Luminescent cocrystals have been received much attention in fluorescence imaging and sensor application. In this work, we report that the high-quality chiral luminescent cocrystal can be obtained through a molecular s...Luminescent cocrystals have been received much attention in fluorescence imaging and sensor application. In this work, we report that the high-quality chiral luminescent cocrystal can be obtained through a molecular self-assembly process of 2,20-binaphthol and 2-（3-pyridyl）-1 H-benzimidazole. The assembly modes and stacking fashions of as-obtained cocrystal were determined by single crystal X-ray diffractometer. The structure and optical properties of the cocrystals were characterized by fluorescence emission, fluorescence decay, Raman and circular dichroism spectra. The results show that both the pristine co-assembled units（R-BINOL and S-BINOL） give rise to the R conformation within the final cocrystal, suggesting that the formation of cocrystal can be an effective way to achieve R/S-isomeric transformation of 2,20-binaphthol. It is also expected that the co-crystallization approach has much flexibility and potential applications for the design and selective formation of chiral luminescent materials.展开更多
Photothermal therapy(PTT)has brought hope for cancer treatments,with hyperthermia-induced immunogenic cell death(ICD),which is a critical part of therapeutically induced antitumor immune responses.Limited immune stimu...Photothermal therapy(PTT)has brought hope for cancer treatments,with hyperthermia-induced immunogenic cell death(ICD),which is a critical part of therapeutically induced antitumor immune responses.Limited immune stimulation response in PTT is the primary reason for incomplete tumor ablation,therefore demonstrating urgent requirements for ICD amplifier.Herein,a sub-10 nm supramolecular nanoassembly was formed by coassembly of clinically approved aluminum adjuvant and commonly used indocyanine green(ICG)under the assistance of lignosulfonate(LS,a green and sustainable multifunctional lignin derivative)for localized photothermal-immunotherapy of breast cancer.The overall results revealed that LS-Al-ICG is capable of inducing amplified ICD,efficiently eliciting solid immune responses through dendritic cells(DCs)activation and cytotoxic T-cell responses initiation for tumor killing.Moreover,anti-PD-1 therapy blocked the PD-1 pathway and led to remarkable anti-tumor efficacy against laser-irradiated primary tumors and distant tumors by potentiating systemic tumor specific T cell immunity.The results of this study demonstrate a handy and extensible approach for engineering green natural lignin nanoparticles for cancer immunotherapy,which shows promise for delivering other therapeutics in biomedical applications.展开更多
We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B...We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B’blocks.The hydrogen bonding interactions are described by Yukawa potentials,where the hydrogen bonding donors and acceptors were modelled as two blocks smeared with opposite screened charges.The hierarchical microstructures with parallelly packed lamellae-in-lamellae(Lam)and 4.8.8 Archimedean tilting pattern(4.8.8)were observed at lower and higher hydrogen bonding density(θ),respectively.The hierarchy of Lam and 4.8.8 were demonstrated by the one-and two-dimensional density profiles and the underlying order of the large-length-scale and small-length-scale microstructures were also clarified.It was found that the 4.8.8 is favorable to the stronger hydrogen bonding density or interactions.Asθincreases,the microphase transition from Lam to 4.8.8 occurs atθ=0.34,which is mainly attributed to the optimization of the electrostatic energy and conformational entropy with sacrificing the interfacial energy.This work can provide a new strategy to understand the supramolecular self-assembly as well as the mechanism behind the formation of complex hierarchical microstructures.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
During the past few years,regulation and controlling of the two-dimension（2D） self-assembled supramolecular structure on surface have drawn increasing attention in nanoscience and technology.External stimuli have be...During the past few years,regulation and controlling of the two-dimension（2D） self-assembled supramolecular structure on surface have drawn increasing attention in nanoscience and technology.External stimuli have been widely used to regulate these 2D nanostructures.Among various external stimuli approaches,photo-regulation as one of the most outstanding means of regulation has been extensively studied because different wave bands can lead to molecular conformation variation and new bonds to gain new molecules.In this review,the photo-regulated self-assembled structure on solid surface as well as the photo-reactions of different molecules substituted with photo-sensitive groups are introduced to give us an insight into on-surface photochemistry,which plays an important role on the nano-devices fabrication.Notably,these photo-sensitive behaviors as well as the formed structures on surface were probed at sub-molecule level by unique scanning tunneling microscopy（STM） technique.展开更多
