The management of iodine species,notorious for their environmental persistence and health risks,requires innovative materials capable of efficient capture and conversion.Herein,we report the self-assembly and characte...The management of iodine species,notorious for their environmental persistence and health risks,requires innovative materials capable of efficient capture and conversion.Herein,we report the self-assembly and characterization of a Zr-based metal-organic tetrahedron(1)functionalized with redox-active triazatriangulenium(TATA+)panels.The cage exhibits a high binding affinity for triiodide(I_(3)^(-))(ca.10^(6) M^(-1))in methanol.The strong host-vip complexation significantly facilitates the disproportionation hydrolysis of I_(2) to generate I_(3)^(-)andHOI.It also enables photocatalytic aerobic oxidation of I−into I_(3)^(-)within its cavity.Mechanistic investigations revealed the key steps involving vip-to-host photoinduced electron transfer(ET)to generate radicals I^(·)∙and 1∙and ET from 1∙to dioxygen to generate superoxide.Solid-state adsorption experiments showed the rapid removal of I_(2) and I_(3)^(-)from water by 1-NTf_(2) because of the high affinity for polyiodides.Importantly,although solid-state 1-NTf_(2) has no ability to directly adsorb I−from water,we have for the first time developed a light-driven strategy that enables removal of I^(-)−through coupled photooxidation and sequestration.This work highlights the significant potential of integrating photoredox-active moieties within stable metal-organic cages for controlling iodine binding and speciation and opens new avenues to address environmental and energy-related sequestration challenges.展开更多
While traditional bulk hydrogels have been widely used in 3D bioprinting for tissue engineering,engineered cell-loaded scaffolds still fall short of expectations because their nanoscale molecular networks impede cell ...While traditional bulk hydrogels have been widely used in 3D bioprinting for tissue engineering,engineered cell-loaded scaffolds still fall short of expectations because their nanoscale molecular networks impede cell function.Microgels,as micronsized hydrogel materials,offer significant advantages in enhancing mass transport and tissue permeability,while concurrently promoting cellular proliferation,migration,and differentiation.Incorporating microgels as bioinks into 3D bioprinting enables customization of shape,mechanical properties,and functionality,significantly expanding the applications of hydrogel materials and addressing diverse bioprinting needs.Hierarchically porous scaffolds formed by microgel assembly leverage dual-scale porosity:nanoporosity inherent in the material and microporosity originating from the assembly.This unique structure promotes tissue regeneration and facilitates microtissue assembly.This review provides an overview of microgel fabrication techniques,describing their role as carriers for cells and biomolecules,as well as their applications in 3D biofabrication.Notably,we throughout present the application of microgels in 3D biofabrication.Finally,we provide an outlook on the potential applications of microgels in biomedical engineering and their integration with emerging printing technologies.展开更多
Exploring the natural availability and intrinsic bioactivity of blood-derived proteins opens new avenues for fabricating bioactive and patient-specific solutions for biomedical applications.Despite their several advan...Exploring the natural availability and intrinsic bioactivity of blood-derived proteins opens new avenues for fabricating bioactive and patient-specific solutions for biomedical applications.Despite their several advantages,their use as inks for 3D printing is limited due to suboptimal rheological properties.To address this,we propose a dual-step strategy based on the initial generation of blood protein-based bulk hydrogels encompassing pristine and photo-responsive protein mixtures to allow their mechanical granularization followed by jamming,establishing injectable and printable granular inks.In this study,two globular-based protein matrices-human platelet lysates(PL)and bovine serum albumin(BSA)-were used as granular inks for 3D printing.We hypothesize that nozzle jamming-in contrast to the typically employed centrifugal jamming-would render optimized results for the granular protein inks’processability.Printability was evaluated in filaments,scaffold grids,and convoluted structures.Taking advantage of the previously introduced photocurable moieties,post-printing photocrosslinking was used for the annealing of themicrogels,leading to increased scaffold mechanical stability and robustness.The nozzle jamming methodology imparted the best print performance and reproducibility,where PLMA-based inks outperformed the BSAMA-based.In addition,the microgel granular constructs allowed primary human-derived adipose stem cells to adhere and proliferate,whereas the PLMA-based ink demonstrated higher cell affinity and enhanced biological performance.We further demonstrated that bioinks could be developed from PLMA-based inks,showcasing high viability without compromising 3D printing performance.Overall,this study gives clear insights into the importance of the jamming process as well as the granularization outcome requirements for the obtention of highly reproducible granular inks for 3D printing.展开更多
The side-chain has a significant influence on the optical properties and aggregation behaviors of the organic small molecule acceptors,which becomes an important strategy to optimize the photovoltaic performance of or...The side-chain has a significant influence on the optical properties and aggregation behaviors of the organic small molecule acceptors,which becomes an important strategy to optimize the photovoltaic performance of organic solar cells.In this work,we designed and synthesized three brand-new nonfused ring electron acceptors(NFREAs)OC4-4Cl-Ph,OC4-4Cl-Th,and OC4-4Cl-C8 with hexylbenzene,hexylthiophene,and octyl side chains on theπ-bridge units.Compared with OC4-4Cl-Ph and OC4-4Cl-Th,OC4-4Cl-C8 with linear alkyl side chain has more red-shift absorption,which is conducive to obtaining higher short-circuit current density.Additionally,the OC4-4Cl-C8 film exhibits a longer exciton diffusion distance,and the D18:OC4-4Cl-C8 blend film displays faster hole transfer,weaker bimolecular recombination,and more efficient exciton transport.Furthermore,The D18:OC4-4Cl-C8 blend films may effectively form interpenetrating networks that resemble nanofibrils,which can facilitate exciton dissociation and charge transport.Finally,OC4-4Cl-C8-based devices can be created a marvellously power conversion efficiency(PCE)of 16.56%,which is much higher than OC4-4Cl-Ph(12.29%)-and OC4-4Cl-Th-based(11.00%)ones,being the highest PCE among the NFREA based binary devices.All in all,we have validated that side-chain engineering is an efficient way to achieve high-performance NFREAs.展开更多
To achieve highly-efficient organic light-emitting diodes(OLEDs),great efforts have been devoted into constructing thermally activated delayed fluorescence(TADF)with high horizontal dipole ratios(Θ//).Here,we propose...To achieve highly-efficient organic light-emitting diodes(OLEDs),great efforts have been devoted into constructing thermally activated delayed fluorescence(TADF)with high horizontal dipole ratios(Θ//).Here,we proposed a design strategy by integrating a rigid electron-accepting oxygen-bridged boron core with triple electron-donating groups,which exhibited a“shamrock-shape”,namely BO-3DMAC and BO-3DPAC.Benefiting from the rigid and large-planar skeletons brought by shamrock-shaped design,BO-3DMAC and BO-3DPAC exhibit highΘ//of 84%/70%and 93%/94%in neat/doped films,respectively,and finally furnish excellent external quantum efficiencies(EQEs)of up to 28.3%and 38.7%in 20 wt%doped OLEDs with sky-blue emission,as well as adequate EQEs of up to 21.0%and 16.7%in nondoped OLEDs.This work unveils a promising strategy to establish high-Θ//TADF emitters by constructing large-planar molecular structures using shamrock-shaped design.展开更多
