Rosa rugosa,commonly known as rugged rose,is a perennial ornamental shrub.It produces beautiful flowers with a mild fragrance and colorful seed pods.Unlike many other cultivated roses,R.rugosa adapts to a wide range o...Rosa rugosa,commonly known as rugged rose,is a perennial ornamental shrub.It produces beautiful flowers with a mild fragrance and colorful seed pods.Unlike many other cultivated roses,R.rugosa adapts to a wide range of habitat types and harsh environmental conditions such as salinity,alkaline,shade,drought,high humidity,and frigid temperatures.Here,we produced and analyzed a high-quality genome sequence for R.rugosa to understand its ecology,floral characteristics and evolution.PacBio HiFi reads were initially used to construct the draft genome of R.rugosa,and then Hi-C sequencing was applied to assemble the contigs into 7 chromosomes.We obtained a 382.6Mb genome encoding 39,704 protein-coding genes.The genome of R.rugosa appears to be conserved with no additional whole-genome duplication after the gamma whole-genome triplication(WGT),which occurred~100 million years ago in the ancestor of core eudicots.Based on a comparative analysis of the high-quality genome assembly of R.rugosa and other high-quality Rosaceae genomes,we found a unique large inverted segment in the Chinese rose R.chinensis and a retroposition in strawberry caused by post-WGT events.We also found that floral development-and stress response signaling-related gene modules were retained after the WGT.Two MADS-box genes involved in floral development and the stress-related transcription factors DREB2A-INTERACTING PROTEIN 2(DRIP2)and PEPTIDE TRANSPORTER 3(PTR3)were found to be positively selected in evolution,which may have contributed to the unique ability of this plant to adapt to harsh environments.In summary,the high-quality genome sequence of R.rugosa provides a map for genetic studies and molecular breeding of this plant and enables comparative genomic studies of Rosa in the near future.展开更多
Background:In the face of continued degradation and loss of wetlands in the Yangtze River floodplain(YRF),there is an urgent need to monitor the abundance and distribution of wintering waterbirds.To understand fully o...Background:In the face of continued degradation and loss of wetlands in the Yangtze River floodplain(YRF),there is an urgent need to monitor the abundance and distribution of wintering waterbirds.To understand fully observed annual changes,we need to monitor demographic rates to understand factors affecting global population size.Annual reproduction success contributes to dynamic changes in population size and age structure,so an assessment of the juvenile ratio(i.e.first winter birds as a proportion of total number aged)of overwintering waterbirds can be an important indicator of the reproductive success in the preceding breeding season.Methods:During 2016-2019,we sampled juvenile ratios among 10 key waterbird species from the wetlands in the YRF.Based on these data,we here attempt to establish a simple,efficient,focused and reliable juvenile ratio monitoring scheme,to assess consistently and accurately relative annual breeding success and its contribution to the age structure among these waterbird species.Results:We compared juvenile ratio data collected throughout the winter and found that the optimal time for undertaking these samples was in the early stages of arrival for migratory waterbirds reaching their wintering area(early to mid-December).We recommend counting consistently at key points(i.e.those where>1%biogeographical flyway population were counted)at sites of major flyway importance(Poyang Lake,East Dongting Lake,Shengjin Lake,Caizi Lake,Longgan Lake and Chen Lake).Based on this,the error rate of the programme(155 planned points,the count of 10 waterbird species is 826-8955)is less than 5%.Conclusions:We established a juvenile ratio monitoring programme for 10 key waterbird species in the wetlands of the YRF,and discuss the feasibility and necessity of implementing such a future programme,and how to use these data in our monitoring and understanding of the population dynamics of these waterbird populations.展开更多
Diterpenes are the most complex and abundant plant metabolites,some of which play significant roles in both primary and secondary metabolism.Ent-kaurene synthase is the key enzyme for gibberellins(GAs)biosynthesis,whi...Diterpenes are the most complex and abundant plant metabolites,some of which play significant roles in both primary and secondary metabolism.Ent-kaurene synthase is the key enzyme for gibberellins(GAs)biosynthesis,which may act as a catalyst in the formation of entkaurene,the precursor for GAs,by cyclization or rearrangement of the substrate ent-copalyl diphosphate(ent-CPP).Ilex latifolia Thunb(Aquifoliaceae)is a widely distributed Chinese plant whose leaves are used to process a popular Chinese bitter tea named'Kudingcha',which has anti-microbial,anti-oxidant and anti-inflammatory properties.Here,we isolated a diterpene synthase gene from the leaf transcriptome of I.latifolia,and further identified its biosynthesis activity by in vitro enzymatic testing.The heterologous expressed ent-kaurene synthase of I.latifolia(IlKS)in E.coli could catalyze ent-copalyl diphosphate(ent-CPP)to form ent-kaurene.Tissue-specific expression indicated that IlKS had the highest transcript level in roots which is maybe the major location of ent-kaurene biosynthesis.This study would help us to determine diterpenoid metabolism and GAs biosynthesis in I.latifolia,to better understand the regulation function of GAs in growth and development.展开更多