Two bis-naphthalimide-based supramolecular gelators(NN-3 and NN-4)with a little difference of position of amino groups were designed and synthesized for the detection of oxaloyl chloride and phosgene.Energy transfer c...Two bis-naphthalimide-based supramolecular gelators(NN-3 and NN-4)with a little difference of position of amino groups were designed and synthesized for the detection of oxaloyl chloride and phosgene.Energy transfer could be occurred between two naphthalimide groups in molecules NN-3 and NN-4.Yellow gels NN-3 and NN-4 were formed in some mixed solvents,and nanofibers with different size were obtained in these gels.The self-assembly processes of NN-3 and NN-4 in different solvents were investigated by UV-vis absorption,fluorescent spectra,SEM,FTIR,XRD and NMR.Gelators NN-3 and NN-4 could selectively detect oxaloyl chloride in solution and film states,but detect phosgene only in solution.NN-3exhibited the ratiometric detection ability towards oxaloyl chloride and phosgene with the low limit of detection(LOD)of 210 nmol/L and 90 nmol/L,respectively.NN-4 as the corresponding control sample,it owned the higher LOD towards oxaloyl chloride and phosgene of 12.4μmol/L and 64μmol/L,respectively.Interestingly,films NN-3 and NN-4 could sensitively detect oxaloyl chloride gases with the low LOD of2.0 ppm and 8.34 ppm,respectively.The detection mechanisms of NN-3 and NN-4 were well studied by1H NMR titration,HRMS and theoretical calculation.展开更多
Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules ...Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules including small molecules and polymers have been originally designed and synthesized with the aim of producing nanostructures with controllable-growth and materials with high-performance. Literature coverage is through 2004-2012. This review gives a full summary of related studies in our group.展开更多
A one-step and facile strategy toward the construction of multicolor polymers via supramolecular selfassembly was proposed.Multicolor polymers were simply prepared by the self-assembly of adamantane-labeled fluorescei...A one-step and facile strategy toward the construction of multicolor polymers via supramolecular selfassembly was proposed.Multicolor polymers were simply prepared by the self-assembly of adamantane-labeled fluorescein,adamantane-labeled rhodamine B and β-cyclodextrin polymers via host-vip interaction between β-cyclodextrin and adamantane.Multicolor polymers showed several interesting properties：multiple emission signatures by a single wavelength excitation,easy tunability,intense fluorescence,high photostablility.In addition,the self-assembly approach implied a facile and flexible strategy for constructing functionalized materials,such as multicolor materials for biological labeling and imaging,and sensing materials for the detection of physiological parameters.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
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
Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their progr...Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their programmable and diverse secondary structures,high metabolic stability and strong self-association propensity can be easily exploited to create variable constructs.We have recently demonstrated that heterochiral,acyclic β^(3)-peptides assembled into striped lamellar nanostructures that induced antibacterial activity.The process of this assembly formation could be exploited in diverse areas,however identifying oligomerisation stages,and more importantly,controlling the spontaneous process at different levels is still lacking.In this study,a set of analogues heterochiral hexameric β^(3)-peptide sequences was investigated to understand how systematic,small variations of the sequences,such as single point mutation or N-terminal chemical modification,can influence the resulting assemblies and allow the control of formed morphologies.TEM and cryo-EM combined with molecular dynamics simulation enabled the identification and differentiation of morphological stages throughout the entire multi-step process.Depending on the position of the sequence modifications,the self-assembled structures formed small oligomers,individual protofibrils,extended,flat lamellae,bundles and macroscopic clusters.These results outline how the self-assembly process of short heterochiral β-peptides can be qualitatively fine-tuned by sequence modifications,which contribute to understanding the general peptide assembly processes for their fibrillar morphologies.展开更多
Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-d...Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-dichloropyridine(PDCC)as a solid additive to fine-tune the self-assembly behavior of Y-series non-fullerene acceptors(NFAs)to tackle the upscaling limitations in green-solvent-processed OSCs.PDCC predominantly interacts with Y-series NFAs,facilitating molecular crystallization and thereby driving the self-assembly of Y-series NFAs during film-forming dynamics,leading to more uniform active layers with improved molecular packing and reduced charge recombination.As a result,PDCC-driven self-assembly strategy enables high-performance OSCs with a power conversion efficiency(PCE)of 20.47%.When translated to sustainable fabrication,this strategy significantly boosts the PCE of large-area green-solvent-processed OSC modules(19.3 cm^(2))from 13.87%to 15.79%,ranking it among the best-performing green-solvent-processed large-area OSC modules(>18 cm^(2)).Beyond its impact on PCE enhancement,PDCC serves as a multifunctional additive to improve long-term stability and exhibits strong universality across multiple material systems.This work establishes a promising approach for advancing sustainable and scalable OSCs,paving the way for their commercialization.展开更多
The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewabilit...The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewability,and tunability,emerge as ideal candidate materials.Entropy-driven self-as sembly promotes the spontaneous formation of ordered structures,serving as a crucial pathway for optimizing cellulose elastomer properties.However,the structure-property relationship between the self-assembled ordered structures of cellulose elastomers and their mechanical and electrical properties remains insufficiently explored.It hinders the expansion of their applications in electronic devices.This paper systematically reviews the structure-property regulation mechanisms of self-assembled cellulosic elastomers from an entropy-driven perspective.It elucidates the application principles and performance optimization strategies for mechanical energy harvesting and self-powered sensing,while also exploring the challenges and prospects for performance enhancement.This work provides a reference for the development of self-assembled cellulosic elastomers in the field of energy devices.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
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
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
Collagen fibrillogenesis underlies the structural and mechanical properties of the extracellular matrix in connective and other tissues,yet its molecular mechanism remains poorly understood.Here,we show that a europi...Collagen fibrillogenesis underlies the structural and mechanical properties of the extracellular matrix in connective and other tissues,yet its molecular mechanism remains poorly understood.Here,we show that a europium(Ⅲ)dipicolinate complex(EuDPA)acts as a luminescent reporter of collagen aggregation.We combine Raman microscopy,circularly polarized luminescence(CPL),and molecular dynamics(MD)simulations to study this process.While Raman imaging directly visualizes the EuDPA-enhanced fibrillar architecture,CPL reveals enantioselective EuDPA-collagen interactions that accompany the fibrillogenesis.MD simulations indicate the presence of stabilizing interactions between hydroxyproline residues and the dipicolinate ligand.The results pave the way to monitoring of protein aggregation in general,and are relevant to fibrotic pathologies and biomimetic materials design.展开更多
Self-assembly of block copolymers(BCPs)is highly intricate and is adsorbing extensive experimental and simulation efforts to reveal it for maximizing structural order and device performances.The coarse-grained(CG)mole...Self-assembly of block copolymers(BCPs)is highly intricate and is adsorbing extensive experimental and simulation efforts to reveal it for maximizing structural order and device performances.The coarse-grained(CG)molecular dynamics(MD)simulation offers a microscopic angle to view the self-assembly of BCPs.Although some molecular details are sacrificed during CG processes,this method exhibits remarkable computational efficiency.In this study,a comprehensive CG model for polystyrene-block-poly(2-vinylpyridine),PS-b-P2VP,one of the most extensively studied BCPs for its high Flory-Huggins interaction parameter,is constructed,with parameters optimized using target values derived from all-atom MD simulations.The CG model precisely coincides with various classical self-assembling morphologies observed in experimental studies,matching the theoretical phase diagrams.Moreover,the conformational asymmetry of the experimental phase diagram is also clearly revealed by our simulation results,and the phase boundaries obtained from simulations are highly consistent with experimental results.The CG model is expected to extend to simulate the self-assembly behaviors of other BCPs in addition to PS-b-P2VP,thus increasing understanding of the microphase separation of BCPs from the molecular level.展开更多
