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
Elastic electronics are increasingly prevalent in information storage,smart sensing and health monitoring due to their softness,stretchability and portability.Wearable electronic devices should possess elasticity and ...Elastic electronics are increasingly prevalent in information storage,smart sensing and health monitoring due to their softness,stretchability and portability.Wearable electronic devices should possess elasticity and stretchability that align with biological tissues.Specifically,their materials should be capable of elastic strain up to 50–80%,while the devices themselves must maintain electric stability under strains that accommodate body movements[1].展开更多
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
Inorganic CsPbI_(3)perovskite with superior thermal stability and photoelectric properties has developed into a promising candidate for photovoltaic applications.Nevertheless,the power conversion efficiency(PCE)of CsP...Inorganic CsPbI_(3)perovskite with superior thermal stability and photoelectric properties has developed into a promising candidate for photovoltaic applications.Nevertheless,the power conversion efficiency(PCE)of CsPbI_(3)perovskite solar cells(PSCs)still lags far behind that of both organic-inorganic hybrid counterparts and the theoretical PCE limit,primarily restricted by severe fill factor(FF)and opencircuit voltage(VOC)deficits.Herein,an in-situ self-crosslinking strategy is proposed to construct high-performance inverted inorganic PSCs by incorporating acrylate monomers as additives into CsPbI_(3)perovskite precursors.During the thermal annealing process of perovskite films,acrylate monomers can form network structures by breaking the C=C groups through an in-situ polymerization reaction,mainly anchored at the grain boundaries(GBs)and on the surfaces of perovskite.Meanwhile,the C=O groups of acrylate polymers can favorably coordinate with uncoordinated Pb^(2+),thereby decreasing defect density and stabilizing the perovskite phase.Particularly,with multiple crosslinking and passivation sites,the incorporation of dipentaerythritol pentaacrylate(DPHA)can effectively improve the perovskite film quality,suppress nonradiative recombination,and block moisture erosion.Consequently,the DPHAbased PSC achieves a champion PCE of 20.05%with a record-high FF of 85.05%,both of which rank among the top in the performance of inverted CsPbI_(3)PSCs.Moreover,the unencapsulated DPHA-based device exhibits negligible hysteresis,remarkably improved long-term storage,and operational stability.This work offers a facile and useful strategy to simultaneously promote the efficiency and device stability of inverted inorganic PSCs.展开更多
All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional l...All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional liquid-state LIBs. However, the practical success of ASLS-LIBs is bottlenecked by the lack of advanced separator technology that can simultaneously realize high performances in puncturing-tolerability,fire-resistance, and importantly, wetting-capability with non-flammable liquid-electrolytes. Here, we propose a concept of inorganic in-situ separator(IISS) by hybrid-sol physical crosslinking directly onto the electrode surface to address the above challenges. Particularly, the hybrid-sol is designed with silica nanoparticles as the building block and poly(vinylidene difluoride) nanoparticles as the crosslinking agent. The critical factors for controlling the IISS microstructures and properties have been systematically investigated. The advantages of the IISS have been confirmed by its fast wetting with various fireresistant liquid-electrolytes, customizable thickness and porous structures, robust interface with planar or three-dimensional(3D)-structured electrodes, and importantly, unexpected self-adaptability against puncturing. Enabled by the above merits, a fire-resistant ASLS-LIB is successfully assembled and demonstrated with stable electrochemical performance. This sol-crosslinked IISS may open an avenue for the studies on the next-generation separator technology, cell assembling, solid electrolyte processing as well as non-flammable secondary batteries.展开更多
AIM:To assess the visual outcomes and corneal biomechanical properties of myopia patients between laser in situ keratomileusis(LASIK)and LASIK combined with accelerated corneal crosslinking(LASIK Xtra).METHODS:This pr...AIM:To assess the visual outcomes and corneal biomechanical properties of myopia patients between laser in situ keratomileusis(LASIK)and LASIK combined with accelerated corneal crosslinking(LASIK Xtra).METHODS:This prospective study analyzed 52 consecutive myopia patients treated with LASIK Xtra and 45 consecutive myopia patients treated with LASIK.Only the right eyes in the two groups were analyzed.The uncorrected distance visual acuity(UDVA),keratometry values,postoperative central corneal thickness(CCT),corneal demarcation line depth,the corneal compensated intraocular pressure(IOPcc),Goldmann-correlated IOP(IOPg),corneal resistance factor(CRF)and corneal hysteresis(CH)from Ocular Response Analyzer(ORA)were analyzed.Further,the correlation between the demarcation line depth and ORA-related biomechanical parameters were analyzed.RESULTS:No significant differences in UDVA,postoperative CCT,or mean K values were found between the 2 groups at 1 to 12mo postoperative follow-up(all P>0.05).The changes of CRF was significantly lower in the LASIK Xtra group compared to the LASIK group(all P<0.05)at all the postoperative visits.The changes of CH were significantly higher in the LASIK Xtra group(all P<0.05).No significant differences were discovered regarding the changes of IOPcc and IOPg posperatively(all P>0.05).Out of 52 cases in the LASIK Xtra group,the demarcation line was present in 40 eyes(77%).The average depth of the demarcation was 220.73±42.70μm(136 to 288μm).No significant correlation was observed between the depth of the demarcation line and any of the ORA-related biomechanical parameters such as IOPcc,IOPg,CRF and CH at 12mo(all P>0.05).CONCLUSION:Both procedures demonstrate comparable outcomes in terms of visual acuity,refraction and ablation predictability.This study confirms that corneal biomechanical properties of the included patients weakened after both procedures,but the cornea after LASIK Xtra are stiffer than conventional LASIK.展开更多
Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chain...Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chains. In this work, crosslinked polyimide fibers(CPI fibers) were produced by intrinsic carboxyl decarboxylation for the first time. The thermal stability of the polyimide fibers containing the intrinsic carboxyl groups(PIC fibers) was studied, and the temperature of the decarboxylation-crosslinking reaction was determined to be 450 ℃. The PIC fibers were hotdrawn to initiate thermal crosslinking of the carboxyl groups and molecular chain orientation at high temperature. The CPI fibers had high tensile strengths(0.72-1.46 GPa) and compressive strengths(401-604 MPa). The oriented macromolecules and chemically crosslinked structure improved the tightness of the molecular chains and endowed the CPI fibers with excellent hydrolytic resistance. The CPI-50 fiber did not dissolve in a 0.5 wt% NaOH solution during heating at 90 ℃ for 10 h, and the tensile strength retention reached 87% when treated in 0.5 wt% NaOH solutions at 90 ℃ for 1 h, providing a guarantee for its application in alkaline corrosive environments.展开更多
●AIM:To explore the clinical efficacy and safety of stromal lenticule addition keratoplasty(SLAK)with corneal crosslinking(CXL)on patients with corneal ectasia secondary to femtosecond laser-assisted in situ keratomi...●AIM:To explore the clinical efficacy and safety of stromal lenticule addition keratoplasty(SLAK)with corneal crosslinking(CXL)on patients with corneal ectasia secondary to femtosecond laser-assisted in situ keratomileusis(FS-LASIK).●METHODS:A series of 5 patients undertaking SLAK with CXL for the treatment of corneal ectasia secondary to FS-LASIK were followed for 4-9mo.The lenticules were collected from patients undertaking small incision lenticule extraction(SMILE)for the correction of myopia.Adding a stromal lenticule was aimed at improving the corneal thickness for the safe application of crosslinking and compensating for the thin cornea to improve its mechanical strength.●RESULTS:All surgeries were conducted successfully with no significant complications.Their best corrected visual acuity(BCVA)ranged from 0.05 to 0.8-2 before surgery.The pre-operational total corneal thickness ranged from 345-404μm and maximum keratometry(Kmax)ranged from 50.8 to 86.3.After the combination surgery,both the corneal keratometry(range 55.9 to 92.8)and total corneal thickness(range 413-482μm)significantly increased.Four out of 5 patients had improvement of corneal biomechanical parameters(reflected by stiffness parameter A1 in Corvis ST).However,3 patients showed decreased BCVA after surgery due to the development of irregular astigmatism and transient haze.Despite the onset of corneal edema right after SLAK,the corneal topography and thickness generally stabilized after 3mo.●CONCLUSION:SLAK with CXL is a potentially beneficial and safe therapy for advanced corneal ectasia.Future work needs to address the poor predictability of corneal refractometry and compare the outcomes of different surgical modes.展开更多
AIM:To investigate changes in choroidal thickness and vascularity in keratoconus patients treated with corneal crosslinking.METHODS:This study evaluated 28 eyes of 22 patients with keratoconus who underwent corneal cr...AIM:To investigate changes in choroidal thickness and vascularity in keratoconus patients treated with corneal crosslinking.METHODS:This study evaluated 28 eyes of 22 patients with keratoconus who underwent corneal crosslinking.The choroidal thicknesses were evaluated on enhanced depth imaging optical coherence tomography at the preoperative and postoperative 3d,1,and 3mo.Choroidal thickness in the four cardinal quadrants and the fovea were evaluated.The choroidal vascularity index was also calculated.RESULTS:There was no significant difference in central choroidal thickness between the preoperative and postoperative 3d,1mo(P>0.05).There was a significant increase in the 3mo(P=0.034)and a significant decrease in the horizontal choroidal vascularity index on the postoperative 3d(P=0.014),there was no statistically significant change in vertical axes and other visits in horizontal sections(P>0.05).CONCLUSION:This study sheds light on choroidal changes in postoperative corneal crosslinking for keratoconus.While it suggests the procedure’s relative safety for submacular choroid,more extensive research is necessary to confirm these findings and their clinical significance.展开更多
Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should t...Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should take precedence over direct composting degradation.The present work adopts a chain breaking-crosslinking strategy,upcycling PBAT into dual covalent adaptable networks(CANs).During the chainbreaking stage,the ammonolysis between PBAT and polyethyleneimine(PEI)established the primary crosslinked network.Subsequently,styrene maleic anhydride copolymer(SMA)reacted with the hydroxyl group,culminating in the formation of dual covalent adaptable networks.In contrast to PBAT,the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa,alongside an inherent resistance to creep and solvents.Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups,the PBAT-dual-CANs exhibited fast stress relaxation.Additionally,they could be recycled through extrusion and hot-press reprocessing,while retaining their biodegradability.This straightforward strategy offers a solution for dealing with plastic waste.展开更多
The Thermomyces lanuginosus lipase(TLLs)was successfully immobilized within a novel hydrogel matrix through a two-step crosslinking method.TLLs were initially crosslinked through the Schiff base reaction by oxidized c...The Thermomyces lanuginosus lipase(TLLs)was successfully immobilized within a novel hydrogel matrix through a two-step crosslinking method.TLLs were initially crosslinked through the Schiff base reaction by oxidized carboxymethyl cellulose(OCMC).The water-soluble OCMC@TLLs complex was subsequently crosslinked by carboxymethyl chitosan(CMCSH)in a microfluidic apparatus to form the CMCHS/OCMC@TLLs microspheres.The CD(Circular Dichroism,CD)and FT-IR(Fourier Transform infrared spectroscopy,FT-IR)spectra demonstrated that the crosslinking of TLLs with OCMC resulted in a less significant impact on their structure compared to that with glutaraldehyde.CMCHS/OCMC@TLLs showed decreased catalytic performance due to the mass transfer resistance,while its thermal stability was greatly improved.The CMCHS/OCMC@TLLs were used to catalyze the lauroylation of arbutin in tetrahydrofuran.After 12 h of reaction under optimal conditions,the yield of 6′-O-lauryl arbutin reached an impres-sive 92.12%.The prepared 6′-O-lauryl arbutin has high lipophilicity and exhibits similar tyrosinase inhibitory activity and higher antioxidant activity compared to its parent compound.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