With the increasing demands of aircraft design,the traditional deterministic design can hardly meet the requirements of fine design optimization because uncertainties may exist throughout the whole lifecycle of the ai...With the increasing demands of aircraft design,the traditional deterministic design can hardly meet the requirements of fine design optimization because uncertainties may exist throughout the whole lifecycle of the aircraft. To enhance the robustness and reliability of the aircraft design, Uncertainty Multidisciplinary Design Optimization( UM DO) has been developing for a long time. This paper presents a comprehensive reviewof UM DO methods for aerospace vehicles,including basic UM DO theory and research progress of its application in aerospace vehicle design. Firstly,the UM DO theory is preliminarily introduced,with giving the definition and classification of uncertainty as well as its sources corresponding to the aircraft design. Then following the UM DO solving process, the application in different coupled disciplines is separately discussed during the aircraft design process,specifically clarifying the UM DO methods for aerostructural optimization. Finally,the main challenges of UM DO and the future research trends are given.展开更多
Nymphaea is a key genus of the ANA grade(Amborellales,Nymphaeales,and Austrobaileyales)of basal flowering plants,which serve as a key model to study the early evolution of floral traits.In this study,we comprehensivel...Nymphaea is a key genus of the ANA grade(Amborellales,Nymphaeales,and Austrobaileyales)of basal flowering plants,which serve as a key model to study the early evolution of floral traits.In this study,we comprehensively investigated the emission,biosynthesis,and biological function of the floral scent in a night-blossoming waterlily Nymphaea prolifera.The headspace volatile collection combined with GC-MS analysis showed that the floral scent of N.prolifera is predominately comprised by methylated benzenoids including anisole,veratrole,guaiacol,and methoxyanisole.Moreover,the emission of these floral benzenoids in N.prolifera exhibited temporal and spatial pattern with circadian rhythm and tissue specificity.By creating and mining transcriptomes of N.prolifera flowers,12 oxygen methyltransferases(NpOMTs)were functionally identified.By in vitro enzymatic assay,NpOMT3,6,and 7 could produce anisole and NpOMT5,7,9,produce guaiacol,whereas NpOMT3,6,9,11 catalyzed the formation of veratrole.Methoxyanisole was identified as the universal product of all NpOMTs.Expression patterns of NpOMTs provided implication for their roles in the production of the respective benzenoids.Phylogenetic analysis of OMTs suggested a Nymphaea-specific expansion of the OMT family,indicating the evolution of lineage-specific functions.In bioassays,anisole,veratrole,and guaiacol in the floral benzenoids were revealed to play the critical role in repelling waterlily aphids.Overall,this study indicates that the basal flowering plant N.prolifera has evolved a diversity and complexity of OMT genes for the biosynthesis of methylated benzenoids that can repel insects from feeding the flowers.These findings provide new insights into the evolutional mechanism and ecological significance of the floral scent from early-diverged flowering plants.展开更多
Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp3)–H bonds using only H_(2)O_(2) as a clean oxidant,while also exhibiting sensitivity to H_(2)O_(2) concentration.CdS...Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp3)–H bonds using only H_(2)O_(2) as a clean oxidant,while also exhibiting sensitivity to H_(2)O_(2) concentration.CdS-based semiconductors are promising for the photosynthesis of H_(2)O_(2) owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process,however,they suffer from fast H_(2)O_(2) decomposition on the surface of pristine CdS.Therefore,[Cp*Rh(bpy)H_(2)O]2+,a highly selective proton-coupled electron transfer catalyst,was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H_(2)O_(2),mitigating the surface issue of pristine CdS,increasing light absorption,accelerating photonic carrier separation,and enhancing oxygen reduction reaction selectivity to H_(2)O_(2).This photocatalyst promoted the light driven H_(2)O_(2) generation rate up to 1345μmol·L^(-1)·g^(-1)·h^(-1),which was 2.4 times that of pristine CdS.The constructed heterojunction photocatalyst could supply H_(2)O_(2) in situ for nonspecific peroxygenases to catalyze the C–H oxyfunctionalization of ethylbenzene,achieving a yield of 81%and an ee value of 99%under optimum conditions.A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system,achieving the corresponding chiral alcohols in good yield(51%–88%)and excellent enantioselectivity(90%–99%ee).展开更多
