The solution processibility of perovskites provides a costeffective and high-throughput route for fabricating state-of-the-art solar cells.However,the fast kinetics of precursor-to-perovskite transformation is suscept...The solution processibility of perovskites provides a costeffective and high-throughput route for fabricating state-of-the-art solar cells.However,the fast kinetics of precursor-to-perovskite transformation is susceptible to processing conditions,resulting in an uncontrollable variance in device performance.Here,we demonstrate a supramolecule confined approach to reproducibly fabricate perovskite films with an ultrasmooth,electronically homogeneous surface.The assembly of a calixarene capping layer on precursor surface can induce host-vip interactions with solvent molecules to tailor the desolvation kinetics,and initiate the perovskite crystallization from the sharp molecule-precursor interface.These combined effects significantly reduced the spatial variance and extended the processing window of perovskite films.As a result,the standard efficiency deviations of device-to-device and batch-to-batch devices were reduced from 0.64-0.26%to 0.67-0.23%,respectively.In addition,the perovskite films with ultrasmooth top surfaces exhibited photoluminescence quantum yield>10%and surface recombination velocities<100 cm s^(-1)for both interfaces that yielded p-i-n structured solar cells with power conversion efficiency over 25%.展开更多
Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/...Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.展开更多
Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(...Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(CB[8])as the host and terpyridine lanthanum ions metal complex as the vip,constructed by layer-by-layer self-assembly through supramolecular interaction.Moreover,nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior.In the tumor micro-environment,the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect.In addition,the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells.The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
Taking a widely contaminated yet abundant waste,such as poultry feathers,and extracting keratin from this struc-ture appears to be a real challenge whenever the preservation of the secondary structure of the protein i...Taking a widely contaminated yet abundant waste,such as poultry feathers,and extracting keratin from this struc-ture appears to be a real challenge whenever the preservation of the secondary structure of the protein is desired.This process would allow exploiting it in ways(e.g.,in the biomedicalfield)that are inspired by a structure that is primarily designed forflight,therefore capable specifically of withstandingflexure and lateral buckling,also with very low thicknesses.The preservation of the structure is based on disulfide crosslinks,and it is offered with pre-ference by some chemical treatments,mainly those based on ionic liquid and on a reduction process.However,the degree of preservation cannot always be precisely assessed;however,beyond chemical characterization,the forma-tion of homogeneous gels can also suggest that the process was successful in this sense.An extraction respectful of nature’s intentions,considering that the secondary structure builds up according to the very function of the feath-ers in the animal,can be deemed to be biomimetic.In particular,biomimetic extractions comply with the very characteristics the protein was designed for to serve in the specific environmental and mechanical situation in which it is inserted.This review tries to elucidate in which cases this aim is achieved and for which specific appli-cations a chicken feather keratin that has preserved its secondary structure can be suited.展开更多
Effective countermeasures against multidrug-resistant nosocomial pathogens,such as carbapenem-resistant Klebsiella pneumoniae and methicillin-resistant Staphylococcus aureus(MRSA),require the development of innovative...Effective countermeasures against multidrug-resistant nosocomial pathogens,such as carbapenem-resistant Klebsiella pneumoniae and methicillin-resistant Staphylococcus aureus(MRSA),require the development of innovative antimicrobial strategies.This study presents a structure-function approach to antimicrobial peptide(AMP)design through the strategic integration of a cationic backbone with a hydrophobic core.This dual-domain architecture enables robust hydrophobic and electrostatic interactions,promoting spontaneous self-assembly and efficient membrane engagement.The lead peptide,Tryptolycin(TRPY),formed stable,monodisperse nanoparticles and demonstrated broad-spectrum bactericidal activity,with minimum inhibitory concentrations≤1μmol/L against multiple strains of MRSA and K.pneumoniae,while exerting minimal cytotoxicity toward mammalian cells.TRPY achieved rapid bacterial elimination,eradicating 99.9%of both planktonic and persister populations within minutes.Mechanistic investigations revealed that TRPY induced membrane permeabilization,promoted reactive oxygen species(ROS)production,and inhibited biofilm formation.In murine infection models,TRPY effectively eradicated established infections,reducing bacterial burden across target organs by 3-to 5-fold without significant cytotoxicity at therapeutic concentrations.Collectively,these findings establish TRPY as a promising therapeutic agent for clinical translation in the treatment of refractory bacterial infections.展开更多