Therapeutic vaccines,an exciting development in cancer immunotherapy,share the goal of priming of personalized antigen-specific T-cell response by precise antigen presentation of dendritic cells(DCs),but major obstacl...Therapeutic vaccines,an exciting development in cancer immunotherapy,share the goal of priming of personalized antigen-specific T-cell response by precise antigen presentation of dendritic cells(DCs),but major obstacles include insufficient antigen loading and off-target to DCs remain to their success.Here,we developed an imageable therapeutic vaccine with whole-antigen loading and target delivery constructed by ovalbumin(OVA)-biomineralized Bi_(2)S_(3) nanoparticles-pulsed DCs.Relying on the strong X-ray absorption and fluorescence labeling performance of Bi_(2)S_(3)@OVA nanoparticles,the in vivo spatiotemporal fate of the vaccine(Bi_(2)S_(3)@OVA@DC)can be noninvasively monitored by computed tomography and near-infrared fluorescence imaging in real time.The Bi_(2)S_(3)@OVA@DC can rapidly and durably accumulate in draining lymph nodes and thus trigger stronger T-cell responses compared to OVA-pulsed DCs.Meanwhile,Bi_(2)S_(3)@OVA@DC can further achieve in vivo antitumor effects against OVA-expressing B16F10 melanoma when combined with fractionated radiotherapy,resulting from the upregulation of cytotoxic CD8^(+)T cells and restraint of regulatory T cells in the tumor microenvironment,and the systemical secretion of OVA-specific IgG1/IgG2α antibody.Overall,we successfully fabricated an engineered DC vaccine featured in high whole-antigen loading capacity that can be precisely delivered to the lymphatic system for visualization,serving as a powerful therapeutic platform for cancer radioimmunotherapy.展开更多
The structural tautomerism of nanoclusters plays an indispensable role in establishing dynamic structure-activity relationship models and designing nanocluster-based intelligent functional materials,yet precise contro...The structural tautomerism of nanoclusters plays an indispensable role in establishing dynamic structure-activity relationship models and designing nanocluster-based intelligent functional materials,yet precise control of this dynamic process remains challenging.This study proposes a steric-hindrance-driven conformational switching strategy,achieving spatial torsion of a Au_(1)(SR)_(2) motif on Au24(SR)16 nanoclusters.The conformational transition alters spatial proximity and electron cloud density of Au_(24)(SR)_(16),thereby modulating reaction kinetics to trigger or inhibit its global structural tautomerism.Crystallographic analysis and density functional theory(DFT)calculations confirm that ligand steric effects and metal-ligand interactions govern the tautomeric pathway.The equilibrium dynamics of this tautomeric system demonstrates pronounced temperature dependence,wherein a mathematical relationship between the absorbance and temperature is established,thus endows it with the function of a nano-thermometer,showing a temperature measurement error of≤0.3℃.In addition,this conformational switching strategy is demonstrated to be extensible to other gold nanocluster systems,thereby establishing its broad applicability.This work offers a paradigm for designing functional nanomaterials through dynamic conformational reconstruction.展开更多
Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric...Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric endohedral metallo-fullerene superatoms based on their own bonding properties.Specifically,stable mirror-symmetric sinister and rectus structures are obtained by selecting a super-atom capable of forming four chemical bonds as the chiral center.Further analysis shows that the chiral vibration frequency of superatomic assemblies can be as low as a few wavenumbers,which greatly expands the range of chiral spectra com-pared to atom-based molecules.We term this type of chirality based on superatoms as“superatomic-based chirality”.It is anticipated that this work will significantly expand the variety of chiral structures at the atomic level.展开更多
The conversion of the biomass into eco-friendly fuels and chemicals has been exten-sively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society.Lignin,as a kind of promising...The conversion of the biomass into eco-friendly fuels and chemicals has been exten-sively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society.Lignin,as a kind of promising biomass energy,has been certified to produce the high-valued chemicals and fuels.Numerous efforts have been made to develop various catalysts for lignin catalytic conversion.Both metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)belong to very important heterogeneous porous catalysts due to their regular porous struc-tures,high specific surface area,and precisely tailored diversities.In the review,thefirst part focused on the catalytic conversion of lignin,lignin model compounds,and lignin derivatives using the pristine MOFs,functional MOF composites,and MOF-derived materials.The second part summarized the catalytic conversion of lignin model compounds using pristine COFs and functional COF composites.The review here mainly concentrated on the design of the materials,screening of catalytic conditions,and explorations of the corresponded mechanisms.Specifically,(1)we summarized the MOF-and COF-based materials for the effects on the catalytic trans-formation of lignin-related substances;(2)we emphasized the catalytic mechanism of C–C and C–O bonds cleavage together with the structure–activity relationships;(3)we in-depth realized the relationship between the chemical/electronic/structural properties of the MOF-and COF-based catalysts and their catalytic performance for lignin-related substances.Finally,the challenges and future perspectives were also discussed on the catalytic conversion of lignin-related substances by MOF-and COF-based catalysts.展开更多
Exciton binding energy(E_(b))has been regarded as a critical parameter in charge separation during photovoltaic conversion.Minimizing the E_(b) of the photovoltaic materials can facilitate the exciton dissociation in ...Exciton binding energy(E_(b))has been regarded as a critical parameter in charge separation during photovoltaic conversion.Minimizing the E_(b) of the photovoltaic materials can facilitate the exciton dissociation in low-driving force organic solar cells(OSCs)and thus improve the power conversion efficiency(PCE);nevertheless,diminishing the E_(b) with deliberate design principles remains a significant challenge.Herein,bulky side chain as steric hindrance structure was inserted into Y-series acceptors to minimize the E_(b) by modulating the intra-and intermolecular interaction.Theoretical and experimental results indicate that steric hindrance-induced optimal intra-and intermolecular interaction can enhance molecular polarizability,promote electronic orbital overlap between molecules,and facilitate delocalized charge trans-fer pathways,thereby resulting in a low E_(b).The conspicuously reduced E_(b) obtained in Y-ChC5 with pinpoint steric hindrance modulation can minimize the detrimental effects on exciton dissociation in low-driving-force OSCs,achieving a remarkable PCE of 19.1%with over 95%internal quantum efficiency.Our study provides a new molecular design rationale to reduce the E_(b).展开更多