Stretchability is a crucial property of flexible all-in-one supercapacitors.This work reports a novel hydrogel electrolyte,polyacrylamidedivinylbenzene-Li2SO4(PAM-DVB-Li)synthesized by using a strategy of combining hy...Stretchability is a crucial property of flexible all-in-one supercapacitors.This work reports a novel hydrogel electrolyte,polyacrylamidedivinylbenzene-Li2SO4(PAM-DVB-Li)synthesized by using a strategy of combining hydrophobic nodes and hydrophilic networks as well as a method of dispersing hydrophobic DVB crosslinker to acrylamide monomer/Li2SO4 aqueous solution by micelles and followedγ-radiation induced polymerization and crosslinking.The resultant PAM-DVB-Li hydrogel electrolyte possesses excellent mechanical properties with 5627±241%stretchability and high ionic conductivity of 53±3 mS cm^(-1).By in situ polymerization of conducting polyaniline(PANI)on the PAM-DVB-Li hydrogel electrolyte,a novel all-in-one supercapacitor,PAM-DVB-Li/PANI,with highly integrated structure is prepared further.Benefiting from the excellent properties of hydrogel electrolyte and the all-in-one structure,the device exhibits a high specific capacitance of 469 mF cm^(-2) at 0.5 mA cm^(-2),good cyclic stability,safety,and deformation damage resistance.More importantly,the device demonstrates a superior tensile resistance(working normally under no more than 300%strain,capacitance stability in 1000 cycles of 1000%stretching and 10 cycles of 3000%stretching)far beyond that of other all-in-one supercapacitors.This work proposes a novel strategy to construct tensile-resistant all-in-one flexible supercapacitors that can be used as an energy storage device for stretchable electronic devices.展开更多
Dielectric films are critical components in the fabrication of capacitors. However, their reliance on petroleum-derived polymers presents significant environmental challenges. To address this issue, we report on a hig...Dielectric films are critical components in the fabrication of capacitors. However, their reliance on petroleum-derived polymers presents significant environmental challenges. To address this issue, we report on a high-performance biomass-based dielectric material derived from vanillin(VA), a renewable aromatic aldehyde. Vanillin was first esterified to synthesize vanillin methacrylate(VMA), which was then copolymerized with methyl methacrylate(MMA) via free-radical polymerization to yield P(VMA-MMA). By crosslinking the aldehyde groups in VMA with the amine groups in the polyether amine D400(PEA), we fabricated a series of P(VMA-MMA)@PEA dielectric films with precisely tunable crosslinking densities. The unique molecular structure of vanillin, featuring both a benzene ring and an ester group, facilitates strong δ-π interactions and dipolar polarization, synergistically enhancing energy storage density while minimizing dielectric loss. At an optimal P(VMA-MMA) ratio of 1:10and 80% theoretical crosslinking degree, the dielectric constant reaches 3.4 at 10^(-3 )Hz, while the breakdown strength reaches 670.2 MV/m. Furthermore, the film exhibits an energy storage density of 7.1 J/cm3at 500 MV/m while maintaining a charge-discharge efficiency exceeding 90%.This study demonstrates a green and reliable strategy for designing biomass-based dielectric materials and opens new avenues for the development of eco-friendly energy-storage technologies.展开更多
This work develops a protein imprinted nanosphere with varied recognition specificity for bovine serum albumin(BSA)and lysozyme(Lyz)under different UV light through a gradient dual crosslinked imprinting strategy(i.e....This work develops a protein imprinted nanosphere with varied recognition specificity for bovine serum albumin(BSA)and lysozyme(Lyz)under different UV light through a gradient dual crosslinked imprinting strategy(i.e.,covalent crosslinking and dynamic reversible crosslinking).The imprinting cavities are initially constructed using irreversible covalent crosslinking to specifically recognize BSA,and then the coumarin residues in the imprinting cavities are crosslinked under 365 nm UV light to further imprint Lyz,because Lyz has smaller size than BSA.Since the photo-crosslinking of coumarin is a reversible reaction,the imprinting cavities of Lyz can be de-crosslinked under 254 nm UV light and restore the imprinting cavities of BSA.Moreover,the N-isopropyl acrylamide(NIPAM)and pyrrolidine residues copolymerized in the polymeric surface of the nanospheres are temperature-and p H-responsive respectively.Therefore,the protein rebinding and release behaviors of the nanospheres are controlled by external temperature and p H.As a result,the materials can selectively separate BSA from real bovine whole blood and Lyz from egg white under different UV light.This study may provide a new strategy for construction of protein imprinted materials with tunable specificity for different proteins.展开更多
Polyimide(PI)is widely used in high-tech fields such as microelectronics,aerospace,and national defense because of its excellent optical properties,high-and low-temperature resistance,and good dimensional stability.To...Polyimide(PI)is widely used in high-tech fields such as microelectronics,aerospace,and national defense because of its excellent optical properties,high-and low-temperature resistance,and good dimensional stability.To achieve the desired properties of PI,the monomers 2,6-diaminopyrimidin-4-ol(DAPD)and 6-(2,3,5,6-tetrafluoro-4-vinylphenoxy)pyrimidin-2,4-diamine(DAFPD),which contains crosslinkable functional groups,were designed and synthesized successfully and copolymerized with 4,4'-oxydianiline(ODA)and 4,4-hexafluoroisopropylphthalic anhydride(6FDA).The prepared PI film(PI-3),with rigid backbones and loose packing had excellent heat resistance(Td5%=489℃)and optical properties(T450=82%).Furthermore,a crosslinked PI film(c-PI-3)with more heat-resistant(Td5%=524℃)and better mechanical properties(σ=125.46MPa),can be obtained through thermal crosslinking of tetrafluorostyrene.In addition,the changes in the properties caused by the proportion of DAFPD added during copolymerization are discussed comprehensively.This study provides a promising candidate for heat-resistant PI materials.展开更多
Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this ...Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this study,novel poly(ε-caprolactone)(PCL)-poly(2-vinyl)ethylene glycol(PVEG)copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate(VEC)with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent.Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance.The thermal properties,mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers,vinyl contents and functionality of thiols.Moreover,high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials.In addition,the utility of the present SMPs is further demonstrated by the post-functionalization via thiol-ene photo-click chemistry.展开更多
With the increasing consumption of non renewable resources such as oil,the traditional polymer manufacturing industry that relies on fossil resources is facing unprecedented challenges.The design,synthesis,and recycli...With the increasing consumption of non renewable resources such as oil,the traditional polymer manufacturing industry that relies on fossil resources is facing unprecedented challenges.The design,synthesis,and recycling of renewable and environmentally friendly bio-based polymers as alternatives to petroleum based polymers have become hot topics in research and industrial fields.Biomass has been used as a raw material to design and synthesize closed-loop recyclable polymers,which is of great significance in addressing the waste of resources and negative impact on the environment in the traditional polymer preparation process.This review summarized recent advances in the design,synthesis,and properties of closed-loop recyclable bio-based polymers,focusing on the sustainability and recyclability of bio-based materials,followed by a brief discussion of the potential applications of closed-loop recyclable bio-based polymers in emerging applications such as 3D printing and friction electric nanogenerators.In addition,perspectives and recommendations for future research on closedloop recyclable bio-based polymers were presented.展开更多
The intrinsic volume changes(about 300%)of Si anode during the lithiation/delithiation leads to the serious degradation of battery performance despite of theoretical capacity of 3579 mAh g^(-1) of Si.Herein,a three-di...The intrinsic volume changes(about 300%)of Si anode during the lithiation/delithiation leads to the serious degradation of battery performance despite of theoretical capacity of 3579 mAh g^(-1) of Si.Herein,a three-dimensional(3D)conductive polymer binder with adjustable crosslinking density has been designed by employing citric acid(CA)as a crosslinker between the carboxymethyl cellulose(CMC)and the poly(3,4-ethylenedioxythiophene)poly-(styrene-4-sulfonate)(PEDOT:PSS)to stabilize Si anode.By adjusting the crosslinking density,the binder can achieve a balance between rigidity and flexibility to adapt the volume expansion upon lithiation and reversible volume recovery after delithiation of Si.Therefore,Si/CMC-CA-PEDOT:PSS(Si/CCP)electrode demonstrates an excellent performance with high capacities of 2792.3 mAh g^(-1) at 0.5 A g^(-1) and a high area capacity above 2.6 mAh cm^(-2) under Si loading of 1.38 mg cm^(-2).The full cell Si/CCP paired with Li(Ni_(0.8)Co_(0.1)Mn_(0.1))O_(2) cathode discharges a capacity of 199.0 mAh g^(-1) with 84.3%ICE at 0.1 C and the capacity retention of 95.6%after 100 cycles.This work validates the effectiveness of 3D polymer binder and provides new insights to boost the performance of Si anode.展开更多
It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible d...It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible display technologies.Herein,a series of fluorinated polyimide films(FPIs)were fabricated by the condensation of 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione)(6FDA)and the fluorinated triphenylmethane diamine monomer(EDA,MEDA and DMEDA)with heat-crosslinkable tetrafluorostyrene side groups,which was incorporated by different numbers of methyl groups pendant in the ortho position of amino groups.Subsequently,the FPI films underwent heating to produce crosslinking FPIs(C-FPIs)through the self-crosslinking of double bonds in the tetrafluorostyrene.The transparency,solvent resistance,thermal stability,mechanical robustness and dielectric properties of FPI and C-FPI films can be tuned by the number of methyl groups and crosslinking,which were deeply investigated by virtue of molecular dynamics(MD)simulations and density functional theory(DFT).As a result,all the films exhibited exceptional optically colorless and transparent,with transmittance in the visible region of 450-700 nm exceeding 79.9%,and the cut-off wavelengths(λ_(off))were nearly 350 nm.The thermal decomposition temperatures at 5% weight loss(T_(d5%))for all samples exceeded 504℃.These films exhibited a wide range of tunable tensile strength(46.5-75.1 MPa).Significantly,they showed exceptional dielectric properties with the dielectric constant of 2.3-2.5 at full frequency(10^(7)-20 Hz).This study not only highlights the relationship between the polymer molecular structure and properties,but offer insights for balancing optical transparency,heat resistance and low dielectric constant in PI films.展开更多
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supported by generous grants from the Natural Science Foundation of Zhejiang Province(LR24E030003)Zhejiang Province Qianjiang Talent Program(ZJ-QJRC-2020-32).
文摘Elastic electronics are increasingly prevalent in information storage,smart sensing and health monitoring due to their softness,stretchability and portability.Wearable electronic devices should possess elasticity and stretchability that align with biological tissues.Specifically,their materials should be capable of elastic strain up to 50–80%,while the devices themselves must maintain electric stability under strains that accommodate body movements[1].
