Triple-negative breast cancer(TNBC)is one of the most lethal diseases and lack of feasible therapeutic methods.Herein,we developed a bioactive covalent organic framework(COF)for adoptive cell therapy(ACT)of TNBC.In ou...Triple-negative breast cancer(TNBC)is one of the most lethal diseases and lack of feasible therapeutic methods.Herein,we developed a bioactive covalent organic framework(COF)for adoptive cell therapy(ACT)of TNBC.In our design,Mn^(2+)functionalized COF was employed as a bioactive CpG carrier,which could simultaneously engineer and polarize macrophages to the antitumor phenotype,via the synergistic interaction of CpG and Mn^(2+).In the in vitro experiments,the engineered macrophages were found to secret high levels of antitumor cytokines for efficient TNBC cell inhibition.In the in vivo antitumor model,bioactive COF-engineered macrophages were found to relieve the hypoxia tumor microenvironment,enabling prevention of immune cell depletion during ACT.Thus,we realized efficient TNBC therapy and metastasis inhibition with the engineered macrophages in a long-term therapy model.This work provides a promising strategy for metastatic TNBC treatment and highlights the importance of bioactive COF in biomedicine.展开更多
Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents...Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents,a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking.We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane(FDEE)as single solvents.By employing quantum calculations,molecular dynamics simulations,and interpretable machine learning,we establish significant correlations between fluorination patterns and electrolyte properties.Higher fluorination levels enhance FDEE stability but decrease conductivity.The symmetry of fluorination sites is critical for stability and viscosity,while exerting minimal influence on ionic conductivity.FDEEs with highly symmetric fluorination sites exhibit favorable viscosity,stability,and overall electrolyte performance.Conductivity primarily depends on lithium-anion dissociation or association.These findings provide design principles for rational fluoroether electrolyte design,emphasizing the trade-offs between stability,viscosity,and conductivity.Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.展开更多
Iron overload has been evidenced to contribute to obesity-associated metabolic disorders,including insulin resistance.Strategies to reduce iron levels might help manage the metabolic complications associated with obes...Iron overload has been evidenced to contribute to obesity-associated metabolic disorders,including insulin resistance.Strategies to reduce iron levels might help manage the metabolic complications associated with obesity.Here,it is demonstrated that the specific accumulation of oleic acid-modified polyoxovanadates(OPOVs)in adipose tissue leads to the reduction of iron concentrations in adipocytes in mice fed with a high-fat diet(HFD).Conjugation of oleic acids to polyoxovanadates enables tissue-specific depletion of iron from white adipose tissue(WAT)by OPOVs,protecting mice from HFD-induced obesity and obesity-associated metabolic deteriorations.Glucose tolerance and insulin sensitivity are improved in OPOV-treated mice,which demonstrates that the OPOV-induced iron depletion can reverse the metabolic degeneration caused by HFD-induced obesity.Furthermore,a decrease in expression of the marker genes of iron overload suggests the participation of OPOVs in maintaining iron homeostasis and a potential medical application of vanadium clusters in targeting the iron overload caused by obesity.These findings underscore the potential of vanadate-based clusters tailored to address the complex interplay between iron metabolism and metabolic health.展开更多
Long-chain polyamides(LCPAs)are a class of bio-based polymers that can bridge conventional polyolefins and polycondensates.In this work,taking the advantage of the amphiphilic nature of polyamide 1012(PA1012),membrane...Long-chain polyamides(LCPAs)are a class of bio-based polymers that can bridge conventional polyolefins and polycondensates.In this work,taking the advantage of the amphiphilic nature of polyamide 1012(PA1012),membranes were prepared by using a non-conventional phase separation approach,namely,mixed‘non-solvents’evaporation induced phase separation(MNEIPS).PA1012 can be dissolved in a mixture of polar and non-polar solvents,both of which are non-solvents of PA1012.During the sequential evaporation of the two solvents,the phase separation of PA1012 occurred,inducing the formation of porous structures.We investigated the process of membrane formation in detail,with a specific focus on the liquid-liquid and liquid-solid phase transitions involved.Moreover,we studied the influence of critical factors,such as polymer concentration and mixed-solvent ratio,on the morphologies and properties of PA1012 membranes.This study provides new insights into the development of porous materials based on long-chain polycondensates.展开更多
The development of high-performance transparent substrates is critical for next-generation flexible electronic devices.Herein,we designed two novel meta-substituted diamines incorporating trifluoromethyl(―CF_(3))and ...The development of high-performance transparent substrates is critical for next-generation flexible electronic devices.Herein,we designed two novel meta-substituted diamines incorporating trifluoromethyl(―CF_(3))and methyl(―CH_(3))groups to synthesize colorless copolyimide(CPI)films via copolymerization with 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)/3,3′,4,4′-biphenyltetracarboxylic dianhydride(BPDA).The combination of meta-substituted architecture and substituents enables the simultaneous attainment of an ultralow dielectric constant(D_k)and high transparency.The meta-substitution geometry and electronic effects of―CF_(3)/―CH_(3) effectively suppressed charge-transfer complex(CTC)formation,expanded fractional free volume(FFV),and restricted π-electron conjugation,as validated by DFT calculations and wide-angle X-ray diffraction(WAXD)analysis.The optimized CPI film(PIA_(1)-6FDA/BPDA(10/0))achieved outstanding transmittance(T_(450)=88.15%),ultralow dielectric constant(D_(k)=2.08 at 1 k Hz),and minimal dielectric loss(D_(f)=0.0012),while maintaining robust thermal stability(T_(d5%)>523℃)and mechanical strength(σ=87.5 MPa).This work establishes a molecular engineering strategy to concurrently enhance the optical and dielectric properties,positioning meta-substituted CPIs as promising candidates for transparent flexible devices.展开更多
In contrast to cyclic polymers with ring-like backbones,side-chain cyclization is another intriguing structural feature that has not been extensively studied.In this study,a library of orthogonally protected monomers ...In contrast to cyclic polymers with ring-like backbones,side-chain cyclization is another intriguing structural feature that has not been extensively studied.In this study,a library of orthogonally protected monomers featuring monocyclic,dicyclic,or tricyclic pendant motifs was designed and prepared based on malic acid derivatives.Polyesters with precise chemical structures and uniform chain lengths were prepared modularly through iterative growth.Meticulous control over the chemical details allows for a close investigation of the topological effects on the polymer properties.Compared to their linear side chain counterparts,the presence of cyclic pendant groups has a significant impact on chain conformation,leading to a reduction in hydrodynamic volume and an enhancement in the glass transition temperature.These results underscore the potential of tailoring polymer properties through rational engineering of side chain topology.展开更多
