Cr(III)ehydrolyzed polyacrylamide(HPAM)gels have been extensively studied as a promising strategy controlling waste water production for mature oilfields.However,the gelation time of the current technologies is not lo...Cr(III)ehydrolyzed polyacrylamide(HPAM)gels have been extensively studied as a promising strategy controlling waste water production for mature oilfields.However,the gelation time of the current technologies is not long enough for in-depth placement.In this study,we report a novel synthesis method to obtain chromium chloride/poly(methyl methacrylate)(PMMA)nanocapsules which can significantly delay the gelation of HPAM through encapsulating the chromium chloride crosslinker.The chromium chloride-loaded nanocapsules(CreNC)are prepared via a facile inverse miniemulsion evaporation method during which the hydrophobic PMMA polymers,pre-dispersed in an organic solvent,were carefully controlled to precipitate onto stable aqueous miniemulsion droplets.The stable aqueous nanodroplets(W)containing Cr(III)are dispersed in a mixture of organic solvent(O1)with PMMA and nonsolvent medium(O2)to prepare an inverse miniemulsion.With the evaporation of the O1,PMMA forms CreNCs around the aqueous droplets.The CreNCs are readily transferred into water from the organic nonsolvent phase.The CreNCs exhibit the tunable size(358-983 nm),Cr loading(7.1%-19.1%),and Cr entrapment efficiency(11.7%-80.2%),with tunable zeta potentials in different PVA solutions.The CreNCs can delay release of Cr(III)and prolong the gelation time of HPAM up to 27 days.展开更多
A novel divinyl ether was synthesized by a convenient method with high yield.Then the divinyl ether was combined with 2- hydroxyethyl methacrylate and acrylic acid,respectively,generating difunctional polymeric crossl...A novel divinyl ether was synthesized by a convenient method with high yield.Then the divinyl ether was combined with 2- hydroxyethyl methacrylate and acrylic acid,respectively,generating difunctional polymeric crosslinkers with（hemi）acetal structure that was labile in acid.The chemical structures of the divinyl ether and crosslinkers were confirmed by ~1H NMR and elemental analysis.The crosslinkers were employed in free-radical polymerization to prepare polymer gel and gel particles. Due to the（hemi）acetal structure in the crosslinking segment,the polymer gel and particles exhibited degradable ability in strong acid.展开更多
A model of crosslinker unbinding is implemented in a highly coarse- grained granular model of F-actin cytoskeleton. We employ this specific granular model to study the mechanisms of the compressive responses of F-acti...A model of crosslinker unbinding is implemented in a highly coarse- grained granular model of F-actin cytoskeleton. We employ this specific granular model to study the mechanisms of the compressive responses of F-actin networks. It is found that the compressive response of F-actin cytoskeleton has dependency on the strain rate. The evolution of deformation energy in the network indicates that crosslinker unbinding events can induce the remodelling of F-actin cytoskele- ton in response to external loadings. The internal stress in F-actin cytoskeleton can efficiently dissipate with the help of crosslinker unbinding, which could lead to the soontaneous relaxation of living cells.展开更多
We have developed a hybrid hydrogel that is formed from a crosslinkable polymeric micelle and a polyamine. Under optimal conditions, the hydrogel rapidly formed in one second after a crosslinkable polymeric micelle so...We have developed a hybrid hydrogel that is formed from a crosslinkable polymeric micelle and a polyamine. Under optimal conditions, the hydrogel rapidly formed in one second after a crosslinkable polymeric micelle solution was mixed with a polyamine solution. We could change the hydrogel’s gelation properties, such as the storage modulus and gelation time by tuning the molecular weights of block copolymers and by tuning the pH of the dissolving-solvent of the hydrogel’s constituent components. Furthermore, we have clarified here that the structural difference among the micelles acting as crosslinkers can affect the gelation properties of the hydrogel. According to our findings, the hydrogel that was formed from the polymeric micelles possessing a highly packed (i.e., well-entangled or crosslinked) inner core exhibited a higher storage modulus than the hydrogel that was formed from the polymeric micelles possessing a lowly packed structure. Our results demonstrate that a microscopic structural difference among crosslinkers can induce a macroscopic change in the properties of the resulting hydrogels. For medical applications, the hydrogel proposed in the present paper can encapsulate the hydrophobic compounds in crosslinkers (polymeric micelles) so that the hydrogel can be available as the biomaterial for their sustained release.展开更多
A kind of aziridine crosslinkers was synthesized and used to crosslink acrylate copolymers. The crosslinking properties and curing kinetics of the resin were studied. It was found that with the increase of the content...A kind of aziridine crosslinkers was synthesized and used to crosslink acrylate copolymers. The crosslinking properties and curing kinetics of the resin were studied. It was found that with the increase of the content of crosslinker in the emulsion, the mechanical properties and solvent resistance of the resin will be apparently improved, but its glass transition temperature (T.) is very low. The lowest amount of crosslinker used in the acrylic resin emulsion is 0.25%. Curing kinetics studied by DSC show that this curing reaction occurs readily because the apparent activation energy of the reaction is low (65.1 kJ/mol). These results demonstrate that the aziridine crosslinker is indeed a low temperature crosslinking agent and can be used at room temperature.展开更多
