Thermosetting polymers exhibit outstanding mechanical properties,thermal stability,and chemical resistance due to their permanently cross-linked network structures.However,the irreversible nature of covalent cross-lin...Thermosetting polymers exhibit outstanding mechanical properties,thermal stability,and chemical resistance due to their permanently cross-linked network structures.However,the irreversible nature of covalent cross-linking renders these materials non-reprocessable and non-recyclable,posing significant environmental challenges.Although healable polymers based on dynamic covalent bonds and supramolecular interactions have emerged as promising alternatives,a broadly applicable strategy utilizing metal-ligand coordination in thermoset systems remains underexplored.In this work,we present a robust and healable thermoset system fabricated via ring-opening metathesis polymerization(ROMP)of commercially available chelating norbornene comonomers.Cross-linking is accomplished through O-donor coordination to Lewis acidic metal centers,yielding polydicyclopentadiene(PDCPD)-based networks that demonstrate high mechanical strength(up to 60.8 MPa)and effective self-healing performance.This methodology offers a simple and scalable approach to developing high-performance,sustainable thermosetting materials.展开更多
Chemically recyclable polythioesters are of particular interest owing to their unique properties and desired sustainability.By the exploit of a benzo-fusion strategy toε-thiocaprolactone,we successfully improved the ...Chemically recyclable polythioesters are of particular interest owing to their unique properties and desired sustainability.By the exploit of a benzo-fusion strategy toε-thiocaprolactone,we successfully improved the chemical recyclability and regulated the thermal and mechanical properties of the resulting polythioesters.The efficient ring-opening polymerization(ROP)of benzo-fused thiolactone monomers(M)containing different substituents gave rise to high-molecular-weight semi-aromatic polythioesters P(M)s.The resulting P(M)s showcased tunable physical and mechanical properties.The debenzylation of P(M3)was able to generate P(M3-OH)with free hydroxyl sidechains.Notably,chemical recycling of the resulting P(M)s back to their corresponding monomers via bulk thermal depolymerization achieved high efficiency(>95%yield,99%purity),establishing a closed-loop lifecycle.展开更多
Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in ...Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in low-concentration electrolytes.Herein,we design a Zn salt-mediated electrolyte with in situ ring-opening polymerization of the small molecule organic solvent.The Zn(TFSI)_(2)salt catalyzes the ring-opening polymerization of(1,3-dioxolane(DOL)),generating oxidation-resistant and non-combustible long-chain polymer(poly(1,3-dioxolane)(pDOL)).The pDOL reduces the active H_(2)O molecules in electrolyte and assists in forming stable organic–inorganic gradient solid electrolyte interphase with rich organic constituents,ZnO and ZnF_(2).The introduction of pDOL endows the electrolyte with several advantages:excellent Zn dendrite inhibition,improved corrosion resistance,widened electrochemical window(2.6 V),and enhanced low-temperature performance(freezing point=-34.9°C).Zn plating/stripping in pDOL-enhanced electrolyte lasts for 4200 cycles at 99.02%Coulomb efficiency and maintains a lifetime of 8200 h.Moreover,Zn metal anodes deliver stable cycling for 2500 h with a high Zn utilization of 60%.A Zn//VO_(2)pouch cell assembled with lean electrolyte(electrolyte/capacity(E/C=41 mL(Ah)^(-1))also demonstrates a capacity retention ratio of 92%after 600 cycles.These results highlight the promising application prospects of practical Zn metal batteries enabled by the Zn(TFSI)2-mediated electrolyte engineering.展开更多
Although solid-state polymer electrolytes(SPEs)are expected to solve the safety hazards and limited energy density in the energy storage systems,they still encounter an inferior electrode/electrolyte interface when pr...Although solid-state polymer electrolytes(SPEs)are expected to solve the safety hazards and limited energy density in the energy storage systems,they still encounter an inferior electrode/electrolyte interface when prepared in an ex situ manner.Recently,in situ polymerization of SPEs favor high interfacial infiltrability,improved interface contact,and reduced interface resistance,owing to the formation of a"superconformal"interface between electrode and electrolyte.Especially,in situ strategies employing ring-opening polymerization(ROP)are emerging as dazzling stars,further enabling moderate polymerization conditions,controllable molecular structure,and reduced interfacial side reaction.As the main monomers that