Natural molecular chaperones utilize spatially ordered multiple molecular forces to effectively regulate protein folding.However,synthesis of such molecules is a big challenge.The concept of“aggregate science”provid...Natural molecular chaperones utilize spatially ordered multiple molecular forces to effectively regulate protein folding.However,synthesis of such molecules is a big challenge.The concept of“aggregate science”provides insights to construct chemical entities(aggregates)beyond molecular levels to mimic both the structure and function of natural chaperone.Inspired by this concept,herein we fabricate a novel multi-interaction(i.e.,electrostatic and hydrophobic interaction)cooperative nanochaperone(multi-co-nChap)to regulating protein folding.This multi-co-nChap is fabricated by rationally introducing electrostatic interactions to the surface(corona)and confined hydrophobic microdomains(shell)of traditional single-hydrophobic interaction nanochaperone.We demonstrate that the corona electrostatic attraction facilitates the diffusion of clients into the hydrophobic microdomains,while the shell electrostatic interaction balances the capture and release of clients.By finely synergizing corona electrostatic attraction with shell electrostatic repulsion and hydrophobic interaction,the optimized multi-co-nChap effectively facilitated de novo folding of nascent polypeptides.Moreover,the synergy between corona electrostatic attraction,shell electrostatic attraction and shell hydrophobic interaction significantly enhanced the capability of multi-co-nChap to protect native proteins from denaturation at harsh temperatures.This work provides important insights for understanding and design of nanochaperone,which is a kind of ordered aggregate with chaperone-like activity that beyond the level of single molecule.展开更多
Pure organic materials with persistent and efficient room-temperature phosphorescence have recently aroused great research interest due to their vast potential in applications.One crucial design principle for such mat...Pure organic materials with persistent and efficient room-temperature phosphorescence have recently aroused great research interest due to their vast potential in applications.One crucial design principle for such materials is to suppress as much as possible the non-radiative decay of the triplet exciton while maintaining a moderate phosphorescent radiative rate.However,molecular engineering often exhibits similar regulation trends for the two processes.Here,we propose that the quantum interference caused by aggregation can be utilized to control the phosphorescent and non-radiative decay channels.We systematically analyze various constructive and destructive transition pathways in aggregates with different molecular packing types and establish clear relationships between the luminescence characters and the signs of the singlet and triplet excitonic couplings.It is shown that the decay channels can be flexibly switched on or off by regulating the packing type and excitonic couplings.Most importantly,an enhanced phosphorescent decay and a completely suppressed non-radiative decay can be simultaneously realized in the aggregate packed with inversion symmetry.This work lays the theoretical foundation for future experimental realization of quantum interference effects in phosphorescence.展开更多
Crosslinking thermosets with hyperbranched polymers confers them superior comprehensive performance.However,it still remains a further understanding of polymer crosslinking from the molecular chains to the role of agg...Crosslinking thermosets with hyperbranched polymers confers them superior comprehensive performance.However,it still remains a further understanding of polymer crosslinking from the molecular chains to the role of aggregates.In this study,three hyperbranched polysiloxane structures(HBPSi-R)are synthesized as model macromolecules,each featuring distinct terminal groups(R denotes amino,epoxy,and vinyl groups)while similar molecular backbone(Si-O-C).These structures were subsequently copolymerized with epoxy monomers to construct interpenetrating HBPSi-R/epoxy/anhydride co-polymer systems.The spatial molecular configuration and flexible Si-O-C branches of HBPSi-R endow them with remarkable reinforcement and toughening effects.Notably,an optimum impact strength of 28.9 kJ mol^(−1) is achieved with a mere 3%loading of HBPSi-V,nearly three times that of the native epoxy(12.9 kJ mol^(−1)).By contrasting the terminal effects,the aggregation states and crosslinking modes were proposed,thus clarifying the supramolecular-dominant aggregation mechanism and covalent-dominant dispersion mechanism,which influences the resulting material properties.This work underscores the significance of aggregate science in comprehending polymer crosslinking and provides theoretical insights for tailoring material properties at a refined molecular level in the field of polymer science.展开更多
Developing new photosystems that integrate broad-band near-infrared(NIR)light harvesting and efficient charge separation is a long-sought goal in the photocatalytic community.In this work,we develop a novel photochemi...Developing new photosystems that integrate broad-band near-infrared(NIR)light harvesting and efficient charge separation is a long-sought goal in the photocatalytic community.In this work,we develop a novel photochemical strategy to prepare light-active carbon dots(CDs)under room temperature and discover that the aggregation of CDs can broaden the light absorption to the NIR region due to the electronic couplings between neighboring CDs.Importantly,the dynamic noncovalent interactions within CD aggregates can stabilize symmetry breaking and thus induce large dipole moments for charge separation and transfer.Furthermore,the weak non-covalent interactions allow for flexible design of the aggregated degrees and the local electronic structures of CD aggregates,further strengthening NIR-light harvesting and charge separation efficiency.As a result,the CD aggregates achieve a record apparent quantum yield of 13.5%at 800 nm,which is one of the best-reported values for NIR-light-driven hydrogen photosynthesis to date.Moreover,we have prepared a series of different CDs and also observed that these CDs after aggregation all exhibit outstanding NIR-responsive photocatalytic hydrogen production activity,suggesting the universality of aggregation-enhanced photocatalysis.This discovery opens a new promising platform for using CD aggregates as efficient light absorbers for solar conversion.展开更多
Nowadays,cancer has become the leading cause of death worldwide,driving the need for effective therapeutics to improve patient prognosis.Photodynamic therapy(PDT)has been widely applied as an antitumor modality,owing ...Nowadays,cancer has become the leading cause of death worldwide,driving the need for effective therapeutics to improve patient prognosis.Photodynamic therapy(PDT)has been widely applied as an antitumor modality,owing to its minimal invasiveness,localized tumor damage,and high safety profile.However,its efficacy is limited by poor stability of photosensitizers,inadequate tumor accumulation,and a complex tumor microenvironment.To overcome these challenges,extensive endeavors have been made to explore the co-assembly of the widely used photosensitizer chlorin e6(Ce6)with various functional small molecules to enhance pharmacodynamic activity.This review provides a comprehensive overview of current studies on Ce6-based nanoparticles for effective PDT and precise delivery of functional molecules.The self-assembly mechanism will be discussed in detail,with a focus on potential strategies for combinational therapy with PDT.展开更多