Recently,colloidal quantum dots(QDs)with high luminescent efficiency and tunable colors have become ideal materials for next-generation display devices.Direct photolithography is a powerful tool for patterning QD devi...Recently,colloidal quantum dots(QDs)with high luminescent efficiency and tunable colors have become ideal materials for next-generation display devices.Direct photolithography is a powerful tool for patterning QD devices,but it faces the serious issue of degradation in the photophysical properties of the patterned QDs.Here,we use relatively rigid cyclopentane as a bridging group to design the crosslinker CPTA,achieving high-resolution direct photolithography of QDs with nearly nondestructive under ambient conditions.The key to the crosslinker design is the introduction of a rigid bridging group that elevates the LUMO level,providing a stronger energy barrier to prevent QD electrons from being trapped or undergoing non-radiative recombination,thus preserving their PL and EL properties.The efficient and high-resolution RGB line and dot arrays were fabricated with pixel sizes down to 1μm and a resolution of up to 6350 PPI.The patterned RGB QD films,especially red QDs,maintained their optical and optoelectronic properties,with patterned red QLEDs achieving peak external quantum efficiency(EQE)of 21%and a maximum luminance(Lmax)of~180,000 cd m^(-2),matching pristine devices.These results highlight the importance of photo-crosslinker design for nondestructive QDs patterning,paving the way for advanced display applications in patterned QLED technology.展开更多
Quantum dot light-emitting diodes(QLEDs)have emerged as a leading platform for next-generation display technologies,gaining substantial research attention in recent years.Among various patterning strategies,direct pho...Quantum dot light-emitting diodes(QLEDs)have emerged as a leading platform for next-generation display technologies,gaining substantial research attention in recent years.Among various patterning strategies,direct photolithography offers distinct advantages through its high resolution,throughput,and process simplicity.However,current direct photolithography approaches face critical limitations in resolution and device performance,primarily arising from surface defect generation and photodamage of quantum dots(QDs)caused by deep-ultraviolet exposure and photochemical byproducts.To overcome these challenges,we present a novel benzophenone-derived photosensitive crosslinker featuring a byproduct-free C–H insertion mechanism with native ligands of QDs.Through precise structure design,the photo-absorption of the crosslinker extends to 365 nm,allowing the long-awaited QD patterning under standard i-line photolithography conditions.The developed crosslinker achieves unprecedented patterning resolution(pixel size≈500 nm)with preserved photoluminescent characteristics.Corresponding QLED devices demonstrate remarkable performance enhancements,including a maximum external quantum efficiency(EQE)of 16.48%and a T95 operational lifetime of 2258.3 h(approximately 2.1 times longer than pristine devices).These advancements establish a promising pathway toward high-resolution and high-performance QLEDs,thereby accelerating the commercialization of high-end optoelectronic devices.展开更多
Currently,development of a single network hydrogel with a high fracture toughness in swelling equilibrium remains challenging.In this work,a novel T-shaped trifunctional crosslinker(T-NAGAX)with dual vinyl on the back...Currently,development of a single network hydrogel with a high fracture toughness in swelling equilibrium remains challenging.In this work,a novel T-shaped trifunctional crosslinker(T-NAGAX)with dual vinyl on the backbone and dual amide group on the side chain is synthesized by Michael addition and acylation.The T-NAGAX is used to prepare chemically crosslinked hydrogel by one-pot photo-initiated polymerization.The resulting single network hydrogels of representative polyacrylamide(PAAm),poly(N-acryloyl 2-glycine)(PACG),and poly(N-isopropyl acrylamide)(PNIPAM)crosslinked with T-NAGAX with additional hydrogen-bonds exhibit much better fracture toughness than that of the corresponding hydrogels crosslinked by N,N'-methylene bisacrylamide,a conventional crosslinker;higher mechanical strengths are observed in the T-NAGAX crosslinked hydrogels.These hydrogels are promising to be exploited as load-bearing soft tissue substitutes.This T-NAGAX crosslinker can be expanded to toughen various types of hydrogels.展开更多
With the growth of global protein demand and the development of plant-based foods,pea protein,as a low-allergenic,nutritionally balanced and environmentally friendly plant protein,has shown great potential in replacin...With the growth of global protein demand and the development of plant-based foods,pea protein,as a low-allergenic,nutritionally balanced and environmentally friendly plant protein,has shown great potential in replacing animal protein.Pea protein is mainly composed of globulin and albumin,with a protein content of 20%to 30%,and has a balanced amino acid composition,as well as being rich in minerals and dietary fiber.It also possesses good foaming,gelling,emulsifying and antioxidant functional properties.However,pea protein also has inherent defects that limit its application in the food industry.This article systematically reviews the extraction techniques,functional properties,modification methods and application fields of pea protein,and focuses on evaluating the effects of different extraction and modification strategies on protein yield and functional properties.Research shows that ultrasonic-assisted alkaline extraction can reduce solvent usage by 55%,shorten extraction time by 50%,and increase extraction rate by 12.51%;under optimized conditions,ultrafiltration membrane technology can achieve a protein purity of 91%.In terms of modification,ultrasonic treatment increases foaming capacity by 37.4%,and phenolic cross-linking increases gel strength from 3.0 kPa to 48 kPa.This article provides data support and theoretical reference for the efficient extraction and functional optimization of pea protein,and has promoting significance for its wide application in plant-based foods.展开更多