There have been significant interests in recent years for incorporating dynamic bonds into polymer materials for achieving multiple functionalities,such as self-healing,recycling,stimuli-responsiveness,and so on.Never...There have been significant interests in recent years for incorporating dynamic bonds into polymer materials for achieving multiple functionalities,such as self-healing,recycling,stimuli-responsiveness,and so on.Nevertheless,the impact of dynamic bonds on the polymer dynamics is actually less explored.In this study,we investigate a self-healing solid-liquid elastomer(SLE),which is a dual-crosslinked network made by coupling a permanently crosslinked polydimethylsiloxane(PDMS)network with polyborosiloxane(PBS)via abundant dynamic boron/oxygen dative bonds.Proton double-quantum(DQ)NMR reveals that the crosslinking degree is reduced while the structural heterogeneity of network is enhanced with increasing PBS content,i.e.,increasing the content of dynamic boron/oxygen dative bonds.Rheological experiments clearly reveal two chain relaxation modes in the SLE samples with a characteristic relaxation time of around 2.1 s and 11.8 s,corresponding to the relaxation of coupled PBS and PDMS chains,respectively.The master curves obtained from variable-temperature frequency-dependent rheological experiments also reveal enhanced heterogeneity of chain relaxation with increasing PBS content.Finally,the impact of boron/oxygen dative bonds on the Rouse dynamics is further revealed by fast-field-cycling(FFC)NMR experiments,where the spinlattice relaxation rate(R_(1))of all SLE samples follows the same power law of R_(1)(ω)∝ω^(-0.33).Nevertheless,the incorporation of PBS did slightly increase the energy barrier of Rouse dynamics.Our study well demonstrates a combined use of rheology and solid-state NMR spectroscopy can provide piercing insights into the interplay of crosslinking structures and dynamics of polymer materials.展开更多
Reversible protonic ceramic electrochemical cells(R-PCECs)demonstrate great feasibility for efficient energy storage and conversion.One critical challenge for the development of R-PCECs is the design of novel air elec...Reversible protonic ceramic electrochemical cells(R-PCECs)demonstrate great feasibility for efficient energy storage and conversion.One critical challenge for the development of R-PCECs is the design of novel air electrodes with the characteristics of high catalytic activity and acceptable durability.Here,we report a donor doping of Hf into the B-site of a cobalt-based double perovskite with a nominal formula of PrBa_(0.8)Ca_(0.2)Co_(1.9)Hf_(0.1)O_(5tδ)(PBCCHf_(0.1)),which is naturally reconfigured to a double perovskite PrBa_(0.8-x)Ca_(0.2)Co_(1.9)Hf_(0.1)-xO5tδ(PBCCHf_(0.1)-x)backbone and nano-sized BaHfO3(BHO)on the surface of PBCCHf_(0.1)x.The air electrode demonstrates enhanced catalytic activity and durability(a stable polarization resistance of 0.269Ωcm2 for~100 h at 600℃),due likely to the fast surface exchange process and bulk diffusion process.When employed as an air electrode of R-PCECs,a cell with PBCCHf_(0.1) air electrode demonstrates encouraging performances in modes of the fuel cell(FC)and electrolysis(EL)at 600℃:a peak power density of 0.998 W cm^(-2)and a current density of1.613 A cm^(-2)at 1.3 V(with acceptable Faradaic efficiencies).More importantly,the single-cell with PBCCHf_(0.1) air electrode demonstrates good cycling stability,switching back and forth from FC mode to EL mode0.5 A cm^(-2)for 200 h and 50 cycles.展开更多
Salt-doped block copolymers have widespread applications in batteries,fuel cells,semiconductors,and various industries,where their properties crucially depend on phase separation behavior.Traditionally,investigations ...Salt-doped block copolymers have widespread applications in batteries,fuel cells,semiconductors,and various industries,where their properties crucially depend on phase separation behavior.Traditionally,investigations into salt-doped diblock copolymers have predominantly focused on microphase separation,overlooking the segregation between ionic and polymeric species.This study employs weak segregation theory to explore the interplay between phase separation dominated by the polymer-modulated mode and the salt-out-modulated mode,corresponding to microscopic and macroscopic phase separations,respectively.By comparing diblock copolymers doped with salts to those doped with neutral solvents,we elucidate the significant role of charged species in modulating phase behavior.The phase separation mode exhibits a transition between the polymer-modulated and salt-out-modulated modes at different wavenumbers.In systems doped with neutral solvents,this transition is stepwise,while in salt-ion-doped systems,it is continuous.With a sufficiently large Flory-Huggins parameter between ions and polymers,the salt-out-modulated mode becomes dominant,promoting macrophase separation.Due to the solvation effect of salt ions,salt-doped systems are more inclined to undergo microphase separation.Furthermore,we explore factors influencing the critical wavenumber of phase separation,including doping level and the Flory-Huggins parameters between two blocks and between ions and polymeric species.Our findings reveal that in a neutral solvent environment,these factors alter only the boundary between micro-and macro-phase separations,leaving the critical wavenumber unchanged in microphase separation cases.However,in a salt-doped environment,the critical wavenumber of microphase separation varies with these parameters.This provides valuable insights into the pivotal role of electrostatics in the phase separation of salt-doped block copolymers.展开更多
Due to the complicated film formation kinetics, morphology control remains a major challenge for the development of efficient and stable all-polymer solar cells(all-PSCs). To overcome this obstacle, the sequential dep...Due to the complicated film formation kinetics, morphology control remains a major challenge for the development of efficient and stable all-polymer solar cells(all-PSCs). To overcome this obstacle, the sequential deposition method is used to fabricate the photoactive layers of all-PSCs comprising a polymer donor PTzBI-oF and a polymer acceptor PS1. The film morphology can be manipulated by incorporating amounts of a dibenzyl ether additive into the PS1 layer. Detailed morphology investigations by grazing incidence wide-angle X-ray scattering and a transmission electron microscope reveal that the combination merits of sequential deposition and DBE additive can render favorable crystalline properties as well as phase separation for PTzBI-oF:PS1 blends. Consequently, the optimized all-PSCs delivered an enhanced power conversion efficiency(PCE) of 15.21%along with improved carrier extraction and suppressed charge recombination. More importantly, the optimized all-PSCs remain over 90% of their initial PCEs under continuous thermal stress at 65 °C for over 500 h. This work validates that control over microstructure morphology via a sequential deposition process is a promising strategy for fabricating highly efficient and stable all-PSCs.展开更多
INADEQUATE(Incredible Natural Abundance DoublE QUAntum Transfer Experiment)is one of the most important techniques in revealing the carbon skeleton of organic solids in solid-state NMR spectroscopy.Nevertheless,its us...INADEQUATE(Incredible Natural Abundance DoublE QUAntum Transfer Experiment)is one of the most important techniques in revealing the carbon skeleton of organic solids in solid-state NMR spectroscopy.Nevertheless,its use for structural analysis is quite limited due to the low natural abundance of^(13)C-^(13)C connectivity(~0.01%)and thus low sensitivity.Particularly,in semi-solids like rubbers,the sensitivity will be further significantly reduced by the inefficient cross polarization from 1H to^(13)C due to molecular motions induced averaging of^(1)H-^(13)C dipolar couplings.Herein,in this study,we demonstrate that transient nuclear Overhauser effect(NOE)can be used to efficiently enhance^(13)C signals,and thus enable rapid acquisition of two-dimensional(2D)^(13)C INADEQUATE spectra of rubbers.Using chlorobutyl rubber as the model system,it is found that an overall signalto-noise ratio(SNR)enhancement about 22%can be achieved,leading to significant timesaving by about 33%as compared to the direct polarization-based INADEQUATE experiment.Further experimental results on natural rubber and ethylene propylene diene monomer(EPDM)rubber are also shown to demonstrate the robust performance of transient NOE enhanced INADEQUATE experiment.展开更多