The relaxation time under zero field reflects the memory retention capabilities of single-molecule magnets(SMMs)when used as storage devices.Intermolecular magnetic dipole interaction is ubiquitous in aggregates of ma...The relaxation time under zero field reflects the memory retention capabilities of single-molecule magnets(SMMs)when used as storage devices.Intermolecular magnetic dipole interaction is ubiquitous in aggregates of magnetic molecules and can greatly influence relaxation times.However,such interaction is often considered harmful and challenging to manipulate in molecular solids,especially for high-performance lanthanide single-ion magnets(SIMs).By an elaborately designed combination of ion pairing and hydrogen bonding,we have synthesized two pseudo-D_(5h) SIMs with supramolecular arrangements of magnetic dipoles in staggered and side-by-side patterns,the latter of which exhibits a 10^(4)-fold slower zero-field relaxation time at 2 K.Intriguingly,the side-by-side complex exhibits a significantly accelerated magnetic relaxation upon diamagnetic dilution,contrary to the general trend observed in the staggered complex.This strongly reveals the presence of aggregation-induced suppression of quantum tunneling in a side-by-side arrangement,which has not been observed in mononuclear SMMs.By leveraging ion-pairing aggregation and converting to a side-by-side pattern,this study successfully demonstrates an approach to transform a harmful intermolecular dipole interaction into a beneficial one,achieving a τ_(QTM) of 980 s ranking among the best-performance SMMs.展开更多
Buckybowl structures as non-uniform electrostatic potential distributions of poly-cyclic aromatic materials show a unique photoelectric performance.In this work,OTC was utilized for dynamic modulation of triplet excit...Buckybowl structures as non-uniform electrostatic potential distributions of poly-cyclic aromatic materials show a unique photoelectric performance.In this work,OTC was utilized for dynamic modulation of triplet exciton transition processes.Five host molecules with different functional units were selected,thus providing dif-ferent intermolecular interactions in the host/vip systems.Therefore,the delayed emissions were regulated from 536 to 624 nm via the tuning of the triplet exciton transition processes of OTC in different hosts.Experimental data and theoretical calculations revealed that the varied triplet transition behaviors resulted from the competition between the intersystem crossing(ISC)process of OTC-monomer and the reverse intersystem crossing(RISC)process of OTC-aggregates.This work proves the superior structure of buckybowl-based luminophore for controlling triplet exciton transition processes and supplies a new perspective for persistent afterglow luminophore design.展开更多
The combination of super-resolution microscopy and synthetic fluorescence probes has emerged as a universal tool to monitor dynamic biological events at the nanometer scale.However,the limited site-specificity and flu...The combination of super-resolution microscopy and synthetic fluorescence probes has emerged as a universal tool to monitor dynamic biological events at the nanometer scale.However,the limited site-specificity and fluorogenicity of synthetic fluorescent probes make it still difficult to realize long-term super-resolution imaging.Herein,we introduce a dynamic aggregation mediated SNAP-tag fluorogenic probe,BGAN-Aze,which can specifically bind to various SNAP-tag fusion proteins with 41-fold fluorescence enhancement.The equilibrium between the non-fluorescent aggregate/dimer(A–D)and the fluorescent monomer(M)of BGAN-Aze acts as an effective method to reduce the fluorescence background and endow BGAN-Aze with the capability of conducting washing-free super-resolution imaging of various intracellular and extracellular proteins.Using this probe,we monitored multiple dynamic biological events,such as MMC,mitophagy,the fusion of nucleolus,and the growth and contact of filopodia.We expect that BGAN-Aze will become a widely used SNAP-tag for super-resolution imaging of dynamic biological events and the A-D-M equilibrium can be a general strategy for designing fluorogenic probes.展开更多
Activity-based approaches for designing AIEgens possess prominent advantages including high selectivity,sensitivity,and signal-to-noise ratio,and they have received more attention in recent years.Excellent activatable...Activity-based approaches for designing AIEgens possess prominent advantages including high selectivity,sensitivity,and signal-to-noise ratio,and they have received more attention in recent years.Excellent activatable AIE probes have been reported for detecting toxic substances,imaging intracellular active molecules/biomolecules,as well as monitoring the activity of overexpressed enzymes in cancers.Moreover,the majority of activatable theranostic AIEgens can be specifically triggered in cancer cells and can kill these cells under light irradiation,while they have no distinct effect on normal cells,demonstrating satisfactory therapeutic selectivity that is superior to that of traditional chemotherapy.Thus,in this review,we systematically summarized the development of activatable AIE bioprobes in recent years from molecular design principles to biological applications.The challenges of activatable AIE probes and the corresponding solutions are described.We hope that the information provided in this review will facilitate the design of more activatable AIE probes to promote practical application of corresponding AIEgens.展开更多
Radioactive iodine produced from nuclear fission in power plants presents substantial environmental risks and requires effective remediation measures.Metal-organic frameworks(MOFs)containing specifically designed pore...Radioactive iodine produced from nuclear fission in power plants presents substantial environmental risks and requires effective remediation measures.Metal-organic frameworks(MOFs)containing specifically designed pore geometries with stable skeletons that allow dense packing of vip molecules are sought after for iodine capture.Here,14 new MOFs were developed through reticular chemistry for a comprehensive study of the iodine capture behavior.Remarkably,one of this family of materials,JOU-20(FeCo_(2)),exhibited an exceptional static vapor iodine uptake capacity of 3.08 g/g at 80℃and a high iodine storage density of 4.69 g/cm^(3).Significantly,single-crystal X-ray diffraction revealed the adsorbed iodine in JOU-20(FeCo_(2))forming an unusual aggregation of the giant trigonal antiprismatic polyiodide anion[I_(13)]^(−).To the best of our knowledge,this is the first time that the polyiodide[I_(13)]^(−)was structurally resolved in a crystalline framework,and it represents the most iodine-rich polyiodide species ever discovered experimentally.Combined spectroscopy and theoretical calculation methods demonstrated that nitrogen/sulfur sites and metal nodes play critical roles in stabilizing[I_(13)]^(−).This work introduces a pore partition strategy to create a confined space with specific pore geometry for the formation of unusual polyiodide[I_(13)]^(−),and multiple binding sites for stabilizing it,which significantly enhances the iodine adsorption performance of MOFs.展开更多
Poly-substituted olefins,one of the most important aggregation-induced emission luminogens(AIEgens),have garnered significant attention due to their various applications in chemical-and bio-sensing,bio-imaging,and opt...Poly-substituted olefins,one of the most important aggregation-induced emission luminogens(AIEgens),have garnered significant attention due to their various applications in chemical-and bio-sensing,bio-imaging,and opto-electronics.However,the synthetic methods for these olefins remain limited,impeding the progress of AIEgens.This study introduces an unprecedented cross-coupling reaction between aryl sulfonium triflates and tosylhydrazones from naturally abundant thioethers and ketones.The generality of this method is exemplified by the facile synthesis of over forty poly-substituted olefins.Importantly,the luminescent properties of these AIEgens(e.g.,quantum yield and emission color)can be easily tuned by adjusting the substituents of the electrophile and nucleophile substrates,exhibiting excellent performance in bio-imaging.Notably,the mechanistic studies reveal the critical role ofβ-H elimination in the formation of the double bond.This contribution provides an efficient method to synthesize poly-substituted olefins,pushing forward the development of AIEgens.展开更多
