A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4(pbeddb)4(H2O)2(DMAC)2] (MOC-18; pbeddb2- = 3,3'-(1,3-phenylenebis(ethyne-2,1-diyl))dibenzoate) was applied to the N-- H insertion reactions wit...A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4(pbeddb)4(H2O)2(DMAC)2] (MOC-18; pbeddb2- = 3,3'-(1,3-phenylenebis(ethyne-2,1-diyl))dibenzoate) was applied to the N-- H insertion reactions with diazo compounds. This method offered an environmentally friendly and highly efficient approach for C--N bond formation.展开更多
Vacuum diffusion bonding of a TiAl based alloy (TAD) to a titanium alloy (TC2) was carried out at 1 273 K for 15~120 min under a pressure of 25 MPa . The kinds of the reaction products and the interface s...Vacuum diffusion bonding of a TiAl based alloy (TAD) to a titanium alloy (TC2) was carried out at 1 273 K for 15~120 min under a pressure of 25 MPa . The kinds of the reaction products and the interface structures of the joints were investigated by SEM, EPMA and XRD. Based on this, a formation mechanism of the interface structure was elucidated. Experimental and analytical results show that two reaction layers have formed during the diffusion bonding of TAD to TC2. One is Al rich α(Ti)layer adjacent to TC2,and the other is (Ti 3Al+TiAl)layer adjacent to TAD,thus the interface structure of the TAD/TC2 joints is TAD/(Ti 3Al+TiAl)/α(Ti)/TC2.This interface structure forms according to a three stage mechanism,namely(a)the occurrence of a single phase α(Ti)layer;(b)the occurrence of a duplex phase(Ti 3Al+TiAl)layer;and(c)the growth of the α(Ti)and (Ti 3Al+TiAl)layers.展开更多
Understanding the seven coordination and O-O coupling pathway of the distinguished Ru-bda catalysts is essential for the development of next generation efficient water-oxidation catalysts based on earthabundant metals...Understanding the seven coordination and O-O coupling pathway of the distinguished Ru-bda catalysts is essential for the development of next generation efficient water-oxidation catalysts based on earthabundant metals.This work reports the synthesis,characterization and catalytic properties of a monomeric ruthenium catalyst Ru-bnda(H2 bnda=2,2’-bi(nicotinic acid)-6,6’-dicarboxylic acid)featuring steric hindrance and enhanced hydrophilicity on the backbone.Combining experimental evidence with systematic density functional theory calculations on the Ru-bnda and related catalysts Ru-bda(H_(2)bda=2,2’-bipyridine-6,6’-dicarboxylic acid),Ru-pda(H_(2)pda=1,10-phenanthroline-2,9-dicarboxylic acid),and Ru-biqa(H_(2)biqa=(1,1’-biisoquinoline)-3,3’-dicarboxylic acid),we emphasized that seven coordination clearly determines presence of Ru^(Ⅴ)=O with high spin density on the ORu^(Ⅴ)=O atom,i.e.oxo with radical properties,which is one of the necessary conditions for reacting through the O-O coupling pathway.However,an additional factor to make the condition sufficient is the favorable intermolecular faceto-face interaction for the generation of the pre-reactive[Ru^(Ⅴ)=O…O=Ru^(Ⅴ)],which may be significantly influenced by the secondary coordination environments.This work provides a new understanding of the structure-activity relationship of water-oxidation catalysts and their potential to adopt I2M pathway for O-O bond formation.展开更多
Self-healing hydrogels have attracted tremendous attention in the field of oil and gas drilling and production engineering because of their excellent self-healing performance after physical damage.In this study,a seri...Self-healing hydrogels have attracted tremendous attention in the field of oil and gas drilling and production engineering because of their excellent self-healing performance after physical damage.In this study,a series of double network self-healing(DN_(SA))hydrogels based on hydrophobic association and ionic bond were prepared for plugging pores and fractures in formations in oil and gas drilling and production engineering.The mechanical,rheological,and self-healing properties of the DN_(SA)hydrogels were investigated.Results revealed that the DN_(SA)hydrogels exhibited excellent mechanical properties with a tensile stress of 0.67 MPa and toughness of 7069 kJ/cm^(3) owing to the synergistic effect of the double network.In addition,the DN_(SA)hydrogels exhibited excellent compression resistance,notch insensitivity,and self-healing properties.The DN_(SA)-2 hydrogel was granulated and made into gel particles with different particle sizes and used as a plugging agent.The self-healing mechanism of DN_(SA)-2 hydrogel particles in fractures was explored,and it’s plugging effect on fractures of different widths and porous media of different permeabilities were investigated.Experimental results revealed that the plugging capacity of the DN_(SA)-2 hydrogel particles for a fracture with width of 5 mm and a porous medium with a permeability of 30μm^(2) was 3.45 and 4.21 MPa,respectively,which is significantly higher than those of commonly used plugging agents in the oilfield.The DN_(SA)hydrogels with excellent mechanical and self-healing properties prepared in this study will provide a new approach for applying hydrogels in oil and gas drilling and production engineering.展开更多