Hair coloring has emerged as an integral part of the cosmetic industry,particularly in response to the increasing global aging phenomenon.The natural melanin analog,polydopamine(PDA),has garnered considerable attentio...Hair coloring has emerged as an integral part of the cosmetic industry,particularly in response to the increasing global aging phenomenon.The natural melanin analog,polydopamine(PDA),has garnered considerable attention as an eco-friendly hair dye,and several kinds of polymerization ways of dopamine(DA)have been proposed including alkali catalysis,metal ion catalysis,strong oxidants,and enzyme-mediated oxidation reactions and polymerizations.Yet the controllability of polymerization and potential toxicity of involved metal ions are still in question.Inspired by the photoprotective mechanism in human skin,we have developed the melanin-inspired hair dyeing strategy that allowed for the in situ oxidative polymerization of DA under ultraviolet(UV)light.This polymerization was triggered by photobase generators(PBGs),a class of compounds that produced organic bases upon UV and sunlight irradiation.The resulting hair showed an adjustable color from light brown to black by tuning the ratio of DA and PBG(DA@PBG),the concentration of DA,and light exposure time.The dyed hairs showed excellent washing resistance and superior anti-static properties.Furthermore,Hair Color Spray DA@PBG also demonstrated a desirable hair dyeing effect and excellent biosecurity by simply spraying it on the hair under sunlight.This novel sunlight-induced method provided a new direction towards the preparation of natural hair dyes and could promote the development of green and safe hair dyes in colorful and brilliant artistic-grade hair coloring.展开更多
High-entropy oxides(HEOs),offering reversible lithium storage and moderate operating potential,are considered promising negative electrodes.However,the intricate lithium storage mechanism within HE polycationic system...High-entropy oxides(HEOs),offering reversible lithium storage and moderate operating potential,are considered promising negative electrodes.However,the intricate lithium storage mechanism within HE polycationic systems remains challenging.Here,we conduct comprehensive investigations into the electrochemical properties and structu ral evolution of(CrMnCoNiZn)_(3)O_(4)(HESO)to clarify lithium storage mechanisms.Density functional theory(DFT)calculations reveal that polycationic synergy modulates the electronic structure and d-band centers of HESO,delivering fast electrode kinetics.Exhaustive in-and exsitu analyses demonstrate that the residual crystalline phases acting as seed crystals maintain the spinel/rock-salt lattice persistence under the entropy stabilization effect,lattice distortion effect,and cation synergy,which guide cation crystallization upon the electric field to drive reversible lithium storage.Such properties underlie the HESO electrode with an exceptional rate and long-term capability.This work clarifies the roles of cationic synergy and seed-crystal-driven structural reversibility,providing a blueprint for designing high-performance HEO negative electrodes for next-generation lithium-ion batteries(LIBs).展开更多
Microporous polyimides(PIM-PIs)have emerged as promising high-performance membranes for gas separation.However,achieving an optimal balance between permeability and selectivity remains a major challenge.In this study,...Microporous polyimides(PIM-PIs)have emerged as promising high-performance membranes for gas separation.However,achieving an optimal balance between permeability and selectivity remains a major challenge.In this study,we designed and synthesized a series of PIM-PIs by combining rigid dianhydrides 9-bis(trifluoromethyl)-2,3,6,7-xanthenetetracarboxylic dianhydride(6FCDA)and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)with contorted diamines,including 9,9-bis(4-aminophenyl)fluorene(FDA),9,9′-spirobifluorene-2,2′-diamine(SBFDA),and 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-5,5′-diamine-6,6′-diol(TSDA),to systematically elucidate the relationship between hierarchical microstructure and gas transport behavior.Comprehensive characterization revealed that the 6FCDA-based polymers exhibited a higher microporosity(V_(micro)/V_(total)up to 54.7%)and fractional free volume compared to their 6FDA counterparts.Gas permeation measurements showed that the 6FCDA/SBFDA membrane delivered a CO_(2)permeability of 386 Barrer and CO_(2)/CH_(4)selectivity of 30.2,exceeding the 2008 Robeson upper bound.Structure-property correlation analyses indicated that diffusion selectivity predominantly governed gas separation performance,with rigid,spirocyclic architectures suppressing chain packing to generate sub-5Åmicropores,as further validated by molecular simulations.The optimized 6FCDA/FDA membrane achieved a BET surface area of 423 m^(2)·g^(−1),while maintaining excellent mechanical strength and high thermal stability.This work establishes an effective monomer design strategy to overcome the permeability-selectivity trade-off through backbone rigidification,thereby advancing PIM-PIs for practical applications in natural gas purification and carbon capture.展开更多
The recent development of flexible display technology raised additional requirements for optical and electric properties of polyimides,accelerating the structure and property tunning of transparent polyimides.The uniq...The recent development of flexible display technology raised additional requirements for optical and electric properties of polyimides,accelerating the structure and property tunning of transparent polyimides.The unique electronic effect and steric hindrance effect of fluorine substitutions make fluorine-containing polyimides occupy an important position in the transparent polyimide family.In this work,a series of transparent aromatic polyimides were prepared from a fixed 4,4’-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)and biphenyl diamines with different substitute groups at the 2,2’,6,6’-positions.We systematically studied the effects of pendant groups on the thermal,mechanical,optical and dielectric properties of these 6FDA-based polyimides with the aid of density function theory(DFT)calculation.In particular,we paid special attention to the simple but compact fluoro group substitution.The simple fluoro substitution brought the advantages of maintaining the linearity of the backbone and dense polymer chain packing,which would minimize the weakening of polyimides’inherent thermal,dimensional and mechanical properties.Comparing with trifluoromethyl substituted polyimides with the best optical transparency,polyimides containing fluoro substitutes exhibited slightly decreased optical transparency,but increased thermal and dimensional stability and higher mechanical strength.These results could shed light on the ultimate transparent polyimide film development toward the application in extreme working condition,e.g.,the colorless polyimide substrate film for the flexible display technology.展开更多
The development of optical films with high transparency,high thermal resistance and low birefringence remains a challenge in the flexible display industry.In this work,we designed and synthesized a series of fluorinat...The development of optical films with high transparency,high thermal resistance and low birefringence remains a challenge in the flexible display industry.In this work,we designed and synthesized a series of fluorinated colorless polyimides(CPIs)materials using 2,5-substituted m-phenylenediamine diamine monomers and 1,2,4,5-cyclohexanetetracarboxylic dianhydride(CHDA).We systematically studied the effects of fluorinated group substitutions on the thermal,mechanical,optical and dielectric properties of CPI films.The introduction of alicyclic CHDA dianhydride affords high transparency and low yellowness,while the 2,5-substituted m-phenylenediamine diamines offer the CPIs with quite low birefringence as well as high glass transition temperatures.A particular CHDA/o3FBDA film with simple chemical structure stands out,exhibiting well-balanced overall properties.展开更多
