The diffusion coefficients(Dapp) and the heterogeneous electron transfer rate constants(ks)for ferrocene in several polymer solvents were determined by using steady-stae voltammetry. Thetemperature dependence of the t...The diffusion coefficients(Dapp) and the heterogeneous electron transfer rate constants(ks)for ferrocene in several polymer solvents were determined by using steady-stae voltammetry. Thetemperature dependence of the two parameters indicates Arrhenius behavior. The polymer solventeffects on diffusion and electron transfer dynamics of ferrocene were discussed展开更多
We investigate the statistics of polymer capture by a nanopore using Brownian dynamics simulations. It is found that when the velocity flux is greater than a critical velocity flux, the capture picture is a random sel...We investigate the statistics of polymer capture by a nanopore using Brownian dynamics simulations. It is found that when the velocity flux is greater than a critical velocity flux, the capture picture is a random selection process, otherwise it tends to a statistical process governed by energetic considerations. In addition, the chain ends capture probability decreases as the chain length increases and satisfies a power-law scaling of P0（N）-N^-0.8.展开更多
Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very g...Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.展开更多
The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer mol...The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics(RPMD)method on a full-dimensional potential energy surface(PES).This PES is the most accurate one for the title reaction,as demonstrated by the correct barrier height and reaction energy,compared to the benchmark calculations by the focal point analysis and the high accuracy extrapolated ab initio thermochemistry methods.The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation technique,and some experimental measurements.As has been found in many RPMD applications,quantum effects,including tunneling and zero-point energy effects,can be efficiently and effectively captured by the RPMD method.In addition,the convergence of the results with respect to the number of beads is rapid,which is also consistent with previous RPMD applications.展开更多
The diffusion coefficients(Dapp) and the heterogeneous electron-transfer rate constants(ks)for ferrocene and its seven derivatives in MPEG/LiClO4 electrolyte were determined by using steadystate voltammetry. The two p...The diffusion coefficients(Dapp) and the heterogeneous electron-transfer rate constants(ks)for ferrocene and its seven derivatives in MPEG/LiClO4 electrolyte were determined by using steadystate voltammetry. The two parameters increase with increasing temperature, indicating Arrhenius behavior. The effects of the nature of electroactive solute molecules on Dapp, ks, and the half-wave potentials(E1/2) are discussed.展开更多
The ditheion coefficients(Dapp) and the heterogeneous electron-transfer rate constan(ks)for ferrocene in MPEG/salt electrolytes were determined by using Steady-stae voltammetry. The temperature dependence of the two p...The ditheion coefficients(Dapp) and the heterogeneous electron-transfer rate constan(ks)for ferrocene in MPEG/salt electrolytes were determined by using Steady-stae voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equstion. The effect of the ionic size of sir supporting electrolytes on diffusion and electron transfer dynamics of fermcene was discussed展开更多
Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics ...Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics of the branch point of a star polymer around its glass transition temperature, four-arm star poly （n-butyl methacrylate） with a fluorescent core was synthesized using perylene diimide as initiator and polymerization conducted via atom transfer radical polymerization. The process is found to be effective in positioning the fluorophore at the branch point with the fluorophore intact, which allows the successful application of single molecule fluorescence defocus imaging in examining the local site- sensitive dynamics. The power spectra of rotation trajectories, the population of rotating fluorophores as well as the distribution of angular displacement were used to revel the difference in local dynamics between branch point and the arm＇s end. It is discovered that the local dynamics at the core of the star polymer is much less activated than that at the arm＇s end. The results demonstrate the strong effect dues to the topological constrain at the branch point and the more free space at the arm＇s end.展开更多