Numerous aspects of the water oxidation mechanism in photosystemⅡhave not been fully elucidated,especially the O-O bond formation pathway.However,a body of experimental evidences have identified the O5 and W2 ligands...Numerous aspects of the water oxidation mechanism in photosystemⅡhave not been fully elucidated,especially the O-O bond formation pathway.However,a body of experimental evidences have identified the O5 and W2 ligands of the oxygen-evolving complex as the highly probable substrate candidates.In this work,we studied O-O bond formation between O5 and W2 based on the native Mn4 Ca cluster by density functional calculations.Structural rearrangements before the formation of the S_(4) state were found as a prerequisite for O-O bond formation between O5 and W2,regardless if the suggested pathways involving the typical Mnl(Ⅳ)-O·species or the recently proposed Mn4(Ⅶ)(O)2 species.Possible alternatives for the S2→S_(3) and S_(3)→S_(4) transitions accounting for such required rearrangements are discussed.These findings reflect that the structural flexibility of the Mn4 Ca cluster is essential to allow structural rearrangements during the catalytic cycle.展开更多
Al2O3-Ni interface formed under vacuum condition is non-wetting and weak. Severe instantaneous intedecial reaction (i.e. wetting) at the Al2O3-Ni interface promoted by oxygen can create a strengthened interface. The N...Al2O3-Ni interface formed under vacuum condition is non-wetting and weak. Severe instantaneous intedecial reaction (i.e. wetting) at the Al2O3-Ni interface promoted by oxygen can create a strengthened interface. The NiAl2O4 spinel-Ni intedece is weak and growth of the spinel interphase is detrimental to the Al2O3-Ni intedecial bonding. A proper control of the oxygen partial pressure can achieve wetting while avoiding the existence of spinel at the interface, producing stronger interfaces by both mechanical interlocking and more intimate chemical bonding in an Al2O3-20 vol pct Ni composite.展开更多
The formation and breaking of intramolecular hydrogen bonds of bilirubin in CDCl_3-DMSO-d_6 binary solvent have been investigated by means of NMR spectroscopy.The chemical shifts of protons at dipyrrinone lactam C=O a...The formation and breaking of intramolecular hydrogen bonds of bilirubin in CDCl_3-DMSO-d_6 binary solvent have been investigated by means of NMR spectroscopy.The chemical shifts of protons at dipyrrinone lactam C=O and N-H,Pyrrole N-H,C-5,C-15 and methylene groups of 8,12-propionic acid side-chains changed markedly as a function of composition of the binary solvent.The hydrogen bond formation is dependent on the conformation of propionic acid side-chains.展开更多
Kluyveromyces marxianus is a food-safe yeast with great potential for producing heterologous proteins.Improving the yield in K.marxianus remains a challenge and incorporating large-scale functional modules poses a tec...Kluyveromyces marxianus is a food-safe yeast with great potential for producing heterologous proteins.Improving the yield in K.marxianus remains a challenge and incorporating large-scale functional modules poses a technical obstacle in engineering.To address these issues,linear and circular yeast artificial chromosomes of K.marxianus(KmYACs)were constructed and loaded with disulfide bond formation modules from Pichia pastoris or K.marxianus.These modules contained up to seven genes with a maximum size of 15 kb.KmYACs carried telomeres either from K.marxianus or Tetrahymena.KmYACs were transferred successfully into K.marxianus and stably propagated without affecting the normal growth of the host,regardless of the type of telomeres and configurations of KmYACs.KmYACs increased the overall expression levels of disulfide bond formation genes and significantly enhanced the yield of various heterologous proteins.In high-density fermentation,the use of KmYACs resulted in a glucoamylase yield of 16.8 g/l,the highest reported level to date in K.marxianus.Transcriptomic and metabolomic analysis of cells containing KmYACs suggested increased flavin adenine dinucleotide biosynthesis,enhanced flux entering the tricarboxylic acid cycle,and a preferred demand for lysine and arginine as features of cells overexpressing heterologous proteins.Consistently,supplementing lysine or arginine further improved the yield.Therefore,KmYAC provides a powerful platform for manipulating large modules with enormous potential for industrial applications and fundamental research.Transferring the disulfide bond formation module via YACs proves to be an efficient strategy for improving the yield of heterologous proteins,and this strategy may be applied to optimize other microbial cell factories.展开更多