can be in situ polymerized via the ROP strategy,cyclic ethers have been used to construct the CE-SPEs with many merits,including good battery electrochemical performances and a simple assembly process.Here,as a systematic summarization of the existing reports,this review focuses on the polymerization mechanism of ROP,the design principles of CE-SPEs electrolytes,and the recent application of in situ CE-SPEs.In particular,this review thoroughly discusses the selection of different cyclic monomers,initiators and various modification approaches in in situ fabricating CE-SPEs.Ending with offering future challenges and perspectives,this review envisions shedding light on the profound understanding and scientific guidance for further development of high-performance in situ CE-SPEs.展开更多
As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of t...As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.展开更多
Mechanochromic polyolefins represent a novel class of functionalized polyolefins,which still remains significant challenges.Pd(II)-catalyzed coordination-insertion copolymerization is a feasible method for achieving t...Mechanochromic polyolefins represent a novel class of functionalized polyolefins,which still remains significant challenges.Pd(II)-catalyzed coordination-insertion copolymerization is a feasible method for achieving this kind of polymers,yet with linear microstructures.Ringopening metathesis polymerization(ROMP)offers another promising avenue for affording functionalized polyolefins.This method exhibits high polar group tolerance and the ability to precisely regulate polymer branches.In this study,we report the method for producing mechanochromic branched polyethylenes via ROMP.By employing the terpolymerization of a well-designed monomer containing the mechanochromic group,NB-ABF,with cyclooctene(COE)and long-chain 5-hexylcyclooctene(COE-C6),following by hydrogenation process,we synthesized a range of functionalized branched polyethylenes characterized by varied branching density and polar monomer incorporation.These polymers bear a structural resemblance to functionalized ethylene-octene copolymers.After crosslinking,mechanochromophores are generated,and mechanochromism is achieved in uniaxial tensile testing.A comprehensive assessment reveals that both the incorporation of polar monomers and variations in branching density significantly influence their mechanical properties.Notably,upon stretching,these materials display pronounced visible color change,confirming the successful development of mechanochromic branched polyethylenes.展开更多
Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic p...Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic polyesters and polycarbonates usually suffer from inferior properties and functionalities.By contrast,precisely modulated block copolymers composed of polyesters and polycarbonates give rise to sustainable materials with tailored performance.An efficient approach to synthesize the block copolymers is the ring-opening(co)polymerization of the heterocycle monomers.Herein,this review presents the heterocycle monomer ring-opening(co)polymerization for the formation of sequence-controlled block polyesters and polycarbonates.Available synthetic strategies,different monomers,monomer combinations and the catalyst systems for the formation of different block polyesters and polycarbonates are summarized.展开更多
The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PC...The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity average molecular weight about 60 x 10 under quite mild conditions: molar ratio of CL to initiator is 1000, 60 C, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chain via the break of acyl-oxygen bond of CL.展开更多
The ring-opening polymerization of 1,4-dioxan-2-one （PDO） was carried out by lanthanum tris（2,6-di-tert-butyl-4- methylphenolate） （La（OAr）3） as novel single component initiaLor. The influences of polymerizatio...The ring-opening polymerization of 1,4-dioxan-2-one （PDO） was carried out by lanthanum tris（2,6-di-tert-butyl-4- methylphenolate） （La（OAr）3） as novel single component initiaLor. The influences of polymerization reaction temperature and the molar ratio of monomer to initiator on the monomer conversion and molecular weight of poly（1,4-dioxan-2-one） （PPDO） were explored. PPDO with high viscosity average molecular weight of 1.95×10^5 can be prepared at 40℃ when [PDO]/ [La（OAr）3] molar ratio was 800. Mechanism investigation shows that the polymerization proceeds through a ＂coordination- insertion＂ mechanism with selective rupture of acyl-oxygen be,nd of PDO.展开更多