The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering.Nevertheless,substantial challenges remain in constructing nanoscale supramolecular a...The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering.Nevertheless,substantial challenges remain in constructing nanoscale supramolecular architectures with precisely controlled giant dimensions.Herein,we report a precision-guided synthetic strategy for constructing giant 2D and 3D supramolecular architectures with rhomboidal motifs,which was achieved through a dovetail joint strategy.Initial assembly of bis-mortise ligand L1 with dovetail tenon ligand L2 in the presence of Cd^(2+)ions yielded the fundamental bis-rhombic supramolecule R1.Subsequent structural elaboration of the dovetail tenon motif enabled the development of multitopic ligands L3 and L4,which facilitated the construction of expanded architectures of the giant bis-propeller supramolecule R2 and tris-propeller supramolecule R3.The synthesized supramolecules R1-R3 were fully characterized multidimensional NMR spectroscopy,electrospray ionization mass spectrometry(ESI-MS),traveling wave ion mobility mass spectrometry(TWIM-MS),transmission electron microscopy(TEM),and atomic force microscopy(AFM).This work develops an innovative dovetail-joint assembly strategy for constructing rigid giant supramolecular architectures,establishing a new paradigm for precision engineering of complex 3D molecular systems.展开更多
The preparation of amorphous pure organic room-temperature phosphorescence materials with high efficiency is still a challenging task. Herein, we introduce a CB[6] derivative-based supramolecular selfassembling strate...The preparation of amorphous pure organic room-temperature phosphorescence materials with high efficiency is still a challenging task. Herein, we introduce a CB[6] derivative-based supramolecular selfassembling strategy. A water soluble and ellipsoidal deformed CB[6] derivative is used to self-assemble with 4-(4-bromophenyl)-1-methylpyridin-1-ium chloride, bromide and hexafluorophosphate in water. After freeze-drying, the obtained amorphous complexes exhibit brilliant green phosphorescence emission under ambient conditions, with phosphorescence efficiency up to 59%, 60% and 72%, respectively. This is the first report of amorphous non-polymeric pure organic room-temperature phosphorescence with such a high efficiency. In view of the dynamic self-assembling property, the complexes are responsive to water,which could enable information encryption.展开更多
Lysine-targeting reversible covalent inhibitors,particularly salicylaldehyde-based compounds such as the Food and Drug Administration(FDA)-approved drug Voxelotor,exhibit significant therapeutic potential but are limi...Lysine-targeting reversible covalent inhibitors,particularly salicylaldehyde-based compounds such as the Food and Drug Administration(FDA)-approved drug Voxelotor,exhibit significant therapeutic potential but are limited by challenges including instability and off-target effects.To overcome these limitations in kinase inhibitor A5,we devised a pH-responsive prodrug strategy by masking its reactive aldehyde group with an acid-labile hydrazone linkage and enhancing intracellular delivery through conjugation with FK506.The optimized prodrug demonstrated robust antitumor efficacy in K562 tumor-bearing mice.Furthermore,the incorporation of the photosensitizer chlorin e6(Ce6)led to the formation of self-assembled nanoparticles(AKNP),which not only improved physiological stability and prolonged tumor retention but also enabled light-triggered release of A5 in conjunction with photodynamic therapy(PDT).Our study thus presents a promising prodrug self-assembly strategy that combines the on-demand release of a novel lysine-targeting,reversible covalent kinase inhibitor with PDT in clinical cancer therapy.展开更多
Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-...Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-C_(3)N_(4) suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m^(2)/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.展开更多
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability...Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.展开更多
Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au...Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au nanoarrays via a liquid-liquid interface self-assembly method.The capacity of sandpaper to float directly on the cyclohexane-water interface allows nanoarrays to be formed directly on it,thereby minimizing stacking issues typically associated with nanoarray assemblies and significantly enhancing the sensitivity of S-fenvalerate detection.Moreover,the SERS sandpaper was reusable and portable due to its strong adhesion of the nanoarrays.Under optimized testing conditions,the developed SERS sandpaper method was capable of detecting S-fenvalerate,demonstrating a strong linear response within a concentration range of 10^(–7)–10^(3)μmol/L,with a limit of detection of 1.92×10^(−8)μmol/L.The analysis of spiked food samples containing S-fenvalerate using the developed SERS sandpaper afforded excellent recoveries(92.2%−109.7%).Additionally,the SERS sandpaper was successfully applied to quantify S-fenvalerate in real food samples,with results consistent with analyses conducted using gas chromatography.展开更多
Molecular tailoring of self-assembled hole-transporting monolayers(SAMs)has been proven as an efficient approach for improving the device performance of inverted perovskite solar cells.Herein,a novel SAM with extended...Molecular tailoring of self-assembled hole-transporting monolayers(SAMs)has been proven as an efficient approach for improving the device performance of inverted perovskite solar cells.Herein,a novel SAM with extended conjugation is designed and synthesized,named NaPh-4PACz.Compared to Ph-4PACz,NaPh-4PACz exhibits a larger adsorption energy with the ITO substrate,enabling the formation of a more uniform and dense film,thereby preventing direct contact between the perovskite and ITO.Additionally,NaPh-4PACz also has a stronger interaction with the perovskite,which can reduce buried interface defects and suppress non-radiative recombination.Consequently,NaPh-4PACz-based devices achieved a power conversion efficiency of 25.48%due to their interfacial“adhesive”ability.Importantly,the stability of the NaPh-4PACz-based devices was significantly improved.展开更多
Two photolabile amphiphilic supramolecules were designed and synthesized with mono-dendrite and tri-dendrite, which can reversibly self-assemble to spheroid and wedge-shaped nanoparticles. With multiple branches of te...Two photolabile amphiphilic supramolecules were designed and synthesized with mono-dendrite and tri-dendrite, which can reversibly self-assemble to spheroid and wedge-shaped nanoparticles. With multiple branches of terminal amine labeled PEG, these nanoparticles can associate with a negatively charged oligonucleotide and their usage for oligonucleotide delivery was evaluated. Oligonucleotide/nanoparticle complex containing tri-dendrite can efficiently deliver oligonucleotide into cells via endocytosis, while the complex containing mono-dendrite almost lost their ability to deliver oligonucleotide. Further light activation triggered the dissociation of tri-dendrite supramolecular assembly via 1,4- and 1,6-quinone-methide rearrangement, leading to the efficient unpacking of the oligonucleotide in cells.展开更多
The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclin...The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclinic , space group P 1 with the cell parameters a =0 592 4(2) nm, b =0 635 7(3) nm, c =1 117 7(6) nm, α =104 18°, β =91 53°, γ =100 19°, V =0 400 6(3) nm 3, Z =2, the final R value is 0 033 5. The supramolecule is made up of coordination chains, which are further extended into a three dimensional network via the hydrogen bonding interactions.展开更多
Supramolecular polymers constructed by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host-vip interactions have received increasing attention due to their elegant structures,outstanding...Supramolecular polymers constructed by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host-vip interactions have received increasing attention due to their elegant structures,outstanding properties,and potential applications.Hydrogen bonding endows these supramolecular polymers with good adaptability and reversibility,while macrocyclic host-vip interactions give them good selectivity and versatile stimuli-responsiveness.Therefore,functional supramolecular polymers fabricated by these two highly specific,noninterfering interactions in an orthogonal way have shown wide applications in the fields of molecular machines,electronics,soft materials,etc.In this review,we discuss the recent advances of functional supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydroge n bonding and host-vip interactions.In particular,we focus on crown ether-and pillar[n]arene-based supramolecular polymers due to their compatibility with multiple hydrogen bonds in organic solution.The fabrication strategies,interesting properties,and potential applications of these advanced supramolecular materials are mainly concerned.展开更多
The inorganic antimicrobial material was inhibited to the microbes with the added metal ion,Zn.The primary wet product carrying 5%-10% zinc ion was generated under the following conditions：temperature was 95 ℃,solut...The inorganic antimicrobial material was inhibited to the microbes with the added metal ion,Zn.The primary wet product carrying 5%-10% zinc ion was generated under the following conditions：temperature was 95 ℃,solution zinc concentration was 1.2-2.0 mol/L,and the ratio of Zn solution to zeolite weight was 5：1.The final stable product was manufactured after baking in an oven for 1-3 h at the temperature of 500-900 ℃.The baked material was tested for its disinfection effectiveness and coloring effect when mixed with paint coating.Based on the final batch of tests,the zinc content of this anti-microbial product was further optimized.展开更多
Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxenepended base ligands.Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(pphenylene-viny...Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxenepended base ligands.Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(pphenylene-vinylene)(u-COPV)suspended by the truxene skeleton,the resulting supramolecular cages were confirmed to exhibit significant aggregation-induced emission(AIE)accompanied by an interesting solvatochromic fluorescent behavior as well as a porous honeycomb-like state during aggregation.In particular,the anti-counterfeiting performance and emission behaviors of the cages in the solid state under external hydrostatic pressure were investigated.展开更多
Vascular endothelial growth factor(VEGF)-vascular endothelial growth factor receptor(VEGFR)pathways are essential in tumor angiogenesis,growth and metastasis.Studies on anti-angiogenic therapy have been mostly focused...Vascular endothelial growth factor(VEGF)-vascular endothelial growth factor receptor(VEGFR)pathways are essential in tumor angiogenesis,growth and metastasis.Studies on anti-angiogenic therapy have been mostly focused on the blockage of VEGF-VEGFR pathways.We report an extracellularly transformable peptide-based nanomaterial to develop artificial extracellular matrix(ECM)-like networks for high-efficient blockage of natural VEGF-VEGFR interactions.The transformable peptide-based nanomaterial transforms from nanoparticles into nanofibers upon binding to VEGFR in solution.In addition,the transformable peptide-based nanomate rial forms ECM-like fibrous netwo rks on VEGFR overexpressed cells,inhibiting the VEGF-VEGFR interactions and the subsequent angiogenesis.The tube formation is reduced by nearly 85.1% after treatment.This strategy shows excellent potential for anti-angiogenesis,and inhibition of tumor invasion and metastasis.展开更多
Zwitterionic polymer materials have been extensively studied,but zwitterionic peptides supramolecular hydrogel materials are rarely studied.In this study,the preparation of two zwitterionic hydrogels using self-assemb...Zwitterionic polymer materials have been extensively studied,but zwitterionic peptides supramolecular hydrogel materials are rarely studied.In this study,the preparation of two zwitterionic hydrogels using self-assembled peptides were reported.The hydrogels could be fabricated easily by changing the temperature or enzyme catalysis in a short time.And the differences in structure and function of the zwitterion peptide hydrogels caused by the two preparation methods were also be compared.We found that the hydrogel prepared by enzyme induced self-assembly has better solubility and lower cytotoxicity than that prepared by the heating-cooling process.The result showed the enzyme induced self-assembly way to form zwitterionic peptides supramolecular hydrogel materials could have further biomedical applications.展开更多
基金financially supported by the National Natural Science Foundation of China(22379044,22472053)the Science and Technology Commission of Shanghai Municipality(23520710700)+6 种基金the Key Program of the National Natural Science Foundation of China(22239001)the Shanghai Pilot Program for Basic Research(22TQ1400100-5)the ShanghaiMunicipal Natural Science Foundation(25ZR1401081)the Fundamental Research Funds for the Central Universities(JKD01251505,JKVD1251041)the Postdoctoral Fellowship Program of CPSF(GZC20250071)the Shanghai Engineering Research Center of Hierarchical Nanomaterials(18DZ2252400)the Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism(Shanghai Municipal Education Commission)。
文摘The solution processibility of perovskites provides a costeffective and high-throughput route for fabricating state-of-the-art solar cells.However,the fast kinetics of precursor-to-perovskite transformation is susceptible to processing conditions,resulting in an uncontrollable variance in device performance.Here,we demonstrate a supramolecule confined approach to reproducibly fabricate perovskite films with an ultrasmooth,electronically homogeneous surface.The assembly of a calixarene capping layer on precursor surface can induce host-vip interactions with solvent molecules to tailor the desolvation kinetics,and initiate the perovskite crystallization from the sharp molecule-precursor interface.These combined effects significantly reduced the spatial variance and extended the processing window of perovskite films.As a result,the standard efficiency deviations of device-to-device and batch-to-batch devices were reduced from 0.64-0.26%to 0.67-0.23%,respectively.In addition,the perovskite films with ultrasmooth top surfaces exhibited photoluminescence quantum yield>10%and surface recombination velocities<100 cm s^(-1)for both interfaces that yielded p-i-n structured solar cells with power conversion efficiency over 25%.