Donor‒acceptor covalent organic frameworks(D‒A COFs)have been regarded as promising materials for photocatalytic water splitting because of their tunable band gaps.However,their efficiency is hindered by fast charge r...Donor‒acceptor covalent organic frameworks(D‒A COFs)have been regarded as promising materials for photocatalytic water splitting because of their tunable band gaps.However,their efficiency is hindered by fast charge recombination and low photostability.Herein,we proposed a donor structural engineering strategy for improving the photocatalytic activity of D‒A COFs to tackle these problems.Two benzothiadiazole-based D‒A COFs(DHU-COF-BB and DHU-COF-BP)with distinct donors were prepared for photocatalytic H2 evolution reaction(HER).As a comparison,DHU-COF-TB without benzothiadiazole moieties was also designed and synthesized.Impressively,the photocatalytic H2 production rate of DHU-COFBB reaches 12.80 mmol g^(−1)h^(−1)under visible light irradiation(≥420 nm),which was nearly 2.0 and 3.1 times higher than that of DHU-COF-BP(6.47 mmol g^(−1)h^(−1))and DHU-COF-TB(4.06 mmol g^(−1)h^(−1)),respectively.In addition,the apparent quantum efficiency(AQE)of DHU-COF-BB was up to 5.04%at 420 nm.Photocatalytic and electrochemical measurements indicate that the enhanced hydrogen evolution activity of DHU-COF-BB can be ascribed to the introduction of appropriate benzene moiety into the donors,which increases the charge separation efficiency and thereby suppresses the electron‒hole recombination.Density functional theory(DFT)calculations revealed that both triphenylamine and benzothiadiazole units are the main active sites for HER over the DHU-COF-BB.This work provides new insight into the photocatalytic hydrogen production activity of D‒A COFs by a donor structural engineering strategy.展开更多
With the rapid advancement of wearable electronics and bioelectronics,the construction of flexible energy-supplying systems that simultaneously integrate high-efficiency energy conversion,excellent body-conformability...With the rapid advancement of wearable electronics and bioelectronics,the construction of flexible energy-supplying systems that simultaneously integrate high-efficiency energy conversion,excellent body-conformability,and mechanical durability has emerged as a critical challenge urgently requiring breakthroughs in the thermoelectric field.Recently,Lei et al.have developed a robust thermoelectric elastomer that simultaneously exhibits a high thermoelectric figure of merit(ZT value),excellent tensile resilience,and low modulus.This innovation overcomes the long-standing challenge of balancing the“mechanical-electricalthermal”performance of thermoelectric materials,thereby opening up new avenues for the continuous self-powering and solidstate cooling of wearable devices.展开更多
Flexible wearables have attracted extensive interests for personal human motion sensing,intelligent disease diagnosis,and multifunctional electronic skins.How-ever,the reported flexible sensors,mostly exhibited narrow...Flexible wearables have attracted extensive interests for personal human motion sensing,intelligent disease diagnosis,and multifunctional electronic skins.How-ever,the reported flexible sensors,mostly exhibited narrow detection range,low sensitivity,limited degradability to aggravate environmental pollution from vast electronic wastes,and poor antibacterial performance to hardly improve skin dis-comfort and skin inflammation from bacterial growth under long-term wearing.Herein,bioinspired from human skin featuring highly sensitive tactile sensation with spinous microstructures for amplifying sensing sensitivity between epidermis and dermis,a wearable antibacterial degradable electronics is prepared from degrad-able elastomeric substrate with MXene-coated spinous microstructures templated from lotus leaf assembled with the interdigitated electrode.The degradable elas-tomer is facilely obtained with tunable modulus to match the modulus of human skin with improved hydrophilicity for rapid degradation.The as-obtained sensor displays ultra-low detection limit(0.2 Pa),higher sensitivity(up to 540.2 kPa^(-1)),outstand-ing cycling stability(>23,000 cycles),a wide detection range,robust degradability,and excellent antibacterial capability.Facilitated by machine learning,the collected sensing signals from the integrated sensors on volunteer's fingers to the related American Sign Language are effectively recognized with an accuracy up to 99%,showing excellent potential in wireless human movement sensing and smart machine learning-enabled human-machine interaction.展开更多
Ultrasound-generated antigens combined with TLR7/8 agonists as adjuvants have demonstrated significant anti-tumor efficacy as an in-situ vaccine.However,the use of TLR7/8 agonists can cause severe inflammatory respons...Ultrasound-generated antigens combined with TLR7/8 agonists as adjuvants have demonstrated significant anti-tumor efficacy as an in-situ vaccine.However,the use of TLR7/8 agonists can cause severe inflammatory responses.In this study,we present a novel tumor-targeting nano-adjuvant termed aPDL1-PLG/R848 NPs,which are composed of aPDL1 antibody,Fc-III-4C peptide linker(Fc-linker)and poly(L-glutamic acid)-grafted-R848.Under ultrasound irradiation,antigen-presenting cells activate immune mechanisms in vivo under dual stimulation of in situ antigens and immune adjuvants.The strategy inhibits primary tumor growth and induces a strong antigen-specific immune memory effect to prevent tumor recurrence in vivo.This work offers a safe and potent platform for an in situ cancer vaccine based on ultrasound therapy.展开更多
基金the National Natural Science Foundation of China(22201075,21971069,and 22501086)G.L.acknowledges the China Postdoctoral Science Foundation(2025M770977)the Postdoctoral Fellowship Program of CPSF(GZC20250659).
文摘The management of iodine species,notorious for their environmental persistence and health risks,requires innovative materials capable of efficient capture and conversion.Herein,we report the self-assembly and characterization of a Zr-based metal-organic tetrahedron(1)functionalized with redox-active triazatriangulenium(TATA+)panels.The cage exhibits a high binding affinity for triiodide(I_(3)^(-))(ca.10^(6) M^(-1))in methanol.The strong host-vip complexation significantly facilitates the disproportionation hydrolysis of I_(2) to generate I_(3)^(-)andHOI.It also enables photocatalytic aerobic oxidation of I−into I_(3)^(-)within its cavity.Mechanistic investigations revealed the key steps involving vip-to-host photoinduced electron transfer(ET)to generate radicals I^(·)∙and 1∙and ET from 1∙to dioxygen to generate superoxide.Solid-state adsorption experiments showed the rapid removal of I_(2) and I_(3)^(-)from water by 1-NTf_(2) because of the high affinity for polyiodides.Importantly,although solid-state 1-NTf_(2) has no ability to directly adsorb I−from water,we have for the first time developed a light-driven strategy that enables removal of I^(-)−through coupled photooxidation and sequestration.This work highlights the significant potential of integrating photoredox-active moieties within stable metal-organic cages for controlling iodine binding and speciation and opens new avenues to address environmental and energy-related sequestration challenges.