In this work, the formation sites, helical parameters and hydrogen bond positions of Konjac glucomannan molecular helices were investigated using molecular dynamic simulation method. To our interest, the KGM chain is ...In this work, the formation sites, helical parameters and hydrogen bond positions of Konjac glucomannan molecular helices were investigated using molecular dynamic simulation method. To our interest, the KGM chain is mainly composed by local left and right helix struetttres. The formation sites of KGM chain might locate at the chain-segments containing acetyl groups, and the left helix is the favorable conformation of KGM. Temperature-dependent molecule conformation study indicates that the right helix is dominant when the temperature is lower than 343 K, above which, however, the left helix is dominating (right helix disappears). In addition, intramolecular hydrogen bonds in the left helix can be found at the -OH groups on C(2), C(4) and C(6) of mannose residues; comparably, the intramolecular hydrogen bonds in the right helix can be mainly observed at the -OH groups on C(4) and C(6) of the mannose residues and C(3) of the glucose residues. In conclusion, molecular dynamic simulation is an efficient method for the microscopic conformation study of glucomannan molecular helices.展开更多
Resultant gradient-information is introduced and applied to problems in chemical reactivity theory. This local measure of the structural information contained in (complex) wavefunctions of electronic states is related...Resultant gradient-information is introduced and applied to problems in chemical reactivity theory. This local measure of the structural information contained in (complex) wavefunctions of electronic states is related to the system overall kinetic energy combining the modulus (probability) and phase (current) contributions. The grand-ensemble representation of thermodynamic equilibria in open systems demonstrates the physical equivalence of the variational energetic and information principles. It is used and to relate the populational derivatives of ensemble-average functionals in both these representations, which represent reactivity criteria for diagnosing the charge-transfer (CT) phenomena. Their equivalence is demonstrated by using the in situ potential and hardness descriptors to predict the direction and optimum amount of CT. The virial theorem is generalized into thermodynamic quantities and used to extract the kinetic energy component from qualitative energy profiles in the bond-formation and (exo/endo)-ergic reactions. The role of electronic kinetic energy in such chemical processes is reexamined, the virial theorem implications for the Hammond postulate of reactivity theory are explored, and variations of the structural-information in chemical processes are addressed. The maximum thermodynamic information rule is formulated and "production" of the gradient-information in chemical reactions is addressed. The Hammond postulate is shown to be indexed by the geometric derivative of resultant gradient-information at transition-state complex.展开更多
The construction of C-N bonds is of great importance in the fields of biology,medicine,chemistry and materials science.Here,the replacement of organic base from pyridine to piperidine in the Knoevenagel condensation p...The construction of C-N bonds is of great importance in the fields of biology,medicine,chemistry and materials science.Here,the replacement of organic base from pyridine to piperidine in the Knoevenagel condensation process unexpectedly yields a series of novel organic molecules containing C-N bonds.Interestingly,the synthesis method does not require any external transition-metals catalysis,and photo-/electro-catalysis.Additionally,when the new compound 1b is added as a third component to a well-known binary system of PM6:Y6,the efficiency of the organic solar cell is significantly improved,resulting in an outstanding efficiency of 18.0%,which is one of the highest values reported to date for PM6:Y6-based ternary organic solar cells.展开更多
We describe an iron-catalyzed amide bond formation from readily available carboxylic acids and isocyanates.This method utilizes an abundant and biocompatible iron catalyst and easily accessible starting materials,gene...We describe an iron-catalyzed amide bond formation from readily available carboxylic acids and isocyanates.This method utilizes an abundant and biocompatible iron catalyst and easily accessible starting materials,generates CO_(2) as the only byproduct,and features broad substrate scopes with good functional group compatibility.Therefore,it provides a cost-effective and practical protocol to access a diverse variety of amides.展开更多