Supramolecular polymers,as a type of dynamic polymers,are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry,whose development has greatly promoted the prosperity of new mater...Supramolecular polymers,as a type of dynamic polymers,are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry,whose development has greatly promoted the prosperity of new materials.Notably,molecular weight is one of the most important parameters of supramolecular polymers,which affects the physical/chemical properties and processing applications of materials.Developing new methods for characterizing the molecular weight of supramolecular polymers is crucial for advancing the development of supramolecular polymers.In this review,we elaborate and summarize three strategies for characterizing the molecular weight of supramolecular polymers that recently reported by our research group according to the characteristics of supramolecular polymers,including(1)the molecular weight distinction corresponding to variable fluorescence colors,(2)matching different molecular weights with different fluorescence lifetime,(3)transforming supramolecular polymers into mechanically interlocked polymers or covalent polymers.Besides,we also discuss the limitations of current methods for characterizing supramolecular polymers.We hope that this review can promote the development of supramolecular polymers and significantly inspire to exploit new methods to characterizing molecular weight of supramolecular polymers.展开更多
Sulfur-containing dynamic polymers had attracted significant attention due to their unique chemical structures with high reversibility.Utilizating sulfur, an inexpensive industrial waste product, to synthesize dynamic...Sulfur-containing dynamic polymers had attracted significant attention due to their unique chemical structures with high reversibility.Utilizating sulfur, an inexpensive industrial waste product, to synthesize dynamic polysulfide polymers through reverse vulcanization has been a notable approach. However, this method required high temperatures and resulted in the release of unpleasant oders. In this study, we presented a robust method for the preparation of sulfur-rich polymers with dynamic polysulfide bonds from elemental sulfur and inexpensive epoxide monomers via a one-pot strategy at the mild room temperature. Different types of polysulfide molecules and polymers were synthesized by reacting various epoxide compounds with sulfur, along with the investigation of their structures and dynamic behaviors. It was noteworthy that the obatined polymers prepared from m-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline and elemental sulfur exhibit multiple dynamic behaviors, including polysulfide metathesis and polysulfide-thiol exchange, enabling their rapid stress relaxation, self-healing, reprocessing and degradable properties of the cross-linked polymer. More importantly, the hydroxyl groups at the side chains from epoxide ring opening exhibited potential transesterification. This work provided a facile strategy for designing dynamic sulfur-rich polymers via a mild synthesis route.展开更多
Imine bonds are among the most explored building motifs in dynamic chemistry,polymers,and materials,and yet,their acid-resistance remains a longstanding issue.Herein we demonstrate a concept of internal protecting gro...Imine bonds are among the most explored building motifs in dynamic chemistry,polymers,and materials,and yet,their acid-resistance remains a longstanding issue.Herein we demonstrate a concept of internal protecting groups for improving the kinetic stability of dynamic imine bonds and polymers.Systematic examination of structure-reactivity relationship of a series of aldehydes/imines bearing a neighboring carboxyl allowed uncovering of required structural features for dynamically masking imine bonds with cyclic structures.Mechanistic studies indicated that noncovalent interactions along with sterics control the ringchain equilibrium and the stability of imine bonds.The incorporation of internal protecting groups into imine polymers further enabled their controlled stability in acidic media.Moreover,a combination of dynamic covalent network and coordination supramolecular network provided a facile means for the modulation of luminescent and mechanical properties of polymers.The strategies and results reported should be beneficial to molecular assemblies,dynamic polymers,biological delivery,and intelligent materials.展开更多
The major difficulty in achieving good performance of industrial polymerization reactors lies in the lack of understanding of their nonlinear dynamics and the lack of well-developed techniques for the control of nonli...The major difficulty in achieving good performance of industrial polymerization reactors lies in the lack of understanding of their nonlinear dynamics and the lack of well-developed techniques for the control of nonlinear processes, which are usually accompanied with bifurcation phenomenon. This work aims at investigating the nonlinear behavior of the parameterized nonlinear system of vinyl acetate polymerization and further modifying the bifurcation characteristics of this process via a washout filter-aid controller, with all the original steady state equilibria preserved. Advantages and possible extensions of the proposed methodology are discussed to provide scientific guide for further controller design and operation improvement.展开更多