What is the most favorite and original chemistry developed in your research group?Ring-opening polymerization-induced self-assembly of N-carboxyanhydrides(NCA-PISA),and fusion-induced particle assembly(FIPA).How do yo...What is the most favorite and original chemistry developed in your research group?Ring-opening polymerization-induced self-assembly of N-carboxyanhydrides(NCA-PISA),and fusion-induced particle assembly(FIPA).How do you get into this specific field?Could you please share some experiences with our readers?NCA-PISA was developed to solve the biodegradability problem of nanoparticles by traditional PISA,while FIPA was inspired by nature.展开更多
基金supported by the National Natural Science Foundation of China(NSFC, Nos. 21771021 and 21473013)the National Basic Research Program of China(973 Program, No. 2014CB932103)Beijing Municipal Natural Science Foundation (No. 2152016)
文摘Luminescent cocrystals have been received much attention in fluorescence imaging and sensor application. In this work, we report that the high-quality chiral luminescent cocrystal can be obtained through a molecular self-assembly process of 2,20-binaphthol and 2-（3-pyridyl）-1 H-benzimidazole. The assembly modes and stacking fashions of as-obtained cocrystal were determined by single crystal X-ray diffractometer. The structure and optical properties of the cocrystals were characterized by fluorescence emission, fluorescence decay, Raman and circular dichroism spectra. The results show that both the pristine co-assembled units（R-BINOL and S-BINOL） give rise to the R conformation within the final cocrystal, suggesting that the formation of cocrystal can be an effective way to achieve R/S-isomeric transformation of 2,20-binaphthol. It is also expected that the co-crystallization approach has much flexibility and potential applications for the design and selective formation of chiral luminescent materials.
基金supported by the National Natural Science Foundation of China (No. 82074027, No. 81873014, No. 82104405, No. 81873018, No.82174096)Natural Science Foundation of Zhejiang Province (No. LZ21H280001)
文摘Photothermal therapy(PTT)has brought hope for cancer treatments,with hyperthermia-induced immunogenic cell death(ICD),which is a critical part of therapeutically induced antitumor immune responses.Limited immune stimulation response in PTT is the primary reason for incomplete tumor ablation,therefore demonstrating urgent requirements for ICD amplifier.Herein,a sub-10 nm supramolecular nanoassembly was formed by coassembly of clinically approved aluminum adjuvant and commonly used indocyanine green(ICG)under the assistance of lignosulfonate(LS,a green and sustainable multifunctional lignin derivative)for localized photothermal-immunotherapy of breast cancer.The overall results revealed that LS-Al-ICG is capable of inducing amplified ICD,efficiently eliciting solid immune responses through dendritic cells(DCs)activation and cytotoxic T-cell responses initiation for tumor killing.Moreover,anti-PD-1 therapy blocked the PD-1 pathway and led to remarkable anti-tumor efficacy against laser-irradiated primary tumors and distant tumors by potentiating systemic tumor specific T cell immunity.The results of this study demonstrate a handy and extensible approach for engineering green natural lignin nanoparticles for cancer immunotherapy,which shows promise for delivering other therapeutics in biomedical applications.
基金financially supported by the Natural Science Foundation of Shanghai(No.21ZR1402800)the Fundamental Research Funds for the Central Universities(No.2232020D-11)+1 种基金the China Postdoctoral Science Foundation(No.2021M690597)the Open Project Program of Fujian Provincial Key Laboratory of Textiles Inspection Technology(Fujian Fiber Inspection Center)(Nos.2020-MXJ-04)。
文摘We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B’blocks.The hydrogen bonding interactions are described by Yukawa potentials,where the hydrogen bonding donors and acceptors were modelled as two blocks smeared with opposite screened charges.The hierarchical microstructures with parallelly packed lamellae-in-lamellae(Lam)and 4.8.8 Archimedean tilting pattern(4.8.8)were observed at lower and higher hydrogen bonding density(θ),respectively.The hierarchy of Lam and 4.8.8 were demonstrated by the one-and two-dimensional density profiles and the underlying order of the large-length-scale and small-length-scale microstructures were also clarified.It was found that the 4.8.8 is favorable to the stronger hydrogen bonding density or interactions.Asθincreases,the microphase transition from Lam to 4.8.8 occurs atθ=0.34,which is mainly attributed to the optimization of the electrostatic energy and conformational entropy with sacrificing the interfacial energy.This work can provide a new strategy to understand the supramolecular self-assembly as well as the mechanism behind the formation of complex hierarchical microstructures.