Obesity,characterized by the dysregulation of energy balance in adipose tissue and other metabolic organs,is frequently accompanied by chronic low-grade inflammation.As long-acting insulin sensitizers,the organically-...Obesity,characterized by the dysregulation of energy balance in adipose tissue and other metabolic organs,is frequently accompanied by chronic low-grade inflammation.As long-acting insulin sensitizers,the organically-derivatized polyoxovanadates(POVs),can extend the dosing interval of antidiabetic drugs from hourly to almost daily.In this work,the protective activity of POVs is investigated by an eight-week in vivo experiment,in which a small amount of POVs was administrated orally to a mouse model of dietinduced obesity every day.The present study shows that administration of POVs significantly decreases the body weight of mice,reduces adipose tissue accumulation,and simultaneously reduces adipose tissue inflammation.In addition,the anti-obesogenic population of i NKT cells is protected potentially by POVs,which subsequently alleviates visceral adipose tissue inflammation in high-fat-diet(HFD)-fed mice against diet-induced obesity.By contrast,the change in body weight after POV treatment is the result of a substantial reduction in fat mass,with no obvious effects on lean body mass.These findings demonstrate that supplementary of POVs would be an effective way to combat obesity and metabolic disorders while lowering metabolic inflammation.展开更多
Comprehensive Summary With the rapid growth of soft electronic and ionotronic devices such as artificial tissues,soft luminescent devices,soft robotics,and human-machine interfaces,there is a demanding need to acceler...Comprehensive Summary With the rapid growth of soft electronic and ionotronic devices such as artificial tissues,soft luminescent devices,soft robotics,and human-machine interfaces,there is a demanding need to accelerate the development of soft ionic conductive materials.To date,the first-generation ionotronic devices are mainly based on hydrogels or ionogels.However,due to their intrinsic drawbacks,such as freezing or volatilization at extreme temperatures,and the leakage problem under external mechanical forces,the reliability of ionotronic devices under harsh conditions remains a great challenge.The advent of liquid-free ionic conductive elastomers(ICEs)has the potentials to solve the issues related to the gel-type soft conductive materials.The free ions shuttling within the ion-dissolvable polymer network enable liquid-free ICEs to exhibit unparalleled ionic conductivity and elasticity.Moreover,by tuning the composition and structure of the polymeric network,it is also feasible to integrate other desirable properties,such as self-healing ability,transparency,biocompatibility,and stimulus responsiveness,into liquid-free ICE materials.In this review,we summarize the design strategies of recently reported liquid-free ICEs,and further explore the methods to introduce multifunctionality,which originate from the rational molecular design and/or the synergy with other materials.Moreover,we highlight the representative applications of liquid-free ICEs in soft ionotronics.It is believed that liquid-free ICEs might provide a unique material platform for the next-generation ionotronics.展开更多
Developing safe and high-performance solid polymer electrolytes(SPEs) remains a critical challenge for all-solid-state batteries.Among various polymer materials,poly(ethylene oxide)(PEO) is most widely studied,while p...Developing safe and high-performance solid polymer electrolytes(SPEs) remains a critical challenge for all-solid-state batteries.Among various polymer materials,poly(ethylene oxide)(PEO) is most widely studied,while poly(vinylidene fluoride)(PVDF)has also attracted great interest recently.However,the intrinsic disadvantages of single polymers make them hardly meet the demands for practical applications.Physical blending of different types of SPEs is a simple and straightforward strategy to optimize their performance.Unfortunately,the direct blending of PEO and PVDF(or PVDF derivatives) usually leads to macrophase separation and fails to couple together.Herein,we designed and synthesized PEO-based block copolymers as compatibilizers to prevent macroscopic phase separation in PVDF/PEO blends.By tuning the interfacial compatibility,continuous nanostructures with high optical transparency are constructed through the microphase segregation.The obtained SPEs combine the merits of high mechanical modulus(380 MPa),high ionic conductivity(2.0 × 10^(-4)S cm^(-1),30 ℃),large transference number(0.60),and electrochemical stability(4.5 V).This simple and efficient chemical modification approach sheds light on alternative solutions for designing high-performance SPEs.展开更多
Innovative advancements in the development of high-performance,eco-friendly adhesives are critical for meeting the demands of diverse applications in various industries.This study reports a significant leap in adhesiv...Innovative advancements in the development of high-performance,eco-friendly adhesives are critical for meeting the demands of diverse applications in various industries.This study reports a significant leap in adhesive technology by enhancing the interfacial toughness and versatility of polyvinyl alcohol(PVA)through complexation with 1-nm Keggin-type polyoxotungstate clusters(POTs)carrying specific negative charges.The POT-PVA nanocomposites exhibit superior adhesion to hydrophilic surfaces,attributed to their high crosslinking densities and exceptional fracture energies surpassing 6.23 kJ·m^(-2).These adhesives,endowed with high flexibility and a wealth of surface hydroxyl groups,are uniquely suited for application on a wide array of substrates including glass,steel,aluminum,and beyond,demonstrating their broad applicability.Specifically,the reduction in PVA crystallinity due to the chaotropic effect of POTs,which significantly enhances polymer chain dynamics.This enhancement confers robust adhesive properties at extreme temperatures,from the cryogenic−196℃ to the high-temperature threshold of 100℃.By capitalizing on the chaotropic effects of charged POTs,the study achieves a notable enhancement in the adhesive capabilities of the POT-PVA nanocomposites,paving the way for the development of for eco-friendly and cost effective adhesives engineered to withstand extreme conditions.展开更多
基金supported by the National Natural Science Foundation of China(No.22304073)the Dongguan Science and Technology of Social Development Program(No.20231800935782)。
文摘Triple-negative breast cancer(TNBC)is one of the most lethal diseases and lack of feasible therapeutic methods.Herein,we developed a bioactive covalent organic framework(COF)for adoptive cell therapy(ACT)of TNBC.In our design,Mn^(2+)functionalized COF was employed as a bioactive CpG carrier,which could simultaneously engineer and polarize macrophages to the antitumor phenotype,via the synergistic interaction of CpG and Mn^(2+).In the in vitro experiments,the engineered macrophages were found to secret high levels of antitumor cytokines for efficient TNBC cell inhibition.In the in vivo antitumor model,bioactive COF-engineered macrophages were found to relieve the hypoxia tumor microenvironment,enabling prevention of immune cell depletion during ACT.Thus,we realized efficient TNBC therapy and metastasis inhibition with the engineered macrophages in a long-term therapy model.This work provides a promising strategy for metastatic TNBC treatment and highlights the importance of bioactive COF in biomedicine.