Core-shell structured magnetic wrinkled organosilica-based metal-enzyme integrated catalysts were synthesized,and their catalytic performances were studied in the chemoenzymatic dynamic kinetic resolution of chiral am...Core-shell structured magnetic wrinkled organosilica-based metal-enzyme integrated catalysts were synthesized,and their catalytic performances were studied in the chemoenzymatic dynamic kinetic resolution of chiral amines in an organic solvent,as well as in the chemoenzymatic synthesis of chiral alcohols in water.Structureperformance studies revealed the important influence of their tunable structure and composition on the optimization of activity,stability,and recyclability in chemoenzymatic catalysis.展开更多
Dendritic mesoporous silica nanoparticles(DMSNs)are a new class of solid porous materials used for enzyme immobilization support due to their intrinsic characteristics,including their unique open central-radial struct...Dendritic mesoporous silica nanoparticles(DMSNs)are a new class of solid porous materials used for enzyme immobilization support due to their intrinsic characteristics,including their unique open central-radial structures with large pore channels and their excellent biocompatibility.In this review,we review the recent progress in research on enzyme immobilization using DMSNs with different structures,namely,flower-like DMSNs and tree-branch-like DMSNs.Three DMSN synthesis methods are briefly compared,and the distinct characteristics of the two DMSN types and their effects on the catalytic performance of immobilized enzymes are comprehensively discussed.Possible directions for future research on enzyme immobilization using DMSNs are also proposed.展开更多
The highly efficient chemoselectivity,stereoselectivity,and regioselectivity render enzyme catalysis an ideal pathway for the synthesis of various chemicals in broad applications.While the cofactor of an enzyme is nec...The highly efficient chemoselectivity,stereoselectivity,and regioselectivity render enzyme catalysis an ideal pathway for the synthesis of various chemicals in broad applications.While the cofactor of an enzyme is necessary but expensive,the conversed state of the cofactor is not beneficial for the positive direction of the reaction.Cofactor regeneration using electrochemical methods has the advantages of simple operation,low cost,easy process monitoring,and easy product separation,and the electrical energy is green and sustainable.Therefore,bioelectrocatalysis has great potential in synthesis by combining electrochemical cofactor regeneration with enzymatic catalysis.In this review,we detail the mechanism of cofactor regeneration and categorize the common electron mediators and enzymes used in cofactor regeneration.The reaction type and the recent progress are summarized in electrochemically coupled enzymatic catalysis.The main challenges of such electroenzymatic catalysis are pointed out and future developments in this field are foreseen.展开更多
The hollow spherical covalent organic frameworks(COFs)have a wide application prospect thanks to their special structures.However,the controllable synthesis of uniform and stable hollow COFs is still a challenge.We he...The hollow spherical covalent organic frameworks(COFs)have a wide application prospect thanks to their special structures.However,the controllable synthesis of uniform and stable hollow COFs is still a challenge.We herein propose a self-templated method for the preparation of hollow COFs through the Ostwald ripening mechanism under ambient conditions,which avoids most disadvantages of the commonly used hard-templating and soft-templating methods.A detailed time-dependent study reveals that the COFs are transformed from initial spheres to hollow spheres because of the inside-out Ostwald ripening process.The obtained hollow spherical COFs have high crystallinity,specific surface area(2,036 m^(2)·g^(−1)),stability,and single-batch yield.Thanks to unique hollow structure,clear through holes,and hydrophobic pore environment of the hollow spherical COFs,the obtained immobilized lipase(BCL@H-COF-OMe)exhibits higher thermostability,polar organic solvent tolerance,and reusability.The BCL@H-COF-OMe also shows higher catalytic performance than the lipase immobilized on non-hollow COF and free lipase in the kinetic resolution of secondary alcohols.This study provides a simple approach for the preparation of hollow spherical COFs,and will promote the valuable research of COFs in the field of biocatalysis.展开更多
Main observation and conclusion Aqueous heterogeneous catalysis is a green,sustainable catalytic process that attracts increasing attention,but it often suffers from poor mass transfer,substrate adsorption and catalys...Main observation and conclusion Aqueous heterogeneous catalysis is a green,sustainable catalytic process that attracts increasing attention,but it often suffers from poor mass transfer,substrate adsorption and catalyst dispersion.Herein,we synthesized a type of amphiphilic core-shell catalysts with a hydrophilic polydopamine(PDA)shell and a hydrophobic dendritic organosilica nanoparticle(DON)core for heterogeneous catalysis in water.展开更多
