The facile synthesis of high-valued polymers from waste molecules or low-cost common chemicals presents a significant challenge.Here,we develop a series of degradable poly(thiocarbonate)s from the new step-growth poly...The facile synthesis of high-valued polymers from waste molecules or low-cost common chemicals presents a significant challenge.Here,we develop a series of degradable poly(thiocarbonate)s from the new step-growth polymerization of diols,carbonyl sulfide(CoS,or carbon disulfide,CS_(2)),and dichlorides.Diols and dichlorides are common chemicals,and CoS(CS_(2))is released as industrial waste.In addition to abun-dant feedstocks,the method is efficient and performed under mild conditions,using common organic bases as catalysts,and affording unprece-dented polymers.When cos,diols,and dihalides were used as monomers,optimized conditions could completely suppress the oxygen-sulfur exchange reaction,enabling the efficient synthesis of well-defined poly(monothiocarbonate)s with melting points ranging from 48°C to 101°C.These polymers,which have a structure similar to polyethylene with low-density in-chain polar groups,exhibit remarkable toughness and ductili-ty that rival those of high-density polyethylene(melting point:90°C,tensile strength:21.6±0.7 MPa,and elongation at break:576%).Moreover,the obtained poly(monothiocarbonate)s can be chemically degraded by alcoholysis to yield small-molecule diols and dithiols.When CS_(2)was used in place of cos,a pronounced oxygen-sulfur exchange reaction occurred.By optimizing reaction condition,it was found that polymers with-S(C=O)S-and-S(C=S)S-as the main repeating units exhibited high thermal stability and crystallinity.Thus,a new approach for regulat-ing the structure of polythiocarbonates via the oxygen-sulfur exchange reaction is developed.Overall,the polymers hold great potential for green materials due to their facile synthesis,readily available feedstocks,excellent performance,and chemical degradability.展开更多
Given the increasing demand for distributed electricity,there is a burning desire to harvest electricity from renewable sources using environmentally friendly methods.Thermoelectric (TE) materials can meet this requir...Given the increasing demand for distributed electricity,there is a burning desire to harvest electricity from renewable sources using environmentally friendly methods.Thermoelectric (TE) materials can meet this requirement not only because of their ability to convert heat directly into electricity,enabling energy harvesting from waste heat and natural heat resources,but also because more than 60%of the energy is lost as waste heat [1].The discovery of the TE effect dates back to the 1820s when T.M.Seebeck observed electricity generation at the junction of two conductors with different temperatures.Additionally,when a voltage is applied to TE materials,they can create a temperature difference to enable solid-state cooling (known as the Peltier effect).Therefore,the TE effect promises both sustainable energy solutions and temperature control technologies.Over the past two decades,the urgent demand for powering ubiquitous Internet of Things devices has sparked significant interest in flexible thermoelectrics(F-TEs),which raises an intriguing question:Is the intrinsically flexible polymer an important candidate for state-of-the-art F-TEs applications?展开更多
Although the certified power conversion efficiency(PCE)of single-junction perovskite solar cells(PSCs)has achieved a high level of 27%,approaching the single-crystalline silicon solar cells,the device stability remain...Although the certified power conversion efficiency(PCE)of single-junction perovskite solar cells(PSCs)has achieved a high level of 27%,approaching the single-crystalline silicon solar cells,the device stability remains an urgent issue to be resolved for the commercialization.Defect passivation emerged as a viable approach to enhance the operational stability of the solar devices.Herein,phenylthiourea(PhTu)derivatives are selected as effective passivation agents to enhance the optoelectronic properties of printed methylammonium lead iodide(MAPbI_(3))films.It is demonstrated that incorporating a small amount of 1-(4-carboxyphenyl)-2-thiourea(PhTu-COOH)significantly reduces the trap-state density and leads to longer carrier lifetime of the perovskite films.As a result,the inverted solar device made of Ph Tu-COOH-modified MAPbI_(3) perovskite film shows remarkably improved efficiency(from 17.29%to 20.22%)and obviously increased open-circuit voltage(V_(OC))(from 1.043 to 1.143 V),as compared with the pristine device.Moreover,the Ph Tu-COOH-modified PSCs exhibit enhanced operational stability due to the significantly reduced trap-state density.Finally,the optimized solar module fabricated with an active area of 11.28 cm^(2) delivers a high PCE of 17.07%with negligible V_(OC)loss,demonstrating the feasibility of the blade-coating method for large-area perovskite film deposition.展开更多
Dynamic melt modification of polyethylene via the direct grafting of peroxide fragments shows promise for the development of processable functionalized materials.In this study,four linear low-density polyethylenes(LLD...Dynamic melt modification of polyethylene via the direct grafting of peroxide fragments shows promise for the development of processable functionalized materials.In this study,four linear low-density polyethylenes(LLDPEs)with comparable molecular weights but different short-chain branch(SCB)contents(ranging of 5-66 per 1000 carbon atoms)were modified via dynamic melt mixing using 2 wt% benzoyl peroxide at 145℃ and 50 r/min for 30 min.The influence of SCB content on the processability and structure of the resulting products was systematically investigated.All modified products exhibited good melt processability with melt flow rates(MFR)ranging from 0.46 g/10min to 1.07 g/10min.Products derived from low-SCB LLDPEs showed a lower MFR,higher cross-linking content,a larger number of long-chain branches,and a higher degree of benzoyl grafting.In contrast,those produced from high-SCB LLDPEs exhibited improved processability,reduced cross-linking,fewer long-chain branches,and lower benzoyl grafting levels.A detailed structural investigation of the soluble and insoluble fractions,which were separated using trichlorobenzene fractionation,was conducted to analyze the structural features of various modified products and demonstrate that the SCB content(i.e.,tertiary carbon density)significantly influences radical coupling during dynamic modification.Elevated tertiary carbon density,by introducing greater steric hindrance,suppresses radical coupling during dynamic modification,thereby reducing the efficiency of both crosslinking and peroxide fragment grafting.These findings provide new insights into the structure-reactivity relationships in peroxide-induced polyethylene modification and lay the foundation for tailoring material properties via dynamic processing.展开更多