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 Program for Science and Technology Innovation Team in Zhejiang(Grant No.2021R01004)the Natural Science Foundation of Ningbo City(No.2023J119)+1 种基金the Ningbo Youth Science and Technology Innovation Leading Talent Project(2023QL029)K.C.Wong Magna Fund in Ningbo University,China。
文摘Inorganic CsPbI_(3)perovskite with superior thermal stability and photoelectric properties has developed into a promising candidate for photovoltaic applications.Nevertheless,the power conversion efficiency(PCE)of CsPbI_(3)perovskite solar cells(PSCs)still lags far behind that of both organic-inorganic hybrid counterparts and the theoretical PCE limit,primarily restricted by severe fill factor(FF)and opencircuit voltage(VOC)deficits.Herein,an in-situ self-crosslinking strategy is proposed to construct high-performance inverted inorganic PSCs by incorporating acrylate monomers as additives into CsPbI_(3)perovskite precursors.During the thermal annealing process of perovskite films,acrylate monomers can form network structures by breaking the C=C groups through an in-situ polymerization reaction,mainly anchored at the grain boundaries(GBs)and on the surfaces of perovskite.Meanwhile,the C=O groups of acrylate polymers can favorably coordinate with uncoordinated Pb^(2+),thereby decreasing defect density and stabilizing the perovskite phase.Particularly,with multiple crosslinking and passivation sites,the incorporation of dipentaerythritol pentaacrylate(DPHA)can effectively improve the perovskite film quality,suppress nonradiative recombination,and block moisture erosion.Consequently,the DPHAbased PSC achieves a champion PCE of 20.05%with a record-high FF of 85.05%,both of which rank among the top in the performance of inverted CsPbI_(3)PSCs.Moreover,the unencapsulated DPHA-based device exhibits negligible hysteresis,remarkably improved long-term storage,and operational stability.This work offers a facile and useful strategy to simultaneously promote the efficiency and device stability of inverted inorganic PSCs.
基金National Natural Science Foundation of China (52203123)Sichuan Science and Technology Program (2023NSFSC0991)+2 种基金State Key Laboratory of Polymer Materials Engineering (sklpme-2023-1-05 and sklpme-2024-2-04)Fundamental Research Funds for the Central UniversitiesThis research was also partially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional liquid-state LIBs. However, the practical success of ASLS-LIBs is bottlenecked by the lack of advanced separator technology that can simultaneously realize high performances in puncturing-tolerability,fire-resistance, and importantly, wetting-capability with non-flammable liquid-electrolytes. Here, we propose a concept of inorganic in-situ separator(IISS) by hybrid-sol physical crosslinking directly onto the electrode surface to address the above challenges. Particularly, the hybrid-sol is designed with silica nanoparticles as the building block and poly(vinylidene difluoride) nanoparticles as the crosslinking agent. The critical factors for controlling the IISS microstructures and properties have been systematically investigated. The advantages of the IISS have been confirmed by its fast wetting with various fireresistant liquid-electrolytes, customizable thickness and porous structures, robust interface with planar or three-dimensional(3D)-structured electrodes, and importantly, unexpected self-adaptability against puncturing. Enabled by the above merits, a fire-resistant ASLS-LIB is successfully assembled and demonstrated with stable electrochemical performance. This sol-crosslinked IISS may open an avenue for the studies on the next-generation separator technology, cell assembling, solid electrolyte processing as well as non-flammable secondary batteries.
基金Supported by Wu Jieping Medical Foundation(No.320.6750.2021-04-15).
文摘AIM:To assess the visual outcomes and corneal biomechanical properties of myopia patients between laser in situ keratomileusis(LASIK)and LASIK combined with accelerated corneal crosslinking(LASIK Xtra).METHODS:This prospective study analyzed 52 consecutive myopia patients treated with LASIK Xtra and 45 consecutive myopia patients treated with LASIK.Only the right eyes in the two groups were analyzed.The uncorrected distance visual acuity(UDVA),keratometry values,postoperative central corneal thickness(CCT),corneal demarcation line depth,the corneal compensated intraocular pressure(IOPcc),Goldmann-correlated IOP(IOPg),corneal resistance factor(CRF)and corneal hysteresis(CH)from Ocular Response Analyzer(ORA)were analyzed.Further,the correlation between the demarcation line depth and ORA-related biomechanical parameters were analyzed.RESULTS:No significant differences in UDVA,postoperative CCT,or mean K values were found between the 2 groups at 1 to 12mo postoperative follow-up(all P>0.05).The changes of CRF was significantly lower in the LASIK Xtra group compared to the LASIK group(all P<0.05)at all the postoperative visits.The changes of CH were significantly higher in the LASIK Xtra group(all P<0.05).No significant differences were discovered regarding the changes of IOPcc and IOPg posperatively(all P>0.05).Out of 52 cases in the LASIK Xtra group,the demarcation line was present in 40 eyes(77%).The average depth of the demarcation was 220.73±42.70μm(136 to 288μm).No significant correlation was observed between the depth of the demarcation line and any of the ORA-related biomechanical parameters such as IOPcc,IOPg,CRF and CH at 12mo(all P>0.05).CONCLUSION:Both procedures demonstrate comparable outcomes in terms of visual acuity,refraction and ablation predictability.This study confirms that corneal biomechanical properties of the included patients weakened after both procedures,but the cornea after LASIK Xtra are stiffer than conventional LASIK.