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The financial support from the National Key Basic Research Program of China(Nos.2016YFA0200700,2013CB934203)the National Natural Science Foundation of China(No.21472029)
文摘During the past few years,regulation and controlling of the two-dimension（2D） self-assembled supramolecular structure on surface have drawn increasing attention in nanoscience and technology.External stimuli have been widely used to regulate these 2D nanostructures.Among various external stimuli approaches,photo-regulation as one of the most outstanding means of regulation has been extensively studied because different wave bands can lead to molecular conformation variation and new bonds to gain new molecules.In this review,the photo-regulated self-assembled structure on solid surface as well as the photo-reactions of different molecules substituted with photo-sensitive groups are introduced to give us an insight into on-surface photochemistry,which plays an important role on the nano-devices fabrication.Notably,these photo-sensitive behaviors as well as the formed structures on surface were probed at sub-molecule level by unique scanning tunneling microscopy（STM） technique.
基金financially supported by the National Natural Science Foundation of China(No.U1704164)the Basic Research Project of Henan Provincial Key Scientific Research Project(No.22ZX002)。
文摘Two bis-naphthalimide-based supramolecular gelators(NN-3 and NN-4)with a little difference of position of amino groups were designed and synthesized for the detection of oxaloyl chloride and phosgene.Energy transfer could be occurred between two naphthalimide groups in molecules NN-3 and NN-4.Yellow gels NN-3 and NN-4 were formed in some mixed solvents,and nanofibers with different size were obtained in these gels.The self-assembly processes of NN-3 and NN-4 in different solvents were investigated by UV-vis absorption,fluorescent spectra,SEM,FTIR,XRD and NMR.Gelators NN-3 and NN-4 could selectively detect oxaloyl chloride in solution and film states,but detect phosgene only in solution.NN-3exhibited the ratiometric detection ability towards oxaloyl chloride and phosgene with the low limit of detection(LOD)of 210 nmol/L and 90 nmol/L,respectively.NN-4 as the corresponding control sample,it owned the higher LOD towards oxaloyl chloride and phosgene of 12.4μmol/L and 64μmol/L,respectively.Interestingly,films NN-3 and NN-4 could sensitively detect oxaloyl chloride gases with the low LOD of2.0 ppm and 8.34 ppm,respectively.The detection mechanisms of NN-3 and NN-4 were well studied by1H NMR titration,HRMS and theoretical calculation.
基金supported by the National Natural Science Foundation of China(21031006)NSFC-DFG joint fund(TRR 61)the National Basic Research 973 Program of China(2011CB932302 and 2012CB932900)
文摘Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules including small molecules and polymers have been originally designed and synthesized with the aim of producing nanostructures with controllable-growth and materials with high-performance. Literature coverage is through 2004-2012. This review gives a full summary of related studies in our group.
基金supported by the National Natural Science Foundation of China(Nos.21190044,21175035)National Basic Research Program(No.2011CB911002)International Science & Technology operation Program of China(No.2010DFB30300)
文摘A one-step and facile strategy toward the construction of multicolor polymers via supramolecular selfassembly was proposed.Multicolor polymers were simply prepared by the self-assembly of adamantane-labeled fluorescein,adamantane-labeled rhodamine B and β-cyclodextrin polymers via host-vip interaction between β-cyclodextrin and adamantane.Multicolor polymers showed several interesting properties：multiple emission signatures by a single wavelength excitation,easy tunability,intense fluorescence,high photostablility.In addition,the self-assembly approach implied a facile and flexible strategy for constructing functionalized materials,such as multicolor materials for biological labeling and imaging,and sensing materials for the detection of physiological parameters.
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.
