A solid electrolyte interphase(SEI)with a robust mechanical property and a high ionic conductivity is imperative for high-performance zinc metal batteries.However,it is difficult to form such a SEI directly from an el...A solid electrolyte interphase(SEI)with a robust mechanical property and a high ionic conductivity is imperative for high-performance zinc metal batteries.However,it is difficult to form such a SEI directly from an electrolyte.In this work,a molecular crowding effect is based on the introduction of Zn(OTF)_(2)and Zn(ClO_(4))_(2)to 2 mol/L ZnSO_(4)electrolytes.Simulations and experiments indicate that the Zn(OTF)_(2)and Zn(ClO_(4))_(2)not only create a molecularly crowded electrolyte environment to promote the interaction of Zn^(2+)and OTF^(-),but also participate in the reduction to construct a robust and high ionic-conductive SEI,thus promoting metal zinc deposition to the(002)crystal surface.With this molecular crowding electrolyte,a high current density of 1 mA/cm^(2)can be obtained by assembling symmetric batteries with Zn as the anode for over 1000 h.And in a temperature environment of-10℃,a current density of 1 mA/cm^(2)can be obtained by assembling symmetric batteries with Zn for over 200 h.Zn//Bi_(2)S_(3)/VS4@C cells achieve a CE rate of up to 99.81%over 1000 cycles.Hence,the utilization of a molecular crowding electrolyte is deemed a highly effective approach to fabricating a sophisticated SEI for a zinc anode.展开更多
Various structures of G-quadruplex in biosystems play an important role in different diseases and are often regulated by a variety of molecular crowding environments induced by internal and even external factors(e.g.,...Various structures of G-quadruplex in biosystems play an important role in different diseases and are often regulated by a variety of molecular crowding environments induced by internal and even external factors(e.g.,a solvent).Dimethyl sulfoxide(DMSO),a universal solvent,has been widely used in biological studies and for drug therapy,but little is known regarding its effect on G-quadruplex structure and stability.Here,we report the influence of molecular crowding environment induced by DMSO on the conformation and stability of G-quadruplex structure.We show that the G-quadruplex-forming sequences such as human telomeric sequence,which may have diverse conformations in different environments,tend to convert their topologies to parallel structures under the molecular crowding stimulated by DMSO.Moreover,DMSO can increase the stability of the parallel and antiparallel topologies,especially the parallel G-quadruplex sequence c-kit,but not the hybrid topologies.Further analysis of c-kit using the CD and NMR technique,combined with the unique structural characteristics of c-kit,reveals that the crowding,dehydration and interaction of DMSO are conductive to the formation and stability of the parallel G-quadruplex.The present study suggests that,DMSO,a common solvent used in DNA experiments,may have a nonnegligible influence on the structure and stability of G-quadruplex.展开更多
Molecular crowding is a new concept to obtain molecularly imprinted polymers（MIPs） with greater capacity and selectivity.In this work,molecular crowding agent was firstly applied to the preparation of MIPs monolithi...Molecular crowding is a new concept to obtain molecularly imprinted polymers（MIPs） with greater capacity and selectivity.In this work,molecular crowding agent was firstly applied to the preparation of MIPs monolithic column.A new polymerization system based on molecular crowding surrounding was developed to prepare enrofloxacin-imprinted monolith,which was composed of polystyrene and tetrahydrofuran.The result showed that the monolithic MIPs under molecular crowding conditions presented good molecular recognition for enrofloxacin with an imprinting factor of 3.03.展开更多
The effect of dextran on the conformation （or secondary structure） and thermal stability of creatine kinase （CK） was studied using the far-ultraviolet （UV） circular dichroism （CD） spectra. The results showed t...The effect of dextran on the conformation （or secondary structure） and thermal stability of creatine kinase （CK） was studied using the far-ultraviolet （UV） circular dichroism （CD） spectra. The results showed that lower concentrations of dextran （less than 60 g/L） induced formation of the secondary CK structures. However, the secondary structure content of CK decreased when the dextran concentrations exceeded 60 g/L. Thermally induced transition curves were measured for CK in the presence of different concentrations of dextran by far-UV CD. The thermal transition curves were fitted to a two-state model by a nonlinear, least-squares method to obtain the transition temperature of the unfolding transition. An increase in the transition temperature was observed with the increase of the dextran concentration. These observations qualitatively accord with predictions of a previously proposed model for the effect of intermolecular excluded volume （macromolecular crowding） on protein stability and conformation. These findings imply that the effects of macromolecular crowding can have an important influence on our understanding of how protein folding occurs in vivo.展开更多