基金supported by the National Natural Science Foundation of China(NSFC No.52271228)the Natural Science Foundation of Shaanxi Province(No.2023-JC-ZD-21)the Doctoral Dissertation Innovation Fund of Xi'an University of Technology(No.101-252072301)。
文摘Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.
基金supported by the National Natural Science Foundation of China(No.82273919)Natural Science Foundation of Heilongjiang Province(No.LH2024H013)China Postdoctoral Science Foundation(No.2022MD723781).
文摘Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(CB[8])as the host and terpyridine lanthanum ions metal complex as the vip,constructed by layer-by-layer self-assembly through supramolecular interaction.Moreover,nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior.In the tumor micro-environment,the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect.In addition,the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells.The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
文摘Taking a widely contaminated yet abundant waste,such as poultry feathers,and extracting keratin from this struc-ture appears to be a real challenge whenever the preservation of the secondary structure of the protein is desired.This process would allow exploiting it in ways(e.g.,in the biomedicalfield)that are inspired by a structure that is primarily designed forflight,therefore capable specifically of withstandingflexure and lateral buckling,also with very low thicknesses.The preservation of the structure is based on disulfide crosslinks,and it is offered with pre-ference by some chemical treatments,mainly those based on ionic liquid and on a reduction process.However,the degree of preservation cannot always be precisely assessed;however,beyond chemical characterization,the forma-tion of homogeneous gels can also suggest that the process was successful in this sense.An extraction respectful of nature’s intentions,considering that the secondary structure builds up according to the very function of the feath-ers in the animal,can be deemed to be biomimetic.In particular,biomimetic extractions comply with the very characteristics the protein was designed for to serve in the specific environmental and mechanical situation in which it is inserted.This review tries to elucidate in which cases this aim is achieved and for which specific appli-cations a chicken feather keratin that has preserved its secondary structure can be suited.
基金supported by the National Key Research and Development Program of China(2022YFC2105003,2022YFC2602500)National Natural Science Foundation of China(92469103,32400769,32300404)+6 种基金Chinese Academy of Sciences(YSBR-111,SAJC202402)Yunnan Provincial Science and Technology Department(202305AH340007,202301AT070343,202502AA310005)Yunnan Characteristic Plant Extraction Laboratory(2025YKZY002)Kunming Science and Technology Bureau(2022SCP007)New Cornerstone Investigator Program from Shenzhen New Cornerstone Science Foundation(NCI202238)Tianfu Jincheng Laboratory Foundation(TFJC2023010007)Chinese Academy of Sciences and World Academy of Sciences(CAS-TWAS)President’s Fellowship Program(2019A8010415001)。
文摘Effective countermeasures against multidrug-resistant nosocomial pathogens,such as carbapenem-resistant Klebsiella pneumoniae and methicillin-resistant Staphylococcus aureus(MRSA),require the development of innovative antimicrobial strategies.This study presents a structure-function approach to antimicrobial peptide(AMP)design through the strategic integration of a cationic backbone with a hydrophobic core.This dual-domain architecture enables robust hydrophobic and electrostatic interactions,promoting spontaneous self-assembly and efficient membrane engagement.The lead peptide,Tryptolycin(TRPY),formed stable,monodisperse nanoparticles and demonstrated broad-spectrum bactericidal activity,with minimum inhibitory concentrations≤1μmol/L against multiple strains of MRSA and K.pneumoniae,while exerting minimal cytotoxicity toward mammalian cells.TRPY achieved rapid bacterial elimination,eradicating 99.9%of both planktonic and persister populations within minutes.Mechanistic investigations revealed that TRPY induced membrane permeabilization,promoted reactive oxygen species(ROS)production,and inhibited biofilm formation.In murine infection models,TRPY effectively eradicated established infections,reducing bacterial burden across target organs by 3-to 5-fold without significant cytotoxicity at therapeutic concentrations.Collectively,these findings establish TRPY as a promising therapeutic agent for clinical translation in the treatment of refractory bacterial infections.