With the rapid advancements in biomedical engineering,bioprinting has emerged as a pivotal solution to address the shortage of organ transplants and advance disease model research.The evolution of bioprinting has prog...With the rapid advancements in biomedical engineering,bioprinting has emerged as a pivotal solution to address the shortage of organ transplants and advance disease model research.The evolution of bioprinting has progressed from the fabrication of simple models(1.0)to the fabrication of permanent implants(2.0),tissue engineering scaffolds(3.0),and complex biostructures utilizing living cells(4.0).Nevertheless,significant challenges remain,particularly in accurately replicating the structure and function of host tissues,selecting appropriate materials,and optimizing printing parameters.The integration of artificial intelligence(AI),especially machine learning,provides promising novel opportunities in bioprinting(5.0).This review systematically summarizes the current applications of AI in bioprinting,discussing both construction strategies and application scenarios.It also explores the potential of AI to improve bioprinting in the preparation of complex functional tissues and in situ tissue repair.Overall,the synergy between AI and bioprinting is poised to drive the development of personalized medicine,facilitate high-throughput preparation of in vitro models,and provide robust tools for regenerative medicine and precision healthcare.展开更多
Modifying polypropylene membranes with interpenetrating polymer networks(IPNs) through the incorporation of poly(glycidyl methacrylate-N-methyl-D-glucamine)(P(GMA-NMG)) was performed by in situ synthesis via radical p...Modifying polypropylene membranes with interpenetrating polymer networks(IPNs) through the incorporation of poly(glycidyl methacrylate-N-methyl-D-glucamine)(P(GMA-NMG)) was performed by in situ synthesis via radical polymerization. The surface of the polypropylene membrane was activated by hydrophilic grafted polyelectrolyte, and then, pressure injection was used for the impregnation of the reactive solution in the membrane.Two types of pore-filled membranes were synthesized, chelating interpenetrating homopolymer networks of P(GMA-NMG), and chelating-ion exchange interpenetrating polymer networks(e.g., P(GMA-NMG)/P(AA),P(GMA-NMG)/P(AMPSA), and P(GMA-NMG)/P(Cl VBTA)). After their synthesis, the modified polypropylene membranes were characterized using techniques such as the electrokinetic potential, SEM, FT-IR, and Donnan dialysis to corroborate the chromium ion transport. The P(GMA-NMG) and complex network membranes exhibited a hydrophilic character with a water-uptake capacity between 20% and 35% and a percentage of modification between 4.0% and 7.0% in comparison with the behavior of the unmodified polypropylene membrane.Hexavalent chromium ions were efficiently transported from the food chamber at p H 9.0 when the 65.2%MTA1 P(Cl VBTA) homopolymer IPN membrane and 48.5% MTAG P(GMA-NMG)/P(Cl VBTA) IPN membrane were used. Similarly, hexavalent chromium ions were removed from the food chamber at pH 3.0 when MTAG(63.30%) and MTA1(35.68%) were used in 1 mol·L^(-1)Na Cl solution as the extraction reagent.展开更多
The short review discusses a family of amorphous porous organic polymers,conjugated microporous polymer（CMP）,which is distinctive in fusion of a large π-electronic conjugation within the topological network platfor...The short review discusses a family of amorphous porous organic polymers,conjugated microporous polymer（CMP）,which is distinctive in fusion of a large π-electronic conjugation within the topological network platform.The kind of polymers has shown the synthetic variety,the advanced capability and the wide applicability in contrast to the reported analogues.Herein,the significant progress of CMP applications has been summarized to showcase their capability in constructing photo-functional systems.展开更多
The synthesis of degradable polymers with easy-to-break in-chain carbon-oxygen bonds has attracted much attention.This minireview introduces the synthesis of a variety of degradable polymers from the(co)polymerization...The synthesis of degradable polymers with easy-to-break in-chain carbon-oxygen bonds has attracted much attention.This minireview introduces the synthesis of a variety of degradable polymers from the(co)polymerizations of several typical oxygenated monomers such as epoxides,cyclic carbonates,cyclic esters,carbon dioxide(CO_(2)),carbonyl sulfide(COS),and cyclic anhydrides.We highlight the catalysts and mechanisms for these(co)polymerizations.The ring-opening copolymerization of five-membered carbonate with cyclic anhydride or COS has been introduced.We also highlight the synthesis of block copolymers and cyclic copolymers with well-defined sequences by the method of growing center switching.We hope that these new polymerization systems can provide new ideas for the development of degradable low-carbon polymers in the future.展开更多
We report here a method for the preparation of amphiphilic dendrimer-like copolymers with dendritic polystyrene (PS) core and protonated poly(2-vinyl pyridine)(P2VP) or poly(methacrylic acid)(PMAA) shell. The method e...We report here a method for the preparation of amphiphilic dendrimer-like copolymers with dendritic polystyrene (PS) core and protonated poly(2-vinyl pyridine)(P2VP) or poly(methacrylic acid)(PMAA) shell. The method employed the efficient coupling reaction of anionic living polymer chains and chlorosilane. The synthesis started from a functionalized 3rd generation dendritic polystyrene, G3PS-g-SiCl, used as the precursor. The dendrimer-like copolymer of styrene and 2-vinyl pyridine, G3PS-g-P2VP, was synthesized by direct coupling of living P2VPLi to the precursor. The dendrimer-like copolymer of styrene and Zer/-butyl methacrylate, G3PS-g-PtBMA, was synthesized by an indirect procedure in which a living polymer containing mainly PtBMA segment was attached to the precursor. Both methods resulted in the formation of dendrimer-like copolymers with the high molecular weights (up to 8.5 × 10^6 Da), large molecular sizes (diameter up to 73 nm), and dense shells (number of arms up to 1300). These products, G3PS-g-P2VP and G3PS-g- PtBMA, were protonated with trifluoroacetic acid and acidic hydrolyzed, respectively. After transformation, amphiphilic dendrimer-like copolymers, G3PS-g-P2VPH^+ and G3PS-g-PMAA, were obtained. Preliminary results on the solution properties of the amphiphilic products were presented.展开更多
A Monte Carlo method was used to take thorough account of the influences of different reactivity ratios and initial feed compositions on copolymer microstructure.The model proves the lack of azeotropic behavior in sys...A Monte Carlo method was used to take thorough account of the influences of different reactivity ratios and initial feed compositions on copolymer microstructure.The model proves the lack of azeotropic behavior in systems in which r_A>1 and r_B<1 or vice versa;it is also able to calculate the drift in the copolymer properties:copolymer composition,and randomness parameter.Moreover,for each reactivity ratio pair given,there is a unique reaction conversion,at which macromolecules produced inherit their ...展开更多