Metal nanoclusters possess excellent electrochemical,optical,and catalytic properties,but correlating these properties remains challenging,which is the foundation to generate electrochemiluminescence(ECL).Herein,we re...Metal nanoclusters possess excellent electrochemical,optical,and catalytic properties,but correlating these properties remains challenging,which is the foundation to generate electrochemiluminescence(ECL).Herein,we report for the first time that a structurally determined Pt1Ag18 nanocluster generates intense ECL and simultaneously enhances the ECL of carbon dots(CDs)via an electrocatalytic effect.Pt^(1)Ag_(18)nanocluster show aggregation-induced emission enhancement and aggregation-induced ECL enhancement under light and electrochemical stimulation,respectively.In the presence of tripropylamine(TPrA)as a coreactant,solid Pt1Ag18 shows unprecedented ECL efficiency,which is more than nine times higher than that of 1 mM Ru(bpy)32+with the same TPrA concentration.Potential-resolved ECL spectra reveal two ECL emission bands in the presence of TPrA.The ECL emission centered at 650 nm is assigned to the solid Pt_(1)Ag_(18)nanocluster,consistent with the peak wavelength in self-annihilation ECL and photoluminescence of the solid state.The ECL emission centered at 820 nm is assigned to the CDs on the glassy carbon electrode.The electrocatalytic effect of the nanoclusters enhanced the ECL of the CDs by a factor of more than 180 in comparison to that without nanoclusters.Based on the combined optical and electrochemical results,the ECL generation pathways and mechanisms of Pt1Ag18 and CDs are proposed.These findings are extremely promising for designing multifunctional nanocluster luminophores with strong emissions and developing ratiometric sensing devices.展开更多
High-pressure chemistry has provided a huge boost to the development of scientific community.Pressure-induced emission(PIE)in halide perovskites is gradually showing its unique charm in both pressure sensing and optoe...High-pressure chemistry has provided a huge boost to the development of scientific community.Pressure-induced emission(PIE)in halide perovskites is gradually showing its unique charm in both pressure sensing and optoelectronic device applications.Moreover,the PIE retention of halide perovskites under ambient conditions is of great commercial value.Herein,we mainly focus on the potential applications of PIE and PIE retention in metal halide perovskites for scintillators and solid-state lighting.Based on the performance requirements of scintillator and single-component white light-emitting diodes(WLEDs),the significance of PIE and PIE retention is critically clarified,aiming to design and synthesize materials used for high-performance optoelectronic devices.This perspective not only demonstrates promising applications of PIE in the fields of scintillators and WLEDs,but also provides potential applications in display imaging and anti-counterfeiting of PIE materials.Furthermore,solving the scientific disputes that exist under ambient conditions is also simply discussed as an outlook by introducing high-pressure dimension to produce PIE.展开更多
Rheumatoid arthritis(RA)is a debilitating autoimmune disease that causes chronic pain and serious complications,presenting a significant challenge to treat.Promising approaches for treating RA involve signaling pathwa...Rheumatoid arthritis(RA)is a debilitating autoimmune disease that causes chronic pain and serious complications,presenting a significant challenge to treat.Promising approaches for treating RA involve signaling pathways modulation and targeted therapy.To this end,a multifunctional nanosystem,TPC-U@HAT,has been designed for RA therapy,featuring multitargeting,dual-stimuli response,and on-demand drug release capabilities.TPC-U@HAT is composed of a probe/prodrug TPC,a JAK1 kinase inhibitor upadacitinib,and the drug carrier HAT.TPC is composed of an aggregation-induced emission(AIE)-active NIR-II chromophore TPY and an NF-κB/NLRP3 inhibitor caffeic acid phenethyl ester(CAPE),connected via boronic ester bond which serves as the reactive-oxygen-species-responsive linker.The carrier,HAT,is created by grafting bone-targeting alendronate and hydrophobic tocopheryl succinate onto hyaluronic acid chains,which can encapsulate TPC and upadacitinib to form TPC-U@HAT.Upon intravenous injection into mice,TPC-U@HAT accumulates at inflamed lesions of RA through both active and passive targeting,and the overexpressed hyaluronidase and H_(2)O_(2) therein cleave the hyaluronic acid polymer chains and boronate bonds,respectively.This generates an AIE-active chromophore for detection and therapeutic evaluation of RA via both optoacoustic imaging and NIR-II fluorescent imaging and concomitantly releases CAPE and upadacitinib to exert efficacious therapy by inhibiting NF-κB/NLRP3 and JAK-STAT pathways.展开更多
Three-dimensional(3D)printing is an emerging technique that has shown promising success in engineering human tissues in recent years.Further development of vatphotopolymerization printing modalities has significantly ...Three-dimensional(3D)printing is an emerging technique that has shown promising success in engineering human tissues in recent years.Further development of vatphotopolymerization printing modalities has significantly enhanced the complexity level for 3D printing of various functional structures and components.Similarly,the development of microfluidic chip systems is an emerging research sector with promising medical applications.This work demonstrates the coupling of a digital light processing(DLP)printing procedure with a microfluidic chip system to produce size-tunable,3D-printable porosities with narrow pore size distributions within a gelatin methacryloyl(GelMA)hydrogel matrix.It is found that the generation of size-tunable gas bubbles trapped within an aqueous GelMA hydrogel-precursor can be controlled with high precision.Furthermore,the porosities are printed in two-dimensional(2D)as well as in 3D using the DLP printer.In addition,the cytocompatibility of the printed porous scaffolds is investigated using fibroblasts,where high cell viabilities as well as cell proliferation,spreading,and migration are confirmed.It is anticipated that the strategy is widely applicable in a range of application areas such as tissue engineering and regenerative medicine,among others.展开更多
Aggregation-induced emission(AIE)is a unique phenomenon whereby aggregation of molecules induces fluorescence emission as opposed to the more commonly known aggregation-caused quenching(ACQ).AIE has the potential to b...Aggregation-induced emission(AIE)is a unique phenomenon whereby aggregation of molecules induces fluorescence emission as opposed to the more commonly known aggregation-caused quenching(ACQ).AIE has the potential to be utilized in the large-scale production of AIE-active polymeric materials because of their wide range of practical applications such as stimuli-responsive sensors,biological imaging agents,and drug delivery systems.This is evident from the increasing number of publications over the years since AIE was first discovered.In addition,the evergrowing interest in this field has led many researchers around the world to develop new and creative methods in the design of monomers,initiators and crosslinkers,with the goal of broadening the scope and utility of AIE polymers.One of the most promising approaches to the design and synthesis of AIE polymers is the use of the reversible-deactivation radical polymerization(RDRP)techniques,which enabled the production of well-controlled AIE materials that are often difficult to achieve by other methods.In this review,a summary of some recent works that utilize RDRP for AIE polymer design and synthesis is presented,including(i)the design of AIE-related monomers,initiators/crosslinkers;the achievements in preparation of AIE polymers using(ii)reversible addition–fragmentation chain transfer(RAFT)technique;(iii)atom transfer radical polymerization(ATRP)technique;(iv)other techniques such as Cu(0)-RDRP technique and nitroxide-mediated polymerization(NMP)technique;(v)the possible applications of these AIE polymers,and finally(vi)a summary/perspective and the future direction of AIE polymers.展开更多