The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segme...The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segmental mobility and limits ionic conductivity,whereas interfacial instability against lithium metal anodes jeopardizes long-term cycling.Based on orthogonal polymerization technology combined with electrolyte structural design concepts,this work achieved a one-step fabrication of a polyester-based block copolymer electrolyte(BCPE)system comprising fluorinated segments(PTFEA)and poly(ε-caprolactone)(PCL).Structurally,this design enables a dual breakthrough in electrochemical performance:on one hand,the introduction of fluorinated segments with steric hindrance effects can effectively disrupt the regular arrangement of the PCL main chain,reduce the crystallinity of PCL within the polymer electrolyte,and significantly enhance the segmental mobility of the polymer matrix;on the other hand,during the charge/discharge cycles of lithium batteries,fluorinated segments can induce the formation of a LiF-rich solid electrolyte interphase(SEI)through in situ decomposition reactions,achieving interface stabilization and homogeneous lithiumion deposition regulation.展开更多
A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted ...A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted acrylates with exclusive E-stereoselectivity at room temperature.Mechanistic investigations indicated that both the hydrogen atom on vinyl group and one oxygen atom on ester group ofα,β-disubstituted acrylates derive from H2O in dimethyl sulfoxide(DMSO).Furthermore,a gram-scale experiment and late-stage modification of the products were accomplished,thereby expanding the application potential of this methodology in organic synthesis.展开更多
Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford prod...Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions.Herein,we report the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene(Et_3B/DBU)pair-mediated four-component switchable polymerization of propylene oxide(PO),CO_(2),phthalic anhydride(PA),and racemic lactide(rac-LA),which enables the on-demand synthesis of four different block copolymers,i.e.,poly(propylene phthalate)-b-polylactide(PPE-b-PLA),PPE-b-PLA-b-poly(propylene carbonate)(PPC),PPE-b-PPC-b-PLA,and PPE-b-PPCb-poly(propylene oxide)(PPO),through rationally modulating the Lewis pair(LP)ratio.Core to this protocol is that increasing the loading of Et_(3)B accelerates the ring-opening of PO while impeding the reactivity of rac-LA,thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization.Therefore,the four polymerization cycles involving PO/PA ring-opening copolymerization(ROCOP),PO/CO_(2) ROCOP,rac-LA ring-opening polymerization(ROP),and PO ROP can be connected and discriminated in precisely programmed manners.展开更多
Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable ...Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds.In comparison with traditional thermal or metal-mediated carbene transfer reactions,visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules.Recently,visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation,mild condition,high atom economy and rich structural diversity.This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles.The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review.The future research direction and challenges in this area are also discussed.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.展开更多
Aggregation-induced emission(AIE)polymers have been extensively studied;however,the integration of AIE units into polyelectrolytes remains largely limited by the laborious multistep synthesis of pre-designed emissive ...Aggregation-induced emission(AIE)polymers have been extensively studied;however,the integration of AIE units into polyelectrolytes remains largely limited by the laborious multistep synthesis of pre-designed emissive monomers.Herein,we report a one-pot multicomponent polymerization method that directly produces main-chain charged polyelectrolytes with intrinsic AIE characteristics from non-emissive building blocks.By optimizing the monomer structures and reaction conditions,a series of soluble high-molecular-weight polymers with welldefined backbones were obtained in high yields.The resulting polyelectrolytes displayed robust AIE behavior,exhibiting fluorescence enhancement up to about 60-fold in an aqueous environment,and maintained excellent thermal stability.Owing to their cationic backbones,these polymers interact strongly with microbial surfaces and exhibit remarkable antimicrobial activities.This study establishes a synthetically efficient route to AIE polyelectrolytes and highlights their potential applications as multifunctional materials for bioimaging,antimicrobial therapy,and other applications.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