In unit cell simulations,identification of ordered phases in block copolymers(BCPs)is a tedious and time-consuming task,impeding the advancement of more streamlined and potentially automated research workflows.In this...In unit cell simulations,identification of ordered phases in block copolymers(BCPs)is a tedious and time-consuming task,impeding the advancement of more streamlined and potentially automated research workflows.In this study,we propose a scattering-based automated identification strategy(SAIS)for characterization and identification of ordered phases of BCPs based on their computed scattering patterns.Our approach leverages the scattering theory of perfect crystals to efficiently compute the scattering patterns of periodic morphologies in a unit cell.In the first stage of the SAIS,phases are identified by comparing reflection conditions at a sequence of Miller indices.To confirm or refine the identification results of the first stage,the second stage of the SAIS introduces a tailored residual between the test phase and each of the known candidate phases.Furthermore,our strategy incorporates a variance-like criterion to distinguish background species,enabling its extension to multi-species BCP systems.It has been demonstrated that our strategy achieves exceptional accuracy and robustness while requiring minimal computational resources.Additionally,the approach allows for real-time expansion and improvement to the candidate phase library,facilitating the development of automated research workflows for designing specific ordered structures and discovering new ordered phases in BCPs.展开更多
Tumor-associated carbohydrate antigens(TACAs)provide a special class of tumor-specific antigens that show promising applications in cancer immunotherapy.However,the weak immunogenicity and structural complexity of TAC...Tumor-associated carbohydrate antigens(TACAs)provide a special class of tumor-specific antigens that show promising applications in cancer immunotherapy.However,the weak immunogenicity and structural complexity of TACAs are obstacles to their clinical application.Here,based on a fast and low-cost purification strategy for oligosaccharide synthesis,the synthesis of tumour-associated carbohydrate antigens Globo H and mannobiose which resembles repeat unit of mannan was achieved.To enhance the immunogenicity and multivalent effect,Globo H and mannobiose were covalently attached to degradable polymer backbones.2D spindle-like lamellar micelle and globular micelle were obtained from glycopolymer through a solvent-exchange method of self-assembly.The glyconanoparticle showed good biocompatibility and degradability.Immunological functions of these glyconanoparticles such as stimulation of BMDC to cause upregulation of inflammatory factors were preliminarily explored.展开更多
Negative thermal expansion(NTE) behavior has roused wide interest for the control of thermomechanical properties of functional materials.Although NTE behaviors have been found in kinds of compounds,it remains challeng...Negative thermal expansion(NTE) behavior has roused wide interest for the control of thermomechanical properties of functional materials.Although NTE behaviors have been found in kinds of compounds,it remains challenging for polymers to achieve intrinsic NTE property.In this work,we systematically studied the conformational change of dibenzocyclooctadiene(DBCOD) derivatives between chair(C) and twist-boat(TB) forms based on density-functional theo ry(DFT) calculations,and found clear evidence of the relationship between the structure of DBCOD units and the thermal contraction behavior of the related polymers.In order to obtain the polymer with NTE property,two conditions should be met for the thermal contracting DBCOD related units as follows:(i) the TB conformation can turn into C conformation as the temperature increases,and(ii) the volume of C conformation is smaller than that of TB conformation.This rule should offer a guidance to exploration of the new intrinsic NTE polymers in the future.展开更多
Multi-component polymer systems exhibit exceptional versatility and structural diversity,making them indispensable in the polymer industry as well as in advanced and high performance applications.However,constructing ...Multi-component polymer systems exhibit exceptional versatility and structural diversity,making them indispensable in the polymer industry as well as in advanced and high performance applications.However,constructing accurate phase diagrams for these systems remains challenging due to inhomogeneous structures arising from the introduction of block copolymer components.Here,we present a unified and model-agnostic framework for computing phase equilibria in multi-component polymeric systems based on the concept of“effective chemical potential”.This approach directly connects key thermodynamic variables in the canonical ensemble to other ensembles,unifying phase coexistence determination without requiring the reformulation of self-consistent field theory(SCFT)calculations across different ensembles.By decoupling phase equilibrium determination from specific ensemble formulations,our approach enables the reuse of existing SCFT solvers.Moreover,it provides a useful framework to develop highly efficient phase equilibrium solvers for multi-component polymer systems.展开更多
Advancing the integration of artificial intelligence and polymer science requires high-quality,open-source,and large-scale datasets.However,existing polymer databases often suffer from data sparsity,lack of polymer-pr...Advancing the integration of artificial intelligence and polymer science requires high-quality,open-source,and large-scale datasets.However,existing polymer databases often suffer from data sparsity,lack of polymer-property labels,and limited accessibility,hindering system-atic modeling across property prediction tasks.Here,we present OpenPoly,a curated experimental polymer database derived from extensive lit-erature mining and manual validation,comprising 3985 unique polymer-property data points spanning 26 key properties.We further develop a multi-task benchmarking framework that evaluates property prediction using four encoding methods and eight representative models.Our re-sults highlight that the optimized degree-of-polymerization encoding coupled with Morgan fingerprints achieves an optimal trade-off between computational cost and accuracy.In data-scarce condition,XGBoost outperforms deep learning models on key properties such as dielectric con-stant,glass transition temperature,melting point,and mechanical strength,achieving R2 scores of 0.65-0.87.To further showcase the practical utility of the database,we propose potential polymers for two energy-relevant applications:high temperature polymer dielectrics and fuel cell membranes.By offering a consistent and accessible benchmark and database,OpenPoly paves the way for more accurate polymer-property modeling and fosters data-driven advances in polymer genome engineering.展开更多