The photothermal conversion capacity of pristine organic phase change materials(PCMs)is inherently insufficient in solar energy utilization.To upgrade their photothermal conversion capacity,we developed bimetallic zeo...The photothermal conversion capacity of pristine organic phase change materials(PCMs)is inherently insufficient in solar energy utilization.To upgrade their photothermal conversion capacity,we developed bimetallic zeolitic imidazolate framework(ZIF)derived Co/N co-doped flower-like carbon(Co/N-FLC)-based composite PCMs toward solar energy harvesting.3D interconnected carbon framework with low interfacial thermal resistance,abundant carbon defects and high content of nitrogen doping,excellent localized surface plasmon resonance(LSPR)effect of Co nanoparticles,and light absorber Co_(3)ZnC in Co/N-FLC synergistically upgrade the photothermal capacity of(polyethylene glycol)PEG@Co/N-FLC composite PCMs with an ultrahigh photothermal conversion efficiency of 94.8%under 0.16 W/cm^(2).Uniformly anchored Co and Co_(3)ZnC nanoparticles in carbon framework guarantee excellent photon capture ability.Bridging carbon nanotubes(CNTs)in 2D carbon nanosheets further accelerate the rapid transport of phonons by constructing cross-connected heat transfer paths.Additionally,PEG@Co/N-FLC exhibits a thermal energy storage density of 100.69 J/g and excellent thermal stability and durable reliability.Therefore,PEG@Co/N-FLC composite PCMs are promising candidates to accelerate the efficient utilization of solar energy.展开更多
Antibiotic resistance is a major challenge in the clinical treatment of bacterial infectious diseases.Herein,we constructed a multifunctional DNA nanoplatform as a versatile carrier for bacteria-specific delivery of c...Antibiotic resistance is a major challenge in the clinical treatment of bacterial infectious diseases.Herein,we constructed a multifunctional DNA nanoplatform as a versatile carrier for bacteria-specific delivery of clinical antibiotic ciprofloxacin(CIP)and classic nanoantibiotic silver nanoparticles(AgNP).In our rational design,CIP was efficiently loaded in the self-assembly double-bundle DNA tetrahedron through intercalation with DNA duplex,and single-strand DNA-modified AgNP was embedded in the cavity of the DNA tetrahedron through hybridization.With the site-specific assembly of targeting aptamer in the well-defined DNA tetrahedron,the bacteria-specific dual-antibiotic delivery system exhibited excellent combined bactericidal properties.With enhanced antibiotic accumulation through breaking the out membrane of bacteria,the antibiotic delivery system effectively inhibited biofilm formation and promoted the healing of infected wounds in vivo.This DNAbased antibiotic delivery system provides a promising strategy for the treatment of antibiotic-resistant infections.展开更多
The design of novel materials for sulfur dioxide(SO_(2))capture and conversion with considerable efficiency under mild conditions is of great significance for human health and environmental protection yet highly chall...The design of novel materials for sulfur dioxide(SO_(2))capture and conversion with considerable efficiency under mild conditions is of great significance for human health and environmental protection yet highly challenging.Herein,we report a series of triazine-based multicomponent metallacages via coordination-driven self-assembly of 2,4,6-tri(4-pyridyl)-1,3,5-triazine,cis-Pt(PEt3)2(OTf)2 and different tetracarboxylic ligands.As the increase of the length of the tetracarboxylates,the structures of the metallacages change from pyramids to extended octahedrons.Owing to their N-rich structure,these metallacages are further used for selective SO_(2)capture,showing good adsorption capacity and remarkable SO_(2)/CO_(2)selectivity in ambient conditions,suggesting their potential applications toward real flue gas desulfurization.The metallacages are further employed for the conversion of SO_(2)into value-added compounds,showing exceptional efficiency even dilute SO_(2)is used as the reactant.This study represents a type of structure-tunable triazinebased metallacages for SO_(2)capture and conversion,which will pave the way on the applications of metal-organic complexes for gas adsorption.展开更多
Engineered nanoparticles have emerged as new types of materials for a wide range of applications from therapeutics to energy.Still,fabricating nanomaterials presenting complex inner morphologies and shapes in a simple...Engineered nanoparticles have emerged as new types of materials for a wide range of applications from therapeutics to energy.Still,fabricating nanomaterials presenting complex inner morphologies and shapes in a simple manner remains a great challenge.Herein,we report the template-free one-pot continuous gradient nanoprecipitation of different types of non-compatible polymers to spontaneously form nanostructured particles.The continuous addition of antisolvent induces precipitation and(re)organization of polymer chains at the forming particle interface,ultimately and naturally developing complex inner morphologies and shapes while particle grows.This low-energy-cost bottom-up assembly approach applies to various functional polymers,possibly embedded with metal nanoparticles,for continuous growth into well-organized nanoparticles.UV crosslinking of the particles and core removal allows both confirming the building process and leading to hollow or multivoid nanomaterials.展开更多
Molecular rotor-based fluorophores(RBFs)activate fluorescence upon increase of micro-viscosity,thus bearing a broad application promise in many fields.However,it remains a challenge to control how fluorescence of RBFs...Molecular rotor-based fluorophores(RBFs)activate fluorescence upon increase of micro-viscosity,thus bearing a broad application promise in many fields.However,it remains a challenge to control how fluorescence of RBFs responds to viscosity changes.Herein,we demonstrate that the formation and regulation of intramolecular hydrogen bonds in the excited state of RBFs could modulate their rotational barrier,leading to a rational control of how their fluorescence can be activated by micro-viscosity.Based on this strategy,a series of RBFs were developed based on 4-hydroxybenzylidene-imidazolinone(HBI)that span a wide range of viscosity sensitivity.Combined with the AggTag method that we previously reported,the varying viscosity sensitivity and emission spectra of these probes enabled a dualcolor imaging strategy that detects both protein oligomers and aggregates during the multistep aggregation process of proteins in live cells.In summary,our work indicates that installing intracellular excited state hydrogen bonds to RBFs allows for a rational control of rotational barrier,thus allow for a fine tune of their viscosity sensitivity.Beyond RBFs,we envision similar strategies can be applied to control the fluorogenic behavior of a large group of fluorophores whose emission is dependent on excited state rotational motion,including aggregation-induced emission fluorophores.展开更多
Centrifugal and shear forces are produced when solids or liquids rotate.Rotary systems and devices that use these forces,such as dynamic thin-film flow technology,are evolving continuously,improve material structure-p...Centrifugal and shear forces are produced when solids or liquids rotate.Rotary systems and devices that use these forces,such as dynamic thin-film flow technology,are evolving continuously,improve material structure-property relationships at the nanoscale,representing a rapidly thriving and expanding field of research high with green chemistry metrics,consolidated at the inception of science.The vortex fluidic device(VFD)provides many advantages over conventional batch processing,with fluidic waves causing high shear and producing large surface areas for micro-mixing as well as rapid mass and heat transfer,enabling reactions beyond diffusion control.Combining these abilities allows for a green and innovative approach to altering materials for various research and industry applications by controlling small-scale flows and regulating molecular and macromolecular chemical reactivity,self-organization phenomena,and the synthesis of novel materials.This review highlights the aptitude of the VFD as clean technology,with an increase in efficiency for a diversity of top-down,bottom-up,and novel material transformations which benefit from effective vortex-based processing to control material structure-property relationships.展开更多