基金supported by the National Natural Science Foundation of China(NSFC)Program(No.32201183).
文摘While traditional bulk hydrogels have been widely used in 3D bioprinting for tissue engineering,engineered cell-loaded scaffolds still fall short of expectations because their nanoscale molecular networks impede cell function.Microgels,as micronsized hydrogel materials,offer significant advantages in enhancing mass transport and tissue permeability,while concurrently promoting cellular proliferation,migration,and differentiation.Incorporating microgels as bioinks into 3D bioprinting enables customization of shape,mechanical properties,and functionality,significantly expanding the applications of hydrogel materials and addressing diverse bioprinting needs.Hierarchically porous scaffolds formed by microgel assembly leverage dual-scale porosity:nanoporosity inherent in the material and microporosity originating from the assembly.This unique structure promotes tissue regeneration and facilitates microtissue assembly.This review provides an overview of microgel fabrication techniques,describing their role as carriers for cells and biomolecules,as well as their applications in 3D biofabrication.Notably,we throughout present the application of microgels in 3D biofabrication.Finally,we provide an outlook on the potential applications of microgels in biomedical engineering and their integration with emerging printing technologies.
基金supported by the European Union(EU)Horizon 2020 for the project InterLynk(Grant agreement:953169)Funda玢o para a Ciência e Tecnologia(10.54499/2022.04605.CEECIND/CP1720/CT0021,BI/UI89/10303/2022,PTDC/BTM-MAT/3201/2020,and PRT/BD/154735/2023)+3 种基金FCT/MEC(PIDDAC)Säo Paulo Research Foundation(FAPESP)grants#2018/12871-0,#2021/10844-8,and#2013/07296-2(CEPID)National Council for Scientific and Technological Development(CNPq)Coordination of Superior Level Staff Improvement(CAPES)Finance Code 001.
文摘Exploring the natural availability and intrinsic bioactivity of blood-derived proteins opens new avenues for fabricating bioactive and patient-specific solutions for biomedical applications.Despite their several advantages,their use as inks for 3D printing is limited due to suboptimal rheological properties.To address this,we propose a dual-step strategy based on the initial generation of blood protein-based bulk hydrogels encompassing pristine and photo-responsive protein mixtures to allow their mechanical granularization followed by jamming,establishing injectable and printable granular inks.In this study,two globular-based protein matrices-human platelet lysates(PL)and bovine serum albumin(BSA)-were used as granular inks for 3D printing.We hypothesize that nozzle jamming-in contrast to the typically employed centrifugal jamming-would render optimized results for the granular protein inks’processability.Printability was evaluated in filaments,scaffold grids,and convoluted structures.Taking advantage of the previously introduced photocurable moieties,post-printing photocrosslinking was used for the annealing of themicrogels,leading to increased scaffold mechanical stability and robustness.The nozzle jamming methodology imparted the best print performance and reproducibility,where PLMA-based inks outperformed the BSAMA-based.In addition,the microgel granular constructs allowed primary human-derived adipose stem cells to adhere and proliferate,whereas the PLMA-based ink demonstrated higher cell affinity and enhanced biological performance.We further demonstrated that bioinks could be developed from PLMA-based inks,showcasing high viability without compromising 3D printing performance.Overall,this study gives clear insights into the importance of the jamming process as well as the granularization outcome requirements for the obtention of highly reproducible granular inks for 3D printing.
基金National Natural Science Foundation of China,Grant/Award Numbers:52173174,51933001,22109080Natural Science Foundation of Shandong Province,Grant/Award Number:ZR2022YQ45Taishan Scholars Program,Grant/Award Numbers:tstp20221121,tsqnz20221134。
文摘The side-chain has a significant influence on the optical properties and aggregation behaviors of the organic small molecule acceptors,which becomes an important strategy to optimize the photovoltaic performance of organic solar cells.In this work,we designed and synthesized three brand-new nonfused ring electron acceptors(NFREAs)OC4-4Cl-Ph,OC4-4Cl-Th,and OC4-4Cl-C8 with hexylbenzene,hexylthiophene,and octyl side chains on theπ-bridge units.Compared with OC4-4Cl-Ph and OC4-4Cl-Th,OC4-4Cl-C8 with linear alkyl side chain has more red-shift absorption,which is conducive to obtaining higher short-circuit current density.Additionally,the OC4-4Cl-C8 film exhibits a longer exciton diffusion distance,and the D18:OC4-4Cl-C8 blend film displays faster hole transfer,weaker bimolecular recombination,and more efficient exciton transport.Furthermore,The D18:OC4-4Cl-C8 blend films may effectively form interpenetrating networks that resemble nanofibrils,which can facilitate exciton dissociation and charge transport.Finally,OC4-4Cl-C8-based devices can be created a marvellously power conversion efficiency(PCE)of 16.56%,which is much higher than OC4-4Cl-Ph(12.29%)-and OC4-4Cl-Th-based(11.00%)ones,being the highest PCE among the NFREA based binary devices.All in all,we have validated that side-chain engineering is an efficient way to achieve high-performance NFREAs.
基金Natural Science Foundation of China,Grant/Award Numbers:51733010,52073316Guangdong Basic and Applied Basic Research Foundation,Grant/Award Numbers:2022B1515020052,2021A1515110119。
文摘To achieve highly-efficient organic light-emitting diodes(OLEDs),great efforts have been devoted into constructing thermally activated delayed fluorescence(TADF)with high horizontal dipole ratios(Θ//).Here,we proposed a design strategy by integrating a rigid electron-accepting oxygen-bridged boron core with triple electron-donating groups,which exhibited a“shamrock-shape”,namely BO-3DMAC and BO-3DPAC.Benefiting from the rigid and large-planar skeletons brought by shamrock-shaped design,BO-3DMAC and BO-3DPAC exhibit highΘ//of 84%/70%and 93%/94%in neat/doped films,respectively,and finally furnish excellent external quantum efficiencies(EQEs)of up to 28.3%and 38.7%in 20 wt%doped OLEDs with sky-blue emission,as well as adequate EQEs of up to 21.0%and 16.7%in nondoped OLEDs.This work unveils a promising strategy to establish high-Θ//TADF emitters by constructing large-planar molecular structures using shamrock-shaped design.
