The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-drive...The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-driven self-assembly strategy by half-sandwich Cp^(*)Rh units was employed to construct diverse molecular links.The pyridyl ligand,adorned with thiophene moieties,assembles into[2]catenanes(2_(1)^(2)links),whereas the isoquinolinyl ligand produces molecular Borromean links(6_(2)^(3)links).Intriguingly,when utilizing extended bithiophene segments,the pyridyl ligand forms Borromean rings(6_(2)^(3)links),while isoquinolinyl counterparts produced a rare low-symmetry cyclic[3]catenane(6_(3)^(3)topology).The results were confirmed through single-crystal X-ray diffraction analysis,nuclear magnetic resonance(NMR)spectroscopy,and electrospray ionization time-of-flight mass spectrometry(ESI-TOF/MS)experiments.Synergistic π-π stacking,C-H···π interactions,and solvophobic effects governed the complex self-assembly system,with independent gradient model(IGM)analyses and solventaccessible surface area(SASA)calculations providing atomistic insights into the pathway selectivity of distinct topological links.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
Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a s...Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a significant challenge and has not yet been reported.In this work,we develop a hydrogen bond self-assembly(HBSA)strategy that is triggered by the acidic tumor microenvironment to enable the photodynamic transition of tetra(4-carboxylphenyl)porphyrin(TCPP)PSs from type Ⅱ to type Ⅰ reactions.Upon self-assembly of TCPP monomers into TCPP assemblies(TCPP-ass),the generated reactive oxygen species shift from singlet oxygen to superoxide anions,which induces caspase-3/GSDME-mediated programmed pyroptosis,enabling rapid and complete solid tumor elimination with minimized adverse effects and enhanced therapeutic efficacy.Crucially,the HBSA process occurs exclusively within tumor cells,and this tumor-specific self-assembly strategy not only utilizes high tissue penetration of TCPP molecular-PSs,but also avoids phototoxicity caused by the formation and accumulation of TCPP-ass nano-PSs in normal tissue,providing an innovative approach for precise 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
Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practica...Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.展开更多
Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,whic...Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.展开更多
Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous met...Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous metal detection,however,encounters unstable and weak signals due to nonuniform distribution of analytes.Herein,we developed an interface self-assembly(ISA)method to create a uniformly distributed gold nanolayer at a liquid-liquid interface for positive heavy metal ions capture and NELIBS analysis.The electrostatically selfassembled Au nanoparticles(NPs)-analytes membrane was prepared at the oil-water interface by injecting ethanol into the mixture of cyclohexane and Au NPs-analytes water solution.Then,the interface self-assembled Au NPs-analytes membrane was transformed onto a laser-processed superhydrophilic Si slide for detection.Three heavy metals(cadmium(Cd),barium(Ba),and chromium(Cr))were analyzed to evaluate the stability and sensitivity of the ISA method for NELIBS.The results(Cd:RSD=3.6%,LoD=0.654 mg/L;Ba:RSD=3.4%,LoD=0.236 mg/L;Cr:RSD=7.7%,LoD=1.367 mg/L)demonstrated signal enhancement and high-stable and ultrasensitive detection.The actual sample detection(Cd:RE=7.71%,Ba:RE=6.78%)illustrated great reliability.The ISA method,creating a uniform distribution of NP-analytes at the interface,has promising prospects in NELIBS.展开更多
Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analo...Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analogs with ethylenediamine linkers(PA,P=phenylalanine,and A=analog)can self-assemble into spherical assemblies,which can serve as novel anticancer drug carriers.In this work,to understand the assembly pathways,drug loading behavior,and formation mechanism of PA aggregates at the molecular level,we carried out dissipative particle dynamics(DPD)simulations of PA molecule systems.Our simulation results demonstrate that PA molecules spontaneously assemble into nanospheres and can self-assemble into drug-loaded nanospheres upon addition of the cancer chemotherapeutic agent doxorubicin(DOX).We also found that the hydrophobic side chain beads of PA molecules exhibited a unique onion-like distribution inside the nanospheres,which was not observed in the experiment.The onion-like nanospheres were verified by calculating the radial distribution function(RDF)of the DPD beads.Furthermore,based on the analysis of the percentages of different interaction components in the total nonbonded energies,main chain-side chain interactions between PA molecules may be important in the formation of onion-like nanospheres,and the synergistic effects of main chain-side chain,main chain-drug,side chain-drug,and main chain-solvent interactions are significant in the formation of drug-loaded nanospheres.These findings provide new insights into the structure and self-assembly pathway of PA assemblies,which may be helpful for the design of efficient and effective drug delivery systems.展开更多