Recently,many lead-free metal halides with diverse structures and highly efficient emission have been reported.However,their poor stability and single-mode emission color severely limit their applications.Herein,three...Recently,many lead-free metal halides with diverse structures and highly efficient emission have been reported.However,their poor stability and single-mode emission color severely limit their applications.Herein,three homologous Sb^(3+)-doped zero-dimensional(0D)air-stable Sn(IV)-based metal halides with different crystal structures were developed by inserting a single organic ligand into SnCl_(4)lattice,which brings different optical properties.Under photoexcitation,(C_(25)H_(22)P)SnC_(l5)@Sb⋅CH_(4O)(Sb^(3+)−1)does not emit light,(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-α(Sb^(3+)−2α)shines bright yellow emission with a photoluminescence quantum yield(PLQY)of 92%,and(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-β(Sb^(3+)−2β)exhibits intense red emission with a PLQY of 78%.The above three compounds show quite different optical properties should be due to their different crystal structures and the lattice distortions.Particularly,Sb^(3+)−1 can be successfully converted into Sb^(3+)−2αunder the treatment of C_(25)H_(22)PCl solution,accompanied by a transition from nonemission to efficient yellow emission,serving as a“turn-on”photoluminescence(PL)switching.Parallelly,a reversible structure conversion between Sb^(3+)−2αand Sb^(3+)−2βwas witnessed after dichloromethane or volatilization treatment,accompanied by yellow and red emission switching.Thereby,a triple-mode tunable PL switching of off-onI-onII can be constructed in Sb^(3+)-doped Sn(IV)-based compounds.Finally,we demonstrated the as-synthesized compounds in fluorescent anticounterfeiting,information encryption,and optical logic gates.展开更多
Quantitatively establishing the correlation between nanoparticle size and fluorescence is essential for understanding the behavior and functionality of fluorescent nanoparticles(FNPs).However,such exploration focusing...Quantitatively establishing the correlation between nanoparticle size and fluorescence is essential for understanding the behavior and functionality of fluorescent nanoparticles(FNPs).However,such exploration focusing on organic FNPs has not been achieved to date.Herein,we employ the use of supramolecular polymeric FNPs prepared from tetraphenylethylene-based bis-ureidopyrimidinone monomers(bis-UPys)to relate the size to the fluorescence of organic nanoparticles.At an equal concentration of bis-UPys,a logarithmic relationship between them is built with a correlation coefficient higher than 0.96.Theoretical calculations indicate that variations in fluorescence intensity among FNPs of different sizes are attributed to the distinct molecular packing environments at the surface and within the interior of the nanoparticles.This leads to different nonradiative decay rates of the embedded and exposed bis-UPys and thereby changes the overall fluorescence quantum yield of nanoparticles due to their different specific surface areas.The established fluorescence intensity-size correlation possesses fine universality and reliability,and it is successfully utilized to estimate the sizes of other nanoparticles,including those in highly diluted dispersions of FNPs.This work paves a new way for the simple and real-time determination of nanoparticle sizes and offers an attractive paradigm to optimize nanoparticle functionalities by the size effect.展开更多
The efficacy of nanoparticle(NP)-based drug delivery technology is hampered by aberrant tumor stromal microenvironments(TSMs)that hinder NP transportation.Therefore,the promotion of NP permeation into deep tumor sites...The efficacy of nanoparticle(NP)-based drug delivery technology is hampered by aberrant tumor stromal microenvironments(TSMs)that hinder NP transportation.Therefore,the promotion of NP permeation into deep tumor sites via the regulation of tumor microenvironments is of critical importance.Herein,we propose a potential solution using a dihydralazine(HDZ)-loaded nanoparticle drug delivery system containing a pH-responsive,cyclic RGD peptide-modified prodrug based on doxorubicin(cRGD-Dex-DOX).With a combined experimental and theoretical approach,we find that the designed NP system can recognize the acid tumor environments and precisely release the encapsulated HDZ into tumor tissues.HDZ can notably downregulate the expression levels of hypoxia-inducible factor 1α(HIF1α),α-smooth muscle actin,and fibronectin through the dilation of tumor blood vessels.These changes in the TSMs enhance the enrichment and penetration of NPs and also unexpectedly promote the infiltration of activated T cells into tumors,suggesting that such a system may offer an effective“multifunctional therapy”through both improving the chemotherapeutic effect and enhancing the immune response to tumors.In vivo experiments on 4T1 breast cancer bearing mice indeed validate that this therapy has the most outstanding antitumor effects over all the other tested control regimens,with the lowest side effects as well.展开更多
Peculiar hierarchical microstructures in creatures inspire modern material design with distinct functionalities.Creatures can effortlessly construct sophisticated yet long-range ordered microstructure across bio-membr...Peculiar hierarchical microstructures in creatures inspire modern material design with distinct functionalities.Creatures can effortlessly construct sophisticated yet long-range ordered microstructure across bio-membrane through ion secretion and precipitation.However,microstructure biomimicry in current technology generally requires elaborate,point-by-point fabrication.Herein,a spontaneous yet controllable strategy is developed to achieve surface microstructure engineering through a natural surface phenomenon similar to ion secretion-precipitation,that is,coupled dissolution-precipitation.A series of hierarchical microstructures on mineral surfaces in fluids with tunable morphology,orientation,dimension,and spatial distribution are achieved by simply controlling initial dissolution and fluid chemistry.In seawater,long-range ordered film of vertically aligned brucite flakes forms through interfacial dissolution,nucleation,and confinement-induced orientation of flakes with vertically grown{110}plane,on the edge of which,fusiform aragonite epitaxially precipitates.With negligible initial surface dissolution,prismatic aragonite epitaxially grows on a calcite polyhedron-packed surface.By tuning fluid chemistry,closely packed calcite polyhedron and loosely packed calcite micro-pillars are engineered through rapid and retarded precipitation,respectively.Surprisingly,the spontaneously grown microstructures resemble those deliberately created by human or found in nature,and tremendously modulate surface functionality.These findings open new possibilities for facile and customizable engineering of microstructural surfaces,hierarchical heterostructures,and biomimetic materials.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:51933006,52373153,52293383National Key Research and Development Program of China,Grant/Award Number:2022YFA1205702Haihe Laboratory of Sustainable Chemical Transformations,Grant/Award Number:YYJC202102。
文摘Natural molecular chaperones utilize spatially ordered multiple molecular forces to effectively regulate protein folding.However,synthesis of such molecules is a big challenge.The concept of“aggregate science”provides insights to construct chemical entities(aggregates)beyond molecular levels to mimic both the structure and function of natural chaperone.Inspired by this concept,herein we fabricate a novel multi-interaction(i.e.,electrostatic and hydrophobic interaction)cooperative nanochaperone(multi-co-nChap)to regulating protein folding.This multi-co-nChap is fabricated by rationally introducing electrostatic interactions to the surface(corona)and confined hydrophobic microdomains(shell)of traditional single-hydrophobic interaction nanochaperone.We demonstrate that the corona electrostatic attraction facilitates the diffusion of clients into the hydrophobic microdomains,while the shell electrostatic interaction balances the capture and release of clients.By finely synergizing corona electrostatic attraction with shell electrostatic repulsion and hydrophobic interaction,the optimized multi-co-nChap effectively facilitated de novo folding of nascent polypeptides.Moreover,the synergy between corona electrostatic attraction,shell electrostatic attraction and shell hydrophobic interaction significantly enhanced the capability of multi-co-nChap to protect native proteins from denaturation at harsh temperatures.This work provides important insights for understanding and design of nanochaperone,which is a kind of ordered aggregate with chaperone-like activity that beyond the level of single molecule.