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funded by the National Research,Development and Inno-vation Office,Hungary(TKP2021-EGA-31,2020-1.1.2-PIACI-KFI-2020-00021,KKP_22 Project no.144180 and FK_23 Project no.146081).Support from Hungarian Research Network(Eötvös Loránd Research Network)grant no.SA-87/2021 and KEP-5/2021 are also acknowledged.Project no.RRF-2.3.1-21-2022-00015+1 种基金supported by the European Union,Recovery and Resilience Facility.The János Bolyai Research Fellowship(A.W.)of the Hungarian Academy of Sciences is greatly acknowledged.The authors acknowledge CF CryoEM of CIISB,Instruct-CZ Centre,supported by Ministry of Education,Youth and Sports,Czech Republic(MEYS CR)(no.LM2023042)European Regional Development Fund-Project"UP CIISB"(n0.CZ.02.1.01/0.0/0.0/18_046/0015974).
文摘Peptide-based assemblies have gained increasing attention in different areas of nanotechnology,drug delivery and molecular biology.Among these,non-natural β-peptide scaffolds are particularly promising,as their programmable and diverse secondary structures,high metabolic stability and strong self-association propensity can be easily exploited to create variable constructs.We have recently demonstrated that heterochiral,acyclic β^(3)-peptides assembled into striped lamellar nanostructures that induced antibacterial activity.The process of this assembly formation could be exploited in diverse areas,however identifying oligomerisation stages,and more importantly,controlling the spontaneous process at different levels is still lacking.In this study,a set of analogues heterochiral hexameric β^(3)-peptide sequences was investigated to understand how systematic,small variations of the sequences,such as single point mutation or N-terminal chemical modification,can influence the resulting assemblies and allow the control of formed morphologies.TEM and cryo-EM combined with molecular dynamics simulation enabled the identification and differentiation of morphological stages throughout the entire multi-step process.Depending on the position of the sequence modifications,the self-assembled structures formed small oligomers,individual protofibrils,extended,flat lamellae,bundles and macroscopic clusters.These results outline how the self-assembly process of short heterochiral β-peptides can be qualitatively fine-tuned by sequence modifications,which contribute to understanding the general peptide assembly processes for their fibrillar morphologies.
基金the research grant from the Youth Fund of the National Natural Science Foundation of China(62305340)the financial support from the Hong Kong Research Grant Council via STEM Postdoctoral Fellowship(Project no.9446002)+6 种基金the Alexander von Humboldt Foundation and the support during his stay in Christoph J.Brabec’s group at Friedrich-Alexander-Universität Erlangen-Nürnberg and Helmholtz-Institute Erlangen-Nürnberg(HI ERN)the research grant from KAUST global fellowship postdocfinancial support from the Innovation and Technology Commission(Grant no.MHP/104/21)Shenzhen Science and Technology Innovation Commission(JCYJ20210324125612035,R-IND12303,and R-IND12304)the National Key Research and Development Program of China(no.2021YFA1500900)the National Natural Science Foundation of China(no.52071174)the support from the Hong Kong Jockey Club under the research work Hong Kong JC STEM Lab for Circular Bio-economy(Project No.2023-0078)。
文摘Sustainability and scalability remain critical hurdles for the commercialization of organic solar cells(OSCs).However,addressing both poses challenge.Herein,we introduce a simple yet effective strategy utilizing 3,5-dichloropyridine(PDCC)as a solid additive to fine-tune the self-assembly behavior of Y-series non-fullerene acceptors(NFAs)to tackle the upscaling limitations in green-solvent-processed OSCs.PDCC predominantly interacts with Y-series NFAs,facilitating molecular crystallization and thereby driving the self-assembly of Y-series NFAs during film-forming dynamics,leading to more uniform active layers with improved molecular packing and reduced charge recombination.As a result,PDCC-driven self-assembly strategy enables high-performance OSCs with a power conversion efficiency(PCE)of 20.47%.When translated to sustainable fabrication,this strategy significantly boosts the PCE of large-area green-solvent-processed OSC modules(19.3 cm^(2))from 13.87%to 15.79%,ranking it among the best-performing green-solvent-processed large-area OSC modules(>18 cm^(2)).Beyond its impact on PCE enhancement,PDCC serves as a multifunctional additive to improve long-term stability and exhibits strong universality across multiple material systems.This work establishes a promising approach for advancing sustainable and scalable OSCs,paving the way for their commercialization.