The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence em...The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters(Au NCs).Interestingly,the gold ion complexes coated with proteins of low isoelectric point(pI)nucleate at the secondary structure of proteins with high p I through ionic exchange within cells,generating fluorescent Au NCs.It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs,the distance between Au NCs can be controlled,avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ.This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects.Therefore,this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.展开更多
The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycola...The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide,MPyEDChDGA) with a new structure was synthesized,and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure.Using MPyEDChDGA for efficient enrichment of rare earth ions,the self-assembled solids were recovered by simple filtration without further backextraction and final precipitation,achieving a one-step strategy for the recovery of rare earth ions.Several important parameters affecting the self-assembly extraction,including pH,diluent,temperature,and extractant concentration,were systematically evaluated using La(NO_(3))_(3),Tb(NO_(3))_(3),and Lu(NO_(3))_(3) as representatives.The self-assembled solids were investigated in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),1H nuclear magnetic resonance(1H NMR),Fourier transform infrared spectroscopy(FT-IR),Raman,and X-ray photoelectron spectroscopy(XPS) analyses.The stoichiometry of the extraction species was characterized using the Job's method and electrospray ionization mass spectrometry(ESI-MS).In addition,MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid,and the results show that MPyEDChDGA has good selectivity of Sm from transition metals(Co,Cu).The separation factor of Sm/Co can reach 6281±117,which provides a new approach to recovering Sm from SmCoCu scrap magnets.This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.展开更多
Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AAB...Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.展开更多
The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades.Nevertheless,the synthesis of a series of interlocked topologies possess...The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades.Nevertheless,the synthesis of a series of interlocked topologies possessing similar structural characteristic and clarifying their photothermal performance law remains a challenge.Herein,we introduce a new dipyridinyl ligand L1 featuring two methoxy groups,which act as electron-donating species and provide electrons to the central benzene ring,resulting in an enhanced electron rich effect.Previous research indicates that this feature significantly contributes to forming π-stacking interactions.Furthermore,four half-sandwich rhodium-based building blocks exhibiting different metal-to-metal distances and conjugated effect were selected and used to combine with L1 for the synthesis of[2]catenanes and metallamacrocycles for studying the influence of half-sandwich building blocks on photothermal conversion performance under the same accumulation effect.Three new metalla[2]catenanes and one metallamacrocycle have been obtained in high yields and their structure has been unambiguously confirmed by single crystal X-ray diffraction analysis,NMR spectroscopy,and ESI-TOF-MS.In addition,dynamic structural transformation between[2]catenanes and the corresponding metallamacrocycles has been observed through concentration changes and polar solvent induced effect.Photothermal conversion abilities of the isolated complexes were studied and we observed that[2]catenane 3a displayed significant temperature changes(from 25.8℃ to 50.3℃)under laser irradiation of 1.5 W/cm^(2),thereby reaching a photothermal conversion efficiency of 40.42%.Recorded EPR data indicates that the synergistic cooperation of the free radical effect at the building unit and the stacking effect of[2]catenanes most likely generated photothermal conversion.展开更多
The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we...The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we report a fluorinated N-heterocyclic carbene(NHC)–based pillarplex with a tunable quaternary structure,employed as an efficient building block for constructing hierarchical superstructures.Initially,multiple noncovalent interactions in the NHC-based pillarplex,particularly those between the fluorinated pillarplex and PF_(6)-anions,induce the formation of a supramolecular gel at high concentrations.Additionally,this hierarchical self-assembled structure can be regulated by adjusting anion types,facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions.The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.展开更多
Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric de...Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric demands. To address this, we design and synthesize a conformationally adaptive ligand 4,7-bis(3-(pyridin-4-yl) phenyl) benzo[c][1,2,5]thiadiazole (L1) with a tunable torsional angle θ of N1C1C2N2 ranging from 7.5° to 108.9°. Utilizing coordination-driven self-assembly at ambient temperature, L1 selectively assembles with binuclear half-sandwich units RhB1, RhB2, RhB3, and RhB4 featuring Cp*^(Rh^(Ⅲ)) (Cp* = η^(5)-pentam-ethylcyclopentadienyl) into distinct topologies: Solomon links Rh-1, trefoil knots Rh-2, molecular tweezers Rh 3, and Rh-4, respectively. Crucially, the self-adaptability of ligand L1 directs topology formation through pro-gramming different combination of noncovalent interactions (π-x stacking, CH..π interaction, and lone pair-π interaction), thus navigating divergent assembly pathways by conformational switching, as evidenced by X-ray crystallography analysis, independent gradient model (IGM) analysis, detailed nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization time-of-flight/mass spectrometry (ESI-TOF/MS). This strategy can also be extended to construct Cp*^(Irl^(Ⅲ)) analogs (Solomon links Ir-1, trefoil knots Ir-2, molecular tweezers Ir-3 and Ir-4), demonstrating metal-independent control and achieving intricate topologies in a high yield.展开更多
Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction ...Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored.Herein,a series of multifunctional macromolecular chain transfer agents(macro-CTAs)were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers(CTMs).These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of styrene(St)to prepare block copolymers with different core-forming block structures and the assemblies.The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail.Transmission electron microscopy(TEM)analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies,while the branched core-forming block structure favored the formation of lower-order morphologies.Moreover,it was found that using macroCTAs with a shorter length also promoted the formation of higher-order morphologies.Finally,structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs.We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.展开更多
Antiferromagnetic(AFM)spintronics have sparked extensive research interest in the field of information storage due to the considerable advantages offered by antiferromagnets,including non-volatile data storage,higher ...Antiferromagnetic(AFM)spintronics have sparked extensive research interest in the field of information storage due to the considerable advantages offered by antiferromagnets,including non-volatile data storage,higher storage density,and accelerating data processing.However,the manipulation and detection of internal AFM order in antiferromagnets hinders their applications in spintronic devices.Here,we proposed a design idea for an AFM material that is self-assembled from one-dimensional(1D)ferromagnetic(FM)chains.To validate this idea,we screened a two-dimensional(2D)selfassembled CrBr_(2)antiferromagnet of an AFM semiconductor from a large amount of data.This 2D CrBr_(2)antiferromagnet is composed of 1D FM CrBr_(2)chains that are arranged in a staggered and parallel configuration.In this type of antiferromagnet,the write-data operation of information is achieved in 1D FM chains,followed by a self-assembly process driving the assembly of 1D FM chains into an antiferromagnet.These constituent 1D FM chains become decoupled by external perturbations,such as heat,pressure,strain,etc.,thereby realizing the read-data operation of information.We anticipate that this antiferromagnet,composed of 1D FM chains,can be realized not only in the 1D to 2D system,but also is expected to expand to 2D to three-dimensional(3D)system,and even 1D to 3D system.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
基金supported by the Department of Chemistry,Fudan Universitythe National Natural Science Foundation of China(22031003,21720102004)the Shanghai Science Technology Committee(19DZ2270100)。
文摘The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-driven self-assembly strategy by half-sandwich Cp^(*)Rh units was employed to construct diverse molecular links.The pyridyl ligand,adorned with thiophene moieties,assembles into[2]catenanes(2_(1)^(2)links),whereas the isoquinolinyl ligand produces molecular Borromean links(6_(2)^(3)links).Intriguingly,when utilizing extended bithiophene segments,the pyridyl ligand forms Borromean rings(6_(2)^(3)links),while isoquinolinyl counterparts produced a rare low-symmetry cyclic[3]catenane(6_(3)^(3)topology).The results were confirmed through single-crystal X-ray diffraction analysis,nuclear magnetic resonance(NMR)spectroscopy,and electrospray ionization time-of-flight mass spectrometry(ESI-TOF/MS)experiments.Synergistic π-π stacking,C-H···π interactions,and solvophobic effects governed the complex self-assembly system,with independent gradient model(IGM)analyses and solventaccessible surface area(SASA)calculations providing atomistic insights into the pathway selectivity of distinct topological links.