Although Ziegler-Natta(Z-N)polyolefins have been widely used as raw materials to produce pharmaceutical or food packaging,the migration of acid scavengers,an additive usually introduced in Z-N polyolefins,from the pac...Although Ziegler-Natta(Z-N)polyolefins have been widely used as raw materials to produce pharmaceutical or food packaging,the migration of acid scavengers,an additive usually introduced in Z-N polyolefins,from the packaging to its contents has not been reported.In this work,the migration of the two most used acid scavengers,calcium stearate(CaSt_(2))and zinc stearate(ZnSt_(2)),from a Z-N polypropylene random copolymer(PPR)into water during autoclaving at 121℃ were comparatively investigated.It was found that,for PPR plates containing 0.1 wt%CaSt_(2)or ZnSt_(2)(PPR-0.1CaSt_(2),PPR-0.1ZnSt_(2),respectively),the concentration of migrated calcium ion into water increased with autoclaving time,while that of zinc ion was much lower at same treatment durations and did not show a significant increase with treatment time.Interestingly,after removing all plates and acidification treatment,a considerable amount of stearic acid was detected in sterilized water for PPR-0.1ZnSt_(2),but no such significant stearic acid was detected in sterilized water for PPR-0.1CaSt_(2).Based on the structural evolution of the two soaps upon heating,possible mechanisms for the different migration behavior of CaSt_(2)and ZnSt_(2)from PPR into water during autoclaving treatment were proposed.Our results suggest that the migration issue of acid scavengers is worthy of attention in pharmaceutical packaging materials produced from Z-N polyolefins.展开更多
In recent years,ultrathin polymer-based electrolytes(UPEs)have emerged as a promising strategy to enhance the energy density of rechargeable batteries for wearable devices by minimizing electrolyte volume,demonstratin...In recent years,ultrathin polymer-based electrolytes(UPEs)have emerged as a promising strategy to enhance the energy density of rechargeable batteries for wearable devices by minimizing electrolyte volume,demonstrating higher ionic conductance and lower internal resistance,and more compact battery stacking compared to conventional thick polymer-based electrolyte.This mini review systematically summarizes recent advances in ultrathin solid-state and gel-state electrolytes,focusing on their preparation strategies,advantages,and disadvantages,where the energy density,interfacial stability,mechanical properties,and ion-transport mechanisms are also analyzed for understanding the UPE application.Moreover,the challenges such as dendrite penetration and instability(thermal,chemical and interface),along with their solutions are also introduced through interfacial engineering,polymer matrix design,and fillers incorporation.Furthermore,for practical application,the demands of working current density,operating temperature and scale-up production are also illustrated.This mini review is hoped to spark insights into improving the energy density of batteries and ultimately bring us a step closer to realizing superior rechargeable batteries.展开更多
Owing to their excellent biocompatibility and potential for durability enhancement,polymeric heart valves(PHVs)are emerging as a promising alternative to traditional prostheses.Unlike conventional materials,PHVs can b...Owing to their excellent biocompatibility and potential for durability enhancement,polymeric heart valves(PHVs)are emerging as a promising alternative to traditional prostheses.Unlike conventional materials,PHVs can be manufactured under precise design criteria,enabling targeted performance improvements.This study introduces a geometric optimization strategy for enhancing the durability of PHVs.The finite element method(FEM)is combined with a dip-molding technique to develop a novel polymeric aortic valve with improved mechanical properties.The tri-leaflet geometry is parameterized using B-spline curves,and the maximum stress in the valve is reduced from 2.4802 to 1.7773 MPa using a multiobjective optimization algorithm NSGA-II(non-dominated sorting genetic algorithm II).Pre-optimized and optimized valve prototypes were fabricated via dip-molding and evaluated during pulsatile-flow tests and accelerated wear tests.The optimized design meets the ISO 5840 standards,with an effective orifice area of 2.019 cm^(2),a regurgitant fraction of 5.693%,and a transvalvular pressure gradient of 7.576 mmHg.Moreover,the optimized valve maintained its structural integrity and functionality over 14 million cycles of the accelerated wear test,whereas the unoptimized valve failed after two million cycles.These findings confirm that the FEM-based geometric optimization method enhances both the mechanical performance and durability of PHVs.展开更多
Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context...Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context of[2]catenane topologies.In this study,we present a novel supramolecular transformation between a Hopf link and a macrocycle,induced by the Diels–Alder click reaction.By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent,we successfully integrated tetrazine moieties into the metalla[2]catenane structure.We demonstrated that the introduction of 2,5-norbornadiene(NBD)as an external stimulus allows for the transformation of the novel metalla[2]catenane,featuring reactive tetrazine sites,into the corresponding monomeric ring through postmodification for the first time.The synthetic results are corroborated by single-crystal X-ray diffraction analysis,ESI-TOF/MS,elemental analysis,and detailed solution-state NMR techniques.展开更多
Graphene fiber supercapacitors(GFSCs)have garnered significant attention due to their exceptional features,including high power density,rapid charge/discharge rates,prolonged cycling durability,and versatile weaving c...Graphene fiber supercapacitors(GFSCs)have garnered significant attention due to their exceptional features,including high power density,rapid charge/discharge rates,prolonged cycling durability,and versatile weaving capabilities.Nevertheless,inherent challenges in graphene fibers(GFs),particularly the restricted ion-accessible specific surface area(SSA)and sluggish ion transport kinetics,hinder the achievement of optimal capacitance and rate performance.Despite existing reviews on GFSCs,a notable gap exists in thoroughly exploring the kinetics governing the energy storage process in GFSCs.This review aims to address this gap by thoroughly analyzing the energy storage mechanism,fabrication methodologies,property manipulation,and wearable applications of GFSCs.Through theoretical analysis of the energy storage process,specific parameters in advanced GF fabrication methodologies are carefully summarized,which can be used to modulate nano/micro-structures,thereby enhancing energy storage kinetics.In particular,enhanced ion storage is realized by creating more ion-accessible SSA and introducing extra-capacitive components,while accelerated ion transport is achieved by shortening the transport channel length and improving the accessibility of electrolyte ions.Building on the established structure-property relationship,several critical strategies for constructing optimal surface and structure profiles of GF electrodes are summarized.Capitalizing on the exceptional flexibility and wearability of GFSCs,the review further underscores their potential as foundational elements for constructing multifunctional e-textiles using conventional textile technologies.In conclusion,this review provides insights into current challenges and suggests potential research directions for GFSCs.展开更多
基金supported by the National Natural Science Foundation of China(Nos.223B2119,U23A2083,52373014,52203129).