RNA binding proteins(RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process.Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progre...RNA binding proteins(RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process.Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases,making RBPs potential therapeutic targets.However,the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA-protein interactions in mammal tissues.Additionally,RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes(RPCs).Due to these inherent limitations,globally profiling the RNA binding proteome in mammal organs has long been a challenge.Herein,we proposed a novel method,which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation,metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver,called FTYc_UV.In this method,formaldehyde is first used to crosslink the crude RNA-protein complexes(cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation.Furthermore,this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging.After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates,formaldehyde decrosslinking is employed to remove non-specific proteins,leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking.Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75 % of previously reported RBPs.Furthermore,420 candidate RBPs,including 151metabolic enzymes,were also obtained,demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA-protein interactions in biological and clinical research.展开更多
Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the...Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.展开更多
In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still face...In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.展开更多
Cu (I) catalyzed alkyne-azide cycloaddition (CuAAC) reaction,a typical "click" reaction,is one of the modular synthetic approaches which has been broadly used in various organic syntheses,medicinal chemistry...Cu (I) catalyzed alkyne-azide cycloaddition (CuAAC) reaction,a typical "click" reaction,is one of the modular synthetic approaches which has been broadly used in various organic syntheses,medicinal chemistry,materials development and bioconjugation applications.We have for the first time synthesized two dialkyne derivatized fluorescent crosslinkers which could be applied to crosslink two biomolecules using CuAAC reaction.Turnip yellow mosaic virus,a plant virus with unique structural and chemical properties,was used as a prototypical scaffold to form a 2D single layer at the interface of two immiscible liquids and crosslinked with these two linkers by the CuAAC reaction.Upon crosslinking,the fluorescence of both linkers diminished,likely due to the distortion of the polymethylene backbone,which therefore could be used to indicate the completion of the reaction.展开更多
Chemistry of the polyamide active layer of a desalination membrane is critical in determining both its physical and chemical properties.In this study,we designed and fabricated three novel membranes with different act...Chemistry of the polyamide active layer of a desalination membrane is critical in determining both its physical and chemical properties.In this study,we designed and fabricated three novel membranes with different active layers using the crosslinkers:terephthaloyl chloride,isophthaloyl chloride,and trimesoyl chloride.The crosslinkers were reacted with an aqueous solution of an aliphatic tetra-amine.Because these crosslinkers differ in their structures and crosslinking mechanisms during interfacial polymerization,the resultant membranes also possess different structural properties.The water contact angle of the fabricated membranes also varies;the water contact angles of 4A-3P-TPC@PSF/PET,4A-3P-TMC@PSF/PET,and 4A-3P-IPC@PSF/PET,are 68.9°,65.6°,and 53.9°,respectively.Similarly,the desalination performance of resultant membranes also showed variations,with 4A-3P-TPC@PSF/PET,4A-3P-IPC@PSF/PET,and 4A-3P-TMC@PSF/PET having a permeate flux of 17.14,25.70,and 30.90 L·m^(−2)·h^(−1),respectively,at 2.5 MPa.The 4A-3P-TPC@PSF/PET membrane exhibited extensive crosslinking with aliphatic linear amine,and cationic dye rhodamine B,MgCl_(2),and amitriptyline rejection rates of 98.6%,92.7%and 80.9%,respectively.The 4A-3P-TMC@PSF/PET membrane showed mediocre performance,while 4A-3P-IPC@PSF/PET membrane showed even lower performance,with a 35%rejection of methyl orange dye.展开更多
As the most abundant aromatic bio-based polymer,lignin has great potential as a sustainable feedstock for building crosslinked thermoset polymers as bio-based adhesives.However,the potential of hardwood kraft lignin(H...As the most abundant aromatic bio-based polymer,lignin has great potential as a sustainable feedstock for building crosslinked thermoset polymers as bio-based adhesives.However,the potential of hardwood kraft lignin(HKL)is limited due to its poor crosslinking reactivity.Hence,for the first time,the present study reports the facile oxidation of HKL involving a redox reaction with silver-ammonia complexes([(AgNH3)2]+),primarily focusing on oxidation to produce reactive quinones and promote C-C linkages during reaction.This study aims to increases reactivity of oxidized HKL for effective crosslinking with monoethanolamine(MEA)for the development of bio-based wood adhesives.The characterization,including 13C-nuclear magnetic resonance(NMR)and Fourier transform infrared(FT-IR)spectroscopy,confirms the oxidation reaction,such as the formation of quinones(C=O)and subsequent crosslinking between the oxidized HKL molecules and MEA.Additionally,gel permeation chromatography(GPC)confirms the C-C and C-O linkages with increased molecular weight after oxidation,and is supported by differential scanning calorimetry(DSC)which shows the exothermic reaction due to the crosslinking of the oxidized HKL molecules via condensation to form C-C and C-O linkages.The crosslinked HKL/MEA-based adhesives underwent mild reaction and achieved a maximum dry shear strength of 0.77 MPa,which exceeds the standard requirement of 0.6 MPa.These findings demonstrate not only a one-pot oxidation for improving the reactivity of HKL using silver complexes,but also its facile crosslinking with MEA for sustainable bio-based wood adhesives.展开更多