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supported by the National Natural Science Foundation of China(22176058)the Science and Technology Commission of Shanghai Municipality(24DX1400200,23ZR1416100,25ZR1401082)+1 种基金the Program of Introducing Talents of Discipline to Universities(B16017)the Fundamental Research Funds for the Central Universities(222201717003)。
文摘Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a significant challenge and has not yet been reported.In this work,we develop a hydrogen bond self-assembly(HBSA)strategy that is triggered by the acidic tumor microenvironment to enable the photodynamic transition of tetra(4-carboxylphenyl)porphyrin(TCPP)PSs from type Ⅱ to type Ⅰ reactions.Upon self-assembly of TCPP monomers into TCPP assemblies(TCPP-ass),the generated reactive oxygen species shift from singlet oxygen to superoxide anions,which induces caspase-3/GSDME-mediated programmed pyroptosis,enabling rapid and complete solid tumor elimination with minimized adverse effects and enhanced therapeutic efficacy.Crucially,the HBSA process occurs exclusively within tumor cells,and this tumor-specific self-assembly strategy not only utilizes high tissue penetration of TCPP molecular-PSs,but also avoids phototoxicity caused by the formation and accumulation of TCPP-ass nano-PSs in normal tissue,providing an innovative approach for precise 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.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.2020R1C1C1003375)。
文摘Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.
文摘Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.
基金supported by the National Natural Science Foundation of China(No.62075069 and 52303092)the Water Conservancy Technology project of Hunan Province,China(XSKJ2021000-32)+1 种基金the City University of Hong Kong(#7005507)the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(grant number YPML-2023050278).
文摘Nowadays,high-stable and ultrasensitive heavy metal detection is of utmost importance in water quality monitoring.Nanoparticle-enhanced laser-induced breakdown spectroscopy(NELIBS)shows high potential in hazardous metal detection,however,encounters unstable and weak signals due to nonuniform distribution of analytes.Herein,we developed an interface self-assembly(ISA)method to create a uniformly distributed gold nanolayer at a liquid-liquid interface for positive heavy metal ions capture and NELIBS analysis.The electrostatically selfassembled Au nanoparticles(NPs)-analytes membrane was prepared at the oil-water interface by injecting ethanol into the mixture of cyclohexane and Au NPs-analytes water solution.Then,the interface self-assembled Au NPs-analytes membrane was transformed onto a laser-processed superhydrophilic Si slide for detection.Three heavy metals(cadmium(Cd),barium(Ba),and chromium(Cr))were analyzed to evaluate the stability and sensitivity of the ISA method for NELIBS.The results(Cd:RSD=3.6%,LoD=0.654 mg/L;Ba:RSD=3.4%,LoD=0.236 mg/L;Cr:RSD=7.7%,LoD=1.367 mg/L)demonstrated signal enhancement and high-stable and ultrasensitive detection.The actual sample detection(Cd:RE=7.71%,Ba:RE=6.78%)illustrated great reliability.The ISA method,creating a uniform distribution of NP-analytes at the interface,has promising prospects in NELIBS.
基金financially supported by the National Natural Science Foundation of China(Nos.20904047 and 12074151)the Natural Science Foundation of Zhejiang Province(Nos.LY17A040001 and LY19F03004)。
文摘Diphenylalanine and its analogs cause many concerns owing to their perfect self-assembly properties in the fields of biology,medicine,and nanotechnology.Experimental research has shown that diphenylalanine-based analogs with ethylenediamine linkers(PA,P=phenylalanine,and A=analog)can self-assemble into spherical assemblies,which can serve as novel anticancer drug carriers.In this work,to understand the assembly pathways,drug loading behavior,and formation mechanism of PA aggregates at the molecular level,we carried out dissipative particle dynamics(DPD)simulations of PA molecule systems.Our simulation results demonstrate that PA molecules spontaneously assemble into nanospheres and can self-assemble into drug-loaded nanospheres upon addition of the cancer chemotherapeutic agent doxorubicin(DOX).We also found that the hydrophobic side chain beads of PA molecules exhibited a unique onion-like distribution inside the nanospheres,which was not observed in the experiment.The onion-like nanospheres were verified by calculating the radial distribution function(RDF)of the DPD beads.Furthermore,based on the analysis of the percentages of different interaction components in the total nonbonded energies,main chain-side chain interactions between PA molecules may be important in the formation of onion-like nanospheres,and the synergistic effects of main chain-side chain,main chain-drug,side chain-drug,and main chain-solvent interactions are significant in the formation of drug-loaded nanospheres.These findings provide new insights into the structure and self-assembly pathway of PA assemblies,which may be helpful for the design of efficient and effective drug delivery systems.
基金supported by the National Natural Science Foundation of China(Nos.82061148012,82027806,21974019)SEU Innovation Capability Enhancement Plan for Doctoral Students(No.CXJH_SEU 24138)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX24_0469)。
文摘The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching(ACQ).In this study,an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters(Au NCs).Interestingly,the gold ion complexes coated with proteins of low isoelectric point(pI)nucleate at the secondary structure of proteins with high p I through ionic exchange within cells,generating fluorescent Au NCs.It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs,the distance between Au NCs can be controlled,avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ.This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects.Therefore,this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.