Chiral organosulfur compounds are not only widely distributed in bioactive natural products and pharmaceuticals,but also play a significant role in chiral ligands/catalysts.Throughout the history of synthetic organic ...Chiral organosulfur compounds are not only widely distributed in bioactive natural products and pharmaceuticals,but also play a significant role in chiral ligands/catalysts.Throughout the history of synthetic organic chemistry,chemists have been absorbed in the construction of centrally chiral organosulfur compounds.Nevertheless,there are relatively few reports on installing sulfur functional groups into axially chiral compounds.Atropisomerism is one of the fundamental phenomena in nature,which ubiquitously exists in natural products.After more than a century of development,atropisomers have been designed and extensively applied to pharmaceuticals,functional materials and chiral ligands/catalysts.Due to the importance of chiral sulfurcontaining atropisomers,there is an increasing demand for enantioselective synthesis of them.Recently,a diversity of approaches by C-S bond formations have been established for the construction of enantioenriched sulfur-containing atropisomers,however,there is no comprehensive review to summarize this great progress.In this mini-review,we summarize recent progress in catalytic asymmetric synthesis of sulfur-containing atropisomers by C-S bond formations,which includes sulfur nucleophilic reactions,sulfur electrophilic reactions and sulfur radical reactions.Furthermore,the reaction mechanisms are also discussed.We hope that this mini-review will enable more researchers to further explore this field.展开更多
We report a molecular trinuclear nickel(TNC-Ni)catalyst for water oxidation that exhibited high catalytic performance and stability under neutral conditions(pH 7).Electrochemical studies disclosed that cooperation amo...We report a molecular trinuclear nickel(TNC-Ni)catalyst for water oxidation that exhibited high catalytic performance and stability under neutral conditions(pH 7).Electrochemical studies disclosed that cooperation among the three nickel sites plays a vital role in both charge accumulation and O-O bond formation.This TNC-Ni catalyst could accomplish 4e−oxidation of water by involving all three nickel sites and the O-O bond formation was triggered by a charge distribution process from 5 to 5_(dp) via proton-coupled electron transfer.展开更多
Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of thi...Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of this synthetic strategy for the Csp^(3)-Csp^(3) bond forming reactions are surprisingly scarce.Herein,we present an efficient approach for the rapid formation of Csp^(3)–Csp^(3) bond through copper-catalyzed decarboxylative Csp^(3)–H functionalization.The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities.Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation.This strategy offers a promising synthesis method for the construction of Csp^(3)–Csp^(3) bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp^(3)–Csp^(3) bond forming reaction.展开更多
The bond length of ^4HeH^+ resulting from collision-induced destruction is measured at 1.4420 MeV using the Coulomb Explosion Technique. The measured bond length of ^4HeH^+ is 0.094±0.003nm. The bond length of ...The bond length of ^4HeH^+ resulting from collision-induced destruction is measured at 1.4420 MeV using the Coulomb Explosion Technique. The measured bond length of ^4HeH^+ is 0.094±0.003nm. The bond length of ^4HeH^+ obtained with our radio frequency (RF) ion source is larger than that obtained with a duoplasmatron ion source at Argonne National Laboratory (ANL), but the bond lengths of H^+2 and H^+3obtained separately by ANL and by us with the two different ion sources are consistent with each other, which implies that there exists an ion source effect on the bond length of ^4HeH^+. The main reason why the 4^4HeH^+ bond lengths obtained by the two different ion sources are different is also discussed.展开更多
In view of the importance of picolinic acid (Pa) in preventing cell growth and arresting cell cycle, attempts were made to design, synthesize and characterize two new Pa based tetradentate ligands (DPPTR and DPPTY) wi...In view of the importance of picolinic acid (Pa) in preventing cell growth and arresting cell cycle, attempts were made to design, synthesize and characterize two new Pa based tetradentate ligands (DPPTR and DPPTY) with a modified procedure. The procedure reported here avoids by-products and provides better yield and purity.展开更多
文摘A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4(pbeddb)4(H2O)2(DMAC)2] (MOC-18; pbeddb2- = 3,3'-(1,3-phenylenebis(ethyne-2,1-diyl))dibenzoate) was applied to the N-- H insertion reactions with diazo compounds. This method offered an environmentally friendly and highly efficient approach for C--N bond formation.