Temperature is a critical factor influencing avian phenology,due to its direct impact on food and water availability.Most previous studies have focused on the timing of spring migration and the arrival of birds at bre...Temperature is a critical factor influencing avian phenology,due to its direct impact on food and water availability.Most previous studies have focused on the timing of spring migration and the arrival of birds at breeding grounds along the European and American flyways;little is known about migration ecology at the wintering sites along the Asian flyways.Using linear regression models,this study investigates how local temperature variation and EI Niño Southern Oscillation(ENSO)influences the arrival and departure timing of 9 waterbird species breeding in Mongolia or Siberia and overwintering in Poyang,China from 2002 to 2013.Birds mainly arrive at Poyang in October and depart for their breeding sites in March.Out of the 9 species,6 show a strong negative relationship between departure time and overwintering temperature in Poyang.Departure dates also show a negative association with overwintering ENSO and March ENSO for two species.Both local and large-scale climate indices show no influence on the arrival timing of waterbirds.We suggest that birds react to the annual variation of overwintering temperature:an earlier departure of waterbirds is facilitated by a warmer overwintering period and vice versa.The long-term accumulated temperature effect is more pronounced than ENSO and the short-term local temperature effect.Our findings could help quantify the potential impact of global warming on waterbirds.展开更多
In situ encapsulation is an effective way to synthesize enzyme@metal–organic framework biocatalysts;however,it is limited by the conditions of metal–organic framework synthesis and its acid-base stability.Herein,a b...In situ encapsulation is an effective way to synthesize enzyme@metal–organic framework biocatalysts;however,it is limited by the conditions of metal–organic framework synthesis and its acid-base stability.Herein,a biocatalytic platform with improved acid-base stability was constructed via a one-pot method using bismuth-ellagic acid as the carrier.Bismuth-ellagic acid is a green phenol-based metal–organic framework whose organic precursor is extracted from natural plants.After encapsulation,the stability,especially the acid-base stability,of amyloglucosidases@bismuth-ellagic acid was enhanced,which remained stable over a wide pH range(2–12)and achieved multiple recycling.By selecting a suitable buffer,bismuth-ellagic acid can encapsulate different types of enzymes and enable interactions between the encapsulated enzymes and cofactors,as well as between multiple enzymes.The green precursor,simple and convenient preparation process provided a versatile strategy for enzymes encapsulation.展开更多
基金F.C.acknowledges funding from the National Natural Science Foundation of China(31801898)This work is supported by the high-performance computing platform of the Bioinformatics Center,Nanjing Agricultural UniversityThis work is supported by the Fundamental Funds for the Central Universities,NJAU(KYXJ202004)。
文摘Rosa rugosa,commonly known as rugged rose,is a perennial ornamental shrub.It produces beautiful flowers with a mild fragrance and colorful seed pods.Unlike many other cultivated roses,R.rugosa adapts to a wide range of habitat types and harsh environmental conditions such as salinity,alkaline,shade,drought,high humidity,and frigid temperatures.Here,we produced and analyzed a high-quality genome sequence for R.rugosa to understand its ecology,floral characteristics and evolution.PacBio HiFi reads were initially used to construct the draft genome of R.rugosa,and then Hi-C sequencing was applied to assemble the contigs into 7 chromosomes.We obtained a 382.6Mb genome encoding 39,704 protein-coding genes.The genome of R.rugosa appears to be conserved with no additional whole-genome duplication after the gamma whole-genome triplication(WGT),which occurred~100 million years ago in the ancestor of core eudicots.Based on a comparative analysis of the high-quality genome assembly of R.rugosa and other high-quality Rosaceae genomes,we found a unique large inverted segment in the Chinese rose R.chinensis and a retroposition in strawberry caused by post-WGT events.We also found that floral development-and stress response signaling-related gene modules were retained after the WGT.Two MADS-box genes involved in floral development and the stress-related transcription factors DREB2A-INTERACTING PROTEIN 2(DRIP2)and PEPTIDE TRANSPORTER 3(PTR3)were found to be positively selected in evolution,which may have contributed to the unique ability of this plant to adapt to harsh environments.In summary,the high-quality genome sequence of R.rugosa provides a map for genetic studies and molecular breeding of this plant and enables comparative genomic studies of Rosa in the near future.