Sequence regulation provides an effective approach to controlling the properties of polymer materials.However,this approach remains an open question in the field of dynamic polymers,which emerge as more and more impor...Sequence regulation provides an effective approach to controlling the properties of polymer materials.However,this approach remains an open question in the field of dynamic polymers,which emerge as more and more important new generation materials.Herein,we systematically investigate the effect of sequence control of dynamic covalent units in tuning the properties of materials.Different sequence-controlled poly(oxime-urethanes)are designed.The dynamic oxime-urethane groups are relatively dispersed(SCP-1)or concentrated(SCP-2)distributed in their molecular chains.The sequence control strategy provides an efficient way to decouple the mechanical and self-healing performance of polymers,which is one of the most pressing challenges in the field.The relatively dispersed oxime-urethane groups in SCP-1 not only facilitate the reorganization of the dynamic covalent bonds but also increase the probability of the reformation of hydrogen bonds.The reversible dissociation/reassociation of dynamic bonds is conducive to dissipating energy to enhance mechanical performance and promote self-healing properties.As a result,SCP-1 exhibits much faster self-healing than SCP-2,and its tensile strength is nearly twice that of SCP-2.In addition,energy dissipation capacity and degradation behavior also show significant sequence dependence.Overall,this work reveals a new molecular structure-property relationship and provides a powerful strategy to construct high-performance polymers.展开更多
Dynamic polymers based on dynamic covalent chemistry represent a promising class of smart and responsive materials that have garnered significant research interest in recent years.Oxime-urethane chemistry,typically de...Dynamic polymers based on dynamic covalent chemistry represent a promising class of smart and responsive materials that have garnered significant research interest in recent years.Oxime-urethane chemistry,typically derived from the reaction between oximes and isocyanates,is remarkable for its multiple reversible reactivity nature under specific stimuli.In this review,we provide a comprehensive overview of the development of dynamic polymers,with a specific focus on oxime-urethane based polymers.We summarize key design strategies,including the structural characteristics and sources of oximes,methods for polymer preparation,and the design of network topology.Additionally,we outline the major applications of oxime-urethane based dynamic polymers in flexible electronics,three-dimensional(3D)printing,biomedicine,and other fields.Finally,we discuss the current challenges and future directions within this field.展开更多
We propose an experimental setup to measure the threshold pressure gradient （TPG） of microchannels with different wettability surfaces by the static method in microchannels with diameters from 20 μm to 320 μm, and...We propose an experimental setup to measure the threshold pressure gradient （TPG） of microchannels with different wettability surfaces by the static method in microchannels with diameters from 20 μm to 320 μm, and compare the TPG of microchannels with adsorption of cetyl trimethyl ammonium bromide （CTAB） with that without CTAB adsorption. The results show the existence of TPG in microchannels. The TPG of microchannels increases with decreasing hydrodynamic diameter, and the relation between TPG and diameter is in agreement with the single-log normalization. The TPG of a microchannel with CTAB adsorption decreases obviously as compared with the microchannel without CTAB adsorption. The TPG of microchannels with different wettabilities of boundary surface are different, and the resistance of liquid flow can be reduced by changing the wettability of boundary surfaces.展开更多
Effects of variable viscosity on the flow and heat transfer in a thin film on a horizontal porous stretching sheet are analyzed. The steady boundary layer equations for momentum and thermal energy are simplified by us...Effects of variable viscosity on the flow and heat transfer in a thin film on a horizontal porous stretching sheet are analyzed. The steady boundary layer equations for momentum and thermal energy are simplified by using similarity transformations. The resulted and coupled nonlinear differential equations are solved by Homotopy analysis method. The results are presented graphically to interpret various physical parameters appearing in the problem.展开更多
A drug delivery system via multi-walled carbon nanotube （MWNT） vehicle was synthesized in aqueous solution. MWNTs were first noncovalently functionalized with chitosan oligomers （CS） with a molecule weight of 4000...A drug delivery system via multi-walled carbon nanotube （MWNT） vehicle was synthesized in aqueous solution. MWNTs were first noncovalently functionalized with chitosan oligomers （CS） with a molecule weight of 4000-6000, making MWNTs water-soluble, and then a cancer ancillary drug tea polyphenols （TP） was conjugated mainly via the hydrogen bond between CS and TP molecules, making MWNTs efficient vehicle for drug delivering. The release of drug molecules can be realized by pH variation and γ-radiation, leading to new methods for controlling drug release from carbon nanotubes carrier. Due to the high penetrability of γ-rays, γ-radiation shows up new opportunities in controlled drug release, possibly facilitating the future cancer treatment in vivo.展开更多