文摘Vacuum diffusion bonding of a TiAl based alloy (TAD) to a titanium alloy (TC2) was carried out at 1 273 K for 15~120 min under a pressure of 25 MPa . The kinds of the reaction products and the interface structures of the joints were investigated by SEM, EPMA and XRD. Based on this, a formation mechanism of the interface structure was elucidated. Experimental and analytical results show that two reaction layers have formed during the diffusion bonding of TAD to TC2. One is Al rich α(Ti)layer adjacent to TC2,and the other is (Ti 3Al+TiAl)layer adjacent to TAD,thus the interface structure of the TAD/TC2 joints is TAD/(Ti 3Al+TiAl)/α(Ti)/TC2.This interface structure forms according to a three stage mechanism,namely(a)the occurrence of a single phase α(Ti)layer;(b)the occurrence of a duplex phase(Ti 3Al+TiAl)layer;and(c)the growth of the α(Ti)and (Ti 3Al+TiAl)layers.
基金the financial support from the Swedish Research Council(2017-00935)Swedish Energy Agency+3 种基金the Knut and Alice Wallenberg Foundationthe National Natural Science Foundation of China(21120102036)the National Basic Research Program of China(973 program,2014CB239402)the China Scholarship Council(CSC)。
文摘Understanding the seven coordination and O-O coupling pathway of the distinguished Ru-bda catalysts is essential for the development of next generation efficient water-oxidation catalysts based on earthabundant metals.This work reports the synthesis,characterization and catalytic properties of a monomeric ruthenium catalyst Ru-bnda(H2 bnda=2,2’-bi(nicotinic acid)-6,6’-dicarboxylic acid)featuring steric hindrance and enhanced hydrophilicity on the backbone.Combining experimental evidence with systematic density functional theory calculations on the Ru-bnda and related catalysts Ru-bda(H_(2)bda=2,2’-bipyridine-6,6’-dicarboxylic acid),Ru-pda(H_(2)pda=1,10-phenanthroline-2,9-dicarboxylic acid),and Ru-biqa(H_(2)biqa=(1,1’-biisoquinoline)-3,3’-dicarboxylic acid),we emphasized that seven coordination clearly determines presence of Ru^(Ⅴ)=O with high spin density on the ORu^(Ⅴ)=O atom,i.e.oxo with radical properties,which is one of the necessary conditions for reacting through the O-O coupling pathway.However,an additional factor to make the condition sufficient is the favorable intermolecular faceto-face interaction for the generation of the pre-reactive[Ru^(Ⅴ)=O…O=Ru^(Ⅴ)],which may be significantly influenced by the secondary coordination environments.This work provides a new understanding of the structure-activity relationship of water-oxidation catalysts and their potential to adopt I2M pathway for O-O bond formation.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52074327 and 51991361)。
文摘Self-healing hydrogels have attracted tremendous attention in the field of oil and gas drilling and production engineering because of their excellent self-healing performance after physical damage.In this study,a series of double network self-healing(DN_(SA))hydrogels based on hydrophobic association and ionic bond were prepared for plugging pores and fractures in formations in oil and gas drilling and production engineering.The mechanical,rheological,and self-healing properties of the DN_(SA)hydrogels were investigated.Results revealed that the DN_(SA)hydrogels exhibited excellent mechanical properties with a tensile stress of 0.67 MPa and toughness of 7069 kJ/cm^(3) owing to the synergistic effect of the double network.In addition,the DN_(SA)hydrogels exhibited excellent compression resistance,notch insensitivity,and self-healing properties.The DN_(SA)-2 hydrogel was granulated and made into gel particles with different particle sizes and used as a plugging agent.The self-healing mechanism of DN_(SA)-2 hydrogel particles in fractures was explored,and it’s plugging effect on fractures of different widths and porous media of different permeabilities were investigated.Experimental results revealed that the plugging capacity of the DN_(SA)-2 hydrogel particles for a fracture with width of 5 mm and a porous medium with a permeability of 30μm^(2) was 3.45 and 4.21 MPa,respectively,which is significantly higher than those of commonly used plugging agents in the oilfield.The DN_(SA)hydrogels with excellent mechanical and self-healing properties prepared in this study will provide a new approach for applying hydrogels in oil and gas drilling and production engineering.