Polyethylene glycol(PEG)with different chains was used to modify epoxy asphalt.Molecular models of PEG⁃modified epoxy asphalt were developed using molecu⁃lar simulations(MS).The thermodynamic and mechanical properties...Polyethylene glycol(PEG)with different chains was used to modify epoxy asphalt.Molecular models of PEG⁃modified epoxy asphalt were developed using molecu⁃lar simulations(MS).The thermodynamic and mechanical properties of PEG⁃modified epoxy asphalt were analyzed,and its toughening mechanisms were explored.A method based on the Dijkstra algorithm was proposed to evaluate ep⁃oxy asphalt crosslinked networks.The results show that the introduction of PEG chains into epoxy asphalt can lower the glass transition temperature and enhance its toughness be⁃cause of the extended length of the PEG chains,which can in⁃crease the free volume and improve the mobility of the epoxy resin in the epoxy asphalt.The crosslinked network quantita⁃tive evaluation method based on the Dijkstra algorithm can ef⁃fectively evaluate the distribution of epoxy asphalt crosslink⁃ing bonds,providing further explanation of the toughening mechanism of PEG⁃modified epoxy asphalt.The feasibility of designing and screening epoxy asphalt materials by MS is verified,and a guide for toughening mechanism research of epoxy asphalt at the molecular level is provided.展开更多
Heavy metal pollution poses serious risks to the human health and the natural environment,and there is an urgent need to develop efficient heavy metal removal technologies.The adsorption strategy is one of the most fa...Heavy metal pollution poses serious risks to the human health and the natural environment,and there is an urgent need to develop efficient heavy metal removal technologies.The adsorption strategy is one of the most famous strategies for the capture of heavy metal ions.In recent years,hyper crosslinked polymers(HCPs),a kind of hyper crosslinked porous material prepared by Friedel-Crafts alkylation reaction,have attracted more and more attention because of their advantages of ultra-light framework,wide range of building monomers,easy modification and functionalization.This review focuses on the advances of HCPs in the efficient applications to the removal of heavy metal ions.The fundamentals are presented including physicochemical properties,adsorption mechanism,and preparation strategies.Subsequently,the application and influencing factors of HCPs toward heavy metal ion adsorption are discussed in detail.Furthermore,the opportunities and challenges of HCPs in this promising research field are summarized and anticipated.We are convinced that the advanced HCP-based materials will make further contributions to heavy metal removal in wastewater treatment,further paving the way of advancing researches in this field.展开更多
Corresponding author’s name was incorrectly written as“Dadang Guo”instead of“Dagang Guo”.The correct author name should be“Dagang Guo”.The authors would like to apologise for any inconvenience caused.
Reader proteins that bind specific methyllysine are important to biological functions of lysine methylation,but readers of many methyllysine sites are still unknown.Therefore,development of covalent probes is importan...Reader proteins that bind specific methyllysine are important to biological functions of lysine methylation,but readers of many methyllysine sites are still unknown.Therefore,development of covalent probes is important to identify readers from cell samples so as to understand biological roles of lysine methylation.Generally,readers bind methyllysine via aromatic cages that contain tryptophan,tyrosine and phenylalanine,that offer a unique motif for selective crosslinking.We recently reported a site-selective tryptophan crosslinking strategy based on dimethylsulfonium that mimics dimethyllysine to crosslink tryptophan in aromatic cages of readers.Since tyrosine is a key residue for binding affinity to methyllysine,especially some readers that do not contain tryptophan residues in the binding pocket.Here we developed strategies of site-selective crosslinking to tyrosine.Ultraviolet(UV)source was applied to excite tyrosine at neutral pH or phenoxide at basic p H,and subsequent single-electron transfer(SET)from Tyr*to sulfonium inside the binding pocket enables selective crosslinking.In consequence,methyllysine readers with tyrosine-containing aromatic cages could be selectively crosslinked by site-specific sulfonium peptide probes.In addition,we expanded substrates from aromatic cages to tyrosine residues of proximate contact with sulfonium probes.The pair of LgBiT and SmBiT exhibited orthogonal crosslinking in complicated cell samples.As a result,we may expand sulfonium tools to target local tyrosine in future investigations.展开更多
High-temperature performance of energy storage dielectric polymers is desired for many electronics and electrical applications,but the trade-off between energy density and temperature stability remains fundamentally c...High-temperature performance of energy storage dielectric polymers is desired for many electronics and electrical applications,but the trade-off between energy density and temperature stability remains fundamentally challenging.Here,we report a general material design strategy to enhance energy storage performance at high temperatures by crosslinking a polar polymer and a high glass-transition temperature polymer as a crosslinked binary blend.Such crosslinked binary polymers display a temperature-insensitive and high energy density behavior of about6.2~8.5 J cm^(-3) up to 110℃,showing a significant enhancement in thermal resistant properties and consequently outperforming most of the other ferroelectric polymers.Further microstructural investigations reveal that the improved thermal stability stems from the confinement effect on conformational motion of the crosslinking network,which is evidenced by the increased rigid amorphous fraction and steady intermolecular distance of amorphous regions from temperature-dependent X-ray diffraction results.Our findings provide a general and straightforward strategy to attain temperature-stable,high-energy-density polymer-based dielectrics for energy storage capacitors.展开更多
基金The authors were also supported by the National Natural Science Foundation of China(grant number 52104057 and 52204041)Natural Science Foundation of Shandong Province(grant number ZR2021QE106)China Postdoctoral Science Foundation(grant number 2021M693506)during the writing of this paper at China University of Petroleum(East China).