基金supported by the Hunan Science and Technology Innovation Plan(No.2024RC3015)the National Natural Science Foundation of China(No.22501053)+1 种基金National Key Research and Development Program(Nos.2022YFC3900902 and 2024YFC3907900)Major Science and Technology Projects of Yunnan Province(No.202302AB080016).
文摘The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering.Nevertheless,substantial challenges remain in constructing nanoscale supramolecular architectures with precisely controlled giant dimensions.Herein,we report a precision-guided synthetic strategy for constructing giant 2D and 3D supramolecular architectures with rhomboidal motifs,which was achieved through a dovetail joint strategy.Initial assembly of bis-mortise ligand L1 with dovetail tenon ligand L2 in the presence of Cd^(2+)ions yielded the fundamental bis-rhombic supramolecule R1.Subsequent structural elaboration of the dovetail tenon motif enabled the development of multitopic ligands L3 and L4,which facilitated the construction of expanded architectures of the giant bis-propeller supramolecule R2 and tris-propeller supramolecule R3.The synthesized supramolecules R1-R3 were fully characterized multidimensional NMR spectroscopy,electrospray ionization mass spectrometry(ESI-MS),traveling wave ion mobility mass spectrometry(TWIM-MS),transmission electron microscopy(TEM),and atomic force microscopy(AFM).This work develops an innovative dovetail-joint assembly strategy for constructing rigid giant supramolecular architectures,establishing a new paradigm for precision engineering of complex 3D molecular systems.
基金financially supported by Shanghai Municipal Science and Technology Major Project (No.2018SHZDZX03)National Natural Science Foundation of China (Nos.21788102,21572063)the Fundamental Research Funds for the Central Universities。
文摘The preparation of amorphous pure organic room-temperature phosphorescence materials with high efficiency is still a challenging task. Herein, we introduce a CB[6] derivative-based supramolecular selfassembling strategy. A water soluble and ellipsoidal deformed CB[6] derivative is used to self-assemble with 4-(4-bromophenyl)-1-methylpyridin-1-ium chloride, bromide and hexafluorophosphate in water. After freeze-drying, the obtained amorphous complexes exhibit brilliant green phosphorescence emission under ambient conditions, with phosphorescence efficiency up to 59%, 60% and 72%, respectively. This is the first report of amorphous non-polymeric pure organic room-temperature phosphorescence with such a high efficiency. In view of the dynamic self-assembling property, the complexes are responsive to water,which could enable information encryption.
基金supported by the grants from National Key R&D Program of China(No.2022YFA1104800)Shenzhen Science and Technology Program(No.JCYJ20210324124214038)+4 种基金National Natural Science Foundation of China(Nos.52072418,82300016)Natural Science Foundation of Guangdong Province(No.2023A1515140072)Shenzhen Key Laboratory of Neural Cell Reprogramming and Drug Research,Social Development Science and Technology Key Project of Dongguan(No.20231800940512)the National Medical Research Council(NMRC,No.23-0740-A0001)the Ministry of Education(MOE,No.T2EP10222-0002)of Singapore.
文摘Lysine-targeting reversible covalent inhibitors,particularly salicylaldehyde-based compounds such as the Food and Drug Administration(FDA)-approved drug Voxelotor,exhibit significant therapeutic potential but are limited by challenges including instability and off-target effects.To overcome these limitations in kinase inhibitor A5,we devised a pH-responsive prodrug strategy by masking its reactive aldehyde group with an acid-labile hydrazone linkage and enhancing intracellular delivery through conjugation with FK506.The optimized prodrug demonstrated robust antitumor efficacy in K562 tumor-bearing mice.Furthermore,the incorporation of the photosensitizer chlorin e6(Ce6)led to the formation of self-assembled nanoparticles(AKNP),which not only improved physiological stability and prolonged tumor retention but also enabled light-triggered release of A5 in conjunction with photodynamic therapy(PDT).Our study thus presents a promising prodrug self-assembly strategy that combines the on-demand release of a novel lysine-targeting,reversible covalent kinase inhibitor with PDT in clinical cancer therapy.