基金Project supported by the Natural Science Foundation of Shandong Province (ZR2022QB067)。
文摘The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements.In this pape r,the extractant(N,N-methyl py ridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide,MPyEDChDGA) with a new structure was synthesized,and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure.Using MPyEDChDGA for efficient enrichment of rare earth ions,the self-assembled solids were recovered by simple filtration without further backextraction and final precipitation,achieving a one-step strategy for the recovery of rare earth ions.Several important parameters affecting the self-assembly extraction,including pH,diluent,temperature,and extractant concentration,were systematically evaluated using La(NO_(3))_(3),Tb(NO_(3))_(3),and Lu(NO_(3))_(3) as representatives.The self-assembled solids were investigated in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),1H nuclear magnetic resonance(1H NMR),Fourier transform infrared spectroscopy(FT-IR),Raman,and X-ray photoelectron spectroscopy(XPS) analyses.The stoichiometry of the extraction species was characterized using the Job's method and electrospray ionization mass spectrometry(ESI-MS).In addition,MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid,and the results show that MPyEDChDGA has good selectivity of Sm from transition metals(Co,Cu).The separation factor of Sm/Co can reach 6281±117,which provides a new approach to recovering Sm from SmCoCu scrap magnets.This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.
基金supported by the National Science Foundation for Distinguished Young Scholars(No.52325308)the National Natural Science Foundation of China(Nos.52273008 and 52073092)+1 种基金Shanghai Scientific and Technological Innovation Projects(No.22ZR1479300)Shanghai Rising-Star Program(No.23QA1402500).
文摘Amphiphilic asymmetric brush copolymers(AABCs)possess unique self-assembly behaviors owing to their asymmetric brush architecture and multiple functionalities of multicomponent side chains.However,the synthesis of AABCs presents challenges,which greatly limits the exploration of their self-assembly behaviors.In this work,we employed dissipative particle dynamics(DPD)simulations to investigate the self-assembly behaviors of AABCs in selective solution.By varying the copolymer concentration and structure,we conducted the self-assembly phase diagrams of AABCs,revealing complex morphologies such as channelized micelles with one or more solvophilic channels.Moreover,the number,surface area,and one-dimensional density distribution of the channelized micelles were calculated to demonstrate the internal structure and morphological transformation during the self-assembly process.Our findings indicate that the morphology of the internal solvophilic channels is greatly influenced by the copolymer structure,concentration,and interaction parameters between the different side chains.The simulation results are consistent with available experimental observations,which can offer theoretical insights into the self-assembly of AABCs.
基金supported by the National Natural Science Foundation of China(Nos.22471113 and 22171123)Natural Science Foundation of Henan Province(Nos.242300421139,232300421232)the Science and Technology Innovation Talent Program of University in Henan Province(No.25HASTIT001)。
文摘The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades.Nevertheless,the synthesis of a series of interlocked topologies possessing similar structural characteristic and clarifying their photothermal performance law remains a challenge.Herein,we introduce a new dipyridinyl ligand L1 featuring two methoxy groups,which act as electron-donating species and provide electrons to the central benzene ring,resulting in an enhanced electron rich effect.Previous research indicates that this feature significantly contributes to forming π-stacking interactions.Furthermore,four half-sandwich rhodium-based building blocks exhibiting different metal-to-metal distances and conjugated effect were selected and used to combine with L1 for the synthesis of[2]catenanes and metallamacrocycles for studying the influence of half-sandwich building blocks on photothermal conversion performance under the same accumulation effect.Three new metalla[2]catenanes and one metallamacrocycle have been obtained in high yields and their structure has been unambiguously confirmed by single crystal X-ray diffraction analysis,NMR spectroscopy,and ESI-TOF-MS.In addition,dynamic structural transformation between[2]catenanes and the corresponding metallamacrocycles has been observed through concentration changes and polar solvent induced effect.Photothermal conversion abilities of the isolated complexes were studied and we observed that[2]catenane 3a displayed significant temperature changes(from 25.8℃ to 50.3℃)under laser irradiation of 1.5 W/cm^(2),thereby reaching a photothermal conversion efficiency of 40.42%.Recorded EPR data indicates that the synergistic cooperation of the free radical effect at the building unit and the stacking effect of[2]catenanes most likely generated photothermal conversion.