基金supported by the National Natural Science Foundation of China(32571991)Guangxi Natural Science Foundation of China(2023GXNSFGA026001&2025GXNSFAA069870)the Foundation of State Key Laboratory of Biobased Material and Green Papermaking.(No.GZKF202323)。
文摘The rapid advancement of flexible electronics technology has placed higher demands on the structural design and performance regulation of elastic materials.Cellulosic elastomers,with their biodegradability,renewability,and tunability,emerge as ideal candidate materials.Entropy-driven self-as sembly promotes the spontaneous formation of ordered structures,serving as a crucial pathway for optimizing cellulose elastomer properties.However,the structure-property relationship between the self-assembled ordered structures of cellulose elastomers and their mechanical and electrical properties remains insufficiently explored.It hinders the expansion of their applications in electronic devices.This paper systematically reviews the structure-property regulation mechanisms of self-assembled cellulosic elastomers from an entropy-driven perspective.It elucidates the application principles and performance optimization strategies for mechanical energy harvesting and self-powered sensing,while also exploring the challenges and prospects for performance enhancement.This work provides a reference for the development of self-assembled cellulosic elastomers in the field of energy devices.
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.
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 Czech Science Foundation(23-05378S to TW and 2515726S to PB)the Ministry of Education,Youth and Sports of the Czech Republic through the e-INFRA CZ(ID:90140).
文摘Collagen fibrillogenesis underlies the structural and mechanical properties of the extracellular matrix in connective and other tissues,yet its molecular mechanism remains poorly understood.Here,we show that a europium(Ⅲ)dipicolinate complex(EuDPA)acts as a luminescent reporter of collagen aggregation.We combine Raman microscopy,circularly polarized luminescence(CPL),and molecular dynamics(MD)simulations to study this process.While Raman imaging directly visualizes the EuDPA-enhanced fibrillar architecture,CPL reveals enantioselective EuDPA-collagen interactions that accompany the fibrillogenesis.MD simulations indicate the presence of stabilizing interactions between hydroxyproline residues and the dipicolinate ligand.The results pave the way to monitoring of protein aggregation in general,and are relevant to fibrotic pathologies and biomimetic materials design.
基金supported by the National Natural Science Foundation of China(22438005,22108117).
文摘Self-assembly of block copolymers(BCPs)is highly intricate and is adsorbing extensive experimental and simulation efforts to reveal it for maximizing structural order and device performances.The coarse-grained(CG)molecular dynamics(MD)simulation offers a microscopic angle to view the self-assembly of BCPs.Although some molecular details are sacrificed during CG processes,this method exhibits remarkable computational efficiency.In this study,a comprehensive CG model for polystyrene-block-poly(2-vinylpyridine),PS-b-P2VP,one of the most extensively studied BCPs for its high Flory-Huggins interaction parameter,is constructed,with parameters optimized using target values derived from all-atom MD simulations.The CG model precisely coincides with various classical self-assembling morphologies observed in experimental studies,matching the theoretical phase diagrams.Moreover,the conformational asymmetry of the experimental phase diagram is also clearly revealed by our simulation results,and the phase boundaries obtained from simulations are highly consistent with experimental results.The CG model is expected to extend to simulate the self-assembly behaviors of other BCPs in addition to PS-b-P2VP,thus increasing understanding of the microphase separation of BCPs from the molecular level.
基金This work was supported by the National Natural Science Foundation of China(Nos.21925505,52003195,and 22101207)Shanghai International Scientific Collaboration Fund(No.21520710100)+1 种基金the China Postdoctoral Science Foundation(Nos.2019M661614 and 2020M671197)J.D.is a recipient of the National Science Fund for Distinguished Young Scholars.
文摘What is the most favorite and original chemistry developed in your research group?Ring-opening polymerization-induced self-assembly of N-carboxyanhydrides(NCA-PISA),and fusion-induced particle assembly(FIPA).How do you get into this specific field?Could you please share some experiences with our readers?NCA-PISA was developed to solve the biodegradability problem of nanoparticles by traditional PISA,while FIPA was inspired by nature.