文摘The facile synthesis of high-valued polymers from waste molecules or low-cost common chemicals presents a significant challenge.Here,we develop a series of degradable poly(thiocarbonate)s from the new step-growth polymerization of diols,carbonyl sulfide(CoS,or carbon disulfide,CS_(2)),and dichlorides.Diols and dichlorides are common chemicals,and CoS(CS_(2))is released as industrial waste.In addition to abun-dant feedstocks,the method is efficient and performed under mild conditions,using common organic bases as catalysts,and affording unprece-dented polymers.When cos,diols,and dihalides were used as monomers,optimized conditions could completely suppress the oxygen-sulfur exchange reaction,enabling the efficient synthesis of well-defined poly(monothiocarbonate)s with melting points ranging from 48°C to 101°C.These polymers,which have a structure similar to polyethylene with low-density in-chain polar groups,exhibit remarkable toughness and ductili-ty that rival those of high-density polyethylene(melting point:90°C,tensile strength:21.6±0.7 MPa,and elongation at break:576%).Moreover,the obtained poly(monothiocarbonate)s can be chemically degraded by alcoholysis to yield small-molecule diols and dithiols.When CS_(2)was used in place of cos,a pronounced oxygen-sulfur exchange reaction occurred.By optimizing reaction condition,it was found that polymers with-S(C=O)S-and-S(C=S)S-as the main repeating units exhibited high thermal stability and crystallinity.Thus,a new approach for regulat-ing the structure of polythiocarbonates via the oxygen-sulfur exchange reaction is developed.Overall,the polymers hold great potential for green materials due to their facile synthesis,readily available feedstocks,excellent performance,and chemical degradability.
文摘Given the increasing demand for distributed electricity,there is a burning desire to harvest electricity from renewable sources using environmentally friendly methods.Thermoelectric (TE) materials can meet this requirement not only because of their ability to convert heat directly into electricity,enabling energy harvesting from waste heat and natural heat resources,but also because more than 60%of the energy is lost as waste heat [1].The discovery of the TE effect dates back to the 1820s when T.M.Seebeck observed electricity generation at the junction of two conductors with different temperatures.Additionally,when a voltage is applied to TE materials,they can create a temperature difference to enable solid-state cooling (known as the Peltier effect).Therefore,the TE effect promises both sustainable energy solutions and temperature control technologies.Over the past two decades,the urgent demand for powering ubiquitous Internet of Things devices has sparked significant interest in flexible thermoelectrics(F-TEs),which raises an intriguing question:Is the intrinsically flexible polymer an important candidate for state-of-the-art F-TEs applications?
基金supported by the National Natural Science Foundation of China(Grant No.62205103)the Natural Science Foundation of Hunan Province(Grant No.2023JJ40216)the Elite Youth Program by the Department of Education of Hunan Province(Grant No.24B0663)。
文摘Although the certified power conversion efficiency(PCE)of single-junction perovskite solar cells(PSCs)has achieved a high level of 27%,approaching the single-crystalline silicon solar cells,the device stability remains an urgent issue to be resolved for the commercialization.Defect passivation emerged as a viable approach to enhance the operational stability of the solar devices.Herein,phenylthiourea(PhTu)derivatives are selected as effective passivation agents to enhance the optoelectronic properties of printed methylammonium lead iodide(MAPbI_(3))films.It is demonstrated that incorporating a small amount of 1-(4-carboxyphenyl)-2-thiourea(PhTu-COOH)significantly reduces the trap-state density and leads to longer carrier lifetime of the perovskite films.As a result,the inverted solar device made of Ph Tu-COOH-modified MAPbI_(3) perovskite film shows remarkably improved efficiency(from 17.29%to 20.22%)and obviously increased open-circuit voltage(V_(OC))(from 1.043 to 1.143 V),as compared with the pristine device.Moreover,the Ph Tu-COOH-modified PSCs exhibit enhanced operational stability due to the significantly reduced trap-state density.Finally,the optimized solar module fabricated with an active area of 11.28 cm^(2) delivers a high PCE of 17.07%with negligible V_(OC)loss,demonstrating the feasibility of the blade-coating method for large-area perovskite film deposition.
基金financially supported by the Science and Technology Project of PetroChina Company Limited,China(No.2022DJ6314)the National Natural Science Foundation of China(No.52173056)。
文摘Dynamic melt modification of polyethylene via the direct grafting of peroxide fragments shows promise for the development of processable functionalized materials.In this study,four linear low-density polyethylenes(LLDPEs)with comparable molecular weights but different short-chain branch(SCB)contents(ranging of 5-66 per 1000 carbon atoms)were modified via dynamic melt mixing using 2 wt% benzoyl peroxide at 145℃ and 50 r/min for 30 min.The influence of SCB content on the processability and structure of the resulting products was systematically investigated.All modified products exhibited good melt processability with melt flow rates(MFR)ranging from 0.46 g/10min to 1.07 g/10min.Products derived from low-SCB LLDPEs showed a lower MFR,higher cross-linking content,a larger number of long-chain branches,and a higher degree of benzoyl grafting.In contrast,those produced from high-SCB LLDPEs exhibited improved processability,reduced cross-linking,fewer long-chain branches,and lower benzoyl grafting levels.A detailed structural investigation of the soluble and insoluble fractions,which were separated using trichlorobenzene fractionation,was conducted to analyze the structural features of various modified products and demonstrate that the SCB content(i.e.,tertiary carbon density)significantly influences radical coupling during dynamic modification.Elevated tertiary carbon density,by introducing greater steric hindrance,suppresses radical coupling during dynamic modification,thereby reducing the efficiency of both crosslinking and peroxide fragment grafting.These findings provide new insights into the structure-reactivity relationships in peroxide-induced polyethylene modification and lay the foundation for tailoring material properties via dynamic processing.