基金supported by the National Natural Science Foundation of China(Grant Nos.31870369,31970433)China Biodiversity Observation Networks(Sino BON)+1 种基金Innovative Research Group Project of the National Natural Science Foundation of China(CN)No.31670424。
文摘Background:In the face of continued degradation and loss of wetlands in the Yangtze River floodplain(YRF),there is an urgent need to monitor the abundance and distribution of wintering waterbirds.To understand fully observed annual changes,we need to monitor demographic rates to understand factors affecting global population size.Annual reproduction success contributes to dynamic changes in population size and age structure,so an assessment of the juvenile ratio(i.e.first winter birds as a proportion of total number aged)of overwintering waterbirds can be an important indicator of the reproductive success in the preceding breeding season.Methods:During 2016-2019,we sampled juvenile ratios among 10 key waterbird species from the wetlands in the YRF.Based on these data,we here attempt to establish a simple,efficient,focused and reliable juvenile ratio monitoring scheme,to assess consistently and accurately relative annual breeding success and its contribution to the age structure among these waterbird species.Results:We compared juvenile ratio data collected throughout the winter and found that the optimal time for undertaking these samples was in the early stages of arrival for migratory waterbirds reaching their wintering area(early to mid-December).We recommend counting consistently at key points(i.e.those where>1%biogeographical flyway population were counted)at sites of major flyway importance(Poyang Lake,East Dongting Lake,Shengjin Lake,Caizi Lake,Longgan Lake and Chen Lake).Based on this,the error rate of the programme(155 planned points,the count of 10 waterbird species is 826-8955)is less than 5%.Conclusions:We established a juvenile ratio monitoring programme for 10 key waterbird species in the wetlands of the YRF,and discuss the feasibility and necessity of implementing such a future programme,and how to use these data in our monitoring and understanding of the population dynamics of these waterbird populations.
基金the National Natural Science Foundation of China(31470693,31100503)the Natural Science Foundation of Zhejiang Province(LY18C160006)+2 种基金the Central Public-interest Scientific Institution Basal Research Fund(1610212018004,1610212016017)the Science and Technology Innovation Project of the Chinese Academy of Agricultural Sciences(CAAS-ASTIP-2014-TRICAAS)the Key Project of International Science&Technology Cooperation,National Key Research and Development Program of China(2017YFE0107500).
文摘Diterpenes are the most complex and abundant plant metabolites,some of which play significant roles in both primary and secondary metabolism.Ent-kaurene synthase is the key enzyme for gibberellins(GAs)biosynthesis,which may act as a catalyst in the formation of entkaurene,the precursor for GAs,by cyclization or rearrangement of the substrate ent-copalyl diphosphate(ent-CPP).Ilex latifolia Thunb(Aquifoliaceae)is a widely distributed Chinese plant whose leaves are used to process a popular Chinese bitter tea named'Kudingcha',which has anti-microbial,anti-oxidant and anti-inflammatory properties.Here,we isolated a diterpene synthase gene from the leaf transcriptome of I.latifolia,and further identified its biosynthesis activity by in vitro enzymatic testing.The heterologous expressed ent-kaurene synthase of I.latifolia(IlKS)in E.coli could catalyze ent-copalyl diphosphate(ent-CPP)to form ent-kaurene.Tissue-specific expression indicated that IlKS had the highest transcript level in roots which is maybe the major location of ent-kaurene biosynthesis.This study would help us to determine diterpenoid metabolism and GAs biosynthesis in I.latifolia,to better understand the regulation function of GAs in growth and development.