文摘Cr(III)ehydrolyzed polyacrylamide(HPAM)gels have been extensively studied as a promising strategy controlling waste water production for mature oilfields.However,the gelation time of the current technologies is not long enough for in-depth placement.In this study,we report a novel synthesis method to obtain chromium chloride/poly(methyl methacrylate)(PMMA)nanocapsules which can significantly delay the gelation of HPAM through encapsulating the chromium chloride crosslinker.The chromium chloride-loaded nanocapsules(CreNC)are prepared via a facile inverse miniemulsion evaporation method during which the hydrophobic PMMA polymers,pre-dispersed in an organic solvent,were carefully controlled to precipitate onto stable aqueous miniemulsion droplets.The stable aqueous nanodroplets(W)containing Cr(III)are dispersed in a mixture of organic solvent(O1)with PMMA and nonsolvent medium(O2)to prepare an inverse miniemulsion.With the evaporation of the O1,PMMA forms CreNCs around the aqueous droplets.The CreNCs are readily transferred into water from the organic nonsolvent phase.The CreNCs exhibit the tunable size(358-983 nm),Cr loading(7.1%-19.1%),and Cr entrapment efficiency(11.7%-80.2%),with tunable zeta potentials in different PVA solutions.The CreNCs can delay release of Cr(III)and prolong the gelation time of HPAM up to 27 days.
文摘A novel divinyl ether was synthesized by a convenient method with high yield.Then the divinyl ether was combined with 2- hydroxyethyl methacrylate and acrylic acid,respectively,generating difunctional polymeric crosslinkers with（hemi）acetal structure that was labile in acid.The chemical structures of the divinyl ether and crosslinkers were confirmed by ~1H NMR and elemental analysis.The crosslinkers were employed in free-radical polymerization to prepare polymer gel and gel particles. Due to the（hemi）acetal structure in the crosslinking segment,the polymer gel and particles exhibited degradable ability in strong acid.
基金supported by the ARC Future Fellowship Grant(FT100100172)
文摘A model of crosslinker unbinding is implemented in a highly coarse- grained granular model of F-actin cytoskeleton. We employ this specific granular model to study the mechanisms of the compressive responses of F-actin networks. It is found that the compressive response of F-actin cytoskeleton has dependency on the strain rate. The evolution of deformation energy in the network indicates that crosslinker unbinding events can induce the remodelling of F-actin cytoskele- ton in response to external loadings. The internal stress in F-actin cytoskeleton can efficiently dissipate with the help of crosslinker unbinding, which could lead to the soontaneous relaxation of living cells.
文摘We have developed a hybrid hydrogel that is formed from a crosslinkable polymeric micelle and a polyamine. Under optimal conditions, the hydrogel rapidly formed in one second after a crosslinkable polymeric micelle solution was mixed with a polyamine solution. We could change the hydrogel’s gelation properties, such as the storage modulus and gelation time by tuning the molecular weights of block copolymers and by tuning the pH of the dissolving-solvent of the hydrogel’s constituent components. Furthermore, we have clarified here that the structural difference among the micelles acting as crosslinkers can affect the gelation properties of the hydrogel. According to our findings, the hydrogel that was formed from the polymeric micelles possessing a highly packed (i.e., well-entangled or crosslinked) inner core exhibited a higher storage modulus than the hydrogel that was formed from the polymeric micelles possessing a lowly packed structure. Our results demonstrate that a microscopic structural difference among crosslinkers can induce a macroscopic change in the properties of the resulting hydrogels. For medical applications, the hydrogel proposed in the present paper can encapsulate the hydrophobic compounds in crosslinkers (polymeric micelles) so that the hydrogel can be available as the biomaterial for their sustained release.
文摘A kind of aziridine crosslinkers was synthesized and used to crosslink acrylate copolymers. The crosslinking properties and curing kinetics of the resin were studied. It was found that with the increase of the content of crosslinker in the emulsion, the mechanical properties and solvent resistance of the resin will be apparently improved, but its glass transition temperature (T.) is very low. The lowest amount of crosslinker used in the acrylic resin emulsion is 0.25%. Curing kinetics studied by DSC show that this curing reaction occurs readily because the apparent activation energy of the reaction is low (65.1 kJ/mol). These results demonstrate that the aziridine crosslinker is indeed a low temperature crosslinking agent and can be used at room temperature.
基金supported by the Natural Science Foundation of Beijing,China(Z220007)the National Key Research and Development Program of China(2022YFB3606501)the National Natural Science Foundation of China(22405016).
文摘Recently,colloidal quantum dots(QDs)with high luminescent efficiency and tunable colors have become ideal materials for next-generation display devices.Direct photolithography is a powerful tool for patterning QD devices,but it faces the serious issue of degradation in the photophysical properties of the patterned QDs.Here,we use relatively rigid cyclopentane as a bridging group to design the crosslinker CPTA,achieving high-resolution direct photolithography of QDs with nearly nondestructive under ambient conditions.The key to the crosslinker design is the introduction of a rigid bridging group that elevates the LUMO level,providing a stronger energy barrier to prevent QD electrons from being trapped or undergoing non-radiative recombination,thus preserving their PL and EL properties.The efficient and high-resolution RGB line and dot arrays were fabricated with pixel sizes down to 1μm and a resolution of up to 6350 PPI.The patterned RGB QD films,especially red QDs,maintained their optical and optoelectronic properties,with patterned red QLEDs achieving peak external quantum efficiency(EQE)of 21%and a maximum luminance(Lmax)of~180,000 cd m^(-2),matching pristine devices.These results highlight the importance of photo-crosslinker design for nondestructive QDs patterning,paving the way for advanced display applications in patterned QLED technology.