We report on a first observation of a floating- spherical Hg （density 13g/cm3） drop on top of a glycerin （density 1.26g/cm3） drop, the latter is hemispherical and about four times larger in volume. This observatio...We report on a first observation of a floating- spherical Hg （density 13g/cm3） drop on top of a glycerin （density 1.26g/cm3） drop, the latter is hemispherical and about four times larger in volume. This observation is clearly against nature＇s gravity law and has never been reported before. Here we present spectacular high resolution photos that clearly demonstrate this remarkable floating phenomenon. Using milli-Q water, the Hg drop would stay down adhered at the triple line. Instead, the coincidental use of tap water displays the same phenomenon. Increasing the volume of the supporting liquid to a certain value causes the Hg drop to sink. A 5-M NaCl aqueous solution is found enough to show the same floating phenomenon. This floating mercury as a phenomenon is puzzling. On this length scale it seems that surface tension and curvature dominate over gravity.展开更多
Evolution of viscosity of some aqueous poly （ethylene oxide） gels is observed as functions of polymeric concentration and temperature for samples subjected to thermal shock. The experimental data are analyzed follow...Evolution of viscosity of some aqueous poly （ethylene oxide） gels is observed as functions of polymeric concentration and temperature for samples subjected to thermal shock. The experimental data are analyzed following an appropriate algorithm, and reveal the transient effect from Newtonian to non-Newtonian flow as a function of the polymeric concentration.展开更多
The capture of circulating tumor cells(CTCs)is of great significance in reducing cancer mortality and complications.However,the nonspecific binding of proteins and white blood cells(WBCs)weakens the targeting capabili...The capture of circulating tumor cells(CTCs)is of great significance in reducing cancer mortality and complications.However,the nonspecific binding of proteins and white blood cells(WBCs)weakens the targeting capabilities of the capture surfaces,which critically hampers the efficiency and purity of the captured CTCs.Herein,we propose a liquid-like interface design strategy that consists of liquid-like polymer chains and anti-EpCAM modification processes for high-purity and high-efficiency capture of CTCs.The dynamic flexible feature of the liquid-like chains endows the modified surfaces with excellent antiadhesion property for proteins and blood cells.The liquid-like surfaces can capture the target CTCs and show high cell viability due to the environmentfriendly surface modification processes.When liquid-like surface designs were introduced in the deterministic lateral displacement(DLD)-patterned microfluidic chip,the nonspecific adhesion rate of WBCs was reduced by more than fivefold compared to that in the DLD chip without liquid-like interface design,while maintaining comparable capture efficiency.Overall,this strategy provides a novel perspective on surface design for achieving high purity and efficient capture of CTCs.展开更多
We report the synthesis and characterization of a photocleavable fluorescent dye dyad.The two constituting dyes show a large spectral overlap and are in close proximity to each other,leading to efficient Förster Reso...We report the synthesis and characterization of a photocleavable fluorescent dye dyad.The two constituting dyes show a large spectral overlap and are in close proximity to each other,leading to efficient Förster Resonance Energy Transfer(FRET).Photocleavage of the dyad and the subsequent independent diffusion of both fluorophores qualifies the system to be used for high accuracy diffusion measurements.In contrast to previous work,the dyad reported here can be applied in polar solvents and cleaved by UV-A light.Beneficially,the photolabile linker provides two orthogonal labeling sites for various commercially available fluorescent labels.In this work,we chose the cationic organic dyes ATTO565 and ATTO647N.We outline the synthesis and spectral characterization of the system with UV-Vis and fluorescence spectroscopy as well as fluorescence lifetime and fluorescence quantum yield measurements.Furthermore,we performed proof-of-principle microscopy experiments to demonstrate its capability in polyvinyl acetate films.展开更多
文摘The diffusion coefficients(Dapp) and the heterogeneous electron transfer rate constants(ks)for ferrocene in several polymer solvents were determined by using steady-stae voltammetry. Thetemperature dependence of the two parameters indicates Arrhenius behavior. The polymer solventeffects on diffusion and electron transfer dynamics of ferrocene were discussed
基金financially supported by the National Basic Research Program of China(No.2009CB930100)the National Natural Science Foundation of China(Nos.21234007,21304097 and 51473168)the Joint Research Fund for Overseas Chinese,Hong Kong and Macao Young Scientists of the National Natural Science Foundation of China(No.51028301)
文摘We investigate the statistics of polymer capture by a nanopore using Brownian dynamics simulations. It is found that when the velocity flux is greater than a critical velocity flux, the capture picture is a random selection process, otherwise it tends to a statistical process governed by energetic considerations. In addition, the chain ends capture probability decreases as the chain length increases and satisfies a power-law scaling of P0（N）-N^-0.8.