基金National Science Foundation of China,Grant/Award Numbers:22033006,21833006,22173074,22203068China Postdoctoral Science Foundation,Grant/Award Number:2021M702734。
文摘Pure organic materials with persistent and efficient room-temperature phosphorescence have recently aroused great research interest due to their vast potential in applications.One crucial design principle for such materials is to suppress as much as possible the non-radiative decay of the triplet exciton while maintaining a moderate phosphorescent radiative rate.However,molecular engineering often exhibits similar regulation trends for the two processes.Here,we propose that the quantum interference caused by aggregation can be utilized to control the phosphorescent and non-radiative decay channels.We systematically analyze various constructive and destructive transition pathways in aggregates with different molecular packing types and establish clear relationships between the luminescence characters and the signs of the singlet and triplet excitonic couplings.It is shown that the decay channels can be flexibly switched on or off by regulating the packing type and excitonic couplings.Most importantly,an enhanced phosphorescent decay and a completely suppressed non-radiative decay can be simultaneously realized in the aggregate packed with inversion symmetry.This work lays the theoretical foundation for future experimental realization of quantum interference effects in phosphorescence.
基金National Natural Science Foundation of China,Grant/Award Number:22175143Key Research and Development Project of Shaanxi,Grant/Award Number:2022GY-353+1 种基金Science Center for Gas Turbine Project,Grant/Award Number:P2022-DB-V-001-001Fundamental Research Funds for the Central Universities,Grant/Award Number:D5000230086。
文摘Crosslinking thermosets with hyperbranched polymers confers them superior comprehensive performance.However,it still remains a further understanding of polymer crosslinking from the molecular chains to the role of aggregates.In this study,three hyperbranched polysiloxane structures(HBPSi-R)are synthesized as model macromolecules,each featuring distinct terminal groups(R denotes amino,epoxy,and vinyl groups)while similar molecular backbone(Si-O-C).These structures were subsequently copolymerized with epoxy monomers to construct interpenetrating HBPSi-R/epoxy/anhydride co-polymer systems.The spatial molecular configuration and flexible Si-O-C branches of HBPSi-R endow them with remarkable reinforcement and toughening effects.Notably,an optimum impact strength of 28.9 kJ mol^(−1) is achieved with a mere 3%loading of HBPSi-V,nearly three times that of the native epoxy(12.9 kJ mol^(−1)).By contrasting the terminal effects,the aggregation states and crosslinking modes were proposed,thus clarifying the supramolecular-dominant aggregation mechanism and covalent-dominant dispersion mechanism,which influences the resulting material properties.This work underscores the significance of aggregate science in comprehending polymer crosslinking and provides theoretical insights for tailoring material properties at a refined molecular level in the field of polymer science.
基金National Natural Science Foundation of China,Grant/Award Numbers:22372094,21703039,21776168Natural Science Foundation of Shanxi Province,Grant/Award Number:20210302123461+2 种基金The Central Guidance Local Science and Technology Development in Shanxi Province Project,Grant/Award Number:YDZJSX2021A001Science and Technology Major Project of the Shanxi Science and Technology Department,Grant/Award Numbers:201903D121003,20181102019Foundation of State Key Laboratory of Coal Conversion,Grant/Award Number:J22-23-605。
文摘Developing new photosystems that integrate broad-band near-infrared(NIR)light harvesting and efficient charge separation is a long-sought goal in the photocatalytic community.In this work,we develop a novel photochemical strategy to prepare light-active carbon dots(CDs)under room temperature and discover that the aggregation of CDs can broaden the light absorption to the NIR region due to the electronic couplings between neighboring CDs.Importantly,the dynamic noncovalent interactions within CD aggregates can stabilize symmetry breaking and thus induce large dipole moments for charge separation and transfer.Furthermore,the weak non-covalent interactions allow for flexible design of the aggregated degrees and the local electronic structures of CD aggregates,further strengthening NIR-light harvesting and charge separation efficiency.As a result,the CD aggregates achieve a record apparent quantum yield of 13.5%at 800 nm,which is one of the best-reported values for NIR-light-driven hydrogen photosynthesis to date.Moreover,we have prepared a series of different CDs and also observed that these CDs after aggregation all exhibit outstanding NIR-responsive photocatalytic hydrogen production activity,suggesting the universality of aggregation-enhanced photocatalysis.This discovery opens a new promising platform for using CD aggregates as efficient light absorbers for solar conversion.
基金National Natural Science Foundation of China,Grant/Award Number:82222903Li Ka Shing Faculty of Medicine(Start-up Fund)of The University of Hong Kong.
文摘Nowadays,cancer has become the leading cause of death worldwide,driving the need for effective therapeutics to improve patient prognosis.Photodynamic therapy(PDT)has been widely applied as an antitumor modality,owing to its minimal invasiveness,localized tumor damage,and high safety profile.However,its efficacy is limited by poor stability of photosensitizers,inadequate tumor accumulation,and a complex tumor microenvironment.To overcome these challenges,extensive endeavors have been made to explore the co-assembly of the widely used photosensitizer chlorin e6(Ce6)with various functional small molecules to enhance pharmacodynamic activity.This review provides a comprehensive overview of current studies on Ce6-based nanoparticles for effective PDT and precise delivery of functional molecules.The self-assembly mechanism will be discussed in detail,with a focus on potential strategies for combinational therapy with PDT.
基金National Natural Science Foundation of China,Grant/Award Numbers:22004001,21631001,21871001Anhui Provincial Natural Science Foundation,Grant/Award Number:2008085QB84the Ministry of Education,the University Synergy Innovation Program of Anhui Province,Grant/Award Number:GXXT-2020-053。
文摘Metal nanoclusters possess excellent electrochemical,optical,and catalytic properties,but correlating these properties remains challenging,which is the foundation to generate electrochemiluminescence(ECL).Herein,we report for the first time that a structurally determined Pt1Ag18 nanocluster generates intense ECL and simultaneously enhances the ECL of carbon dots(CDs)via an electrocatalytic effect.Pt^(1)Ag_(18)nanocluster show aggregation-induced emission enhancement and aggregation-induced ECL enhancement under light and electrochemical stimulation,respectively.In the presence of tripropylamine(TPrA)as a coreactant,solid Pt1Ag18 shows unprecedented ECL efficiency,which is more than nine times higher than that of 1 mM Ru(bpy)32+with the same TPrA concentration.Potential-resolved ECL spectra reveal two ECL emission bands in the presence of TPrA.The ECL emission centered at 650 nm is assigned to the solid Pt_(1)Ag_(18)nanocluster,consistent with the peak wavelength in self-annihilation ECL and photoluminescence of the solid state.The ECL emission centered at 820 nm is assigned to the CDs on the glassy carbon electrode.The electrocatalytic effect of the nanoclusters enhanced the ECL of the CDs by a factor of more than 180 in comparison to that without nanoclusters.Based on the combined optical and electrochemical results,the ECL generation pathways and mechanisms of Pt1Ag18 and CDs are proposed.These findings are extremely promising for designing multifunctional nanocluster luminophores with strong emissions and developing ratiometric sensing devices.
