics and the wide range of fillers that are available have made modifications as precise as the tailored resins themselves. To modify the properties of polymer either by using fillers or by prep...With the advent of plastics and the wide range of fillers that are available have made modifications as precise as the tailored resins themselves. To modify the properties of polymer either by using fillers or by preparation of polymer blends gives rise to new materials with tailored properties. More complex, three-component systems, obtained by the addition of polymeric modifier to polymer filled composites may be of interest. Use of Fly ash cenospheres is very attractive because it is inexpensive and its use can reduce the environmental pollution to a significant extent. In the present study, Poly (Methyl Methacrylate) (PMMA)-Fly ash cenospheres composites were prepared using extrusion followed by Injection molding. The effect of matrix modification with Methyl methacrylate– acrylonitrile -butadiene–styrene (MABS) on the performance of PMMA- Fly ash cenospheres compositions was also, studied. It was found that with the addition of Fly ash cenospheres particulate as filler in PMMA showed marginal reduction in Tensile Strength, % Elongation and Impact strength and improvement in Flexural Strength, Heat Deflection Temperature and Vicat Softening Point. Compared with PMMA-cenospheres composites, the notched Impact Strength of the PMMA/MABS/cenospheres composites showed marginal enhancement in values at higher loading of cenospheres. The optimum performances in mechanical and thermal properties were obtained when the ratio of MABS to cenospheres was 1:2.展开更多
A series of bifunctional Zn Ce@SBA-15 catalysts with different Zn/Ce ratios were prepared by a solid-state grinding strategy and used in the conversion of ethanol to 1,3-butadiene(ETB).For the supported metal oxides,Z...A series of bifunctional Zn Ce@SBA-15 catalysts with different Zn/Ce ratios were prepared by a solid-state grinding strategy and used in the conversion of ethanol to 1,3-butadiene(ETB).For the supported metal oxides,Zn O serves as the active sites for the dehydrogenation of ethanol,and CeO_(2) promotes the aldolcondensation reaction.Based on the results of Py-FTIR and NH_(3)-TPD,it suggests that the yield of 1,3-butadiene is positively correlated with the number of weak Lewis acid sites on the catalyst surface,given their benefit for aldol-condensation reactions.The catalyst with an optimal Zn/Ce ratio of about 1:5 has the highest concentration of weak Lewis acid.Coupling with the Zn O sites,it contributes to a 98.4%conversion of ethanol and a 45.2%selective of 1,3-butadiene under relatively mild reaction conditions(375°C,101.325 k Pa,and 0.54 h^(-1)).展开更多
A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4...A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.展开更多
基金Supported by the National Natural Science Foundation of China(No.31970429)the Shandong Provincial Natural Science Foundation(No.ZR 2022 MC 032)。
文摘Homeodomains,a 60-amino acid sequence encoded by 180 nucleotides,are highly conserved DNA-binding motifs that are present in a variety of transcription factors in species ranging from yeast to humans.The NKX proteins belong to the homeodomain(HD)-containing transcription factor family.They play vital roles in the regulation of morphogenesis.NKX1-2 is one member of the NKX subfamily.At present,information about its nuclear localization signal(NLS)sequence is limited.We studied the NLS sequence of zebrafish Nkx1.2 by introducing sequence changes such as deletion,mutation,and truncation,and identified an NLS motif(QNRRTKWKKQ)that is localized at the C-terminus of the homeodomain.Moreover,the deletion of two amino acid residues(RR)in this NLS motif prevents Nkx1.2 from entering the nucleus,indicating that the two amino acids are essential for Nkx1.2 nuclear localization.However,the NLS motif alone is unable to target cytoplasmic protein glutathione S-transferase(GST)to the nucleus.An intact homeodomain is necessary for mediating the complete nuclear transport of cytoplasmic protein.Unlike most nuclear import proteins with short NLS sequences,a long NLS is present in zebrafish Nkx1.2.We also demonstrated that the sequences of homeodomain of NKX1.2 are well conserved among different species.This study is informative to verify the function of the NKX1.2 protein.