基金supported by the Major Research Plan of the National Natural Science Foundation of China(92372104)Guangdong Basic and Applied Basic Research Foundation(2022A1515110016)+3 种基金the Recruitment Program of Guangdong(2016ZT06C322)R&D Program of Guangzhou(2023A04J1364)Fundamental Research Funds for the Central Universities(2024ZYGXZR043)TCL Science and Technology Innovation Fund。
文摘Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents,a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking.We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane(FDEE)as single solvents.By employing quantum calculations,molecular dynamics simulations,and interpretable machine learning,we establish significant correlations between fluorination patterns and electrolyte properties.Higher fluorination levels enhance FDEE stability but decrease conductivity.The symmetry of fluorination sites is critical for stability and viscosity,while exerting minimal influence on ionic conductivity.FDEEs with highly symmetric fluorination sites exhibit favorable viscosity,stability,and overall electrolyte performance.Conductivity primarily depends on lithium-anion dissociation or association.These findings provide design principles for rational fluoroether electrolyte design,emphasizing the trade-offs between stability,viscosity,and conductivity.Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.
基金supported by the National Natural Science Foundation of China(No.22101086)Guangzhou Basic and Applied Basic Research Project(No.202201010052)Guangdong Basic and Applied Basic Research Foundation(No.2023A1515140030).
文摘Iron overload has been evidenced to contribute to obesity-associated metabolic disorders,including insulin resistance.Strategies to reduce iron levels might help manage the metabolic complications associated with obesity.Here,it is demonstrated that the specific accumulation of oleic acid-modified polyoxovanadates(OPOVs)in adipose tissue leads to the reduction of iron concentrations in adipocytes in mice fed with a high-fat diet(HFD).Conjugation of oleic acids to polyoxovanadates enables tissue-specific depletion of iron from white adipose tissue(WAT)by OPOVs,protecting mice from HFD-induced obesity and obesity-associated metabolic deteriorations.Glucose tolerance and insulin sensitivity are improved in OPOV-treated mice,which demonstrates that the OPOV-induced iron depletion can reverse the metabolic degeneration caused by HFD-induced obesity.Furthermore,a decrease in expression of the marker genes of iron overload suggests the participation of OPOVs in maintaining iron homeostasis and a potential medical application of vanadium clusters in targeting the iron overload caused by obesity.These findings underscore the potential of vanadate-based clusters tailored to address the complex interplay between iron metabolism and metabolic health.
基金supported by the Fundamental Research Funds for the Central Universities(No.2023ZYGXZR107)the TCL Science and Technology Innovation Fund。
文摘Long-chain polyamides(LCPAs)are a class of bio-based polymers that can bridge conventional polyolefins and polycondensates.In this work,taking the advantage of the amphiphilic nature of polyamide 1012(PA1012),membranes were prepared by using a non-conventional phase separation approach,namely,mixed‘non-solvents’evaporation induced phase separation(MNEIPS).PA1012 can be dissolved in a mixture of polar and non-polar solvents,both of which are non-solvents of PA1012.During the sequential evaporation of the two solvents,the phase separation of PA1012 occurred,inducing the formation of porous structures.We investigated the process of membrane formation in detail,with a specific focus on the liquid-liquid and liquid-solid phase transitions involved.Moreover,we studied the influence of critical factors,such as polymer concentration and mixed-solvent ratio,on the morphologies and properties of PA1012 membranes.This study provides new insights into the development of porous materials based on long-chain polycondensates.
基金financially supported by the National Key R&D Program of China(No.2023YFB3812400)the National Natural Science Foundation of China(No.51890871)the GJYC Program of Guangzhou(No.2024D02J0004)。
文摘The development of high-performance transparent substrates is critical for next-generation flexible electronic devices.Herein,we designed two novel meta-substituted diamines incorporating trifluoromethyl(―CF_(3))and methyl(―CH_(3))groups to synthesize colorless copolyimide(CPI)films via copolymerization with 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)/3,3′,4,4′-biphenyltetracarboxylic dianhydride(BPDA).The combination of meta-substituted architecture and substituents enables the simultaneous attainment of an ultralow dielectric constant(D_k)and high transparency.The meta-substitution geometry and electronic effects of―CF_(3)/―CH_(3) effectively suppressed charge-transfer complex(CTC)formation,expanded fractional free volume(FFV),and restricted π-electron conjugation,as validated by DFT calculations and wide-angle X-ray diffraction(WAXD)analysis.The optimized CPI film(PIA_(1)-6FDA/BPDA(10/0))achieved outstanding transmittance(T_(450)=88.15%),ultralow dielectric constant(D_(k)=2.08 at 1 k Hz),and minimal dielectric loss(D_(f)=0.0012),while maintaining robust thermal stability(T_(d5%)>523℃)and mechanical strength(σ=87.5 MPa).This work establishes a molecular engineering strategy to concurrently enhance the optical and dielectric properties,positioning meta-substituted CPIs as promising candidates for transparent flexible devices.
基金financially supported by the National Natural Science Foundation of China(No.22273026)Scientific Research Innovation Capability Support Project for Young Faculty(No.ZYGXQNJSKYCXNLZCXM-I15)+3 种基金Basic and Applied Basic Research Foundation of Guangdong Province(2024A1515012401)GJYC program of Guangzhou(No.2024D03J0002)the China Postdoctoral Science Foundation(No.2024M750938)Postdoctoral Fellowship Program of CPSF(No.GZC20240492)for their financial support。
文摘In contrast to cyclic polymers with ring-like backbones,side-chain cyclization is another intriguing structural feature that has not been extensively studied.In this study,a library of orthogonally protected monomers featuring monocyclic,dicyclic,or tricyclic pendant motifs was designed and prepared based on malic acid derivatives.Polyesters with precise chemical structures and uniform chain lengths were prepared modularly through iterative growth.Meticulous control over the chemical details allows for a close investigation of the topological effects on the polymer properties.Compared to their linear side chain counterparts,the presence of cyclic pendant groups has a significant impact on chain conformation,leading to a reduction in hydrodynamic volume and an enhancement in the glass transition temperature.These results underscore the potential of tailoring polymer properties through rational engineering of side chain topology.