文摘Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-C_(3)N_(4) suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m^(2)/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.
基金The National Natural Science Foundation of China (NSFC,Nos.92256201,52273006,22071041,92356302,and 21971052)Natural Science Foundation of Jilin Province (No.20240101181JC) are gratefully appreciated for financial the supportssupported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.
基金financially supported by the Key R&D Program of Shandong Province,China(2023CXGC010712).
文摘Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au nanoarrays via a liquid-liquid interface self-assembly method.The capacity of sandpaper to float directly on the cyclohexane-water interface allows nanoarrays to be formed directly on it,thereby minimizing stacking issues typically associated with nanoarray assemblies and significantly enhancing the sensitivity of S-fenvalerate detection.Moreover,the SERS sandpaper was reusable and portable due to its strong adhesion of the nanoarrays.Under optimized testing conditions,the developed SERS sandpaper method was capable of detecting S-fenvalerate,demonstrating a strong linear response within a concentration range of 10^(–7)–10^(3)μmol/L,with a limit of detection of 1.92×10^(−8)μmol/L.The analysis of spiked food samples containing S-fenvalerate using the developed SERS sandpaper afforded excellent recoveries(92.2%−109.7%).Additionally,the SERS sandpaper was successfully applied to quantify S-fenvalerate in real food samples,with results consistent with analyses conducted using gas chromatography.
基金supported by the National Natural Science Foundation of China(61904053,22279033)the National Key Research and Development Program of China(2023YFB4204502)+2 种基金the 111 Project(B16016)the Fundamental Research Funds for the Central Universities(2025MS043)the Special Foundation for Carbon Peak Carbon Neutralization Technology Innovation Program of Jiangsu Province(BE2022026).
文摘Molecular tailoring of self-assembled hole-transporting monolayers(SAMs)has been proven as an efficient approach for improving the device performance of inverted perovskite solar cells.Herein,a novel SAM with extended conjugation is designed and synthesized,named NaPh-4PACz.Compared to Ph-4PACz,NaPh-4PACz exhibits a larger adsorption energy with the ITO substrate,enabling the formation of a more uniform and dense film,thereby preventing direct contact between the perovskite and ITO.Additionally,NaPh-4PACz also has a stronger interaction with the perovskite,which can reduce buried interface defects and suppress non-radiative recombination.Consequently,NaPh-4PACz-based devices achieved a power conversion efficiency of 25.48%due to their interfacial“adhesive”ability.Importantly,the stability of the NaPh-4PACz-based devices was significantly improved.
基金National Natural Science Foundation of China(Grant No.21372018)the National Basic Research Program of China(973 Program,Grant No.2013CB933800)+1 种基金Program for New Century Excellent Talents in University(Grant No.NCET-10-0203)the State Key Laboratory of Pharmaceutical Biotechnology(Grant No.KF-GN-201305)
文摘Two photolabile amphiphilic supramolecules were designed and synthesized with mono-dendrite and tri-dendrite, which can reversibly self-assemble to spheroid and wedge-shaped nanoparticles. With multiple branches of terminal amine labeled PEG, these nanoparticles can associate with a negatively charged oligonucleotide and their usage for oligonucleotide delivery was evaluated. Oligonucleotide/nanoparticle complex containing tri-dendrite can efficiently deliver oligonucleotide into cells via endocytosis, while the complex containing mono-dendrite almost lost their ability to deliver oligonucleotide. Further light activation triggered the dissociation of tri-dendrite supramolecular assembly via 1,4- and 1,6-quinone-methide rearrangement, leading to the efficient unpacking of the oligonucleotide in cells.
基金Supported by the Education Comm ission of Zhejiang Province(No. 2 0 0 10 12 9) and " 5 5 1" Distinguished PersonFoundation of Wenzhou.
文摘The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclinic , space group P 1 with the cell parameters a =0 592 4(2) nm, b =0 635 7(3) nm, c =1 117 7(6) nm, α =104 18°, β =91 53°, γ =100 19°, V =0 400 6(3) nm 3, Z =2, the final R value is 0 033 5. The supramolecule is made up of coordination chains, which are further extended into a three dimensional network via the hydrogen bonding interactions.