基金financially supported by the Scientific Research Innovation Plan of Shanghai Education Commission (No. 2019-01-07-00-03-E00001)the National Natural Science Foundation of China (Nos. U21A2087 and 21975040)the Natural Science Foundation of Shanghai (No. 21ZR1400200)。
文摘Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chains. In this work, crosslinked polyimide fibers(CPI fibers) were produced by intrinsic carboxyl decarboxylation for the first time. The thermal stability of the polyimide fibers containing the intrinsic carboxyl groups(PIC fibers) was studied, and the temperature of the decarboxylation-crosslinking reaction was determined to be 450 ℃. The PIC fibers were hotdrawn to initiate thermal crosslinking of the carboxyl groups and molecular chain orientation at high temperature. The CPI fibers had high tensile strengths(0.72-1.46 GPa) and compressive strengths(401-604 MPa). The oriented macromolecules and chemically crosslinked structure improved the tightness of the molecular chains and endowed the CPI fibers with excellent hydrolytic resistance. The CPI-50 fiber did not dissolve in a 0.5 wt% NaOH solution during heating at 90 ℃ for 10 h, and the tensile strength retention reached 87% when treated in 0.5 wt% NaOH solutions at 90 ℃ for 1 h, providing a guarantee for its application in alkaline corrosive environments.
基金Supported by the Science&Technology Department of Sichuan Province(China)Funding Project(No.2021YFS0221,No.2023YFS0179)1.3.5 Project for Disciplines of Excellence,West China Hospital,Sichuan University(No.2022HXFH032,No.ZYJC21058)the Postdoctoral Research Funding of West China Hospital,Sichuan University,China(No.2020HXBH044).
文摘●AIM:To explore the clinical efficacy and safety of stromal lenticule addition keratoplasty(SLAK)with corneal crosslinking(CXL)on patients with corneal ectasia secondary to femtosecond laser-assisted in situ keratomileusis(FS-LASIK).●METHODS:A series of 5 patients undertaking SLAK with CXL for the treatment of corneal ectasia secondary to FS-LASIK were followed for 4-9mo.The lenticules were collected from patients undertaking small incision lenticule extraction(SMILE)for the correction of myopia.Adding a stromal lenticule was aimed at improving the corneal thickness for the safe application of crosslinking and compensating for the thin cornea to improve its mechanical strength.●RESULTS:All surgeries were conducted successfully with no significant complications.Their best corrected visual acuity(BCVA)ranged from 0.05 to 0.8-2 before surgery.The pre-operational total corneal thickness ranged from 345-404μm and maximum keratometry(Kmax)ranged from 50.8 to 86.3.After the combination surgery,both the corneal keratometry(range 55.9 to 92.8)and total corneal thickness(range 413-482μm)significantly increased.Four out of 5 patients had improvement of corneal biomechanical parameters(reflected by stiffness parameter A1 in Corvis ST).However,3 patients showed decreased BCVA after surgery due to the development of irregular astigmatism and transient haze.Despite the onset of corneal edema right after SLAK,the corneal topography and thickness generally stabilized after 3mo.●CONCLUSION:SLAK with CXL is a potentially beneficial and safe therapy for advanced corneal ectasia.Future work needs to address the poor predictability of corneal refractometry and compare the outcomes of different surgical modes.
文摘AIM:To investigate changes in choroidal thickness and vascularity in keratoconus patients treated with corneal crosslinking.METHODS:This study evaluated 28 eyes of 22 patients with keratoconus who underwent corneal crosslinking.The choroidal thicknesses were evaluated on enhanced depth imaging optical coherence tomography at the preoperative and postoperative 3d,1,and 3mo.Choroidal thickness in the four cardinal quadrants and the fovea were evaluated.The choroidal vascularity index was also calculated.RESULTS:There was no significant difference in central choroidal thickness between the preoperative and postoperative 3d,1mo(P>0.05).There was a significant increase in the 3mo(P=0.034)and a significant decrease in the horizontal choroidal vascularity index on the postoperative 3d(P=0.014),there was no statistically significant change in vertical axes and other visits in horizontal sections(P>0.05).CONCLUSION:This study sheds light on choroidal changes in postoperative corneal crosslinking for keratoconus.While it suggests the procedure’s relative safety for submacular choroid,more extensive research is necessary to confirm these findings and their clinical significance.
基金financially supported by the National Natural Science Foundation of China(Nos.52373007 and 52073296)Innovative Leading Talent of Taihu Lake Talent Plan in Wuxi City+1 种基金Zhejiang Ten Thousand Talent ProgramResearch startup fund from Jiangnan University。
文摘Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should take precedence over direct composting degradation.The present work adopts a chain breaking-crosslinking strategy,upcycling PBAT into dual covalent adaptable networks(CANs).During the chainbreaking stage,the ammonolysis between PBAT and polyethyleneimine(PEI)established the primary crosslinked network.Subsequently,styrene maleic anhydride copolymer(SMA)reacted with the hydroxyl group,culminating in the formation of dual covalent adaptable networks.In contrast to PBAT,the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa,alongside an inherent resistance to creep and solvents.Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups,the PBAT-dual-CANs exhibited fast stress relaxation.Additionally,they could be recycled through extrusion and hot-press reprocessing,while retaining their biodegradability.This straightforward strategy offers a solution for dealing with plastic waste.
基金supported by the Youth Foundation of Southeast University ChengXian College(z0055).