基金financial support of this work by the Swedish Research Council(2017-00935)Swedish Energy Agency and Knut and Alice Wallenberg Foundation(KAW 2016.0072)。
文摘Numerous aspects of the water oxidation mechanism in photosystemⅡhave not been fully elucidated,especially the O-O bond formation pathway.However,a body of experimental evidences have identified the O5 and W2 ligands of the oxygen-evolving complex as the highly probable substrate candidates.In this work,we studied O-O bond formation between O5 and W2 based on the native Mn4 Ca cluster by density functional calculations.Structural rearrangements before the formation of the S_(4) state were found as a prerequisite for O-O bond formation between O5 and W2,regardless if the suggested pathways involving the typical Mnl(Ⅳ)-O·species or the recently proposed Mn4(Ⅶ)(O)2 species.Possible alternatives for the S2→S_(3) and S_(3)→S_(4) transitions accounting for such required rearrangements are discussed.These findings reflect that the structural flexibility of the Mn4 Ca cluster is essential to allow structural rearrangements during the catalytic cycle.
文摘Al2O3-Ni interface formed under vacuum condition is non-wetting and weak. Severe instantaneous intedecial reaction (i.e. wetting) at the Al2O3-Ni interface promoted by oxygen can create a strengthened interface. The NiAl2O4 spinel-Ni intedece is weak and growth of the spinel interphase is detrimental to the Al2O3-Ni intedecial bonding. A proper control of the oxygen partial pressure can achieve wetting while avoiding the existence of spinel at the interface, producing stronger interfaces by both mechanical interlocking and more intimate chemical bonding in an Al2O3-20 vol pct Ni composite.
文摘The formation and breaking of intramolecular hydrogen bonds of bilirubin in CDCl_3-DMSO-d_6 binary solvent have been investigated by means of NMR spectroscopy.The chemical shifts of protons at dipyrrinone lactam C=O and N-H,Pyrrole N-H,C-5,C-15 and methylene groups of 8,12-propionic acid side-chains changed markedly as a function of composition of the binary solvent.The hydrogen bond formation is dependent on the conformation of propionic acid side-chains.
基金supported by the National Key Research and Development Program of China(Nos.2021YFA0910601 and 2021YFC2100203)Shanghai Municipal Education Commission(2021-03-52)Science and Technology Research Program of Shanghai(19DZ2282100).
文摘Kluyveromyces marxianus is a food-safe yeast with great potential for producing heterologous proteins.Improving the yield in K.marxianus remains a challenge and incorporating large-scale functional modules poses a technical obstacle in engineering.To address these issues,linear and circular yeast artificial chromosomes of K.marxianus(KmYACs)were constructed and loaded with disulfide bond formation modules from Pichia pastoris or K.marxianus.These modules contained up to seven genes with a maximum size of 15 kb.KmYACs carried telomeres either from K.marxianus or Tetrahymena.KmYACs were transferred successfully into K.marxianus and stably propagated without affecting the normal growth of the host,regardless of the type of telomeres and configurations of KmYACs.KmYACs increased the overall expression levels of disulfide bond formation genes and significantly enhanced the yield of various heterologous proteins.In high-density fermentation,the use of KmYACs resulted in a glucoamylase yield of 16.8 g/l,the highest reported level to date in K.marxianus.Transcriptomic and metabolomic analysis of cells containing KmYACs suggested increased flavin adenine dinucleotide biosynthesis,enhanced flux entering the tricarboxylic acid cycle,and a preferred demand for lysine and arginine as features of cells overexpressing heterologous proteins.Consistently,supplementing lysine or arginine further improved the yield.Therefore,KmYAC provides a powerful platform for manipulating large modules with enormous potential for industrial applications and fundamental research.Transferring the disulfide bond formation module via YACs proves to be an efficient strategy for improving the yield of heterologous proteins,and this strategy may be applied to optimize other microbial cell factories.