基金financial support from the National Natural Science Foundation of China (Nos. 21702020, 21672102, 21572026)
文摘Supramolecular polymers constructed by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host-vip interactions have received increasing attention due to their elegant structures,outstanding properties,and potential applications.Hydrogen bonding endows these supramolecular polymers with good adaptability and reversibility,while macrocyclic host-vip interactions give them good selectivity and versatile stimuli-responsiveness.Therefore,functional supramolecular polymers fabricated by these two highly specific,noninterfering interactions in an orthogonal way have shown wide applications in the fields of molecular machines,electronics,soft materials,etc.In this review,we discuss the recent advances of functional supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydroge n bonding and host-vip interactions.In particular,we focus on crown ether-and pillar[n]arene-based supramolecular polymers due to their compatibility with multiple hydrogen bonds in organic solution.The fabrication strategies,interesting properties,and potential applications of these advanced supramolecular materials are mainly concerned.
基金Funded by the Construct Plan of Cooperation Project from the Beijing Education Committee(No. XK100080432)
文摘The inorganic antimicrobial material was inhibited to the microbes with the added metal ion,Zn.The primary wet product carrying 5%-10% zinc ion was generated under the following conditions：temperature was 95 ℃,solution zinc concentration was 1.2-2.0 mol/L,and the ratio of Zn solution to zeolite weight was 5：1.The final stable product was manufactured after baking in an oven for 1-3 h at the temperature of 500-900 ℃.The baked material was tested for its disinfection effectiveness and coloring effect when mixed with paint coating.Based on the final batch of tests,the zinc content of this anti-microbial product was further optimized.
基金the National Natural Science Foundation of China(Nos.22101267,21672192,21803059,U2004191,U1904212,21801063)for financial support。
文摘Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxenepended base ligands.Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(pphenylene-vinylene)(u-COPV)suspended by the truxene skeleton,the resulting supramolecular cages were confirmed to exhibit significant aggregation-induced emission(AIE)accompanied by an interesting solvatochromic fluorescent behavior as well as a porous honeycomb-like state during aggregation.In particular,the anti-counterfeiting performance and emission behaviors of the cages in the solid state under external hydrostatic pressure were investigated.
基金the National Natural Science Foundation of China(Nos.51890891,51725302,21807020,51573031 and 51573032)National Key R&D Program of China(No.2018YFE0205400)Science Fund for Creative Research Groups of the National Natural Science Foundation of China(No.11621505)。
文摘Vascular endothelial growth factor(VEGF)-vascular endothelial growth factor receptor(VEGFR)pathways are essential in tumor angiogenesis,growth and metastasis.Studies on anti-angiogenic therapy have been mostly focused on the blockage of VEGF-VEGFR pathways.We report an extracellularly transformable peptide-based nanomaterial to develop artificial extracellular matrix(ECM)-like networks for high-efficient blockage of natural VEGF-VEGFR interactions.The transformable peptide-based nanomaterial transforms from nanoparticles into nanofibers upon binding to VEGFR in solution.In addition,the transformable peptide-based nanomate rial forms ECM-like fibrous netwo rks on VEGFR overexpressed cells,inhibiting the VEGF-VEGFR interactions and the subsequent angiogenesis.The tube formation is reduced by nearly 85.1% after treatment.This strategy shows excellent potential for anti-angiogenesis,and inhibition of tumor invasion and metastasis.
基金supported by National Natural Science Foundation of China(Nos.51773097 and 51973096)the Young Elite Scientists Sponsorship Program by Tianjin(No.TJSQNTJ-2017-16)the Fundamental Research Funds for the Central Universities.
文摘Zwitterionic polymer materials have been extensively studied,but zwitterionic peptides supramolecular hydrogel materials are rarely studied.In this study,the preparation of two zwitterionic hydrogels using self-assembled peptides were reported.The hydrogels could be fabricated easily by changing the temperature or enzyme catalysis in a short time.And the differences in structure and function of the zwitterion peptide hydrogels caused by the two preparation methods were also be compared.We found that the hydrogel prepared by enzyme induced self-assembly has better solubility and lower cytotoxicity than that prepared by the heating-cooling process.The result showed the enzyme induced self-assembly way to form zwitterionic peptides supramolecular hydrogel materials could have further biomedical applications.