基金supported by the National Key R&D Program of China(Nos.2022YFB3606501,2022YFB3602902)the National Natural Science Foundation of China(Nos.62404227 and U23A2092)+7 种基金the China National Postdoctoral Program for Innovative Talents(No.BX20240391)the China Postdoctoral Science Foundation(No.2023M743623)the Key projects of National Natural Science Foundation of China(No.62234004)“Pioneer”and“Leading Goose”R&D Program of Zhejiang(Nos.2024C01191,2024C01092)Ningbo Key Technologies R&D Program(No.2022Z085)Ningbo 3315 Programme(No.2020A-01-B)YONGJIANG Talent Introduction Programme(No.2021A-038-B,2021A-159-G)Ningbo Science and Technology Yongjiang 2035 Key Technology Breakthrough Plan Project(Nos.2025Z079,2024Z146).
文摘Quantum dot light-emitting diodes(QLEDs)have emerged as a leading platform for next-generation display technologies,gaining substantial research attention in recent years.Among various patterning strategies,direct photolithography offers distinct advantages through its high resolution,throughput,and process simplicity.However,current direct photolithography approaches face critical limitations in resolution and device performance,primarily arising from surface defect generation and photodamage of quantum dots(QDs)caused by deep-ultraviolet exposure and photochemical byproducts.To overcome these challenges,we present a novel benzophenone-derived photosensitive crosslinker featuring a byproduct-free C–H insertion mechanism with native ligands of QDs.Through precise structure design,the photo-absorption of the crosslinker extends to 365 nm,allowing the long-awaited QD patterning under standard i-line photolithography conditions.The developed crosslinker achieves unprecedented patterning resolution(pixel size≈500 nm)with preserved photoluminescent characteristics.Corresponding QLED devices demonstrate remarkable performance enhancements,including a maximum external quantum efficiency(EQE)of 16.48%and a T95 operational lifetime of 2258.3 h(approximately 2.1 times longer than pristine devices).These advancements establish a promising pathway toward high-resolution and high-performance QLEDs,thereby accelerating the commercialization of high-end optoelectronic devices.
基金supported by the National Key Research and Development Program of China(Grant No.2018YFA0703100)the National Natural Science Foundation of China(Grant No.51733006)。
文摘Currently,development of a single network hydrogel with a high fracture toughness in swelling equilibrium remains challenging.In this work,a novel T-shaped trifunctional crosslinker(T-NAGAX)with dual vinyl on the backbone and dual amide group on the side chain is synthesized by Michael addition and acylation.The T-NAGAX is used to prepare chemically crosslinked hydrogel by one-pot photo-initiated polymerization.The resulting single network hydrogels of representative polyacrylamide(PAAm),poly(N-acryloyl 2-glycine)(PACG),and poly(N-isopropyl acrylamide)(PNIPAM)crosslinked with T-NAGAX with additional hydrogen-bonds exhibit much better fracture toughness than that of the corresponding hydrogels crosslinked by N,N'-methylene bisacrylamide,a conventional crosslinker;higher mechanical strengths are observed in the T-NAGAX crosslinked hydrogels.These hydrogels are promising to be exploited as load-bearing soft tissue substitutes.This T-NAGAX crosslinker can be expanded to toughen various types of hydrogels.
文摘With the growth of global protein demand and the development of plant-based foods,pea protein,as a low-allergenic,nutritionally balanced and environmentally friendly plant protein,has shown great potential in replacing animal protein.Pea protein is mainly composed of globulin and albumin,with a protein content of 20%to 30%,and has a balanced amino acid composition,as well as being rich in minerals and dietary fiber.It also possesses good foaming,gelling,emulsifying and antioxidant functional properties.However,pea protein also has inherent defects that limit its application in the food industry.This article systematically reviews the extraction techniques,functional properties,modification methods and application fields of pea protein,and focuses on evaluating the effects of different extraction and modification strategies on protein yield and functional properties.Research shows that ultrasonic-assisted alkaline extraction can reduce solvent usage by 55%,shorten extraction time by 50%,and increase extraction rate by 12.51%;under optimized conditions,ultrafiltration membrane technology can achieve a protein purity of 91%.In terms of modification,ultrasonic treatment increases foaming capacity by 37.4%,and phenolic cross-linking increases gel strength from 3.0 kPa to 48 kPa.This article provides data support and theoretical reference for the efficient extraction and functional optimization of pea protein,and has promoting significance for its wide application in plant-based foods.
基金financial support from the National Key R&D Program of China (No.2021YFA1302604)Scientific and technological innovation project of China Academy of Chinese Medical Sciences (No.CI2021B017)China Postdoctoral Science Foundation (No.2023T160727)。
文摘RNA binding proteins(RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process.Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases,making RBPs potential therapeutic targets.However,the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA-protein interactions in mammal tissues.Additionally,RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes(RPCs).Due to these inherent limitations,globally profiling the RNA binding proteome in mammal organs has long been a challenge.Herein,we proposed a novel method,which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation,metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver,called FTYc_UV.In this method,formaldehyde is first used to crosslink the crude RNA-protein complexes(cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation.Furthermore,this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging.After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates,formaldehyde decrosslinking is employed to remove non-specific proteins,leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking.Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75 % of previously reported RBPs.Furthermore,420 candidate RBPs,including 151metabolic enzymes,were also obtained,demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA-protein interactions in biological and clinical research.