基金National Natural Science Foundation of China,Grant/Award Numbers:22122407,12175162,32171403,12075164,31971319,21874097National Key Research Program of China,Grant/Award Number:2018YFA0208800+1 种基金Tang Scholar ProgramScientific Research Program for Young Talents of China National Nuclear Corporation and A Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘Therapeutic vaccines,an exciting development in cancer immunotherapy,share the goal of priming of personalized antigen-specific T-cell response by precise antigen presentation of dendritic cells(DCs),but major obstacles include insufficient antigen loading and off-target to DCs remain to their success.Here,we developed an imageable therapeutic vaccine with whole-antigen loading and target delivery constructed by ovalbumin(OVA)-biomineralized Bi_(2)S_(3) nanoparticles-pulsed DCs.Relying on the strong X-ray absorption and fluorescence labeling performance of Bi_(2)S_(3)@OVA nanoparticles,the in vivo spatiotemporal fate of the vaccine(Bi_(2)S_(3)@OVA@DC)can be noninvasively monitored by computed tomography and near-infrared fluorescence imaging in real time.The Bi_(2)S_(3)@OVA@DC can rapidly and durably accumulate in draining lymph nodes and thus trigger stronger T-cell responses compared to OVA-pulsed DCs.Meanwhile,Bi_(2)S_(3)@OVA@DC can further achieve in vivo antitumor effects against OVA-expressing B16F10 melanoma when combined with fractionated radiotherapy,resulting from the upregulation of cytotoxic CD8^(+)T cells and restraint of regulatory T cells in the tumor microenvironment,and the systemical secretion of OVA-specific IgG1/IgG2α antibody.Overall,we successfully fabricated an engineered DC vaccine featured in high whole-antigen loading capacity that can be precisely delivered to the lymphatic system for visualization,serving as a powerful therapeutic platform for cancer radioimmunotherapy.
基金support from the National Natural Science Foundation of China(22371003,22301001,22575001,U24A20480,and U23A2090)the Ministry of Education,the Anhui Provincial Natural Science Foundation(2308085QB40,2508085MB032)the Hunan Provincial Natural Science Foundation(2025JJ60119).
文摘The structural tautomerism of nanoclusters plays an indispensable role in establishing dynamic structure-activity relationship models and designing nanocluster-based intelligent functional materials,yet precise control of this dynamic process remains challenging.This study proposes a steric-hindrance-driven conformational switching strategy,achieving spatial torsion of a Au_(1)(SR)_(2) motif on Au24(SR)16 nanoclusters.The conformational transition alters spatial proximity and electron cloud density of Au_(24)(SR)_(16),thereby modulating reaction kinetics to trigger or inhibit its global structural tautomerism.Crystallographic analysis and density functional theory(DFT)calculations confirm that ligand steric effects and metal-ligand interactions govern the tautomeric pathway.The equilibrium dynamics of this tautomeric system demonstrates pronounced temperature dependence,wherein a mathematical relationship between the absorbance and temperature is established,thus endows it with the function of a nano-thermometer,showing a temperature measurement error of≤0.3℃.In addition,this conformational switching strategy is demonstrated to be extensible to other gold nanocluster systems,thereby establishing its broad applicability.This work offers a paradigm for designing functional nanomaterials through dynamic conformational reconstruction.
基金National Natural Science Foundation of China,Grant/Award Numbers:11974136,12174272。
文摘Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric endohedral metallo-fullerene superatoms based on their own bonding properties.Specifically,stable mirror-symmetric sinister and rectus structures are obtained by selecting a super-atom capable of forming four chemical bonds as the chiral center.Further analysis shows that the chiral vibration frequency of superatomic assemblies can be as low as a few wavenumbers,which greatly expands the range of chiral spectra com-pared to atom-based molecules.We term this type of chirality based on superatoms as“superatomic-based chirality”.It is anticipated that this work will significantly expand the variety of chiral structures at the atomic level.
基金National Natural Science Foundation of China,Grant/Award Numbers:22101089,22225109,22175094,21871141,21871142,22071109,92061101Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110836Open Fund of Energy and Materials Chemistry Joint Laboratory of SCNU and TINCI,Grant/Award Number:SCNU-TINCI-202204。
文摘The conversion of the biomass into eco-friendly fuels and chemicals has been exten-sively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society.Lignin,as a kind of promising biomass energy,has been certified to produce the high-valued chemicals and fuels.Numerous efforts have been made to develop various catalysts for lignin catalytic conversion.Both metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)belong to very important heterogeneous porous catalysts due to their regular porous struc-tures,high specific surface area,and precisely tailored diversities.In the review,thefirst part focused on the catalytic conversion of lignin,lignin model compounds,and lignin derivatives using the pristine MOFs,functional MOF composites,and MOF-derived materials.The second part summarized the catalytic conversion of lignin model compounds using pristine COFs and functional COF composites.The review here mainly concentrated on the design of the materials,screening of catalytic conditions,and explorations of the corresponded mechanisms.Specifically,(1)we summarized the MOF-and COF-based materials for the effects on the catalytic trans-formation of lignin-related substances;(2)we emphasized the catalytic mechanism of C–C and C–O bonds cleavage together with the structure–activity relationships;(3)we in-depth realized the relationship between the chemical/electronic/structural properties of the MOF-and COF-based catalysts and their catalytic performance for lignin-related substances.Finally,the challenges and future perspectives were also discussed on the catalytic conversion of lignin-related substances by MOF-and COF-based catalysts.
基金National Natural Science Foundation of China,Grant/Award Numbers:52203225,52073122,22375077,22008184Key R&D Project of Hubei Province,Grant/Award Number:2022BAA095+3 种基金Hubei Natural Science Foundation,Grant/Award Number:2022CFB903Special Project from Jianghan University,Grant/Award Number:2022XKZX02Ministry of Science and Technology of China,Grant/Award Number:2021YFE0113600Excellent Discipline Cultivation Project by JHUN,Grant/Award Numbers:2023XKZ010,2023XKZ014。
文摘Exciton binding energy(E_(b))has been regarded as a critical parameter in charge separation during photovoltaic conversion.Minimizing the E_(b) of the photovoltaic materials can facilitate the exciton dissociation in low-driving force organic solar cells(OSCs)and thus improve the power conversion efficiency(PCE);nevertheless,diminishing the E_(b) with deliberate design principles remains a significant challenge.Herein,bulky side chain as steric hindrance structure was inserted into Y-series acceptors to minimize the E_(b) by modulating the intra-and intermolecular interaction.Theoretical and experimental results indicate that steric hindrance-induced optimal intra-and intermolecular interaction can enhance molecular polarizability,promote electronic orbital overlap between molecules,and facilitate delocalized charge trans-fer pathways,thereby resulting in a low E_(b).The conspicuously reduced E_(b) obtained in Y-ChC5 with pinpoint steric hindrance modulation can minimize the detrimental effects on exciton dissociation in low-driving-force OSCs,achieving a remarkable PCE of 19.1%with over 95%internal quantum efficiency.Our study provides a new molecular design rationale to reduce the E_(b).