基金Jilin Provincial Science and Technology Development Program,Grant/Award Number:20220101002JCNational Natural Science Foundation of China,Grant/Award Number:12174144Fundamental Research Funds for the Central Universities。
文摘High-pressure chemistry has provided a huge boost to the development of scientific community.Pressure-induced emission(PIE)in halide perovskites is gradually showing its unique charm in both pressure sensing and optoelectronic device applications.Moreover,the PIE retention of halide perovskites under ambient conditions is of great commercial value.Herein,we mainly focus on the potential applications of PIE and PIE retention in metal halide perovskites for scintillators and solid-state lighting.Based on the performance requirements of scintillator and single-component white light-emitting diodes(WLEDs),the significance of PIE and PIE retention is critically clarified,aiming to design and synthesize materials used for high-performance optoelectronic devices.This perspective not only demonstrates promising applications of PIE in the fields of scintillators and WLEDs,but also provides potential applications in display imaging and anti-counterfeiting of PIE materials.Furthermore,solving the scientific disputes that exist under ambient conditions is also simply discussed as an outlook by introducing high-pressure dimension to produce PIE.
基金NSFC,Grant/Award Numbers:22274057,21875069,21788102Guangdong Provincial Basic and Applied Basic Research Fund Regional Joint Fund Project(Youth Fund Project),Grant/Award Number:2022A1515110842Chinese Postdoctoral Science Foundation,Grant/Award Number:2022M711194。
文摘Rheumatoid arthritis(RA)is a debilitating autoimmune disease that causes chronic pain and serious complications,presenting a significant challenge to treat.Promising approaches for treating RA involve signaling pathways modulation and targeted therapy.To this end,a multifunctional nanosystem,TPC-U@HAT,has been designed for RA therapy,featuring multitargeting,dual-stimuli response,and on-demand drug release capabilities.TPC-U@HAT is composed of a probe/prodrug TPC,a JAK1 kinase inhibitor upadacitinib,and the drug carrier HAT.TPC is composed of an aggregation-induced emission(AIE)-active NIR-II chromophore TPY and an NF-κB/NLRP3 inhibitor caffeic acid phenethyl ester(CAPE),connected via boronic ester bond which serves as the reactive-oxygen-species-responsive linker.The carrier,HAT,is created by grafting bone-targeting alendronate and hydrophobic tocopheryl succinate onto hyaluronic acid chains,which can encapsulate TPC and upadacitinib to form TPC-U@HAT.Upon intravenous injection into mice,TPC-U@HAT accumulates at inflamed lesions of RA through both active and passive targeting,and the overexpressed hyaluronidase and H_(2)O_(2) therein cleave the hyaluronic acid polymer chains and boronate bonds,respectively.This generates an AIE-active chromophore for detection and therapeutic evaluation of RA via both optoacoustic imaging and NIR-II fluorescent imaging and concomitantly releases CAPE and upadacitinib to exert efficacious therapy by inhibiting NF-κB/NLRP3 and JAK-STAT pathways.
基金National Science Centre Poland(NCN),Grant/Award Number:2020/37/B/ST8/02167European Union’s Horizon 2020 research and innovation program,Grant/Award Number:813786+2 种基金National Institutes of Health,Grant/Award Number:R21EB025270National Science Foundation,Grant/Award Number:CBET-EBMS-1936105Brigham Research Institute。
文摘Three-dimensional(3D)printing is an emerging technique that has shown promising success in engineering human tissues in recent years.Further development of vatphotopolymerization printing modalities has significantly enhanced the complexity level for 3D printing of various functional structures and components.Similarly,the development of microfluidic chip systems is an emerging research sector with promising medical applications.This work demonstrates the coupling of a digital light processing(DLP)printing procedure with a microfluidic chip system to produce size-tunable,3D-printable porosities with narrow pore size distributions within a gelatin methacryloyl(GelMA)hydrogel matrix.It is found that the generation of size-tunable gas bubbles trapped within an aqueous GelMA hydrogel-precursor can be controlled with high precision.Furthermore,the porosities are printed in two-dimensional(2D)as well as in 3D using the DLP printer.In addition,the cytocompatibility of the printed porous scaffolds is investigated using fibroblasts,where high cell viabilities as well as cell proliferation,spreading,and migration are confirmed.It is anticipated that the strategy is widely applicable in a range of application areas such as tissue engineering and regenerative medicine,among others.
基金Australian Research Council,Grant/Award Number:CE200100009。
文摘Aggregation-induced emission(AIE)is a unique phenomenon whereby aggregation of molecules induces fluorescence emission as opposed to the more commonly known aggregation-caused quenching(ACQ).AIE has the potential to be utilized in the large-scale production of AIE-active polymeric materials because of their wide range of practical applications such as stimuli-responsive sensors,biological imaging agents,and drug delivery systems.This is evident from the increasing number of publications over the years since AIE was first discovered.In addition,the evergrowing interest in this field has led many researchers around the world to develop new and creative methods in the design of monomers,initiators and crosslinkers,with the goal of broadening the scope and utility of AIE polymers.One of the most promising approaches to the design and synthesis of AIE polymers is the use of the reversible-deactivation radical polymerization(RDRP)techniques,which enabled the production of well-controlled AIE materials that are often difficult to achieve by other methods.In this review,a summary of some recent works that utilize RDRP for AIE polymer design and synthesis is presented,including(i)the design of AIE-related monomers,initiators/crosslinkers;the achievements in preparation of AIE polymers using(ii)reversible addition–fragmentation chain transfer(RAFT)technique;(iii)atom transfer radical polymerization(ATRP)technique;(iv)other techniques such as Cu(0)-RDRP technique and nitroxide-mediated polymerization(NMP)technique;(v)the possible applications of these AIE polymers,and finally(vi)a summary/perspective and the future direction of AIE polymers.
基金Beijing Natural Science Foundation,Grant/Award Number:2232053National Natural Science Foundation of China,Grant/Award Number:51902025。
文摘The photothermal conversion capacity of pristine organic phase change materials(PCMs)is inherently insufficient in solar energy utilization.To upgrade their photothermal conversion capacity,we developed bimetallic zeolitic imidazolate framework(ZIF)derived Co/N co-doped flower-like carbon(Co/N-FLC)-based composite PCMs toward solar energy harvesting.3D interconnected carbon framework with low interfacial thermal resistance,abundant carbon defects and high content of nitrogen doping,excellent localized surface plasmon resonance(LSPR)effect of Co nanoparticles,and light absorber Co_(3)ZnC in Co/N-FLC synergistically upgrade the photothermal capacity of(polyethylene glycol)PEG@Co/N-FLC composite PCMs with an ultrahigh photothermal conversion efficiency of 94.8%under 0.16 W/cm^(2).Uniformly anchored Co and Co_(3)ZnC nanoparticles in carbon framework guarantee excellent photon capture ability.Bridging carbon nanotubes(CNTs)in 2D carbon nanosheets further accelerate the rapid transport of phonons by constructing cross-connected heat transfer paths.Additionally,PEG@Co/N-FLC exhibits a thermal energy storage density of 100.69 J/g and excellent thermal stability and durable reliability.Therefore,PEG@Co/N-FLC composite PCMs are promising candidates to accelerate the efficient utilization of solar energy.