基金financially supported by the National Natural Science Foundation of China(Nos.32471396,82230071,82172098,82201716,and 61973206)the National Key R&D Program of China(No.2023YFC2411303)+4 种基金the Integrated Project of Major Research Plan of the National Natural Science Foundation of China(No.92249303)the Shanghai Committee of Science and Technology(No.23141900600,Laboratory Animal Research Project)the Shanghai Clinical Research Plan of SHDC2023CRT01the Young Elite Scientist Sponsorship Program by the China Association for Science and Technology(No.YESS20230049)the Baoshan District Health Commission Talents(Excellent Academic Leaders)Program(No.BSWSYX-2024-05)。
文摘With the rapid advancements in biomedical engineering,bioprinting has emerged as a pivotal solution to address the shortage of organ transplants and advance disease model research.The evolution of bioprinting has progressed from the fabrication of simple models(1.0)to the fabrication of permanent implants(2.0),tissue engineering scaffolds(3.0),and complex biostructures utilizing living cells(4.0).Nevertheless,significant challenges remain,particularly in accurately replicating the structure and function of host tissues,selecting appropriate materials,and optimizing printing parameters.The integration of artificial intelligence(AI),especially machine learning,provides promising novel opportunities in bioprinting(5.0).This review systematically summarizes the current applications of AI in bioprinting,discussing both construction strategies and application scenarios.It also explores the potential of AI to improve bioprinting in the preparation of complex functional tissues and in situ tissue repair.Overall,the synergy between AI and bioprinting is poised to drive the development of personalized medicine,facilitate high-throughput preparation of in vitro models,and provide robust tools for regenerative medicine and precision healthcare.
基金Supported by FONDECYT(Project no.1150510)PIA(Anillo ACT-130)+4 种基金7FP-MC Actions Grant,REDOC(MINEDUC Project UCO1202 at U.de Concepción)CHILTURPOL2(PIRSES-GA-2009 Project,Grant No.269153)the Marie Curie Program(n°269153)FONDECYT Grant No.11140324CIPA(No.20301.934.15),Chile
文摘Modifying polypropylene membranes with interpenetrating polymer networks(IPNs) through the incorporation of poly(glycidyl methacrylate-N-methyl-D-glucamine)(P(GMA-NMG)) was performed by in situ synthesis via radical polymerization. The surface of the polypropylene membrane was activated by hydrophilic grafted polyelectrolyte, and then, pressure injection was used for the impregnation of the reactive solution in the membrane.Two types of pore-filled membranes were synthesized, chelating interpenetrating homopolymer networks of P(GMA-NMG), and chelating-ion exchange interpenetrating polymer networks(e.g., P(GMA-NMG)/P(AA),P(GMA-NMG)/P(AMPSA), and P(GMA-NMG)/P(Cl VBTA)). After their synthesis, the modified polypropylene membranes were characterized using techniques such as the electrokinetic potential, SEM, FT-IR, and Donnan dialysis to corroborate the chromium ion transport. The P(GMA-NMG) and complex network membranes exhibited a hydrophilic character with a water-uptake capacity between 20% and 35% and a percentage of modification between 4.0% and 7.0% in comparison with the behavior of the unmodified polypropylene membrane.Hexavalent chromium ions were efficiently transported from the food chamber at p H 9.0 when the 65.2%MTA1 P(Cl VBTA) homopolymer IPN membrane and 48.5% MTAG P(GMA-NMG)/P(Cl VBTA) IPN membrane were used. Similarly, hexavalent chromium ions were removed from the food chamber at pH 3.0 when MTAG(63.30%) and MTA1(35.68%) were used in 1 mol·L^(-1)Na Cl solution as the extraction reagent.
基金financial support of the NSFC(No. 21474015)STCSM(No.14ZR1402300)
文摘The short review discusses a family of amorphous porous organic polymers,conjugated microporous polymer（CMP）,which is distinctive in fusion of a large π-electronic conjugation within the topological network platform.The kind of polymers has shown the synthetic variety,the advanced capability and the wide applicability in contrast to the reported analogues.Herein,the significant progress of CMP applications has been summarized to showcase their capability in constructing photo-functional systems.
基金the National Science Foundation of China(Nos.52203129,51973190)Zhejiang Provincial Department of Science and Technology(No.2020R52006).
文摘The synthesis of degradable polymers with easy-to-break in-chain carbon-oxygen bonds has attracted much attention.This minireview introduces the synthesis of a variety of degradable polymers from the(co)polymerizations of several typical oxygenated monomers such as epoxides,cyclic carbonates,cyclic esters,carbon dioxide(CO_(2)),carbonyl sulfide(COS),and cyclic anhydrides.We highlight the catalysts and mechanisms for these(co)polymerizations.The ring-opening copolymerization of five-membered carbonate with cyclic anhydride or COS has been introduced.We also highlight the synthesis of block copolymers and cyclic copolymers with well-defined sequences by the method of growing center switching.We hope that these new polymerization systems can provide new ideas for the development of degradable low-carbon polymers in the future.
基金financially supported by the National Natural Science Foundation of China (No. 21474016)Senior Visiting Scholar Foundation of Key Laboratory in Fudan University (Nos. 16FHJ08 & 18FGJ01)
文摘We report here a method for the preparation of amphiphilic dendrimer-like copolymers with dendritic polystyrene (PS) core and protonated poly(2-vinyl pyridine)(P2VP) or poly(methacrylic acid)(PMAA) shell. The method employed the efficient coupling reaction of anionic living polymer chains and chlorosilane. The synthesis started from a functionalized 3rd generation dendritic polystyrene, G3PS-g-SiCl, used as the precursor. The dendrimer-like copolymer of styrene and 2-vinyl pyridine, G3PS-g-P2VP, was synthesized by direct coupling of living P2VPLi to the precursor. The dendrimer-like copolymer of styrene and Zer/-butyl methacrylate, G3PS-g-PtBMA, was synthesized by an indirect procedure in which a living polymer containing mainly PtBMA segment was attached to the precursor. Both methods resulted in the formation of dendrimer-like copolymers with the high molecular weights (up to 8.5 × 10^6 Da), large molecular sizes (diameter up to 73 nm), and dense shells (number of arms up to 1300). These products, G3PS-g-P2VP and G3PS-g- PtBMA, were protonated with trifluoroacetic acid and acidic hydrolyzed, respectively. After transformation, amphiphilic dendrimer-like copolymers, G3PS-g-P2VPH^+ and G3PS-g-PMAA, were obtained. Preliminary results on the solution properties of the amphiphilic products were presented.