基金National Key Research and Development Program of China,Grant/Award Number:2018YFA0306001NSFC,Grant/Award Numbers:22073115,22131011,21821003+2 种基金Pearl River Talent Plan of Guangdong,Grant/Award Number:2017BT01C161Science and Technology Projects in Guangzhou,Grant/Award Number:202201011095Guangdong Basic Research Center of Excellence for Functional Molecular Engineering。
文摘The relaxation time under zero field reflects the memory retention capabilities of single-molecule magnets(SMMs)when used as storage devices.Intermolecular magnetic dipole interaction is ubiquitous in aggregates of magnetic molecules and can greatly influence relaxation times.However,such interaction is often considered harmful and challenging to manipulate in molecular solids,especially for high-performance lanthanide single-ion magnets(SIMs).By an elaborately designed combination of ion pairing and hydrogen bonding,we have synthesized two pseudo-D_(5h) SIMs with supramolecular arrangements of magnetic dipoles in staggered and side-by-side patterns,the latter of which exhibits a 10^(4)-fold slower zero-field relaxation time at 2 K.Intriguingly,the side-by-side complex exhibits a significantly accelerated magnetic relaxation upon diamagnetic dilution,contrary to the general trend observed in the staggered complex.This strongly reveals the presence of aggregation-induced suppression of quantum tunneling in a side-by-side arrangement,which has not been observed in mononuclear SMMs.By leveraging ion-pairing aggregation and converting to a side-by-side pattern,this study successfully demonstrates an approach to transform a harmful intermolecular dipole interaction into a beneficial one,achieving a τ_(QTM) of 980 s ranking among the best-performance SMMs.
基金National Natural Scientific Foundation of China,Grant/Award Numbers:21975021,21975020,21875019,21871119,22105019,22175023Beijing National Laboratory for Molecular Sciences,Grant/Award Number:BNLMS192007BIT Research and Innovation Promoting Project,Grant/Award Number:2022YCXZ035。
文摘Buckybowl structures as non-uniform electrostatic potential distributions of poly-cyclic aromatic materials show a unique photoelectric performance.In this work,OTC was utilized for dynamic modulation of triplet exciton transition processes.Five host molecules with different functional units were selected,thus providing dif-ferent intermolecular interactions in the host/vip systems.Therefore,the delayed emissions were regulated from 536 to 624 nm via the tuning of the triplet exciton transition processes of OTC in different hosts.Experimental data and theoretical calculations revealed that the varied triplet transition behaviors resulted from the competition between the intersystem crossing(ISC)process of OTC-monomer and the reverse intersystem crossing(RISC)process of OTC-aggregates.This work proves the superior structure of buckybowl-based luminophore for controlling triplet exciton transition processes and supplies a new perspective for persistent afterglow luminophore design.
基金National Natural Science Foundation of China,Grant/Award Numbers:22078314,21878286,21908216Dalian Institute of Chemical Physics,Grant/Award Numbers:DICPI202142,DICPI201938,DICPZZBS201805+1 种基金Advanced Manufacturing and Engineering Program,Grant/Award Number:A2083c0051Ministry of Education,Singapore,Grant/Award Number:MOE-MOET2EP10120-0007。
文摘The combination of super-resolution microscopy and synthetic fluorescence probes has emerged as a universal tool to monitor dynamic biological events at the nanometer scale.However,the limited site-specificity and fluorogenicity of synthetic fluorescent probes make it still difficult to realize long-term super-resolution imaging.Herein,we introduce a dynamic aggregation mediated SNAP-tag fluorogenic probe,BGAN-Aze,which can specifically bind to various SNAP-tag fusion proteins with 41-fold fluorescence enhancement.The equilibrium between the non-fluorescent aggregate/dimer(A–D)and the fluorescent monomer(M)of BGAN-Aze acts as an effective method to reduce the fluorescence background and endow BGAN-Aze with the capability of conducting washing-free super-resolution imaging of various intracellular and extracellular proteins.Using this probe,we monitored multiple dynamic biological events,such as MMC,mitophagy,the fusion of nucleolus,and the growth and contact of filopodia.We expect that BGAN-Aze will become a widely used SNAP-tag for super-resolution imaging of dynamic biological events and the A-D-M equilibrium can be a general strategy for designing fluorogenic probes.
基金National Research Foundation of Korea,Grant/Award Number:2012R1A3A2048814National Natural Science Foundation of China,Grant/Award Number:22090011。
文摘Activity-based approaches for designing AIEgens possess prominent advantages including high selectivity,sensitivity,and signal-to-noise ratio,and they have received more attention in recent years.Excellent activatable AIE probes have been reported for detecting toxic substances,imaging intracellular active molecules/biomolecules,as well as monitoring the activity of overexpressed enzymes in cancers.Moreover,the majority of activatable theranostic AIEgens can be specifically triggered in cancer cells and can kill these cells under light irradiation,while they have no distinct effect on normal cells,demonstrating satisfactory therapeutic selectivity that is superior to that of traditional chemotherapy.Thus,in this review,we systematically summarized the development of activatable AIE bioprobes in recent years from molecular design principles to biological applications.The challenges of activatable AIE probes and the corresponding solutions are described.We hope that the information provided in this review will facilitate the design of more activatable AIE probes to promote practical application of corresponding AIEgens.
基金financially supported by the National Natural Science Foundation of China(22271103)Guangdong Provincial Basic and Applied Basic Research Foundation(2024A1515012322)+1 种基金the Postdoctoral Fund of Lianyungang City(LYG20230016)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Radioactive iodine produced from nuclear fission in power plants presents substantial environmental risks and requires effective remediation measures.Metal-organic frameworks(MOFs)containing specifically designed pore geometries with stable skeletons that allow dense packing of vip molecules are sought after for iodine capture.Here,14 new MOFs were developed through reticular chemistry for a comprehensive study of the iodine capture behavior.Remarkably,one of this family of materials,JOU-20(FeCo_(2)),exhibited an exceptional static vapor iodine uptake capacity of 3.08 g/g at 80℃and a high iodine storage density of 4.69 g/cm^(3).Significantly,single-crystal X-ray diffraction revealed the adsorbed iodine in JOU-20(FeCo_(2))forming an unusual aggregation of the giant trigonal antiprismatic polyiodide anion[I_(13)]^(−).To the best of our knowledge,this is the first time that the polyiodide[I_(13)]^(−)was structurally resolved in a crystalline framework,and it represents the most iodine-rich polyiodide species ever discovered experimentally.Combined spectroscopy and theoretical calculation methods demonstrated that nitrogen/sulfur sites and metal nodes play critical roles in stabilizing[I_(13)]^(−).This work introduces a pore partition strategy to create a confined space with specific pore geometry for the formation of unusual polyiodide[I_(13)]^(−),and multiple binding sites for stabilizing it,which significantly enhances the iodine adsorption performance of MOFs.