基金Sponsored by the National Natural Science Foundation of China(Grant Nos.303QKJJ2016105002 and 30300002014105011)
文摘With the increasing demands of aircraft design,the traditional deterministic design can hardly meet the requirements of fine design optimization because uncertainties may exist throughout the whole lifecycle of the aircraft. To enhance the robustness and reliability of the aircraft design, Uncertainty Multidisciplinary Design Optimization( UM DO) has been developing for a long time. This paper presents a comprehensive reviewof UM DO methods for aerospace vehicles,including basic UM DO theory and research progress of its application in aerospace vehicle design. Firstly,the UM DO theory is preliminarily introduced,with giving the definition and classification of uncertainty as well as its sources corresponding to the aircraft design. Then following the UM DO solving process, the application in different coupled disciplines is separately discussed during the aircraft design process,specifically clarifying the UM DO methods for aerostructural optimization. Finally,the main challenges of UM DO and the future research trends are given.
基金This work was supported by the National Natural Science Foundation of China(31872140,31470693,31100503)the Natural Science Foundation of Zhejiang Province(LY18C160006)+1 种基金the Zhejiang Provincial Key Laboratory of Characteristic Aquatic Vegetable Breeding and Cultivation Open Fund Project(KL-2022-01,KL-2022-02)the Project for Science and Technology in Jinhua City(Grant No.2019-2-002).The authors thank TopEdit(www.topeditsci.com)for its linguistic assistance during the preparation of this manuscript.
文摘Nymphaea is a key genus of the ANA grade(Amborellales,Nymphaeales,and Austrobaileyales)of basal flowering plants,which serve as a key model to study the early evolution of floral traits.In this study,we comprehensively investigated the emission,biosynthesis,and biological function of the floral scent in a night-blossoming waterlily Nymphaea prolifera.The headspace volatile collection combined with GC-MS analysis showed that the floral scent of N.prolifera is predominately comprised by methylated benzenoids including anisole,veratrole,guaiacol,and methoxyanisole.Moreover,the emission of these floral benzenoids in N.prolifera exhibited temporal and spatial pattern with circadian rhythm and tissue specificity.By creating and mining transcriptomes of N.prolifera flowers,12 oxygen methyltransferases(NpOMTs)were functionally identified.By in vitro enzymatic assay,NpOMT3,6,and 7 could produce anisole and NpOMT5,7,9,produce guaiacol,whereas NpOMT3,6,9,11 catalyzed the formation of veratrole.Methoxyanisole was identified as the universal product of all NpOMTs.Expression patterns of NpOMTs provided implication for their roles in the production of the respective benzenoids.Phylogenetic analysis of OMTs suggested a Nymphaea-specific expansion of the OMT family,indicating the evolution of lineage-specific functions.In bioassays,anisole,veratrole,and guaiacol in the floral benzenoids were revealed to play the critical role in repelling waterlily aphids.Overall,this study indicates that the basal flowering plant N.prolifera has evolved a diversity and complexity of OMT genes for the biosynthesis of methylated benzenoids that can repel insects from feeding the flowers.These findings provide new insights into the evolutional mechanism and ecological significance of the floral scent from early-diverged flowering plants.
基金supported by the National Natural Science Foundation of China(Grant No.22378096)the Natural Science Foundation of Hebei Province(Grant No.B2023202014)+1 种基金the Science Technology Research Project of Higher Education of Hebei Province(Grant Nos.QN2021045,and QN2023207)the Tianjin Science and Technology Project(Grant No.22KPHDRC00260).
文摘Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp3)–H bonds using only H_(2)O_(2) as a clean oxidant,while also exhibiting sensitivity to H_(2)O_(2) concentration.CdS-based semiconductors are promising for the photosynthesis of H_(2)O_(2) owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process,however,they suffer from fast H_(2)O_(2) decomposition on the surface of pristine CdS.Therefore,[Cp*Rh(bpy)H_(2)O]2+,a highly selective proton-coupled electron transfer catalyst,was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H_(2)O_(2),mitigating the surface issue of pristine CdS,increasing light absorption,accelerating photonic carrier separation,and enhancing oxygen reduction reaction selectivity to H_(2)O_(2).This photocatalyst promoted the light driven H_(2)O_(2) generation rate up to 1345μmol·L^(-1)·g^(-1)·h^(-1),which was 2.4 times that of pristine CdS.The constructed heterojunction photocatalyst could supply H_(2)O_(2) in situ for nonspecific peroxygenases to catalyze the C–H oxyfunctionalization of ethylbenzene,achieving a yield of 81%and an ee value of 99%under optimum conditions.A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system,achieving the corresponding chiral alcohols in good yield(51%–88%)and excellent enantioselectivity(90%–99%ee).