基金supported by the National Natural Science Foundation of China(No.21773251 and No.21973098)the Youth Innovation Promotion Association CAS(No.2018045)the Beijing National Laboratory for Molecular Sciences。
文摘Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.
基金supported by the National Natural Science Foundation of China(No.21573027)
文摘The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics(RPMD)method on a full-dimensional potential energy surface(PES).This PES is the most accurate one for the title reaction,as demonstrated by the correct barrier height and reaction energy,compared to the benchmark calculations by the focal point analysis and the high accuracy extrapolated ab initio thermochemistry methods.The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation technique,and some experimental measurements.As has been found in many RPMD applications,quantum effects,including tunneling and zero-point energy effects,can be efficiently and effectively captured by the RPMD method.In addition,the convergence of the results with respect to the number of beads is rapid,which is also consistent with previous RPMD applications.
文摘The diffusion coefficients(Dapp) and the heterogeneous electron-transfer rate constants(ks)for ferrocene and its seven derivatives in MPEG/LiClO4 electrolyte were determined by using steadystate voltammetry. The two parameters increase with increasing temperature, indicating Arrhenius behavior. The effects of the nature of electroactive solute molecules on Dapp, ks, and the half-wave potentials(E1/2) are discussed.
文摘The ditheion coefficients(Dapp) and the heterogeneous electron-transfer rate constan(ks)for ferrocene in MPEG/salt electrolytes were determined by using Steady-stae voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equstion. The effect of the ionic size of sir supporting electrolytes on diffusion and electron transfer dynamics of fermcene was discussed
基金supported by National Basic Research Program of China(No. 2014CB643601)
文摘Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics of the branch point of a star polymer around its glass transition temperature, four-arm star poly （n-butyl methacrylate） with a fluorescent core was synthesized using perylene diimide as initiator and polymerization conducted via atom transfer radical polymerization. The process is found to be effective in positioning the fluorophore at the branch point with the fluorophore intact, which allows the successful application of single molecule fluorescence defocus imaging in examining the local site- sensitive dynamics. The power spectra of rotation trajectories, the population of rotating fluorophores as well as the distribution of angular displacement were used to revel the difference in local dynamics between branch point and the arm＇s end. It is discovered that the local dynamics at the core of the star polymer is much less activated than that at the arm＇s end. The results demonstrate the strong effect dues to the topological constrain at the branch point and the more free space at the arm＇s end.
基金supported by the National Natural Science Foundation of China(No.22001087)supported by Fundamental Research Funds for the Central Universities(No.2020kfy XJJS013)Interdisciplinary Research Program of HUST(No.2023JCYJ013)。
文摘Supramolecular polymers,as a type of dynamic polymers,are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry,whose development has greatly promoted the prosperity of new materials.Notably,molecular weight is one of the most important parameters of supramolecular polymers,which affects the physical/chemical properties and processing applications of materials.Developing new methods for characterizing the molecular weight of supramolecular polymers is crucial for advancing the development of supramolecular polymers.In this review,we elaborate and summarize three strategies for characterizing the molecular weight of supramolecular polymers that recently reported by our research group according to the characteristics of supramolecular polymers,including(1)the molecular weight distinction corresponding to variable fluorescence colors,(2)matching different molecular weights with different fluorescence lifetime,(3)transforming supramolecular polymers into mechanically interlocked polymers or covalent polymers.Besides,we also discuss the limitations of current methods for characterizing supramolecular polymers.We hope that this review can promote the development of supramolecular polymers and significantly inspire to exploit new methods to characterizing molecular weight of supramolecular polymers.