基金National Key R&D Program of China,Grant/Award Numbers:2021YFA1200302,2021YFC2302200,2018YFA0208900National Natural Science Foundation of China,Grant/Award Numbers:22025201,22077023,82202532,82272248,82002244,81972019+1 种基金Natural Science Fund of Guangdong Province for Distinguished Young Scholars,Grant/Award Number:2022B1515020089China Postdoctoral Science Foundation,Grant/Award Numbers:2022M711528,2021M691428。
文摘Antibiotic resistance is a major challenge in the clinical treatment of bacterial infectious diseases.Herein,we constructed a multifunctional DNA nanoplatform as a versatile carrier for bacteria-specific delivery of clinical antibiotic ciprofloxacin(CIP)and classic nanoantibiotic silver nanoparticles(AgNP).In our rational design,CIP was efficiently loaded in the self-assembly double-bundle DNA tetrahedron through intercalation with DNA duplex,and single-strand DNA-modified AgNP was embedded in the cavity of the DNA tetrahedron through hybridization.With the site-specific assembly of targeting aptamer in the well-defined DNA tetrahedron,the bacteria-specific dual-antibiotic delivery system exhibited excellent combined bactericidal properties.With enhanced antibiotic accumulation through breaking the out membrane of bacteria,the antibiotic delivery system effectively inhibited biofilm formation and promoted the healing of infected wounds in vivo.This DNAbased antibiotic delivery system provides a promising strategy for the treatment of antibiotic-resistant infections.
基金China Postdoctoral Science Foundation,Grant/Award Number:2021M702588Shaanxi Provincial Natural Science Foundation of China,Grant/Award Number:2023-JC-QN-0105+1 种基金National Natural Science Foundation of China,Grant/Award Numbers:22171219,22222112Innovation Talent Promotion Plan of Shaanxi Province for Science and Technology Innovation Team„Grant/Award Number:2023-CX-TD-51。
文摘The design of novel materials for sulfur dioxide(SO_(2))capture and conversion with considerable efficiency under mild conditions is of great significance for human health and environmental protection yet highly challenging.Herein,we report a series of triazine-based multicomponent metallacages via coordination-driven self-assembly of 2,4,6-tri(4-pyridyl)-1,3,5-triazine,cis-Pt(PEt3)2(OTf)2 and different tetracarboxylic ligands.As the increase of the length of the tetracarboxylates,the structures of the metallacages change from pyramids to extended octahedrons.Owing to their N-rich structure,these metallacages are further used for selective SO_(2)capture,showing good adsorption capacity and remarkable SO_(2)/CO_(2)selectivity in ambient conditions,suggesting their potential applications toward real flue gas desulfurization.The metallacages are further employed for the conversion of SO_(2)into value-added compounds,showing exceptional efficiency even dilute SO_(2)is used as the reactant.This study represents a type of structure-tunable triazinebased metallacages for SO_(2)capture and conversion,which will pave the way on the applications of metal-organic complexes for gas adsorption.
基金National Natural Science Foundation of China,Grant/Award Number:21902117Natural Science Foundation of Tianjin,Grant/Award Number:20JCQNJC01110。
文摘Engineered nanoparticles have emerged as new types of materials for a wide range of applications from therapeutics to energy.Still,fabricating nanomaterials presenting complex inner morphologies and shapes in a simple manner remains a great challenge.Herein,we report the template-free one-pot continuous gradient nanoprecipitation of different types of non-compatible polymers to spontaneously form nanostructured particles.The continuous addition of antisolvent induces precipitation and(re)organization of polymer chains at the forming particle interface,ultimately and naturally developing complex inner morphologies and shapes while particle grows.This low-energy-cost bottom-up assembly approach applies to various functional polymers,possibly embedded with metal nanoparticles,for continuous growth into well-organized nanoparticles.UV crosslinking of the particles and core removal allows both confirming the building process and leading to hollow or multivoid nanomaterials.
基金Research Center for Industries of the Future(RCIF),Westlake UniversityNational Natural Science Foundation of China„Grant/Award Numbers:22007048,22222410Natural Science Foundation of Jiangsu Basic Research Program„Grant/Award Number:BK20221324。
文摘Molecular rotor-based fluorophores(RBFs)activate fluorescence upon increase of micro-viscosity,thus bearing a broad application promise in many fields.However,it remains a challenge to control how fluorescence of RBFs responds to viscosity changes.Herein,we demonstrate that the formation and regulation of intramolecular hydrogen bonds in the excited state of RBFs could modulate their rotational barrier,leading to a rational control of how their fluorescence can be activated by micro-viscosity.Based on this strategy,a series of RBFs were developed based on 4-hydroxybenzylidene-imidazolinone(HBI)that span a wide range of viscosity sensitivity.Combined with the AggTag method that we previously reported,the varying viscosity sensitivity and emission spectra of these probes enabled a dualcolor imaging strategy that detects both protein oligomers and aggregates during the multistep aggregation process of proteins in live cells.In summary,our work indicates that installing intracellular excited state hydrogen bonds to RBFs allows for a rational control of rotational barrier,thus allow for a fine tune of their viscosity sensitivity.Beyond RBFs,we envision similar strategies can be applied to control the fluorogenic behavior of a large group of fluorophores whose emission is dependent on excited state rotational motion,including aggregation-induced emission fluorophores.
基金Postgraduate Research Scholarship and Flinders University Research Investment Fund 2022,and the Australian Research Council,Grant/Award Numbers:DP200101105,DP200101106。
文摘Centrifugal and shear forces are produced when solids or liquids rotate.Rotary systems and devices that use these forces,such as dynamic thin-film flow technology,are evolving continuously,improve material structure-property relationships at the nanoscale,representing a rapidly thriving and expanding field of research high with green chemistry metrics,consolidated at the inception of science.The vortex fluidic device(VFD)provides many advantages over conventional batch processing,with fluidic waves causing high shear and producing large surface areas for micro-mixing as well as rapid mass and heat transfer,enabling reactions beyond diffusion control.Combining these abilities allows for a green and innovative approach to altering materials for various research and industry applications by controlling small-scale flows and regulating molecular and macromolecular chemical reactivity,self-organization phenomena,and the synthesis of novel materials.This review highlights the aptitude of the VFD as clean technology,with an increase in efficiency for a diversity of top-down,bottom-up,and novel material transformations which benefit from effective vortex-based processing to control material structure-property relationships.