基金financially supported by the International Cooperation Program of the Ministry of Science and Technology of Hubei Province(No.2023EHA069)Shenzhen Science and Technology Program(No.JCYJ20230807143702005)the National Foreign Experts Program(No.G2022027015L)。
文摘Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.
基金the financial support from the National Natural Science Foundation of China (No. 52072390)the National High-Level Talents Special Support Program (Leading Talent of Technological Innovation)+2 种基金the China Postdoctoral Science Foundation (No. 2023M743648)the Young Scientists Fund of the National Natural Science Foundation of China (No. 52302330)the support from the Shanghai Emperor of Cleaning Hi-Tech Co.,LTD
文摘In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.
基金We are grateful for the support from the US NSF CAREER Award (CHE-0748690)US DoD–ARO (W911NF-09-1-0236), US DoE+4 种基金the W. M. Keck Foundationthe Camille Dreyfus Teacher-Scholarshipthe Alfred P. Sloan Foundationthe National Natural Science Foundation of China (50673025)the National Basic Research 973 Program (2006CB806200)
文摘Cu (I) catalyzed alkyne-azide cycloaddition (CuAAC) reaction,a typical "click" reaction,is one of the modular synthetic approaches which has been broadly used in various organic syntheses,medicinal chemistry,materials development and bioconjugation applications.We have for the first time synthesized two dialkyne derivatized fluorescent crosslinkers which could be applied to crosslink two biomolecules using CuAAC reaction.Turnip yellow mosaic virus,a plant virus with unique structural and chemical properties,was used as a prototypical scaffold to form a 2D single layer at the interface of two immiscible liquids and crosslinked with these two linkers by the CuAAC reaction.Upon crosslinking,the fluorescence of both linkers diminished,likely due to the distortion of the polymethylene backbone,which therefore could be used to indicate the completion of the reaction.
基金gratefully appreciate the support offered by the KFUPM Fund received from Mr.Al-Bin Saleh donated through project MWS-90130027 to the Interdisciplinary Research Center for Membranes and Water Security,King Fahd University of Petroleum and Minerals,Saudi Arabia.
文摘Chemistry of the polyamide active layer of a desalination membrane is critical in determining both its physical and chemical properties.In this study,we designed and fabricated three novel membranes with different active layers using the crosslinkers:terephthaloyl chloride,isophthaloyl chloride,and trimesoyl chloride.The crosslinkers were reacted with an aqueous solution of an aliphatic tetra-amine.Because these crosslinkers differ in their structures and crosslinking mechanisms during interfacial polymerization,the resultant membranes also possess different structural properties.The water contact angle of the fabricated membranes also varies;the water contact angles of 4A-3P-TPC@PSF/PET,4A-3P-TMC@PSF/PET,and 4A-3P-IPC@PSF/PET,are 68.9°,65.6°,and 53.9°,respectively.Similarly,the desalination performance of resultant membranes also showed variations,with 4A-3P-TPC@PSF/PET,4A-3P-IPC@PSF/PET,and 4A-3P-TMC@PSF/PET having a permeate flux of 17.14,25.70,and 30.90 L·m^(−2)·h^(−1),respectively,at 2.5 MPa.The 4A-3P-TPC@PSF/PET membrane exhibited extensive crosslinking with aliphatic linear amine,and cationic dye rhodamine B,MgCl_(2),and amitriptyline rejection rates of 98.6%,92.7%and 80.9%,respectively.The 4A-3P-TMC@PSF/PET membrane showed mediocre performance,while 4A-3P-IPC@PSF/PET membrane showed even lower performance,with a 35%rejection of methyl orange dye.
基金supported by the National Research Foundation(NRF)of Korea,funded by the Korean Government(MSIT)(Grant No.RS-2023-00240043).
文摘As the most abundant aromatic bio-based polymer,lignin has great potential as a sustainable feedstock for building crosslinked thermoset polymers as bio-based adhesives.However,the potential of hardwood kraft lignin(HKL)is limited due to its poor crosslinking reactivity.Hence,for the first time,the present study reports the facile oxidation of HKL involving a redox reaction with silver-ammonia complexes([(AgNH3)2]+),primarily focusing on oxidation to produce reactive quinones and promote C-C linkages during reaction.This study aims to increases reactivity of oxidized HKL for effective crosslinking with monoethanolamine(MEA)for the development of bio-based wood adhesives.The characterization,including 13C-nuclear magnetic resonance(NMR)and Fourier transform infrared(FT-IR)spectroscopy,confirms the oxidation reaction,such as the formation of quinones(C=O)and subsequent crosslinking between the oxidized HKL molecules and MEA.Additionally,gel permeation chromatography(GPC)confirms the C-C and C-O linkages with increased molecular weight after oxidation,and is supported by differential scanning calorimetry(DSC)which shows the exothermic reaction due to the crosslinking of the oxidized HKL molecules via condensation to form C-C and C-O linkages.The crosslinked HKL/MEA-based adhesives underwent mild reaction and achieved a maximum dry shear strength of 0.77 MPa,which exceeds the standard requirement of 0.6 MPa.These findings demonstrate not only a one-pot oxidation for improving the reactivity of HKL using silver complexes,but also its facile crosslinking with MEA for sustainable bio-based wood adhesives.