基金support from the National Natural Science Foundation of China(51925306,52120105006,52222309,52173187,and 52303221)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB 0520103)+3 种基金Beijing Natural Science Foundation(Z210017)the Science and Technology Innovation Commission of Shenzhen(JCYJ20220530150604009)Project of International Cooperation of Chinese Academy of Sciences(124GJHZ2023079MI)Xiaomi Young Talents Program,and Fundamental Research Funds for the Central University.
文摘Poly-substituted olefins,one of the most important aggregation-induced emission luminogens(AIEgens),have garnered significant attention due to their various applications in chemical-and bio-sensing,bio-imaging,and opto-electronics.However,the synthetic methods for these olefins remain limited,impeding the progress of AIEgens.This study introduces an unprecedented cross-coupling reaction between aryl sulfonium triflates and tosylhydrazones from naturally abundant thioethers and ketones.The generality of this method is exemplified by the facile synthesis of over forty poly-substituted olefins.Importantly,the luminescent properties of these AIEgens(e.g.,quantum yield and emission color)can be easily tuned by adjusting the substituents of the electrophile and nucleophile substrates,exhibiting excellent performance in bio-imaging.Notably,the mechanistic studies reveal the critical role ofβ-H elimination in the formation of the double bond.This contribution provides an efficient method to synthesize poly-substituted olefins,pushing forward the development of AIEgens.
基金support from the National Natural Science Foundation of China(52203006 and 22375036)the Fundamental Research Funds for the Central Universities(2232022D-06)+1 种基金the Fellowship of the China Postdoctoral Science Foundation(2022TQ0141)the Jiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB6).
文摘Donor‒acceptor covalent organic frameworks(D‒A COFs)have been regarded as promising materials for photocatalytic water splitting because of their tunable band gaps.However,their efficiency is hindered by fast charge recombination and low photostability.Herein,we proposed a donor structural engineering strategy for improving the photocatalytic activity of D‒A COFs to tackle these problems.Two benzothiadiazole-based D‒A COFs(DHU-COF-BB and DHU-COF-BP)with distinct donors were prepared for photocatalytic H2 evolution reaction(HER).As a comparison,DHU-COF-TB without benzothiadiazole moieties was also designed and synthesized.Impressively,the photocatalytic H2 production rate of DHU-COFBB reaches 12.80 mmol g^(−1)h^(−1)under visible light irradiation(≥420 nm),which was nearly 2.0 and 3.1 times higher than that of DHU-COF-BP(6.47 mmol g^(−1)h^(−1))and DHU-COF-TB(4.06 mmol g^(−1)h^(−1)),respectively.In addition,the apparent quantum efficiency(AQE)of DHU-COF-BB was up to 5.04%at 420 nm.Photocatalytic and electrochemical measurements indicate that the enhanced hydrogen evolution activity of DHU-COF-BB can be ascribed to the introduction of appropriate benzene moiety into the donors,which increases the charge separation efficiency and thereby suppresses the electron‒hole recombination.Density functional theory(DFT)calculations revealed that both triphenylamine and benzothiadiazole units are the main active sites for HER over the DHU-COF-BB.This work provides new insight into the photocatalytic hydrogen production activity of D‒A COFs by a donor structural engineering strategy.
基金support from the National Natural Science Foundation of China(No.62288102).
文摘With the rapid advancement of wearable electronics and bioelectronics,the construction of flexible energy-supplying systems that simultaneously integrate high-efficiency energy conversion,excellent body-conformability,and mechanical durability has emerged as a critical challenge urgently requiring breakthroughs in the thermoelectric field.Recently,Lei et al.have developed a robust thermoelectric elastomer that simultaneously exhibits a high thermoelectric figure of merit(ZT value),excellent tensile resilience,and low modulus.This innovation overcomes the long-standing challenge of balancing the“mechanical-electricalthermal”performance of thermoelectric materials,thereby opening up new avenues for the continuous self-powering and solidstate cooling of wearable devices.
基金National Natural Science Foundation of China,Grant/Award Numbers:52222303,51973008Joint Project of BRC-BC(Biomedical Translational Engineering Research Center of BUCT-CJFH),Grant/Award Number:XK2022-03Fundamental Research Funds for the Central Universities。
文摘Flexible wearables have attracted extensive interests for personal human motion sensing,intelligent disease diagnosis,and multifunctional electronic skins.How-ever,the reported flexible sensors,mostly exhibited narrow detection range,low sensitivity,limited degradability to aggravate environmental pollution from vast electronic wastes,and poor antibacterial performance to hardly improve skin dis-comfort and skin inflammation from bacterial growth under long-term wearing.Herein,bioinspired from human skin featuring highly sensitive tactile sensation with spinous microstructures for amplifying sensing sensitivity between epidermis and dermis,a wearable antibacterial degradable electronics is prepared from degrad-able elastomeric substrate with MXene-coated spinous microstructures templated from lotus leaf assembled with the interdigitated electrode.The degradable elas-tomer is facilely obtained with tunable modulus to match the modulus of human skin with improved hydrophilicity for rapid degradation.The as-obtained sensor displays ultra-low detection limit(0.2 Pa),higher sensitivity(up to 540.2 kPa^(-1)),outstand-ing cycling stability(>23,000 cycles),a wide detection range,robust degradability,and excellent antibacterial capability.Facilitated by machine learning,the collected sensing signals from the integrated sensors on volunteer's fingers to the related American Sign Language are effectively recognized with an accuracy up to 99%,showing excellent potential in wireless human movement sensing and smart machine learning-enabled human-machine interaction.
基金Ministry of Science and Technology of China,Grant/Award Number:2022YFE0110200Natural Science Foundation of Jilin Province,Grant/Award Number:20230101037JCNational Natural Science Foundation of China,Grant/Award Numbers:52203198,52025035。
文摘Ultrasound-generated antigens combined with TLR7/8 agonists as adjuvants have demonstrated significant anti-tumor efficacy as an in-situ vaccine.However,the use of TLR7/8 agonists can cause severe inflammatory responses.In this study,we present a novel tumor-targeting nano-adjuvant termed aPDL1-PLG/R848 NPs,which are composed of aPDL1 antibody,Fc-III-4C peptide linker(Fc-linker)and poly(L-glutamic acid)-grafted-R848.Under ultrasound irradiation,antigen-presenting cells activate immune mechanisms in vivo under dual stimulation of in situ antigens and immune adjuvants.The strategy inhibits primary tumor growth and induces a strong antigen-specific immune memory effect to prevent tumor recurrence in vivo.This work offers a safe and potent platform for an in situ cancer vaccine based on ultrasound therapy.