基金supported by the National Natural Science Foundation of China,Nos.U2004106 (to WY),81971061 (to JC)the Key Scientific Research Project of Colleges and Universities in Henan Province,No.21A320039 (to WY)。
文摘Thalamic hemorrhage can lead to the development of central post-stroke pain.Changes in histone acetylation levels,which are regulated by histone deacetylases,affect the excitability of neurons surrounding the hemorrhagic area.However,the regulato ry mechanism of histone deacetylases in central post-stroke pain remains unclea r.Here,we show that iron overload leads to an increase in histone deacetylase 2expression in damaged ventral posterolateral nucleus neurons.Inhibiting this increase restored histone H3 acetylation in the Kcna2 promoter region of the voltage-dependent potassium(Kv)channel subunit gene in a rat model of central post-stroke pain,thereby increasing Kcna2expression and relieving central pain.However,in the absence of nerve injury,increasing histone deacetylase 2 expression decreased Kcna2expression,decreased Kv current,increased the excitability of neurons in the ventral posterolateral nucleus area,and led to neuropathic pain symptoms.Moreover,treatment with the iron chelator deferiprone effectively reduced iron overload in the ventral posterolateral nucleus after intracerebral hemorrhage,reversed histone deacetylase 2 upregulation and Kv1.2 downregulation,and alleviated mechanical hypersensitivity in central post-stroke pain rats.These results suggest that histone deacetylase 2 upregulation and Kv1.2 downregulation,mediated by iron overload,are important factors in central post-stroke pain pathogenesis and co uld se rve as new to rgets for central poststroke pain treatment.
文摘Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most important parameter to the extractive distillation process. The article has given out the proper solvent ratios, reflux ratios, distillate ratios, and bottom product ratios of the columns. It also discusses the thermal loads of several columns. The results of simulation are consequently compared with the plant data, which shows good accordance with each other.
基金This work is supported by the National Natural Science Foundation of China （No.51476155, No.51622605, No.91541201）, the National Key Sci- entific Instruments and Equipment Development Program of China （No.2012YQ22011305）, the National Postdoctoral Program for Innovative Talents （No.BX201600100）, and China Postdoctoral Science Foundation （No.2016M600312）.
文摘A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation. A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments. The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments, as well as the synergistic effect between 1,3- butadiene and propyne on the formation of a series of aromatic hydrocarbons. Based on the rate of production and sensitivity analyses, key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved. The synergistic effect results from the interaction between 1,3-butadiene and propyne. The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons. Besides, the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously, which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene.
文摘We have investigated the dynamics of the F＋C4H6 reaction using the universal crossed molecular beam method. The C4H5F＋H reaction channel was observed in this experiment. Angular resolved time-of-flight spectra have been measured for the C4H5F product. Prod- uct angular distributions as well as kinetic energy distributions were determined for this product channel. Experimental results show that the C4H5F product is largely backward scattered with considerable forward scattering signal, relative to the F atom beam direction. This suggests that the reaction channel mainly proceeds via a long-lived complex formation mechanism, with possible contribution from a direct SN2 type mechanism.
基金This work was supported by the National Natural Science Foundation of China(No.22078257,No.22038011,and No.22108213)the National Key R&D Program of China(No.2020YFA0710000)+1 种基金the China Postdoctoral Science Foundation(No.2018T111034 and No.2021M692548)the Rising Star Program in Science and Technology of Shaanxi Province(No.2020KJXX-079).Chun-Ran Chang also acknowledges the support from the K.C.Wong Education Foundation.The calculations were performed by using the HPC Platform at Xi’an Jiaotong University。
文摘The one-step conversion of ethanol to 1,3-butadiene has achieved a breakthrough with the development of beta zeolite supported dual metal catalysts.However,the reaction mechanism from ethanol to butadiene is complex and has not yet been fully elucidated,and no catalyst screening effort has been done based on central metal atoms.In this work,density functional theory(DFT)calculations were employed to study the mechanism of one-step conversion of ethanol to butadiene over ZnY/BEA catalyst.The results show that ethanol dehydrogenation prefers to proceed on Zn site with a reaction energy of 0.77 eV in the rate-determining step,and the aldol condensation to produce butadiene prefers to proceed on Y site with a reaction energy of 0.69 eV in the rate-determining step.Based on the mechanism revealed,six elements were selected to replace Y for screening superior combination of Zn-M/BEA(M=Sn,Nb,Ta,Hf,Zr,Ti;BEA:beta polymorph A)for this reaction.As a result,Zn-Y/BEA(0.69 eV)is proven to be the most preferring catalyst compared with the other six ones,and Zn-Zr/BEA(0.85 eV),Zn-Ti/BEA(0.87 eV),and Zn-Sn/BEA(0.93 eV)can be potential candidates for the conversion of ethanol to butadiene.This work not only provides mechanistic insights into one-step catalytic conversion of ethanol to butadiene over Zn-Y/BEA catalyst but also offers more promising catalyst candidates for this reaction.