Objectives:Drug resistance is the major determinant of chemotherapy failure,leading to relapse and tumor progression,demonstrating the urgent need for novel antineoplastic drugs.This study aimed to evaluate the antica...Objectives:Drug resistance is the major determinant of chemotherapy failure,leading to relapse and tumor progression,demonstrating the urgent need for novel antineoplastic drugs.This study aimed to evaluate the anticancer potential of two novel pyrazole derivatives,P3C.1 and P3C.2,and to elucidate their mechanism of action in cancer cells.Methods:The cytotoxicity of the compounds was evaluated across 27 different cancer cell lines via a nuclear staining assay.Subsequent flow cytometric and biochemical analyses were performed to assess reactive oxygen species(ROS)generation,apoptosis induction,mitochondrial integrity,and cell cycle progression.Additional studies included transcriptome analyses and immunoassays to characterize the molecular mechanisms underlying drug activity.Results:Two novel pyrazole derivatives,P3C.1 and P3C.2,were identified with potent cytotoxicity on a variety of cancer cell lines.Among the adherent cell lines tested,the triple-negative breast cancer(TNBC)cell line MDA-MB-231 exhibited the highest sensitivity to both compounds and was therefore selected for further experimentation.In vitro assays demonstrated that both compounds induced ROS generation,mitochondrial membrane depolarization,cell cycle arrest and apoptosis.Whole-transcriptome sequencing of P3C.1 and P3C.2-treated MDA-MB-231 and two lymphoblastic leukemia cell lines revealed four genes in common associated with cell signaling and membrane dynamics.Connectivity Map(CMAP)database comparisons of shared genes for each cancer subtype revealed a strong similarity between the two compounds with tubulin inhibitors,and subsequent assays confirmed that these compounds act as microtubule-disrupting agents.Moreover,protein phosphorylation analysis indicated that both compounds induced hyperphosphorylation of JNK,and ERK1/2,along with hypophosphorylation of p38 kinases.Conclusions:P3C.1 and P3C.2 emerged as promising anti-breast cancer agents with dual mechanisms of action involving microtubule disruption and altered kinase signaling,leading to induction of apoptosis.展开更多
A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-ca...A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-caprolactone, exhibiting notably high activity at ambient temperature, The influence of imine bridge length and substituents of diketone over the course of polymerization was investigated in details. Remarkably, 4a was confirmed to be a rare example of exceedingly active and robust zinc catalysts, achieving major transformation of lactide under extremely low loading （0.025 mol%） within 18 rain. The influence of various monomers as well as the polymerization mechanism have also been discussed.展开更多
In this paper,ring-opening polymerization of trimethylene carbonate(TMC)with rare earth(Nd,Y,La)ρ-tert- butylcalix[n]arene(n=4,6,and 8)complexes as catalysts has been studied.Poly(trimethylene carbonate)(PTMC)with M_...In this paper,ring-opening polymerization of trimethylene carbonate(TMC)with rare earth(Nd,Y,La)ρ-tert- butylcalix[n]arene(n=4,6,and 8)complexes as catalysts has been studied.Poly(trimethylene carbonate)(PTMC)with M_v of 21,400 was produced by bulk polymerization under the conditions as follows:[TMC]_0/[Nd](molar ratio)=1000,80℃, 8 h.Mechanism study reveals that the polymerization proceeds via a coordination mechanism.展开更多
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)the National Natural Science Foundation of China(Nos.22301294,52025031 and 22261142664)the USTC Research Funds of the Double First-Class Initiative(No.YD9990002030)。
文摘Thermosetting polymers exhibit outstanding mechanical properties,thermal stability,and chemical resistance due to their permanently cross-linked network structures.However,the irreversible nature of covalent cross-linking renders these materials non-reprocessable and non-recyclable,posing significant environmental challenges.Although healable polymers based on dynamic covalent bonds and supramolecular interactions have emerged as promising alternatives,a broadly applicable strategy utilizing metal-ligand coordination in thermoset systems remains underexplored.In this work,we present a robust and healable thermoset system fabricated via ring-opening metathesis polymerization(ROMP)of commercially available chelating norbornene comonomers.Cross-linking is accomplished through O-donor coordination to Lewis acidic metal centers,yielding polydicyclopentadiene(PDCPD)-based networks that demonstrate high mechanical strength(up to 60.8 MPa)and effective self-healing performance.This methodology offers a simple and scalable approach to developing high-performance,sustainable thermosetting materials.