基金the financial supports by the R&D program of Guangzhou(No.202102020941)the National Natural Science Foundation of China(Nos.21973031 and 22173046)the Natural Science Foundation of Guangdong Province,China(No.2019A1515011140)。
文摘There have been significant interests in recent years for incorporating dynamic bonds into polymer materials for achieving multiple functionalities,such as self-healing,recycling,stimuli-responsiveness,and so on.Nevertheless,the impact of dynamic bonds on the polymer dynamics is actually less explored.In this study,we investigate a self-healing solid-liquid elastomer(SLE),which is a dual-crosslinked network made by coupling a permanently crosslinked polydimethylsiloxane(PDMS)network with polyborosiloxane(PBS)via abundant dynamic boron/oxygen dative bonds.Proton double-quantum(DQ)NMR reveals that the crosslinking degree is reduced while the structural heterogeneity of network is enhanced with increasing PBS content,i.e.,increasing the content of dynamic boron/oxygen dative bonds.Rheological experiments clearly reveal two chain relaxation modes in the SLE samples with a characteristic relaxation time of around 2.1 s and 11.8 s,corresponding to the relaxation of coupled PBS and PDMS chains,respectively.The master curves obtained from variable-temperature frequency-dependent rheological experiments also reveal enhanced heterogeneity of chain relaxation with increasing PBS content.Finally,the impact of boron/oxygen dative bonds on the Rouse dynamics is further revealed by fast-field-cycling(FFC)NMR experiments,where the spinlattice relaxation rate(R_(1))of all SLE samples follows the same power law of R_(1)(ω)∝ω^(-0.33).Nevertheless,the incorporation of PBS did slightly increase the energy barrier of Rouse dynamics.Our study well demonstrates a combined use of rheology and solid-state NMR spectroscopy can provide piercing insights into the interplay of crosslinking structures and dynamics of polymer materials.
基金the financial support from the National Natural Science Foundation of China(Nos.22179039)the Introduced Innovative R&D Team of Guangdong(No.2021ZT09L392)+3 种基金the Fundamental Research Funds for the Central Universities(2022ZYGXZR002)Zijin Mining Group Co.,Ltd(5405-ZC-2023-00008)the Pearl River Talent Recruitment Program(2019QN01C693)the Natural Science Foundation of Guangdong Province(No.2022A1515011785).
文摘Reversible protonic ceramic electrochemical cells(R-PCECs)demonstrate great feasibility for efficient energy storage and conversion.One critical challenge for the development of R-PCECs is the design of novel air electrodes with the characteristics of high catalytic activity and acceptable durability.Here,we report a donor doping of Hf into the B-site of a cobalt-based double perovskite with a nominal formula of PrBa_(0.8)Ca_(0.2)Co_(1.9)Hf_(0.1)O_(5tδ)(PBCCHf_(0.1)),which is naturally reconfigured to a double perovskite PrBa_(0.8-x)Ca_(0.2)Co_(1.9)Hf_(0.1)-xO5tδ(PBCCHf_(0.1)-x)backbone and nano-sized BaHfO3(BHO)on the surface of PBCCHf_(0.1)x.The air electrode demonstrates enhanced catalytic activity and durability(a stable polarization resistance of 0.269Ωcm2 for~100 h at 600℃),due likely to the fast surface exchange process and bulk diffusion process.When employed as an air electrode of R-PCECs,a cell with PBCCHf_(0.1) air electrode demonstrates encouraging performances in modes of the fuel cell(FC)and electrolysis(EL)at 600℃:a peak power density of 0.998 W cm^(-2)and a current density of1.613 A cm^(-2)at 1.3 V(with acceptable Faradaic efficiencies).More importantly,the single-cell with PBCCHf_(0.1) air electrode demonstrates good cycling stability,switching back and forth from FC mode to EL mode0.5 A cm^(-2)for 200 h and 50 cycles.
基金supported by the Major Research Plan of the National Natural Science Foundation of China(No.92372104)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110016)the Recruitment Program of Guangdong(No.2016ZT06C322),and TCL Science and Technology Innovation Fund.
文摘Salt-doped block copolymers have widespread applications in batteries,fuel cells,semiconductors,and various industries,where their properties crucially depend on phase separation behavior.Traditionally,investigations into salt-doped diblock copolymers have predominantly focused on microphase separation,overlooking the segregation between ionic and polymeric species.This study employs weak segregation theory to explore the interplay between phase separation dominated by the polymer-modulated mode and the salt-out-modulated mode,corresponding to microscopic and macroscopic phase separations,respectively.By comparing diblock copolymers doped with salts to those doped with neutral solvents,we elucidate the significant role of charged species in modulating phase behavior.The phase separation mode exhibits a transition between the polymer-modulated and salt-out-modulated modes at different wavenumbers.In systems doped with neutral solvents,this transition is stepwise,while in salt-ion-doped systems,it is continuous.With a sufficiently large Flory-Huggins parameter between ions and polymers,the salt-out-modulated mode becomes dominant,promoting macrophase separation.Due to the solvation effect of salt ions,salt-doped systems are more inclined to undergo microphase separation.Furthermore,we explore factors influencing the critical wavenumber of phase separation,including doping level and the Flory-Huggins parameters between two blocks and between ions and polymeric species.Our findings reveal that in a neutral solvent environment,these factors alter only the boundary between micro-and macro-phase separations,leaving the critical wavenumber unchanged in microphase separation cases.However,in a salt-doped environment,the critical wavenumber of microphase separation varies with these parameters.This provides valuable insights into the pivotal role of electrostatics in the phase separation of salt-doped block copolymers.
基金financially supported by Guangdong Major Project of Basic and Applied Basic Research (No.2019B030302007)National Key Research and Development Program of China (No. 2019YFA0705900) funded by MOSTthe financial support by State Key Lab of Luminescent Materials and Devices,South China University of Technology (Skllmd-2022-03)。
文摘Due to the complicated film formation kinetics, morphology control remains a major challenge for the development of efficient and stable all-polymer solar cells(all-PSCs). To overcome this obstacle, the sequential deposition method is used to fabricate the photoactive layers of all-PSCs comprising a polymer donor PTzBI-oF and a polymer acceptor PS1. The film morphology can be manipulated by incorporating amounts of a dibenzyl ether additive into the PS1 layer. Detailed morphology investigations by grazing incidence wide-angle X-ray scattering and a transmission electron microscope reveal that the combination merits of sequential deposition and DBE additive can render favorable crystalline properties as well as phase separation for PTzBI-oF:PS1 blends. Consequently, the optimized all-PSCs delivered an enhanced power conversion efficiency(PCE) of 15.21%along with improved carrier extraction and suppressed charge recombination. More importantly, the optimized all-PSCs remain over 90% of their initial PCEs under continuous thermal stress at 65 °C for over 500 h. This work validates that control over microstructure morphology via a sequential deposition process is a promising strategy for fabricating highly efficient and stable all-PSCs.
基金support of National Natural Science Foundation of China(No.22173033,and 22241501)Natural Science Foundation of Guangdong Province,China(No.2023A1515011395).