Nanozymes are widely used in various applications as nanosized catalysts for replacing enzymes.An accurate estimation of the catalytic activity of nanozymes in real conditions is critical.In this article,for the first...Nanozymes are widely used in various applications as nanosized catalysts for replacing enzymes.An accurate estimation of the catalytic activity of nanozymes in real conditions is critical.In this article,for the first time,we systematically studied the effect of macromolecular molecules co-existing in the real system on the oxidoreductase(peroxidase,oxidase,and catalase)-mimicking nanozymes made of a gold nanoparticle core and a platinum shell,Prussian Blue,Mn_(2)O_(3) and CoO nanoparticles.Comparisons were made with horseradish peroxidase.We distinguished two main mechanisms of the negative impact of macromolecules on nanozyme catalysis—slowed diffusion and surface shielding of nanoparticles.While the first mechanism is typical for enzymes,the second one is specific only for nanozymes.Understanding the mechanisms is essential for developing approaches to reduce the unavoidable impact of macromolecules for various analytical and biomedical applications.展开更多
Solid surfaces that are immobilized with DNA molecules underlie an array of biotechnological devices.These surfaces may also mediate the self-assembly of hierarchical DNA nanostructures.However,a number of fundamental...Solid surfaces that are immobilized with DNA molecules underlie an array of biotechnological devices.These surfaces may also mediate the self-assembly of hierarchical DNA nanostructures.However,a number of fundamental questions concerning the structure–function relationship of these biointerfaces remain,including how these DNA probe molecules organize on the surface and how the spatial organization influences molecular recognition kinetics and interfacial affinity of these DNA molecules at the regime where crowding interactions are important(1–10 nm).This mini-review covers recent advances in understanding this structure–function relationship by spatially resolving surface hybridization events at the single-molecule level.Counterintuitive cooperative effects in surface hybridization are discussed and as is how modeling these cooperative effects can be used to predict the hybridization kinetics of a prototypical DNA sensor.Future opportunities in using mechanistic understanding to improve the performance and reliability of DNA sensors and form hierarchical supramolecular structures are also discussed.展开更多
基金supported by Jilin Provincial Natural Fund(No.20230101205JC)Chongqing Natural Science Foundation(Nos.cstc2022jcyj-msxmX0184 and CSTB2022NSCQ-MSX0241)the International Cooperation Foundation(No.20220402026GH)of Science and Technology Department of Jilin Province。
文摘A solid electrolyte interphase(SEI)with a robust mechanical property and a high ionic conductivity is imperative for high-performance zinc metal batteries.However,it is difficult to form such a SEI directly from an electrolyte.In this work,a molecular crowding effect is based on the introduction of Zn(OTF)_(2)and Zn(ClO_(4))_(2)to 2 mol/L ZnSO_(4)electrolytes.Simulations and experiments indicate that the Zn(OTF)_(2)and Zn(ClO_(4))_(2)not only create a molecularly crowded electrolyte environment to promote the interaction of Zn^(2+)and OTF^(-),but also participate in the reduction to construct a robust and high ionic-conductive SEI,thus promoting metal zinc deposition to the(002)crystal surface.With this molecular crowding electrolyte,a high current density of 1 mA/cm^(2)can be obtained by assembling symmetric batteries with Zn as the anode for over 1000 h.And in a temperature environment of-10℃,a current density of 1 mA/cm^(2)can be obtained by assembling symmetric batteries with Zn for over 200 h.Zn//Bi_(2)S_(3)/VS4@C cells achieve a CE rate of up to 99.81%over 1000 cycles.Hence,the utilization of a molecular crowding electrolyte is deemed a highly effective approach to fabricating a sophisticated SEI for a zinc anode.