基金financially supported by the National Key R&D Program of China(No.2021YFA1501700)the National Natural Science Foundation of China(Nos.22371194 and 22301197)Fundamental Research Funds from Sichuan University(Nos.2023SCUNL103 and 2024SCUQJTX005)。
文摘Chemically recyclable polythioesters are of particular interest owing to their unique properties and desired sustainability.By the exploit of a benzo-fusion strategy toε-thiocaprolactone,we successfully improved the chemical recyclability and regulated the thermal and mechanical properties of the resulting polythioesters.The efficient ring-opening polymerization(ROP)of benzo-fused thiolactone monomers(M)containing different substituents gave rise to high-molecular-weight semi-aromatic polythioesters P(M)s.The resulting P(M)s showcased tunable physical and mechanical properties.The debenzylation of P(M3)was able to generate P(M3-OH)with free hydroxyl sidechains.Notably,chemical recycling of the resulting P(M)s back to their corresponding monomers via bulk thermal depolymerization achieved high efficiency(>95%yield,99%purity),establishing a closed-loop lifecycle.
基金financially supported by the National Natural Science Foundation of China(52162036 and 22378342)Key Project of Nature Science Foundation of Xinjiang(2021D01D08)+2 种基金Major Projects of Xinjiang(2022A01005-4 and 2021A01001-1)Key Research and Development Project of Xinjiang(2023B01025-1)the support from the Doctoral Student Special Program of the Young Talents Support Project of the China Association for Science and Technology in 2024。
文摘Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in low-concentration electrolytes.Herein,we design a Zn salt-mediated electrolyte with in situ ring-opening polymerization of the small molecule organic solvent.The Zn(TFSI)_(2)salt catalyzes the ring-opening polymerization of(1,3-dioxolane(DOL)),generating oxidation-resistant and non-combustible long-chain polymer(poly(1,3-dioxolane)(pDOL)).The pDOL reduces the active H_(2)O molecules in electrolyte and assists in forming stable organic–inorganic gradient solid electrolyte interphase with rich organic constituents,ZnO and ZnF_(2).The introduction of pDOL endows the electrolyte with several advantages:excellent Zn dendrite inhibition,improved corrosion resistance,widened electrochemical window(2.6 V),and enhanced low-temperature performance(freezing point=-34.9°C).Zn plating/stripping in pDOL-enhanced electrolyte lasts for 4200 cycles at 99.02%Coulomb efficiency and maintains a lifetime of 8200 h.Moreover,Zn metal anodes deliver stable cycling for 2500 h with a high Zn utilization of 60%.A Zn//VO_(2)pouch cell assembled with lean electrolyte(electrolyte/capacity(E/C=41 mL(Ah)^(-1))also demonstrates a capacity retention ratio of 92%after 600 cycles.These results highlight the promising application prospects of practical Zn metal batteries enabled by the Zn(TFSI)2-mediated electrolyte engineering.
基金supported by the National Natural Science Foundation of China(22022813)the Zhejiang Provincial Natural Science Foundation of China(LQ24B030002)the China Postdoctoral Science Foundation(2022M722729,2023T160571).