文摘INADEQUATE(Incredible Natural Abundance DoublE QUAntum Transfer Experiment)is one of the most important techniques in revealing the carbon skeleton of organic solids in solid-state NMR spectroscopy.Nevertheless,its use for structural analysis is quite limited due to the low natural abundance of^(13)C-^(13)C connectivity(~0.01%)and thus low sensitivity.Particularly,in semi-solids like rubbers,the sensitivity will be further significantly reduced by the inefficient cross polarization from 1H to^(13)C due to molecular motions induced averaging of^(1)H-^(13)C dipolar couplings.Herein,in this study,we demonstrate that transient nuclear Overhauser effect(NOE)can be used to efficiently enhance^(13)C signals,and thus enable rapid acquisition of two-dimensional(2D)^(13)C INADEQUATE spectra of rubbers.Using chlorobutyl rubber as the model system,it is found that an overall signalto-noise ratio(SNR)enhancement about 22%can be achieved,leading to significant timesaving by about 33%as compared to the direct polarization-based INADEQUATE experiment.Further experimental results on natural rubber and ethylene propylene diene monomer(EPDM)rubber are also shown to demonstrate the robust performance of transient NOE enhanced INADEQUATE experiment.
基金financially supported by the National Natural Science Foundation of China(No.52225311)the Fundamental Research Funds for Central Universities.
文摘Hair coloring has emerged as an integral part of the cosmetic industry,particularly in response to the increasing global aging phenomenon.The natural melanin analog,polydopamine(PDA),has garnered considerable attention as an eco-friendly hair dye,and several kinds of polymerization ways of dopamine(DA)have been proposed including alkali catalysis,metal ion catalysis,strong oxidants,and enzyme-mediated oxidation reactions and polymerizations.Yet the controllability of polymerization and potential toxicity of involved metal ions are still in question.Inspired by the photoprotective mechanism in human skin,we have developed the melanin-inspired hair dyeing strategy that allowed for the in situ oxidative polymerization of DA under ultraviolet(UV)light.This polymerization was triggered by photobase generators(PBGs),a class of compounds that produced organic bases upon UV and sunlight irradiation.The resulting hair showed an adjustable color from light brown to black by tuning the ratio of DA and PBG(DA@PBG),the concentration of DA,and light exposure time.The dyed hairs showed excellent washing resistance and superior anti-static properties.Furthermore,Hair Color Spray DA@PBG also demonstrated a desirable hair dyeing effect and excellent biosecurity by simply spraying it on the hair under sunlight.This novel sunlight-induced method provided a new direction towards the preparation of natural hair dyes and could promote the development of green and safe hair dyes in colorful and brilliant artistic-grade hair coloring.
基金supported by the National Natural Science Foundation of China(No.22271101)the R&D Program of Guangzhou(2024A04J2497)+1 种基金the Key Laboratory of Polymer Chemistry&Physics of Ministry of Educationsupported by the High Performance Computing Platform of SCUT。
文摘High-entropy oxides(HEOs),offering reversible lithium storage and moderate operating potential,are considered promising negative electrodes.However,the intricate lithium storage mechanism within HE polycationic systems remains challenging.Here,we conduct comprehensive investigations into the electrochemical properties and structu ral evolution of(CrMnCoNiZn)_(3)O_(4)(HESO)to clarify lithium storage mechanisms.Density functional theory(DFT)calculations reveal that polycationic synergy modulates the electronic structure and d-band centers of HESO,delivering fast electrode kinetics.Exhaustive in-and exsitu analyses demonstrate that the residual crystalline phases acting as seed crystals maintain the spinel/rock-salt lattice persistence under the entropy stabilization effect,lattice distortion effect,and cation synergy,which guide cation crystallization upon the electric field to drive reversible lithium storage.Such properties underlie the HESO electrode with an exceptional rate and long-term capability.This work clarifies the roles of cationic synergy and seed-crystal-driven structural reversibility,providing a blueprint for designing high-performance HEO negative electrodes for next-generation lithium-ion batteries(LIBs).
基金financially supported by the Sinopec Seed Program Project(No.223281)State Key Laboratory of Advanced Papermaking and Paper-based Materials(No.2024ZD06)+3 种基金Guangdong Basic and Applied Basic Research Foundation(Nos.2022A1515110543 and 2023A1515110170)the Natural Science Foundation of Guangdong Province(No.2024B1515040023)Guangjuyingcai program of Guangzhou(No.2024D03J0002)111 Project(No.B18023).
文摘Microporous polyimides(PIM-PIs)have emerged as promising high-performance membranes for gas separation.However,achieving an optimal balance between permeability and selectivity remains a major challenge.In this study,we designed and synthesized a series of PIM-PIs by combining rigid dianhydrides 9-bis(trifluoromethyl)-2,3,6,7-xanthenetetracarboxylic dianhydride(6FCDA)and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)with contorted diamines,including 9,9-bis(4-aminophenyl)fluorene(FDA),9,9′-spirobifluorene-2,2′-diamine(SBFDA),and 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-5,5′-diamine-6,6′-diol(TSDA),to systematically elucidate the relationship between hierarchical microstructure and gas transport behavior.Comprehensive characterization revealed that the 6FCDA-based polymers exhibited a higher microporosity(V_(micro)/V_(total)up to 54.7%)and fractional free volume compared to their 6FDA counterparts.Gas permeation measurements showed that the 6FCDA/SBFDA membrane delivered a CO_(2)permeability of 386 Barrer and CO_(2)/CH_(4)selectivity of 30.2,exceeding the 2008 Robeson upper bound.Structure-property correlation analyses indicated that diffusion selectivity predominantly governed gas separation performance,with rigid,spirocyclic architectures suppressing chain packing to generate sub-5Åmicropores,as further validated by molecular simulations.The optimized 6FCDA/FDA membrane achieved a BET surface area of 423 m^(2)·g^(−1),while maintaining excellent mechanical strength and high thermal stability.This work establishes an effective monomer design strategy to overcome the permeability-selectivity trade-off through backbone rigidification,thereby advancing PIM-PIs for practical applications in natural gas purification and carbon capture.
基金financially supported by the Key-Area Research and Development Program of Guangdong Province(No.2020B010182002)the Recruitment Program of Guangdong(No.2016ZT06C322)the Major Program of National Natural Science Foundation of China(No.51890871)。
文摘The recent development of flexible display technology raised additional requirements for optical and electric properties of polyimides,accelerating the structure and property tunning of transparent polyimides.The unique electronic effect and steric hindrance effect of fluorine substitutions make fluorine-containing polyimides occupy an important position in the transparent polyimide family.In this work,a series of transparent aromatic polyimides were prepared from a fixed 4,4’-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)and biphenyl diamines with different substitute groups at the 2,2’,6,6’-positions.We systematically studied the effects of pendant groups on the thermal,mechanical,optical and dielectric properties of these 6FDA-based polyimides with the aid of density function theory(DFT)calculation.In particular,we paid special attention to the simple but compact fluoro group substitution.The simple fluoro substitution brought the advantages of maintaining the linearity of the backbone and dense polymer chain packing,which would minimize the weakening of polyimides’inherent thermal,dimensional and mechanical properties.Comparing with trifluoromethyl substituted polyimides with the best optical transparency,polyimides containing fluoro substitutes exhibited slightly decreased optical transparency,but increased thermal and dimensional stability and higher mechanical strength.These results could shed light on the ultimate transparent polyimide film development toward the application in extreme working condition,e.g.,the colorless polyimide substrate film for the flexible display technology.