基金financially supported by the State Key R&D Program of China (No. 2019YFA0706801)the National Natural Science Foundation of China (No. 52173079)the Fundamental Research Funds for the Central Universities (Nos. xtr052023001 and xzy022024024)。
文摘Sulfur-containing dynamic polymers had attracted significant attention due to their unique chemical structures with high reversibility.Utilizating sulfur, an inexpensive industrial waste product, to synthesize dynamic polysulfide polymers through reverse vulcanization has been a notable approach. However, this method required high temperatures and resulted in the release of unpleasant oders. In this study, we presented a robust method for the preparation of sulfur-rich polymers with dynamic polysulfide bonds from elemental sulfur and inexpensive epoxide monomers via a one-pot strategy at the mild room temperature. Different types of polysulfide molecules and polymers were synthesized by reacting various epoxide compounds with sulfur, along with the investigation of their structures and dynamic behaviors. It was noteworthy that the obatined polymers prepared from m-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline and elemental sulfur exhibit multiple dynamic behaviors, including polysulfide metathesis and polysulfide-thiol exchange, enabling their rapid stress relaxation, self-healing, reprocessing and degradable properties of the cross-linked polymer. More importantly, the hydroxyl groups at the side chains from epoxide ring opening exhibited potential transesterification. This work provided a facile strategy for designing dynamic sulfur-rich polymers via a mild synthesis route.
基金the National Natural Science Foundation of China(NSFC,Nos.22071247,92156010,22101283,and 22101284)the Key Research Program of Frontier Sciences(No.QYZDBSSW-SLH030)of the CAS+1 种基金Natural Science Foundation of Fujian Province(Nos.2020J06035 and 2022J05085)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR112)for support.
文摘Imine bonds are among the most explored building motifs in dynamic chemistry,polymers,and materials,and yet,their acid-resistance remains a longstanding issue.Herein we demonstrate a concept of internal protecting groups for improving the kinetic stability of dynamic imine bonds and polymers.Systematic examination of structure-reactivity relationship of a series of aldehydes/imines bearing a neighboring carboxyl allowed uncovering of required structural features for dynamically masking imine bonds with cyclic structures.Mechanistic studies indicated that noncovalent interactions along with sterics control the ringchain equilibrium and the stability of imine bonds.The incorporation of internal protecting groups into imine polymers further enabled their controlled stability in acidic media.Moreover,a combination of dynamic covalent network and coordination supramolecular network provided a facile means for the modulation of luminescent and mechanical properties of polymers.The strategies and results reported should be beneficial to molecular assemblies,dynamic polymers,biological delivery,and intelligent materials.
基金Supported by the National Basic Research Programme(2012CB720500)the National Natural Science Foundation of China(21306100)
文摘The major difficulty in achieving good performance of industrial polymerization reactors lies in the lack of understanding of their nonlinear dynamics and the lack of well-developed techniques for the control of nonlinear processes, which are usually accompanied with bifurcation phenomenon. This work aims at investigating the nonlinear behavior of the parameterized nonlinear system of vinyl acetate polymerization and further modifying the bifurcation characteristics of this process via a washout filter-aid controller, with all the original steady state equilibria preserved. Advantages and possible extensions of the proposed methodology are discussed to provide scientific guide for further controller design and operation improvement.
基金supported by the National Natural Science Foundation of China(52203169,52173117,52473004,52403163,21991123)the Shenzhen Science and Technology Program(JCYJ202-20530155800001,RCBS20221008093058029,JCYJ20220818102804009,JCYJ20230807093903006)+3 种基金the Ningbo 2025 Science and Technology Major Project(2019B10068)the Science and Technology Commission of Shanghai Municipality(20DZ2254900,20DZ2270800)the Guangdong Basic and Applied Basic Research Foundation(2023A1515110778)the Guangdong High-Level Hospital Construction Fund.