文摘Although solid-state polymer electrolytes(SPEs)are expected to solve the safety hazards and limited energy density in the energy storage systems,they still encounter an inferior electrode/electrolyte interface when prepared in an ex situ manner.Recently,in situ polymerization of SPEs favor high interfacial infiltrability,improved interface contact,and reduced interface resistance,owing to the formation of a"superconformal"interface between electrode and electrolyte.Especially,in situ strategies employing ring-opening polymerization(ROP)are emerging as dazzling stars,further enabling moderate polymerization conditions,controllable molecular structure,and reduced interfacial side reaction.As the main monomers that can be in situ polymerized via the ROP strategy,cyclic ethers have been used to construct the CE-SPEs with many merits,including good battery electrochemical performances and a simple assembly process.Here,as a systematic summarization of the existing reports,this review focuses on the polymerization mechanism of ROP,the design principles of CE-SPEs electrolytes,and the recent application of in situ CE-SPEs.In particular,this review thoroughly discusses the selection of different cyclic monomers,initiators and various modification approaches in in situ fabricating CE-SPEs.Ending with offering future challenges and perspectives,this review envisions shedding light on the profound understanding and scientific guidance for further development of high-performance in situ CE-SPEs.
基金financially supported by National Key R&D Program of China(No.2021YFA1501700)CAS Project for Young Scientists in Basic Research(No.YSBR-094)+1 种基金Natural Science Foundation of Anhui Province(Nos.2308085Y35 and 2023AH030002)Hefei Natural Science Foundation(No.202304)。
文摘As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.
基金supported by the National Natural Science Foundation of China(No.U23B6011)the Jilin Provincial Science and Technology Department Program(No.20230101347JC)。
文摘Mechanochromic polyolefins represent a novel class of functionalized polyolefins,which still remains significant challenges.Pd(II)-catalyzed coordination-insertion copolymerization is a feasible method for achieving this kind of polymers,yet with linear microstructures.Ringopening metathesis polymerization(ROMP)offers another promising avenue for affording functionalized polyolefins.This method exhibits high polar group tolerance and the ability to precisely regulate polymer branches.In this study,we report the method for producing mechanochromic branched polyethylenes via ROMP.By employing the terpolymerization of a well-designed monomer containing the mechanochromic group,NB-ABF,with cyclooctene(COE)and long-chain 5-hexylcyclooctene(COE-C6),following by hydrogenation process,we synthesized a range of functionalized branched polyethylenes characterized by varied branching density and polar monomer incorporation.These polymers bear a structural resemblance to functionalized ethylene-octene copolymers.After crosslinking,mechanochromophores are generated,and mechanochromism is achieved in uniaxial tensile testing.A comprehensive assessment reveals that both the incorporation of polar monomers and variations in branching density significantly influence their mechanical properties.Notably,upon stretching,these materials display pronounced visible color change,confirming the successful development of mechanochromic branched polyethylenes.
基金supported by the National Natural Science Foundation of China,Fund for Distinguished Young Scholars(No.52325301)CAS Project for Young Scientists in Basic Research(YSBR-094)the National Natural Science Foundation of China,Basic Science Center Program(No.51988102).
文摘Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic polyesters and polycarbonates usually suffer from inferior properties and functionalities.By contrast,precisely modulated block copolymers composed of polyesters and polycarbonates give rise to sustainable materials with tailored performance.An efficient approach to synthesize the block copolymers is the ring-opening(co)polymerization of the heterocycle monomers.Herein,this review presents the heterocycle monomer ring-opening(co)polymerization for the formation of sequence-controlled block polyesters and polycarbonates.Available synthetic strategies,different monomers,monomer combinations and the catalyst systems for the formation of different block polyesters and polycarbonates are summarized.
基金supported by the National Natural Science Foundation of China.(Grant No.20174033 and 20254001)the Special Found for Major State Basic Research Project(Grant No.G1999064801)the Committee of Science and Technology of Zhejiang Province.
文摘The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity average molecular weight about 60 x 10 under quite mild conditions: molar ratio of CL to initiator is 1000, 60 C, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chain via the break of acyl-oxygen bond of CL.
基金This work was financially supported by the financial support of National Natural Science Foundation of China (No. 20434020)
文摘The ring-opening polymerization of 1,4-dioxan-2-one （PDO） was carried out by lanthanum tris（2,6-di-tert-butyl-4- methylphenolate） （La（OAr）3） as novel single component initiaLor. The influences of polymerization reaction temperature and the molar ratio of monomer to initiator on the monomer conversion and molecular weight of poly（1,4-dioxan-2-one） （PPDO） were explored. PPDO with high viscosity average molecular weight of 1.95×10^5 can be prepared at 40℃ when [PDO]/ [La（OAr）3] molar ratio was 800. Mechanism investigation shows that the polymerization proceeds through a ＂coordination- insertion＂ mechanism with selective rupture of acyl-oxygen be,nd of PDO.