基金supported by the National Natural Science Foundation of China (30871749,30901004)Natural Science Foundation of Fujian Province(2009J01061)
文摘In this work, the formation sites, helical parameters and hydrogen bond positions of Konjac glucomannan molecular helices were investigated using molecular dynamic simulation method. To our interest, the KGM chain is mainly composed by local left and right helix struetttres. The formation sites of KGM chain might locate at the chain-segments containing acetyl groups, and the left helix is the favorable conformation of KGM. Temperature-dependent molecule conformation study indicates that the right helix is dominant when the temperature is lower than 343 K, above which, however, the left helix is dominating (right helix disappears). In addition, intramolecular hydrogen bonds in the left helix can be found at the -OH groups on C(2), C(4) and C(6) of mannose residues; comparably, the intramolecular hydrogen bonds in the right helix can be mainly observed at the -OH groups on C(4) and C(6) of the mannose residues and C(3) of the glucose residues. In conclusion, molecular dynamic simulation is an efficient method for the microscopic conformation study of glucomannan molecular helices.
文摘Resultant gradient-information is introduced and applied to problems in chemical reactivity theory. This local measure of the structural information contained in (complex) wavefunctions of electronic states is related to the system overall kinetic energy combining the modulus (probability) and phase (current) contributions. The grand-ensemble representation of thermodynamic equilibria in open systems demonstrates the physical equivalence of the variational energetic and information principles. It is used and to relate the populational derivatives of ensemble-average functionals in both these representations, which represent reactivity criteria for diagnosing the charge-transfer (CT) phenomena. Their equivalence is demonstrated by using the in situ potential and hardness descriptors to predict the direction and optimum amount of CT. The virial theorem is generalized into thermodynamic quantities and used to extract the kinetic energy component from qualitative energy profiles in the bond-formation and (exo/endo)-ergic reactions. The role of electronic kinetic energy in such chemical processes is reexamined, the virial theorem implications for the Hammond postulate of reactivity theory are explored, and variations of the structural-information in chemical processes are addressed. The maximum thermodynamic information rule is formulated and "production" of the gradient-information in chemical reactions is addressed. The Hammond postulate is shown to be indexed by the geometric derivative of resultant gradient-information at transition-state complex.
基金supported by the National Natural Science Foundation of China(U21A20331)the National Science Fund for Distinguished Young Scholars(21925506)the Zhejiang Provincial Natural Science Foundation of China(LQ22E030013)。
文摘The construction of C-N bonds is of great importance in the fields of biology,medicine,chemistry and materials science.Here,the replacement of organic base from pyridine to piperidine in the Knoevenagel condensation process unexpectedly yields a series of novel organic molecules containing C-N bonds.Interestingly,the synthesis method does not require any external transition-metals catalysis,and photo-/electro-catalysis.Additionally,when the new compound 1b is added as a third component to a well-known binary system of PM6:Y6,the efficiency of the organic solar cell is significantly improved,resulting in an outstanding efficiency of 18.0%,which is one of the highest values reported to date for PM6:Y6-based ternary organic solar cells.
基金the National Natural Science Foundation of China(2207118522271224)Wuhan University startup funding for financial support.
文摘We describe an iron-catalyzed amide bond formation from readily available carboxylic acids and isocyanates.This method utilizes an abundant and biocompatible iron catalyst and easily accessible starting materials,generates CO_(2) as the only byproduct,and features broad substrate scopes with good functional group compatibility.Therefore,it provides a cost-effective and practical protocol to access a diverse variety of amides.