文摘The Thermomyces lanuginosus lipase(TLLs)was successfully immobilized within a novel hydrogel matrix through a two-step crosslinking method.TLLs were initially crosslinked through the Schiff base reaction by oxidized carboxymethyl cellulose(OCMC).The water-soluble OCMC@TLLs complex was subsequently crosslinked by carboxymethyl chitosan(CMCSH)in a microfluidic apparatus to form the CMCHS/OCMC@TLLs microspheres.The CD(Circular Dichroism,CD)and FT-IR(Fourier Transform infrared spectroscopy,FT-IR)spectra demonstrated that the crosslinking of TLLs with OCMC resulted in a less significant impact on their structure compared to that with glutaraldehyde.CMCHS/OCMC@TLLs showed decreased catalytic performance due to the mass transfer resistance,while its thermal stability was greatly improved.The CMCHS/OCMC@TLLs were used to catalyze the lauroylation of arbutin in tetrahydrofuran.After 12 h of reaction under optimal conditions,the yield of 6′-O-lauryl arbutin reached an impres-sive 92.12%.The prepared 6′-O-lauryl arbutin has high lipophilicity and exhibits similar tyrosinase inhibitory activity and higher antioxidant activity compared to its parent compound.
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.
基金financial support from National Natural Science Foundation of China(No.12375336,11875078)。
文摘Stretchability is a crucial property of flexible all-in-one supercapacitors.This work reports a novel hydrogel electrolyte,polyacrylamidedivinylbenzene-Li2SO4(PAM-DVB-Li)synthesized by using a strategy of combining hydrophobic nodes and hydrophilic networks as well as a method of dispersing hydrophobic DVB crosslinker to acrylamide monomer/Li2SO4 aqueous solution by micelles and followedγ-radiation induced polymerization and crosslinking.The resultant PAM-DVB-Li hydrogel electrolyte possesses excellent mechanical properties with 5627±241%stretchability and high ionic conductivity of 53±3 mS cm^(-1).By in situ polymerization of conducting polyaniline(PANI)on the PAM-DVB-Li hydrogel electrolyte,a novel all-in-one supercapacitor,PAM-DVB-Li/PANI,with highly integrated structure is prepared further.Benefiting from the excellent properties of hydrogel electrolyte and the all-in-one structure,the device exhibits a high specific capacitance of 469 mF cm^(-2) at 0.5 mA cm^(-2),good cyclic stability,safety,and deformation damage resistance.More importantly,the device demonstrates a superior tensile resistance(working normally under no more than 300%strain,capacitance stability in 1000 cycles of 1000%stretching and 10 cycles of 3000%stretching)far beyond that of other all-in-one supercapacitors.This work proposes a novel strategy to construct tensile-resistant all-in-one flexible supercapacitors that can be used as an energy storage device for stretchable electronic devices.
基金supported by the National Natural Science Foundation of China(No.52203011).
文摘Dielectric films are critical components in the fabrication of capacitors. However, their reliance on petroleum-derived polymers presents significant environmental challenges. To address this issue, we report on a high-performance biomass-based dielectric material derived from vanillin(VA), a renewable aromatic aldehyde. Vanillin was first esterified to synthesize vanillin methacrylate(VMA), which was then copolymerized with methyl methacrylate(MMA) via free-radical polymerization to yield P(VMA-MMA). By crosslinking the aldehyde groups in VMA with the amine groups in the polyether amine D400(PEA), we fabricated a series of P(VMA-MMA)@PEA dielectric films with precisely tunable crosslinking densities. The unique molecular structure of vanillin, featuring both a benzene ring and an ester group, facilitates strong δ-π interactions and dipolar polarization, synergistically enhancing energy storage density while minimizing dielectric loss. At an optimal P(VMA-MMA) ratio of 1:10and 80% theoretical crosslinking degree, the dielectric constant reaches 3.4 at 10^(-3 )Hz, while the breakdown strength reaches 670.2 MV/m. Furthermore, the film exhibits an energy storage density of 7.1 J/cm3at 500 MV/m while maintaining a charge-discharge efficiency exceeding 90%.This study demonstrates a green and reliable strategy for designing biomass-based dielectric materials and opens new avenues for the development of eco-friendly energy-storage technologies.
基金financial support from the National Natural Science Foundation of China(No.22275148)National Key R&D Program of China(No.2018YFB1900201)for Qiuyu Zhang+2 种基金the National Natural Science Foundation of China(No.22271232)Fundamental Research Funds for the Central Universities(No.D5000230114)for Shixin Fathe Fundamental Research Funds for the Central Universities(No.D5000220339)for Qing Liu。
文摘This work develops a protein imprinted nanosphere with varied recognition specificity for bovine serum albumin(BSA)and lysozyme(Lyz)under different UV light through a gradient dual crosslinked imprinting strategy(i.e.,covalent crosslinking and dynamic reversible crosslinking).The imprinting cavities are initially constructed using irreversible covalent crosslinking to specifically recognize BSA,and then the coumarin residues in the imprinting cavities are crosslinked under 365 nm UV light to further imprint Lyz,because Lyz has smaller size than BSA.Since the photo-crosslinking of coumarin is a reversible reaction,the imprinting cavities of Lyz can be de-crosslinked under 254 nm UV light and restore the imprinting cavities of BSA.Moreover,the N-isopropyl acrylamide(NIPAM)and pyrrolidine residues copolymerized in the polymeric surface of the nanospheres are temperature-and p H-responsive respectively.Therefore,the protein rebinding and release behaviors of the nanospheres are controlled by external temperature and p H.As a result,the materials can selectively separate BSA from real bovine whole blood and Lyz from egg white under different UV light.This study may provide a new strategy for construction of protein imprinted materials with tunable specificity for different proteins.