文摘Sequence regulation provides an effective approach to controlling the properties of polymer materials.However,this approach remains an open question in the field of dynamic polymers,which emerge as more and more important new generation materials.Herein,we systematically investigate the effect of sequence control of dynamic covalent units in tuning the properties of materials.Different sequence-controlled poly(oxime-urethanes)are designed.The dynamic oxime-urethane groups are relatively dispersed(SCP-1)or concentrated(SCP-2)distributed in their molecular chains.The sequence control strategy provides an efficient way to decouple the mechanical and self-healing performance of polymers,which is one of the most pressing challenges in the field.The relatively dispersed oxime-urethane groups in SCP-1 not only facilitate the reorganization of the dynamic covalent bonds but also increase the probability of the reformation of hydrogen bonds.The reversible dissociation/reassociation of dynamic bonds is conducive to dissipating energy to enhance mechanical performance and promote self-healing properties.As a result,SCP-1 exhibits much faster self-healing than SCP-2,and its tensile strength is nearly twice that of SCP-2.In addition,energy dissipation capacity and degradation behavior also show significant sequence dependence.Overall,this work reveals a new molecular structure-property relationship and provides a powerful strategy to construct high-performance polymers.
基金supported by the National Natural Science Foundation of China(52203169,52403153,52203135)foundation of Yangtze Delta Region Institute(Huzhou)of UESTC(U03220149)+2 种基金Huzhou Science and Technology Program Projects(2023GZ18)Zhejiang Postdoctoral Research Project(ZJ2023133)Science and Technology Cooperation Fund Program of Chengdu-Chinese Academy of Sciences(2023-2025)。
文摘Dynamic polymers based on dynamic covalent chemistry represent a promising class of smart and responsive materials that have garnered significant research interest in recent years.Oxime-urethane chemistry,typically derived from the reaction between oximes and isocyanates,is remarkable for its multiple reversible reactivity nature under specific stimuli.In this review,we provide a comprehensive overview of the development of dynamic polymers,with a specific focus on oxime-urethane based polymers.We summarize key design strategies,including the structural characteristics and sources of oximes,methods for polymer preparation,and the design of network topology.Additionally,we outline the major applications of oxime-urethane based dynamic polymers in flexible electronics,three-dimensional(3D)printing,biomedicine,and other fields.Finally,we discuss the current challenges and future directions within this field.
基金Supported by the National Natural Science Foundation of China under Grant No 10972199, and the Natural Science Foundation of Zhejiang Province under Grant No Y607425.
文摘We propose an experimental setup to measure the threshold pressure gradient （TPG） of microchannels with different wettability surfaces by the static method in microchannels with diameters from 20 μm to 320 μm, and compare the TPG of microchannels with adsorption of cetyl trimethyl ammonium bromide （CTAB） with that without CTAB adsorption. The results show the existence of TPG in microchannels. The TPG of microchannels increases with decreasing hydrodynamic diameter, and the relation between TPG and diameter is in agreement with the single-log normalization. The TPG of a microchannel with CTAB adsorption decreases obviously as compared with the microchannel without CTAB adsorption. The TPG of microchannels with different wettabilities of boundary surface are different, and the resistance of liquid flow can be reduced by changing the wettability of boundary surfaces.
文摘Effects of variable viscosity on the flow and heat transfer in a thin film on a horizontal porous stretching sheet are analyzed. The steady boundary layer equations for momentum and thermal energy are simplified by using similarity transformations. The resulted and coupled nonlinear differential equations are solved by Homotopy analysis method. The results are presented graphically to interpret various physical parameters appearing in the problem.