基金financially supported by the National Key Research and Development Program of China(No.2021YFC2104100)the National Natural Science Foundation of China(Nos.21901058,22178083 and 22078081)+2 种基金the S&T program of Hebei(Nos.21372805D,21372804D and 20372802D)the Natural Science Foundation of Tianjin City(No.20JCYBJC00530)the Natural Science Foundation of Hebei Province(No.B2022202014).
文摘Core-shell structured magnetic wrinkled organosilica-based metal-enzyme integrated catalysts were synthesized,and their catalytic performances were studied in the chemoenzymatic dynamic kinetic resolution of chiral amines in an organic solvent,as well as in the chemoenzymatic synthesis of chiral alcohols in water.Structureperformance studies revealed the important influence of their tunable structure and composition on the optimization of activity,stability,and recyclability in chemoenzymatic catalysis.
基金supported by the National Natural Science Foundation of China(No.22178083)the Natural Science Foundation of Hebei Province(C2019208174 and B2022202014)+1 种基金the S&T Program of Hebei(20372802D,21372804D,and 21372805D)the Natural Science Foundation of Tianjin City(20JCYBJC00530)
文摘Dendritic mesoporous silica nanoparticles(DMSNs)are a new class of solid porous materials used for enzyme immobilization support due to their intrinsic characteristics,including their unique open central-radial structures with large pore channels and their excellent biocompatibility.In this review,we review the recent progress in research on enzyme immobilization using DMSNs with different structures,namely,flower-like DMSNs and tree-branch-like DMSNs.Three DMSN synthesis methods are briefly compared,and the distinct characteristics of the two DMSN types and their effects on the catalytic performance of immobilized enzymes are comprehensively discussed.Possible directions for future research on enzyme immobilization using DMSNs are also proposed.
基金supported by the National Natural Science Foundation of China(Nos.21908040,21878068,and 22178083)the Natural Science Foundation of Hebei Province(B2020202021)+2 种基金the Science and Technology Program Project of Tianjin(20YDTPJC00260)Key Research and Development Program of Hebei Province(20372802D)the Natural Science Foundation of Tianjin(20JCYBJC00530)
文摘The highly efficient chemoselectivity,stereoselectivity,and regioselectivity render enzyme catalysis an ideal pathway for the synthesis of various chemicals in broad applications.While the cofactor of an enzyme is necessary but expensive,the conversed state of the cofactor is not beneficial for the positive direction of the reaction.Cofactor regeneration using electrochemical methods has the advantages of simple operation,low cost,easy process monitoring,and easy product separation,and the electrical energy is green and sustainable.Therefore,bioelectrocatalysis has great potential in synthesis by combining electrochemical cofactor regeneration with enzymatic catalysis.In this review,we detail the mechanism of cofactor regeneration and categorize the common electron mediators and enzymes used in cofactor regeneration.The reaction type and the recent progress are summarized in electrochemically coupled enzymatic catalysis.The main challenges of such electroenzymatic catalysis are pointed out and future developments in this field are foreseen.
基金This work was supported by the National Natural Science Foundation of China(Nos.22078081,21908040,21901058,and 22178083)the Natural Science Foundation of Hebei Province(Nos.B2020202021 and B2019202216)+2 种基金Key Research and Development Program of Hebei Province(No.20372802D)Open Project Funding of the State Key Laboratory of Biocatalysis and Enzyme Engineering(No.SKLBEE2020011)the Natural Science Foundation of Tianjin(No.20JCYBJC00530).