基金supported by the National Key Research and Development Program of China(No.2022YFB3603101)。
文摘Polyimide(PI)is widely used in high-tech fields such as microelectronics,aerospace,and national defense because of its excellent optical properties,high-and low-temperature resistance,and good dimensional stability.To achieve the desired properties of PI,the monomers 2,6-diaminopyrimidin-4-ol(DAPD)and 6-(2,3,5,6-tetrafluoro-4-vinylphenoxy)pyrimidin-2,4-diamine(DAFPD),which contains crosslinkable functional groups,were designed and synthesized successfully and copolymerized with 4,4'-oxydianiline(ODA)and 4,4-hexafluoroisopropylphthalic anhydride(6FDA).The prepared PI film(PI-3),with rigid backbones and loose packing had excellent heat resistance(Td5%=489℃)and optical properties(T450=82%).Furthermore,a crosslinked PI film(c-PI-3)with more heat-resistant(Td5%=524℃)and better mechanical properties(σ=125.46MPa),can be obtained through thermal crosslinking of tetrafluorostyrene.In addition,the changes in the properties caused by the proportion of DAFPD added during copolymerization are discussed comprehensively.This study provides a promising candidate for heat-resistant PI materials.
基金financially supported by the National Natural Science Foundation of China(No.22171182)Sichuan Tianfu Emei Plan.
文摘Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this study,novel poly(ε-caprolactone)(PCL)-poly(2-vinyl)ethylene glycol(PVEG)copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate(VEC)with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent.Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance.The thermal properties,mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers,vinyl contents and functionality of thiols.Moreover,high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials.In addition,the utility of the present SMPs is further demonstrated by the post-functionalization via thiol-ene photo-click chemistry.
基金Natural Science Foundation of China(Grant Nos.32471815 and 32401528)Natural Science Foundation of Jiangsu Province of China(Grant Nos.BK20241745 and BK20240294).
文摘With the increasing consumption of non renewable resources such as oil,the traditional polymer manufacturing industry that relies on fossil resources is facing unprecedented challenges.The design,synthesis,and recycling of renewable and environmentally friendly bio-based polymers as alternatives to petroleum based polymers have become hot topics in research and industrial fields.Biomass has been used as a raw material to design and synthesize closed-loop recyclable polymers,which is of great significance in addressing the waste of resources and negative impact on the environment in the traditional polymer preparation process.This review summarized recent advances in the design,synthesis,and properties of closed-loop recyclable bio-based polymers,focusing on the sustainability and recyclability of bio-based materials,followed by a brief discussion of the potential applications of closed-loop recyclable bio-based polymers in emerging applications such as 3D printing and friction electric nanogenerators.In addition,perspectives and recommendations for future research on closedloop recyclable bio-based polymers were presented.
基金Financial support by the NSFC no. 52371224, 51972156, and 51872131
文摘The intrinsic volume changes(about 300%)of Si anode during the lithiation/delithiation leads to the serious degradation of battery performance despite of theoretical capacity of 3579 mAh g^(-1) of Si.Herein,a three-dimensional(3D)conductive polymer binder with adjustable crosslinking density has been designed by employing citric acid(CA)as a crosslinker between the carboxymethyl cellulose(CMC)and the poly(3,4-ethylenedioxythiophene)poly-(styrene-4-sulfonate)(PEDOT:PSS)to stabilize Si anode.By adjusting the crosslinking density,the binder can achieve a balance between rigidity and flexibility to adapt the volume expansion upon lithiation and reversible volume recovery after delithiation of Si.Therefore,Si/CMC-CA-PEDOT:PSS(Si/CCP)electrode demonstrates an excellent performance with high capacities of 2792.3 mAh g^(-1) at 0.5 A g^(-1) and a high area capacity above 2.6 mAh cm^(-2) under Si loading of 1.38 mg cm^(-2).The full cell Si/CCP paired with Li(Ni_(0.8)Co_(0.1)Mn_(0.1))O_(2) cathode discharges a capacity of 199.0 mAh g^(-1) with 84.3%ICE at 0.1 C and the capacity retention of 95.6%after 100 cycles.This work validates the effectiveness of 3D polymer binder and provides new insights to boost the performance of Si anode.
基金financially supported by the Natural Science Foundation of Shandong Province(Nos.ZR2021ME055,ZR2022QB170 and ZR2022MB034)the Foundation(No.GZKF202128)of State Key Laboratory of Biobased Material and Green Papermaking,Qilu University of Technology,Shandong Academy of Sciencesthe Development Program Project of Young Innovation Team of Institutions of Higher Learning in Shandong Province.
文摘It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible display technologies.Herein,a series of fluorinated polyimide films(FPIs)were fabricated by the condensation of 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione)(6FDA)and the fluorinated triphenylmethane diamine monomer(EDA,MEDA and DMEDA)with heat-crosslinkable tetrafluorostyrene side groups,which was incorporated by different numbers of methyl groups pendant in the ortho position of amino groups.Subsequently,the FPI films underwent heating to produce crosslinking FPIs(C-FPIs)through the self-crosslinking of double bonds in the tetrafluorostyrene.The transparency,solvent resistance,thermal stability,mechanical robustness and dielectric properties of FPI and C-FPI films can be tuned by the number of methyl groups and crosslinking,which were deeply investigated by virtue of molecular dynamics(MD)simulations and density functional theory(DFT).As a result,all the films exhibited exceptional optically colorless and transparent,with transmittance in the visible region of 450-700 nm exceeding 79.9%,and the cut-off wavelengths(λ_(off))were nearly 350 nm.The thermal decomposition temperatures at 5% weight loss(T_(d5%))for all samples exceeded 504℃.These films exhibited a wide range of tunable tensile strength(46.5-75.1 MPa).Significantly,they showed exceptional dielectric properties with the dielectric constant of 2.3-2.5 at full frequency(10^(7)-20 Hz).This study not only highlights the relationship between the polymer molecular structure and properties,but offer insights for balancing optical transparency,heat resistance and low dielectric constant in PI films.