基金Guangxi Graduate Education,Grant/Award Number:YCSW2023026Scientific and Technological Bases and Talents of Guangxi,Grant/Award Numbers:AD23026119,AD21238027Guangxi NSF project,Grant/Award Number:2020GXNSFDA238004。
文摘Recently,many lead-free metal halides with diverse structures and highly efficient emission have been reported.However,their poor stability and single-mode emission color severely limit their applications.Herein,three homologous Sb^(3+)-doped zero-dimensional(0D)air-stable Sn(IV)-based metal halides with different crystal structures were developed by inserting a single organic ligand into SnCl_(4)lattice,which brings different optical properties.Under photoexcitation,(C_(25)H_(22)P)SnC_(l5)@Sb⋅CH_(4O)(Sb^(3+)−1)does not emit light,(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-α(Sb^(3+)−2α)shines bright yellow emission with a photoluminescence quantum yield(PLQY)of 92%,and(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-β(Sb^(3+)−2β)exhibits intense red emission with a PLQY of 78%.The above three compounds show quite different optical properties should be due to their different crystal structures and the lattice distortions.Particularly,Sb^(3+)−1 can be successfully converted into Sb^(3+)−2αunder the treatment of C_(25)H_(22)PCl solution,accompanied by a transition from nonemission to efficient yellow emission,serving as a“turn-on”photoluminescence(PL)switching.Parallelly,a reversible structure conversion between Sb^(3+)−2αand Sb^(3+)−2βwas witnessed after dichloromethane or volatilization treatment,accompanied by yellow and red emission switching.Thereby,a triple-mode tunable PL switching of off-onI-onII can be constructed in Sb^(3+)-doped Sn(IV)-based compounds.Finally,we demonstrated the as-synthesized compounds in fluorescent anticounterfeiting,information encryption,and optical logic gates.
基金National Key R&D Program of China,Grant/Award Number:2022YFA1505900National Natural Science Foundation of China,Grant/Award Numbers:22105016,22173006+1 种基金Open Fund of Guangdong Provincial Key Laboratory of Luminescence,South China University of Technology,Grant/Award Number:2019B030301003Beijing Natural Science Foundation,Grant/Award Number:2222027。
文摘Quantitatively establishing the correlation between nanoparticle size and fluorescence is essential for understanding the behavior and functionality of fluorescent nanoparticles(FNPs).However,such exploration focusing on organic FNPs has not been achieved to date.Herein,we employ the use of supramolecular polymeric FNPs prepared from tetraphenylethylene-based bis-ureidopyrimidinone monomers(bis-UPys)to relate the size to the fluorescence of organic nanoparticles.At an equal concentration of bis-UPys,a logarithmic relationship between them is built with a correlation coefficient higher than 0.96.Theoretical calculations indicate that variations in fluorescence intensity among FNPs of different sizes are attributed to the distinct molecular packing environments at the surface and within the interior of the nanoparticles.This leads to different nonradiative decay rates of the embedded and exposed bis-UPys and thereby changes the overall fluorescence quantum yield of nanoparticles due to their different specific surface areas.The established fluorescence intensity-size correlation possesses fine universality and reliability,and it is successfully utilized to estimate the sizes of other nanoparticles,including those in highly diluted dispersions of FNPs.This work paves a new way for the simple and real-time determination of nanoparticle sizes and offers an attractive paradigm to optimize nanoparticle functionalities by the size effect.
基金National Key Research and Development Program of China,Grant/Award Numbers:2021YFA1201200,2021YFF1200404National Natural Science Foundation of China,Grant/Award Numbers:U1967217,22176137+5 种基金National Independent Innovation Demonstration Zone Shanghai Zhangjiang Major Projects,Grant/Award Number:ZJZX2020014National Center of Technology Innovation for Biopharmaceuticals,Grant/Award Number:NCTIB2022HS02010Shanghai Artificial Intelligence Lab,Grant/Award Number:P22KN00272Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study,Grant/Award Number:SN-ZJU-SIAS-003Natural Science Foundation of the Jiangsu Higher Education Institutions of China,Grant/Award Number:20KJA150010Natural Science Foundation of Zhejiang Province,Grant/Award Number:2022LQ22H220001。
文摘The efficacy of nanoparticle(NP)-based drug delivery technology is hampered by aberrant tumor stromal microenvironments(TSMs)that hinder NP transportation.Therefore,the promotion of NP permeation into deep tumor sites via the regulation of tumor microenvironments is of critical importance.Herein,we propose a potential solution using a dihydralazine(HDZ)-loaded nanoparticle drug delivery system containing a pH-responsive,cyclic RGD peptide-modified prodrug based on doxorubicin(cRGD-Dex-DOX).With a combined experimental and theoretical approach,we find that the designed NP system can recognize the acid tumor environments and precisely release the encapsulated HDZ into tumor tissues.HDZ can notably downregulate the expression levels of hypoxia-inducible factor 1α(HIF1α),α-smooth muscle actin,and fibronectin through the dilation of tumor blood vessels.These changes in the TSMs enhance the enrichment and penetration of NPs and also unexpectedly promote the infiltration of activated T cells into tumors,suggesting that such a system may offer an effective“multifunctional therapy”through both improving the chemotherapeutic effect and enhancing the immune response to tumors.In vivo experiments on 4T1 breast cancer bearing mice indeed validate that this therapy has the most outstanding antitumor effects over all the other tested control regimens,with the lowest side effects as well.
基金National Key R&D Program of China,Grant/Award Number:2021YFB2600900National Science Fund for Distinguished Young Scholars of China,Grant/Award Number:51925903+3 种基金National Natural Science Foundation of China,Grant/Award Numbers:52108195,U21A20150Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20210264Natural Sciences and Engineering Research Council of CanadaCanada Research Chairs Program。
文摘Peculiar hierarchical microstructures in creatures inspire modern material design with distinct functionalities.Creatures can effortlessly construct sophisticated yet long-range ordered microstructure across bio-membrane through ion secretion and precipitation.However,microstructure biomimicry in current technology generally requires elaborate,point-by-point fabrication.Herein,a spontaneous yet controllable strategy is developed to achieve surface microstructure engineering through a natural surface phenomenon similar to ion secretion-precipitation,that is,coupled dissolution-precipitation.A series of hierarchical microstructures on mineral surfaces in fluids with tunable morphology,orientation,dimension,and spatial distribution are achieved by simply controlling initial dissolution and fluid chemistry.In seawater,long-range ordered film of vertically aligned brucite flakes forms through interfacial dissolution,nucleation,and confinement-induced orientation of flakes with vertically grown{110}plane,on the edge of which,fusiform aragonite epitaxially precipitates.With negligible initial surface dissolution,prismatic aragonite epitaxially grows on a calcite polyhedron-packed surface.By tuning fluid chemistry,closely packed calcite polyhedron and loosely packed calcite micro-pillars are engineered through rapid and retarded precipitation,respectively.Surprisingly,the spontaneously grown microstructures resemble those deliberately created by human or found in nature,and tremendously modulate surface functionality.These findings open new possibilities for facile and customizable engineering of microstructural surfaces,hierarchical heterostructures,and biomimetic materials.