文摘A drug delivery system via multi-walled carbon nanotube （MWNT） vehicle was synthesized in aqueous solution. MWNTs were first noncovalently functionalized with chitosan oligomers （CS） with a molecule weight of 4000-6000, making MWNTs water-soluble, and then a cancer ancillary drug tea polyphenols （TP） was conjugated mainly via the hydrogen bond between CS and TP molecules, making MWNTs efficient vehicle for drug delivering. The release of drug molecules can be realized by pH variation and γ-radiation, leading to new methods for controlling drug release from carbon nanotubes carrier. Due to the high penetrability of γ-rays, γ-radiation shows up new opportunities in controlled drug release, possibly facilitating the future cancer treatment in vivo.
文摘We report on a first observation of a floating- spherical Hg （density 13g/cm3） drop on top of a glycerin （density 1.26g/cm3） drop, the latter is hemispherical and about four times larger in volume. This observation is clearly against nature＇s gravity law and has never been reported before. Here we present spectacular high resolution photos that clearly demonstrate this remarkable floating phenomenon. Using milli-Q water, the Hg drop would stay down adhered at the triple line. Instead, the coincidental use of tap water displays the same phenomenon. Increasing the volume of the supporting liquid to a certain value causes the Hg drop to sink. A 5-M NaCl aqueous solution is found enough to show the same floating phenomenon. This floating mercury as a phenomenon is puzzling. On this length scale it seems that surface tension and curvature dominate over gravity.
文摘Evolution of viscosity of some aqueous poly （ethylene oxide） gels is observed as functions of polymeric concentration and temperature for samples subjected to thermal shock. The experimental data are analyzed following an appropriate algorithm, and reveal the transient effect from Newtonian to non-Newtonian flow as a function of the polymeric concentration.
基金supported by the National Natural Science Foundation of China(grant nos.52025132,21975209,22275156,21621091,22021001,22005255,and T2241022)the National Science Foundation of Fujian Province of China(grant no.2022J02059)+4 种基金the Fundamental Research Funds for the Central Universities of China(grant nos.20720220019 and 20720220085)the 111 Project(grant nos.B17027 and B16029)the Science and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(grant no.RD2022070601)the State Key Laboratory of Bio-Fibers and Eco-Textiles(Qingdao University)(grant no.KFKT202221)the Tencent Foundation(The XPLORER PRIZE).
文摘The capture of circulating tumor cells(CTCs)is of great significance in reducing cancer mortality and complications.However,the nonspecific binding of proteins and white blood cells(WBCs)weakens the targeting capabilities of the capture surfaces,which critically hampers the efficiency and purity of the captured CTCs.Herein,we propose a liquid-like interface design strategy that consists of liquid-like polymer chains and anti-EpCAM modification processes for high-purity and high-efficiency capture of CTCs.The dynamic flexible feature of the liquid-like chains endows the modified surfaces with excellent antiadhesion property for proteins and blood cells.The liquid-like surfaces can capture the target CTCs and show high cell viability due to the environmentfriendly surface modification processes.When liquid-like surface designs were introduced in the deterministic lateral displacement(DLD)-patterned microfluidic chip,the nonspecific adhesion rate of WBCs was reduced by more than fivefold compared to that in the DLD chip without liquid-like interface design,while maintaining comparable capture efficiency.Overall,this strategy provides a novel perspective on surface design for achieving high purity and efficient capture of CTCs.
文摘We report the synthesis and characterization of a photocleavable fluorescent dye dyad.The two constituting dyes show a large spectral overlap and are in close proximity to each other,leading to efficient Förster Resonance Energy Transfer(FRET).Photocleavage of the dyad and the subsequent independent diffusion of both fluorophores qualifies the system to be used for high accuracy diffusion measurements.In contrast to previous work,the dyad reported here can be applied in polar solvents and cleaved by UV-A light.Beneficially,the photolabile linker provides two orthogonal labeling sites for various commercially available fluorescent labels.In this work,we chose the cationic organic dyes ATTO565 and ATTO647N.We outline the synthesis and spectral characterization of the system with UV-Vis and fluorescence spectroscopy as well as fluorescence lifetime and fluorescence quantum yield measurements.Furthermore,we performed proof-of-principle microscopy experiments to demonstrate its capability in polyvinyl acetate films.