文摘The hollow spherical covalent organic frameworks(COFs)have a wide application prospect thanks to their special structures.However,the controllable synthesis of uniform and stable hollow COFs is still a challenge.We herein propose a self-templated method for the preparation of hollow COFs through the Ostwald ripening mechanism under ambient conditions,which avoids most disadvantages of the commonly used hard-templating and soft-templating methods.A detailed time-dependent study reveals that the COFs are transformed from initial spheres to hollow spheres because of the inside-out Ostwald ripening process.The obtained hollow spherical COFs have high crystallinity,specific surface area(2,036 m^(2)·g^(−1)),stability,and single-batch yield.Thanks to unique hollow structure,clear through holes,and hydrophobic pore environment of the hollow spherical COFs,the obtained immobilized lipase(BCL@H-COF-OMe)exhibits higher thermostability,polar organic solvent tolerance,and reusability.The BCL@H-COF-OMe also shows higher catalytic performance than the lipase immobilized on non-hollow COF and free lipase in the kinetic resolution of secondary alcohols.This study provides a simple approach for the preparation of hollow spherical COFs,and will promote the valuable research of COFs in the field of biocatalysis.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21901058,21908040 and 22078081)the Science and Technology Research Project of Hebei Higher Education(ZD2019045)+2 种基金the Natural Science Foundation of Hebei province(B2017202056 and B2019202216)the Natural Science Foundation of Tianjin City(20JCYBJC00530)the Foundation of Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-utilization(Tianjin University of Science and Technology),People's Republic of China(BCERE202001).
文摘Main observation and conclusion Aqueous heterogeneous catalysis is a green,sustainable catalytic process that attracts increasing attention,but it often suffers from poor mass transfer,substrate adsorption and catalyst dispersion.Herein,we synthesized a type of amphiphilic core-shell catalysts with a hydrophilic polydopamine(PDA)shell and a hydrophobic dendritic organosilica nanoparticle(DON)core for heterogeneous catalysis in water.
基金supported by the National Natural Science Foundation of China(No.41471347).
文摘Temperature is a critical factor influencing avian phenology,due to its direct impact on food and water availability.Most previous studies have focused on the timing of spring migration and the arrival of birds at breeding grounds along the European and American flyways;little is known about migration ecology at the wintering sites along the Asian flyways.Using linear regression models,this study investigates how local temperature variation and EI Niño Southern Oscillation(ENSO)influences the arrival and departure timing of 9 waterbird species breeding in Mongolia or Siberia and overwintering in Poyang,China from 2002 to 2013.Birds mainly arrive at Poyang in October and depart for their breeding sites in March.Out of the 9 species,6 show a strong negative relationship between departure time and overwintering temperature in Poyang.Departure dates also show a negative association with overwintering ENSO and March ENSO for two species.Both local and large-scale climate indices show no influence on the arrival timing of waterbirds.We suggest that birds react to the annual variation of overwintering temperature:an earlier departure of waterbirds is facilitated by a warmer overwintering period and vice versa.The long-term accumulated temperature effect is more pronounced than ENSO and the short-term local temperature effect.Our findings could help quantify the potential impact of global warming on waterbirds.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22178083,22078081 and 21878068)the Natural Science Foundation of Tianjin China(Grant No.20JCYBJC00530)+3 种基金the Hebei Key Research and Development Project(Grant No.20372802D)Open Funding Project of the State Key Laboratory of Biocatalysis and Enzyme Engineering(Grant No.SKLBEE2020011)Science Technology Research Project of Higher Education of Hebei Province(Grant No.QN2021045)Tianjin Enterprise Science and Technology Commissioner Project(Grant No.21YDTPJC00810).
文摘In situ encapsulation is an effective way to synthesize enzyme@metal–organic framework biocatalysts;however,it is limited by the conditions of metal–organic framework synthesis and its acid-base stability.Herein,a biocatalytic platform with improved acid-base stability was constructed via a one-pot method using bismuth-ellagic acid as the carrier.Bismuth-ellagic acid is a green phenol-based metal–organic framework whose organic precursor is extracted from natural plants.After encapsulation,the stability,especially the acid-base stability,of amyloglucosidases@bismuth-ellagic acid was enhanced,which remained stable over a wide pH range(2–12)and achieved multiple recycling.By selecting a suitable buffer,bismuth-ellagic acid can encapsulate different types of enzymes and enable interactions between the encapsulated enzymes and cofactors,as well as between multiple enzymes.The green precursor,simple and convenient preparation process provided a versatile strategy for enzymes encapsulation.