基金supported by the National Natural Science Foundation of China (22071149,21871178)the Natural Science Foundation of Shanghai (23ZR1428200)the Program for Professor of Special Appointment (Eastern Scholar)at Shanghai Institutions of Higher Learning。
文摘Chiral organosulfur compounds are not only widely distributed in bioactive natural products and pharmaceuticals,but also play a significant role in chiral ligands/catalysts.Throughout the history of synthetic organic chemistry,chemists have been absorbed in the construction of centrally chiral organosulfur compounds.Nevertheless,there are relatively few reports on installing sulfur functional groups into axially chiral compounds.Atropisomerism is one of the fundamental phenomena in nature,which ubiquitously exists in natural products.After more than a century of development,atropisomers have been designed and extensively applied to pharmaceuticals,functional materials and chiral ligands/catalysts.Due to the importance of chiral sulfurcontaining atropisomers,there is an increasing demand for enantioselective synthesis of them.Recently,a diversity of approaches by C-S bond formations have been established for the construction of enantioenriched sulfur-containing atropisomers,however,there is no comprehensive review to summarize this great progress.In this mini-review,we summarize recent progress in catalytic asymmetric synthesis of sulfur-containing atropisomers by C-S bond formations,which includes sulfur nucleophilic reactions,sulfur electrophilic reactions and sulfur radical reactions.Furthermore,the reaction mechanisms are also discussed.We hope that this mini-review will enable more researchers to further explore this field.
基金This research is dedicated to the 10th anniversary of the Center of Basic Molecular Science(CBMS)at Tsinghua University.This work was financially supported by the National Science Foundation of China(grant nos.21933007 and 21873031).The authors appreciate the reviewers for their helpful comments.Q.-F.C.thanks Dr.Hai-Fang Li at Tsinghua University for the help on ESI-HRMS measurements.
文摘We report a molecular trinuclear nickel(TNC-Ni)catalyst for water oxidation that exhibited high catalytic performance and stability under neutral conditions(pH 7).Electrochemical studies disclosed that cooperation among the three nickel sites plays a vital role in both charge accumulation and O-O bond formation.This TNC-Ni catalyst could accomplish 4e−oxidation of water by involving all three nickel sites and the O-O bond formation was triggered by a charge distribution process from 5 to 5_(dp) via proton-coupled electron transfer.
基金supported by the National Natural Science Foundation of China(No.21702119)Natural Science Foundation of Shandong Province(Nos.ZR2016JL012,ZR2020JQ07)the Scientific Research Foundation of Qingdao University of Science and Technology(No.1203043003457)。
文摘Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of this synthetic strategy for the Csp^(3)-Csp^(3) bond forming reactions are surprisingly scarce.Herein,we present an efficient approach for the rapid formation of Csp^(3)–Csp^(3) bond through copper-catalyzed decarboxylative Csp^(3)–H functionalization.The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities.Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation.This strategy offers a promising synthesis method for the construction of Csp^(3)–Csp^(3) bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp^(3)–Csp^(3) bond forming reaction.
基金Project supported by the National Natural Science Foundation of China (Grant Nos 10175041 and 10375040).
文摘The bond length of ^4HeH^+ resulting from collision-induced destruction is measured at 1.4420 MeV using the Coulomb Explosion Technique. The measured bond length of ^4HeH^+ is 0.094±0.003nm. The bond length of ^4HeH^+ obtained with our radio frequency (RF) ion source is larger than that obtained with a duoplasmatron ion source at Argonne National Laboratory (ANL), but the bond lengths of H^+2 and H^+3obtained separately by ANL and by us with the two different ion sources are consistent with each other, which implies that there exists an ion source effect on the bond length of ^4HeH^+. The main reason why the 4^4HeH^+ bond lengths obtained by the two different ion sources are different is also discussed.
文摘In view of the importance of picolinic acid (Pa) in preventing cell growth and arresting cell cycle, attempts were made to design, synthesize and characterize two new Pa based tetradentate ligands (DPPTR and DPPTY) with a modified procedure. The procedure reported here avoids by-products and provides better yield and purity.