基金supported by the National Natural Science Foundation of China(Nos.21977099,22077123 and 21977096)China Academy of Chinese Medical Sciences Innovation Fund(No.CI2021A05011)。
文摘Various structures of G-quadruplex in biosystems play an important role in different diseases and are often regulated by a variety of molecular crowding environments induced by internal and even external factors(e.g.,a solvent).Dimethyl sulfoxide(DMSO),a universal solvent,has been widely used in biological studies and for drug therapy,but little is known regarding its effect on G-quadruplex structure and stability.Here,we report the influence of molecular crowding environment induced by DMSO on the conformation and stability of G-quadruplex structure.We show that the G-quadruplex-forming sequences such as human telomeric sequence,which may have diverse conformations in different environments,tend to convert their topologies to parallel structures under the molecular crowding stimulated by DMSO.Moreover,DMSO can increase the stability of the parallel and antiparallel topologies,especially the parallel G-quadruplex sequence c-kit,but not the hybrid topologies.Further analysis of c-kit using the CD and NMR technique,combined with the unique structural characteristics of c-kit,reveals that the crowding,dehydration and interaction of DMSO are conductive to the formation and stability of the parallel G-quadruplex.The present study suggests that,DMSO,a common solvent used in DNA experiments,may have a nonnegligible influence on the structure and stability of G-quadruplex.
基金supported by the National Natural Science Foundation of China(No.21075090)the Natural Science Foundation of Tianjin(No.08JCYBJC02000)
文摘Molecular crowding is a new concept to obtain molecularly imprinted polymers（MIPs） with greater capacity and selectivity.In this work,molecular crowding agent was firstly applied to the preparation of MIPs monolithic column.A new polymerization system based on molecular crowding surrounding was developed to prepare enrofloxacin-imprinted monolith,which was composed of polystyrene and tetrahydrofuran.The result showed that the monolithic MIPs under molecular crowding conditions presented good molecular recognition for enrofloxacin with an imprinting factor of 3.03.
基金the Scientific Research Foundation for the Returned Overseas Chinese Scholars, the Ministry of Education, China
文摘The effect of dextran on the conformation （or secondary structure） and thermal stability of creatine kinase （CK） was studied using the far-ultraviolet （UV） circular dichroism （CD） spectra. The results showed that lower concentrations of dextran （less than 60 g/L） induced formation of the secondary CK structures. However, the secondary structure content of CK decreased when the dextran concentrations exceeded 60 g/L. Thermally induced transition curves were measured for CK in the presence of different concentrations of dextran by far-UV CD. The thermal transition curves were fitted to a two-state model by a nonlinear, least-squares method to obtain the transition temperature of the unfolding transition. An increase in the transition temperature was observed with the increase of the dextran concentration. These observations qualitatively accord with predictions of a previously proposed model for the effect of intermolecular excluded volume （macromolecular crowding） on protein stability and conformation. These findings imply that the effects of macromolecular crowding can have an important influence on our understanding of how protein folding occurs in vivo.
基金supported by the Natural Sciences and Engineering Research Council of Canada(NSERC).
文摘Nanozymes are widely used in various applications as nanosized catalysts for replacing enzymes.An accurate estimation of the catalytic activity of nanozymes in real conditions is critical.In this article,for the first time,we systematically studied the effect of macromolecular molecules co-existing in the real system on the oxidoreductase(peroxidase,oxidase,and catalase)-mimicking nanozymes made of a gold nanoparticle core and a platinum shell,Prussian Blue,Mn_(2)O_(3) and CoO nanoparticles.Comparisons were made with horseradish peroxidase.We distinguished two main mechanisms of the negative impact of macromolecules on nanozyme catalysis—slowed diffusion and surface shielding of nanoparticles.While the first mechanism is typical for enzymes,the second one is specific only for nanozymes.Understanding the mechanisms is essential for developing approaches to reduce the unavoidable impact of macromolecules for various analytical and biomedical applications.
基金National Science Foundation,Grant/Award Number:CHE-1808213National Institutes of Health,Grant/Award Number:1R35GM133483+1 种基金Division of Chemistry,Grant/Award Number:CHE-1808213National Aeronautics and Space Administration,Grant/Award Number:NNX15AQ01。
文摘Solid surfaces that are immobilized with DNA molecules underlie an array of biotechnological devices.These surfaces may also mediate the self-assembly of hierarchical DNA nanostructures.However,a number of fundamental questions concerning the structure–function relationship of these biointerfaces remain,including how these DNA probe molecules organize on the surface and how the spatial organization influences molecular recognition kinetics and interfacial affinity of these DNA molecules at the regime where crowding interactions are important(1–10 nm).This mini-review covers recent advances in understanding this structure–function relationship by spatially resolving surface hybridization events at the single-molecule level.Counterintuitive cooperative effects in surface hybridization are discussed and as is how modeling these cooperative effects can be used to predict the hybridization kinetics of a prototypical DNA sensor.Future opportunities in using mechanistic understanding to improve the performance and reliability of DNA sensors and form hierarchical supramolecular structures are also discussed.