文摘A Monte Carlo method was used to take thorough account of the influences of different reactivity ratios and initial feed compositions on copolymer microstructure.The model proves the lack of azeotropic behavior in systems in which r_A>1 and r_B<1 or vice versa;it is also able to calculate the drift in the copolymer properties:copolymer composition,and randomness parameter.Moreover,for each reactivity ratio pair given,there is a unique reaction conversion,at which macromolecules produced inherit their ...
基金This work was supported by the National Natural Science Foundation of China(Grants No.21873021).
文摘In unit cell simulations,identification of ordered phases in block copolymers(BCPs)is a tedious and time-consuming task,impeding the advancement of more streamlined and potentially automated research workflows.In this study,we propose a scattering-based automated identification strategy(SAIS)for characterization and identification of ordered phases of BCPs based on their computed scattering patterns.Our approach leverages the scattering theory of perfect crystals to efficiently compute the scattering patterns of periodic morphologies in a unit cell.In the first stage of the SAIS,phases are identified by comparing reflection conditions at a sequence of Miller indices.To confirm or refine the identification results of the first stage,the second stage of the SAIS introduces a tailored residual between the test phase and each of the known candidate phases.Furthermore,our strategy incorporates a variance-like criterion to distinguish background species,enabling its extension to multi-species BCP systems.It has been demonstrated that our strategy achieves exceptional accuracy and robustness while requiring minimal computational resources.Additionally,the approach allows for real-time expansion and improvement to the candidate phase library,facilitating the development of automated research workflows for designing specific ordered structures and discovering new ordered phases in BCPs.
基金supported by the National Key Research and Development Program of China(No.2023YFA0915300)the National Natural Science Foundation of China(Nos.52125303 and 92356305)Innovation Program of Shanghai Municipal Education Commission(No.2023ZKZD02)。
文摘Tumor-associated carbohydrate antigens(TACAs)provide a special class of tumor-specific antigens that show promising applications in cancer immunotherapy.However,the weak immunogenicity and structural complexity of TACAs are obstacles to their clinical application.Here,based on a fast and low-cost purification strategy for oligosaccharide synthesis,the synthesis of tumour-associated carbohydrate antigens Globo H and mannobiose which resembles repeat unit of mannan was achieved.To enhance the immunogenicity and multivalent effect,Globo H and mannobiose were covalently attached to degradable polymer backbones.2D spindle-like lamellar micelle and globular micelle were obtained from glycopolymer through a solvent-exchange method of self-assembly.The glyconanoparticle showed good biocompatibility and degradability.Immunological functions of these glyconanoparticles such as stimulation of BMDC to cause upregulation of inflammatory factors were preliminarily explored.
基金supported by the National Natural Science Foundation of China (Nos.51633001,51721002 and 51873040)National Key R&D Program of China (No.2016YFC1100300)。
文摘Negative thermal expansion(NTE) behavior has roused wide interest for the control of thermomechanical properties of functional materials.Although NTE behaviors have been found in kinds of compounds,it remains challenging for polymers to achieve intrinsic NTE property.In this work,we systematically studied the conformational change of dibenzocyclooctadiene(DBCOD) derivatives between chair(C) and twist-boat(TB) forms based on density-functional theo ry(DFT) calculations,and found clear evidence of the relationship between the structure of DBCOD units and the thermal contraction behavior of the related polymers.In order to obtain the polymer with NTE property,two conditions should be met for the thermal contracting DBCOD related units as follows:(i) the TB conformation can turn into C conformation as the temperature increases,and(ii) the volume of C conformation is smaller than that of TB conformation.This rule should offer a guidance to exploration of the new intrinsic NTE polymers in the future.
基金supported by the National Natural Science Foundation of China(No.21873021).
文摘Multi-component polymer systems exhibit exceptional versatility and structural diversity,making them indispensable in the polymer industry as well as in advanced and high performance applications.However,constructing accurate phase diagrams for these systems remains challenging due to inhomogeneous structures arising from the introduction of block copolymer components.Here,we present a unified and model-agnostic framework for computing phase equilibria in multi-component polymeric systems based on the concept of“effective chemical potential”.This approach directly connects key thermodynamic variables in the canonical ensemble to other ensembles,unifying phase coexistence determination without requiring the reformulation of self-consistent field theory(SCFT)calculations across different ensembles.By decoupling phase equilibrium determination from specific ensemble formulations,our approach enables the reuse of existing SCFT solvers.Moreover,it provides a useful framework to develop highly efficient phase equilibrium solvers for multi-component polymer systems.
基金financially supported by the National Natural Science Foundation of China (Nos. 92372126,52373203)the Excellent Young Scientists Fund Program
文摘Advancing the integration of artificial intelligence and polymer science requires high-quality,open-source,and large-scale datasets.However,existing polymer databases often suffer from data sparsity,lack of polymer-property labels,and limited accessibility,hindering system-atic modeling across property prediction tasks.Here,we present OpenPoly,a curated experimental polymer database derived from extensive lit-erature mining and manual validation,comprising 3985 unique polymer-property data points spanning 26 key properties.We further develop a multi-task benchmarking framework that evaluates property prediction using four encoding methods and eight representative models.Our re-sults highlight that the optimized degree-of-polymerization encoding coupled with Morgan fingerprints achieves an optimal trade-off between computational cost and accuracy.In data-scarce condition,XGBoost outperforms deep learning models on key properties such as dielectric con-stant,glass transition temperature,melting point,and mechanical strength,achieving R2 scores of 0.65-0.87.To further showcase the practical utility of the database,we propose potential polymers for two energy-relevant applications:high temperature polymer dielectrics and fuel cell membranes.By offering a consistent and accessible benchmark and database,OpenPoly paves the way for more accurate polymer-property modeling and fosters data-driven advances in polymer genome engineering.
基金supported by the National Natural Science Foundation of China(No.52173056)the Science and Technology Program of Gansu Province,China(No.23ZDGA001).