基金financially supported by the National Natural Science Foundation of China(No.52573079)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(No.B21003).
文摘The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segmental mobility and limits ionic conductivity,whereas interfacial instability against lithium metal anodes jeopardizes long-term cycling.Based on orthogonal polymerization technology combined with electrolyte structural design concepts,this work achieved a one-step fabrication of a polyester-based block copolymer electrolyte(BCPE)system comprising fluorinated segments(PTFEA)and poly(ε-caprolactone)(PCL).Structurally,this design enables a dual breakthrough in electrochemical performance:on one hand,the introduction of fluorinated segments with steric hindrance effects can effectively disrupt the regular arrangement of the PCL main chain,reduce the crystallinity of PCL within the polymer electrolyte,and significantly enhance the segmental mobility of the polymer matrix;on the other hand,during the charge/discharge cycles of lithium batteries,fluorinated segments can induce the formation of a LiF-rich solid electrolyte interphase(SEI)through in situ decomposition reactions,achieving interface stabilization and homogeneous lithiumion deposition regulation.
文摘A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted acrylates with exclusive E-stereoselectivity at room temperature.Mechanistic investigations indicated that both the hydrogen atom on vinyl group and one oxygen atom on ester group ofα,β-disubstituted acrylates derive from H2O in dimethyl sulfoxide(DMSO).Furthermore,a gram-scale experiment and late-stage modification of the products were accomplished,thereby expanding the application potential of this methodology in organic synthesis.
基金financially supported by National Key R&D Program Young Scientists Project(No.2023YFC3903100)the National Natural Science Foundation of China(No.22322503)analytical and testing assistance from the Analysis and Testing Center of HUST。
文摘Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions.Herein,we report the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene(Et_3B/DBU)pair-mediated four-component switchable polymerization of propylene oxide(PO),CO_(2),phthalic anhydride(PA),and racemic lactide(rac-LA),which enables the on-demand synthesis of four different block copolymers,i.e.,poly(propylene phthalate)-b-polylactide(PPE-b-PLA),PPE-b-PLA-b-poly(propylene carbonate)(PPC),PPE-b-PPC-b-PLA,and PPE-b-PPCb-poly(propylene oxide)(PPO),through rationally modulating the Lewis pair(LP)ratio.Core to this protocol is that increasing the loading of Et_(3)B accelerates the ring-opening of PO while impeding the reactivity of rac-LA,thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization.Therefore,the four polymerization cycles involving PO/PA ring-opening copolymerization(ROCOP),PO/CO_(2) ROCOP,rac-LA ring-opening polymerization(ROP),and PO ROP can be connected and discriminated in precisely programmed manners.
基金Science and Technology Foundation of Guizhou Province(No.QKHJC-ZK[2024]654)Guizhou Provincial University Key Laboratory of Advanced Functional Electronic Materials(No.QJJ[2023]021).