基金The Major Science and Technology Project of Nan⁃jing(No.202209012)the Postgraduate Research and Practice Innova⁃tion Program of Jiangsu Province(No.KYCX22⁃0277).
文摘Polyethylene glycol(PEG)with different chains was used to modify epoxy asphalt.Molecular models of PEG⁃modified epoxy asphalt were developed using molecu⁃lar simulations(MS).The thermodynamic and mechanical properties of PEG⁃modified epoxy asphalt were analyzed,and its toughening mechanisms were explored.A method based on the Dijkstra algorithm was proposed to evaluate ep⁃oxy asphalt crosslinked networks.The results show that the introduction of PEG chains into epoxy asphalt can lower the glass transition temperature and enhance its toughness be⁃cause of the extended length of the PEG chains,which can in⁃crease the free volume and improve the mobility of the epoxy resin in the epoxy asphalt.The crosslinked network quantita⁃tive evaluation method based on the Dijkstra algorithm can ef⁃fectively evaluate the distribution of epoxy asphalt crosslink⁃ing bonds,providing further explanation of the toughening mechanism of PEG⁃modified epoxy asphalt.The feasibility of designing and screening epoxy asphalt materials by MS is verified,and a guide for toughening mechanism research of epoxy asphalt at the molecular level is provided.
基金supported by Innovation Platform(Base)and Talent Special Project,Jilin Provincial Science&Technology Department,China(No.20230508033RC)。
文摘Heavy metal pollution poses serious risks to the human health and the natural environment,and there is an urgent need to develop efficient heavy metal removal technologies.The adsorption strategy is one of the most famous strategies for the capture of heavy metal ions.In recent years,hyper crosslinked polymers(HCPs),a kind of hyper crosslinked porous material prepared by Friedel-Crafts alkylation reaction,have attracted more and more attention because of their advantages of ultra-light framework,wide range of building monomers,easy modification and functionalization.This review focuses on the advances of HCPs in the efficient applications to the removal of heavy metal ions.The fundamentals are presented including physicochemical properties,adsorption mechanism,and preparation strategies.Subsequently,the application and influencing factors of HCPs toward heavy metal ion adsorption are discussed in detail.Furthermore,the opportunities and challenges of HCPs in this promising research field are summarized and anticipated.We are convinced that the advanced HCP-based materials will make further contributions to heavy metal removal in wastewater treatment,further paving the way of advancing researches in this field.
文摘Corresponding author’s name was incorrectly written as“Dadang Guo”instead of“Dagang Guo”.The correct author name should be“Dagang Guo”.The authors would like to apologise for any inconvenience caused.
基金the support from National Natural Science Foundation of China(No.22161132006)Key R&D Program of Zhejiang(No.2024SSYS0036)Westlake University Startup。
文摘Reader proteins that bind specific methyllysine are important to biological functions of lysine methylation,but readers of many methyllysine sites are still unknown.Therefore,development of covalent probes is important to identify readers from cell samples so as to understand biological roles of lysine methylation.Generally,readers bind methyllysine via aromatic cages that contain tryptophan,tyrosine and phenylalanine,that offer a unique motif for selective crosslinking.We recently reported a site-selective tryptophan crosslinking strategy based on dimethylsulfonium that mimics dimethyllysine to crosslink tryptophan in aromatic cages of readers.Since tyrosine is a key residue for binding affinity to methyllysine,especially some readers that do not contain tryptophan residues in the binding pocket.Here we developed strategies of site-selective crosslinking to tyrosine.Ultraviolet(UV)source was applied to excite tyrosine at neutral pH or phenoxide at basic p H,and subsequent single-electron transfer(SET)from Tyr*to sulfonium inside the binding pocket enables selective crosslinking.In consequence,methyllysine readers with tyrosine-containing aromatic cages could be selectively crosslinked by site-specific sulfonium peptide probes.In addition,we expanded substrates from aromatic cages to tyrosine residues of proximate contact with sulfonium probes.The pair of LgBiT and SmBiT exhibited orthogonal crosslinking in complicated cell samples.As a result,we may expand sulfonium tools to target local tyrosine in future investigations.
基金supported by the National Natural Science Foundation of China(Grant No.52207031)the National Key R&D Program of China(Grant No.2020YFA0710500)。
文摘High-temperature performance of energy storage dielectric polymers is desired for many electronics and electrical applications,but the trade-off between energy density and temperature stability remains fundamentally challenging.Here,we report a general material design strategy to enhance energy storage performance at high temperatures by crosslinking a polar polymer and a high glass-transition temperature polymer as a crosslinked binary blend.Such crosslinked binary polymers display a temperature-insensitive and high energy density behavior of about6.2~8.5 J cm^(-3) up to 110℃,showing a significant enhancement in thermal resistant properties and consequently outperforming most of the other ferroelectric polymers.Further microstructural investigations reveal that the improved thermal stability stems from the confinement effect on conformational motion of the crosslinking network,which is evidenced by the increased rigid amorphous fraction and steady intermolecular distance of amorphous regions from temperature-dependent X-ray diffraction results.Our findings provide a general and straightforward strategy to attain temperature-stable,high-energy-density polymer-based dielectrics for energy storage capacitors.