文摘Although Ziegler-Natta(Z-N)polyolefins have been widely used as raw materials to produce pharmaceutical or food packaging,the migration of acid scavengers,an additive usually introduced in Z-N polyolefins,from the packaging to its contents has not been reported.In this work,the migration of the two most used acid scavengers,calcium stearate(CaSt_(2))and zinc stearate(ZnSt_(2)),from a Z-N polypropylene random copolymer(PPR)into water during autoclaving at 121℃ were comparatively investigated.It was found that,for PPR plates containing 0.1 wt%CaSt_(2)or ZnSt_(2)(PPR-0.1CaSt_(2),PPR-0.1ZnSt_(2),respectively),the concentration of migrated calcium ion into water increased with autoclaving time,while that of zinc ion was much lower at same treatment durations and did not show a significant increase with treatment time.Interestingly,after removing all plates and acidification treatment,a considerable amount of stearic acid was detected in sterilized water for PPR-0.1ZnSt_(2),but no such significant stearic acid was detected in sterilized water for PPR-0.1CaSt_(2).Based on the structural evolution of the two soaps upon heating,possible mechanisms for the different migration behavior of CaSt_(2)and ZnSt_(2)from PPR into water during autoclaving treatment were proposed.Our results suggest that the migration issue of acid scavengers is worthy of attention in pharmaceutical packaging materials produced from Z-N polyolefins.
基金funded by the National Natural Science Foundation of China,grant Nos.52373275 and 52303290,received by Peng-Fei Cao and Jiayao Chen,respectively。
文摘In recent years,ultrathin polymer-based electrolytes(UPEs)have emerged as a promising strategy to enhance the energy density of rechargeable batteries for wearable devices by minimizing electrolyte volume,demonstrating higher ionic conductance and lower internal resistance,and more compact battery stacking compared to conventional thick polymer-based electrolyte.This mini review systematically summarizes recent advances in ultrathin solid-state and gel-state electrolytes,focusing on their preparation strategies,advantages,and disadvantages,where the energy density,interfacial stability,mechanical properties,and ion-transport mechanisms are also analyzed for understanding the UPE application.Moreover,the challenges such as dendrite penetration and instability(thermal,chemical and interface),along with their solutions are also introduced through interfacial engineering,polymer matrix design,and fillers incorporation.Furthermore,for practical application,the demands of working current density,operating temperature and scale-up production are also illustrated.This mini review is hoped to spark insights into improving the energy density of batteries and ultimately bring us a step closer to realizing superior rechargeable batteries.
基金funded by the National Natural Science Foundation of China(No.82400370)the Interdisciplinary Innovation Team Incubation Project of Children’s Hospital of Fudan University(No.EKYX202416).
文摘Owing to their excellent biocompatibility and potential for durability enhancement,polymeric heart valves(PHVs)are emerging as a promising alternative to traditional prostheses.Unlike conventional materials,PHVs can be manufactured under precise design criteria,enabling targeted performance improvements.This study introduces a geometric optimization strategy for enhancing the durability of PHVs.The finite element method(FEM)is combined with a dip-molding technique to develop a novel polymeric aortic valve with improved mechanical properties.The tri-leaflet geometry is parameterized using B-spline curves,and the maximum stress in the valve is reduced from 2.4802 to 1.7773 MPa using a multiobjective optimization algorithm NSGA-II(non-dominated sorting genetic algorithm II).Pre-optimized and optimized valve prototypes were fabricated via dip-molding and evaluated during pulsatile-flow tests and accelerated wear tests.The optimized design meets the ISO 5840 standards,with an effective orifice area of 2.019 cm^(2),a regurgitant fraction of 5.693%,and a transvalvular pressure gradient of 7.576 mmHg.Moreover,the optimized valve maintained its structural integrity and functionality over 14 million cycles of the accelerated wear test,whereas the unoptimized valve failed after two million cycles.These findings confirm that the FEM-based geometric optimization method enhances both the mechanical performance and durability of PHVs.
基金the Shanxi Province Science Foundation for Youth(No.202203021212408)the Shanxi Normal University Quality Curriculum(No.2019YZKC-13)the 1331 Project of Shanxi Province。
文摘Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context of[2]catenane topologies.In this study,we present a novel supramolecular transformation between a Hopf link and a macrocycle,induced by the Diels–Alder click reaction.By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent,we successfully integrated tetrazine moieties into the metalla[2]catenane structure.We demonstrated that the introduction of 2,5-norbornadiene(NBD)as an external stimulus allows for the transformation of the novel metalla[2]catenane,featuring reactive tetrazine sites,into the corresponding monomeric ring through postmodification for the first time.The synthetic results are corroborated by single-crystal X-ray diffraction analysis,ESI-TOF/MS,elemental analysis,and detailed solution-state NMR techniques.
基金Shanghai Municipal Commission for Science and Technology,Grant/Award Number:23ZR1402500National Natural Science Foundation of China,Grant/Award Number:51973034+1 种基金National Scholarship CouncilNational Key Research and Development Program of China,Grant/Award Number:2023YFB3809800.
文摘Graphene fiber supercapacitors(GFSCs)have garnered significant attention due to their exceptional features,including high power density,rapid charge/discharge rates,prolonged cycling durability,and versatile weaving capabilities.Nevertheless,inherent challenges in graphene fibers(GFs),particularly the restricted ion-accessible specific surface area(SSA)and sluggish ion transport kinetics,hinder the achievement of optimal capacitance and rate performance.Despite existing reviews on GFSCs,a notable gap exists in thoroughly exploring the kinetics governing the energy storage process in GFSCs.This review aims to address this gap by thoroughly analyzing the energy storage mechanism,fabrication methodologies,property manipulation,and wearable applications of GFSCs.Through theoretical analysis of the energy storage process,specific parameters in advanced GF fabrication methodologies are carefully summarized,which can be used to modulate nano/micro-structures,thereby enhancing energy storage kinetics.In particular,enhanced ion storage is realized by creating more ion-accessible SSA and introducing extra-capacitive components,while accelerated ion transport is achieved by shortening the transport channel length and improving the accessibility of electrolyte ions.Building on the established structure-property relationship,several critical strategies for constructing optimal surface and structure profiles of GF electrodes are summarized.Capitalizing on the exceptional flexibility and wearability of GFSCs,the review further underscores their potential as foundational elements for constructing multifunctional e-textiles using conventional textile technologies.In conclusion,this review provides insights into current challenges and suggests potential research directions for GFSCs.