文摘Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds.In comparison with traditional thermal or metal-mediated carbene transfer reactions,visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules.Recently,visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation,mild condition,high atom economy and rich structural diversity.This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles.The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review.The future research direction and challenges in this area are also discussed.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
基金supported by the National Natural Science Foundation of China(No.22431004)Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(No.2023B1212060003)。
文摘Aggregation-induced emission(AIE)polymers have been extensively studied;however,the integration of AIE units into polyelectrolytes remains largely limited by the laborious multistep synthesis of pre-designed emissive monomers.Herein,we report a one-pot multicomponent polymerization method that directly produces main-chain charged polyelectrolytes with intrinsic AIE characteristics from non-emissive building blocks.By optimizing the monomer structures and reaction conditions,a series of soluble high-molecular-weight polymers with welldefined backbones were obtained in high yields.The resulting polyelectrolytes displayed robust AIE behavior,exhibiting fluorescence enhancement up to about 60-fold in an aqueous environment,and maintained excellent thermal stability.Owing to their cationic backbones,these polymers interact strongly with microbial surfaces and exhibit remarkable antimicrobial activities.This study establishes a synthetically efficient route to AIE polyelectrolytes and highlights their potential applications as multifunctional materials for bioimaging,antimicrobial therapy,and other applications.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金supported by NIH grant 1R16GM149379 to Renato J.Aguilerasupported by the core facilities of the BBRC,funded by the Research Centers in Minority Institutions grant 5U54MD007592 from the National Institute on Minority Health and Health Disparities to Robert A.Kirkensupported Denisse A.Gutierrez,Ana P.Betancourt,Elisa Robles-Escajeda and Armando Varela-Ramirez。
文摘Objectives:Drug resistance is the major determinant of chemotherapy failure,leading to relapse and tumor progression,demonstrating the urgent need for novel antineoplastic drugs.This study aimed to evaluate the anticancer potential of two novel pyrazole derivatives,P3C.1 and P3C.2,and to elucidate their mechanism of action in cancer cells.Methods:The cytotoxicity of the compounds was evaluated across 27 different cancer cell lines via a nuclear staining assay.Subsequent flow cytometric and biochemical analyses were performed to assess reactive oxygen species(ROS)generation,apoptosis induction,mitochondrial integrity,and cell cycle progression.Additional studies included transcriptome analyses and immunoassays to characterize the molecular mechanisms underlying drug activity.Results:Two novel pyrazole derivatives,P3C.1 and P3C.2,were identified with potent cytotoxicity on a variety of cancer cell lines.Among the adherent cell lines tested,the triple-negative breast cancer(TNBC)cell line MDA-MB-231 exhibited the highest sensitivity to both compounds and was therefore selected for further experimentation.In vitro assays demonstrated that both compounds induced ROS generation,mitochondrial membrane depolarization,cell cycle arrest and apoptosis.Whole-transcriptome sequencing of P3C.1 and P3C.2-treated MDA-MB-231 and two lymphoblastic leukemia cell lines revealed four genes in common associated with cell signaling and membrane dynamics.Connectivity Map(CMAP)database comparisons of shared genes for each cancer subtype revealed a strong similarity between the two compounds with tubulin inhibitors,and subsequent assays confirmed that these compounds act as microtubule-disrupting agents.Moreover,protein phosphorylation analysis indicated that both compounds induced hyperphosphorylation of JNK,and ERK1/2,along with hypophosphorylation of p38 kinases.Conclusions:P3C.1 and P3C.2 emerged as promising anti-breast cancer agents with dual mechanisms of action involving microtubule disruption and altered kinase signaling,leading to induction of apoptosis.
基金financially supported by the National Natural Science Foundation of China(Nos.21574124,51503203 and51233004)
文摘A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-caprolactone, exhibiting notably high activity at ambient temperature, The influence of imine bridge length and substituents of diketone over the course of polymerization was investigated in details. Remarkably, 4a was confirmed to be a rare example of exceedingly active and robust zinc catalysts, achieving major transformation of lactide under extremely low loading （0.025 mol%） within 18 rain. The influence of various monomers as well as the polymerization mechanism have also been discussed.
基金This work was financially supported by the Special Fund for Major State Basic Research Project(G1999064801)the National Natural Science Foundation of China(Nos.20174033 and 20434020)
文摘In this paper,ring-opening polymerization of trimethylene carbonate(TMC)with rare earth(Nd,Y,La)ρ-tert- butylcalix[n]arene(n=4,6,and 8)complexes as catalysts has been studied.Poly(trimethylene carbonate)(PTMC)with M_v of 21,400 was produced by bulk polymerization under the conditions as follows:[TMC]_0/[Nd](molar ratio)=1000,80℃, 8 h.Mechanism study reveals that the polymerization proceeds via a coordination mechanism.