基金supported by the Natural Science Foundation of Guangdong Province(No.2022A1515010125)the Key-Area Research and Development Program of Guangdong Province(No.2020B010182002)+5 种基金the Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110543)the R&D Program of Guangzhou(No.2023A04J1577)the Major Program of National Natural Science Foundation of China(No.51890871)the Recruitment Program of Guangdong(No.2016ZT06C322)the 111 Project(No.B18023)Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application at Soochow University.
文摘The development of optical films with high transparency,high thermal resistance and low birefringence remains a challenge in the flexible display industry.In this work,we designed and synthesized a series of fluorinated colorless polyimides(CPIs)materials using 2,5-substituted m-phenylenediamine diamine monomers and 1,2,4,5-cyclohexanetetracarboxylic dianhydride(CHDA).We systematically studied the effects of fluorinated group substitutions on the thermal,mechanical,optical and dielectric properties of CPI films.The introduction of alicyclic CHDA dianhydride affords high transparency and low yellowness,while the 2,5-substituted m-phenylenediamine diamines offer the CPIs with quite low birefringence as well as high glass transition temperatures.A particular CHDA/o3FBDA film with simple chemical structure stands out,exhibiting well-balanced overall properties.
基金supported by the National Natural Science Foundation of China(Nos.22101086,and 21225103)Natural Science Foundation of Guangdong Province(No.2021A1515010271)+1 种基金Tsinghua University Initiative Foundation Research Program(No.20131089204)the State Key Laboratory of Natural and Biomimetic Drugs(No.K20160202)。
文摘Obesity,characterized by the dysregulation of energy balance in adipose tissue and other metabolic organs,is frequently accompanied by chronic low-grade inflammation.As long-acting insulin sensitizers,the organically-derivatized polyoxovanadates(POVs),can extend the dosing interval of antidiabetic drugs from hourly to almost daily.In this work,the protective activity of POVs is investigated by an eight-week in vivo experiment,in which a small amount of POVs was administrated orally to a mouse model of dietinduced obesity every day.The present study shows that administration of POVs significantly decreases the body weight of mice,reduces adipose tissue accumulation,and simultaneously reduces adipose tissue inflammation.In addition,the anti-obesogenic population of i NKT cells is protected potentially by POVs,which subsequently alleviates visceral adipose tissue inflammation in high-fat-diet(HFD)-fed mice against diet-induced obesity.By contrast,the change in body weight after POV treatment is the result of a substantial reduction in fat mass,with no obvious effects on lean body mass.These findings demonstrate that supplementary of POVs would be an effective way to combat obesity and metabolic disorders while lowering metabolic inflammation.
基金Financial support from the National Natural Science Foundation of China(91856128 and U1832220)the Pearl River Talents Scheme(2016ZT06C322)+1 种基金Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices(2019B121203003)the R&D Program of Guangzhou(202102020576)was acknowledged.References。
文摘Comprehensive Summary With the rapid growth of soft electronic and ionotronic devices such as artificial tissues,soft luminescent devices,soft robotics,and human-machine interfaces,there is a demanding need to accelerate the development of soft ionic conductive materials.To date,the first-generation ionotronic devices are mainly based on hydrogels or ionogels.However,due to their intrinsic drawbacks,such as freezing or volatilization at extreme temperatures,and the leakage problem under external mechanical forces,the reliability of ionotronic devices under harsh conditions remains a great challenge.The advent of liquid-free ionic conductive elastomers(ICEs)has the potentials to solve the issues related to the gel-type soft conductive materials.The free ions shuttling within the ion-dissolvable polymer network enable liquid-free ICEs to exhibit unparalleled ionic conductivity and elasticity.Moreover,by tuning the composition and structure of the polymeric network,it is also feasible to integrate other desirable properties,such as self-healing ability,transparency,biocompatibility,and stimulus responsiveness,into liquid-free ICE materials.In this review,we summarize the design strategies of recently reported liquid-free ICEs,and further explore the methods to introduce multifunctionality,which originate from the rational molecular design and/or the synergy with other materials.Moreover,we highlight the representative applications of liquid-free ICEs in soft ionotronics.It is believed that liquid-free ICEs might provide a unique material platform for the next-generation ionotronics.
基金supported by the State Key Laboratory of Pulp and Paper Engineering (2024ZD06)the Natural Science Foundation of Guangdong Province (2024B1515040023)+2 种基金the National Natural Science Foundation of China (52173005)the GJYC Program of Guangzhou(2024D03J0002)the 111 Project (B18023)。
文摘Developing safe and high-performance solid polymer electrolytes(SPEs) remains a critical challenge for all-solid-state batteries.Among various polymer materials,poly(ethylene oxide)(PEO) is most widely studied,while poly(vinylidene fluoride)(PVDF)has also attracted great interest recently.However,the intrinsic disadvantages of single polymers make them hardly meet the demands for practical applications.Physical blending of different types of SPEs is a simple and straightforward strategy to optimize their performance.Unfortunately,the direct blending of PEO and PVDF(or PVDF derivatives) usually leads to macrophase separation and fails to couple together.Herein,we designed and synthesized PEO-based block copolymers as compatibilizers to prevent macroscopic phase separation in PVDF/PEO blends.By tuning the interfacial compatibility,continuous nanostructures with high optical transparency are constructed through the microphase segregation.The obtained SPEs combine the merits of high mechanical modulus(380 MPa),high ionic conductivity(2.0 × 10^(-4)S cm^(-1),30 ℃),large transference number(0.60),and electrochemical stability(4.5 V).This simple and efficient chemical modification approach sheds light on alternative solutions for designing high-performance SPEs.
基金This study was financially supported by the National Natural Science Foundation of China(No.22101086)Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515140030 and 2024A1515030212).
文摘Innovative advancements in the development of high-performance,eco-friendly adhesives are critical for meeting the demands of diverse applications in various industries.This study reports a significant leap in adhesive technology by enhancing the interfacial toughness and versatility of polyvinyl alcohol(PVA)through complexation with 1-nm Keggin-type polyoxotungstate clusters(POTs)carrying specific negative charges.The POT-PVA nanocomposites exhibit superior adhesion to hydrophilic surfaces,attributed to their high crosslinking densities and exceptional fracture energies surpassing 6.23 kJ·m^(-2).These adhesives,endowed with high flexibility and a wealth of surface hydroxyl groups,are uniquely suited for application on a wide array of substrates including glass,steel,aluminum,and beyond,demonstrating their broad applicability.Specifically,the reduction in PVA crystallinity due to the chaotropic effect of POTs,which significantly enhances polymer chain dynamics.This enhancement confers robust adhesive properties at extreme temperatures,from the cryogenic−196℃ to the high-temperature threshold of 100℃.By capitalizing on the chaotropic effects of charged POTs,the study achieves a notable enhancement in the adhesive capabilities of the POT-PVA nanocomposites,paving the way for the development of for eco-friendly and cost effective adhesives engineered to withstand extreme conditions.