基金supported by the U.S.Department of Energy(DOE),Office of Basic Energy Sciences,Division of Chemical Sciences,Biosciences,and Geosciences Catalysis Program(DE-AC05-RL01830,FWP-47319)National Natural Science Foundation of China(21776268)Shandong Chambroad Holding Company。
文摘A series of Ag-ZrO_(2)/SiO_(2) catalysts with different metal-support interfaces were synthesized in an effort to elucidate the roles of specific interfaces in controlling the ethanol to 1,3-butadiene conversion and selectivity.According to the results of detailed characterizations(e.g.CO/pyridine-DRIFTS,XPS,TEM,NH3-TPD,and ^(1)H MAS NMR),it was found that the Ag-O-Si interfaces significantly enhanced the dehydrogenation of ethanol while the presence of ZrO_(2) improved the interaction between Ag and ZrO_(2)/SiO_(2),creating more Ag^(δ+)active sites.The high dispersion of ZrO_(2) on SiO_(2) generated abundant Zr-O-Si interfaces with medium and weak Lewis acidity,promoting the condensation of acetaldehyde to crotonaldehyde.These Zr-O-Si interfaces in close interaction with Ag^(δ+)species played a critical role in the enhanced H transfer during the MPV reduction of crotonaldehyde to crotyl alcohol.The synergies among the interfaces resulted in retarded ethanol dehydration reactivity,balanced ethanol dehydrogenation and condensation reactions,and a subsequent high 1,3-butadiene yield.
文摘With the advent of plastics and the wide range of fillers that are available have made modifications as precise as the tailored resins themselves. To modify the properties of polymer either by using fillers or by preparation of polymer blends gives rise to new materials with tailored properties. More complex, three-component systems, obtained by the addition of polymeric modifier to polymer filled composites may be of interest. Use of Fly ash cenospheres is very attractive because it is inexpensive and its use can reduce the environmental pollution to a significant extent. In the present study, Poly (Methyl Methacrylate) (PMMA)-Fly ash cenospheres composites were prepared using extrusion followed by Injection molding. The effect of matrix modification with Methyl methacrylate– acrylonitrile -butadiene–styrene (MABS) on the performance of PMMA- Fly ash cenospheres compositions was also, studied. It was found that with the addition of Fly ash cenospheres particulate as filler in PMMA showed marginal reduction in Tensile Strength, % Elongation and Impact strength and improvement in Flexural Strength, Heat Deflection Temperature and Vicat Softening Point. Compared with PMMA-cenospheres composites, the notched Impact Strength of the PMMA/MABS/cenospheres composites showed marginal enhancement in values at higher loading of cenospheres. The optimum performances in mechanical and thermal properties were obtained when the ratio of MABS to cenospheres was 1:2.
基金National Natural Science Foundation of China for financial support(21878227)。
文摘A series of bifunctional Zn Ce@SBA-15 catalysts with different Zn/Ce ratios were prepared by a solid-state grinding strategy and used in the conversion of ethanol to 1,3-butadiene(ETB).For the supported metal oxides,Zn O serves as the active sites for the dehydrogenation of ethanol,and CeO_(2) promotes the aldolcondensation reaction.Based on the results of Py-FTIR and NH_(3)-TPD,it suggests that the yield of 1,3-butadiene is positively correlated with the number of weak Lewis acid sites on the catalyst surface,given their benefit for aldol-condensation reactions.The catalyst with an optimal Zn/Ce ratio of about 1:5 has the highest concentration of weak Lewis acid.Coupling with the Zn O sites,it contributes to a 98.4%conversion of ethanol and a 45.2%selective of 1,3-butadiene under relatively mild reaction conditions(375°C,101.325 k Pa,and 0.54 h^(-1)).
基金Zhejiang Normal University for providing the financial support (YS304320035, YS304320036, ZZ323205020521005039)Financial support from the National Natural Science Foundation of China (NSFC, 21606199)+1 种基金the Science and Technology Department of Zhejiang Province (LGG20B060004)the National Key Research and Development Program of China (2021YFA1501800, 2021YFA1501801, 2021YFA1501802) are also gratefully acknowledged。
文摘A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.