基金financial support from the National Natural Science Fund for Distinguished Young Scholars of China(No.22025107)Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHZ003)+2 种基金the Key International Scientific and Technological Cooperation and Exchange Project of Shaanxi Province(No.2023-GHZD-15)the National Youth Top-notch Talent Support Program of Chinathe FM&EM International Joint Laboratory of Northwest University。
文摘The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable.Here,we report a fluorinated N-heterocyclic carbene(NHC)–based pillarplex with a tunable quaternary structure,employed as an efficient building block for constructing hierarchical superstructures.Initially,multiple noncovalent interactions in the NHC-based pillarplex,particularly those between the fluorinated pillarplex and PF_(6)-anions,induce the formation of a supramolecular gel at high concentrations.Additionally,this hierarchical self-assembled structure can be regulated by adjusting anion types,facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions.The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.
基金Department of Chemistry,Fudan Uni-versity,the National Natural Science Foundation of China(22031003,21720102004)the Shanghai Science Technology Committee(19DZ227010O)the Alexander von Humboldt Foundation for a Humboldt Research Award.
文摘Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric demands. To address this, we design and synthesize a conformationally adaptive ligand 4,7-bis(3-(pyridin-4-yl) phenyl) benzo[c][1,2,5]thiadiazole (L1) with a tunable torsional angle θ of N1C1C2N2 ranging from 7.5° to 108.9°. Utilizing coordination-driven self-assembly at ambient temperature, L1 selectively assembles with binuclear half-sandwich units RhB1, RhB2, RhB3, and RhB4 featuring Cp*^(Rh^(Ⅲ)) (Cp* = η^(5)-pentam-ethylcyclopentadienyl) into distinct topologies: Solomon links Rh-1, trefoil knots Rh-2, molecular tweezers Rh 3, and Rh-4, respectively. Crucially, the self-adaptability of ligand L1 directs topology formation through pro-gramming different combination of noncovalent interactions (π-x stacking, CH..π interaction, and lone pair-π interaction), thus navigating divergent assembly pathways by conformational switching, as evidenced by X-ray crystallography analysis, independent gradient model (IGM) analysis, detailed nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization time-of-flight/mass spectrometry (ESI-TOF/MS). This strategy can also be extended to construct Cp*^(Irl^(Ⅲ)) analogs (Solomon links Ir-1, trefoil knots Ir-2, molecular tweezers Ir-3 and Ir-4), demonstrating metal-independent control and achieving intricate topologies in a high yield.
基金financially supported by the National Natural Science Foundation of China(Nos.22171055 and 52222301)the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078)the Science and Technology Program of Guangzhou(No.2024A04J2821)。
文摘Polymerization-induced self-assembly(PISA)has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies.However,the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored.Herein,a series of multifunctional macromolecular chain transfer agents(macro-CTAs)were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers(CTMs).These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of styrene(St)to prepare block copolymers with different core-forming block structures and the assemblies.The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail.Transmission electron microscopy(TEM)analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies,while the branched core-forming block structure favored the formation of lower-order morphologies.Moreover,it was found that using macroCTAs with a shorter length also promoted the formation of higher-order morphologies.Finally,structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs.We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12435001,12304006,and 12404265)the Natural Science Foundation of Shanghai,China(Grant No.23JC1401400)+1 种基金the Fundamental Research Funds for the Central Universities of East China University,the Natural Science Foundation of WIUCAS(Grant No.WIUCASQD2023004)the Natural Science Foundation of Wenzhou(Grant No.L2023005)。
文摘Antiferromagnetic(AFM)spintronics have sparked extensive research interest in the field of information storage due to the considerable advantages offered by antiferromagnets,including non-volatile data storage,higher storage density,and accelerating data processing.However,the manipulation and detection of internal AFM order in antiferromagnets hinders their applications in spintronic devices.Here,we proposed a design idea for an AFM material that is self-assembled from one-dimensional(1D)ferromagnetic(FM)chains.To validate this idea,we screened a two-dimensional(2D)selfassembled CrBr_(2)antiferromagnet of an AFM semiconductor from a large amount of data.This 2D CrBr_(2)antiferromagnet is composed of 1D FM CrBr_(2)chains that are arranged in a staggered and parallel configuration.In this type of antiferromagnet,the write-data operation of information is achieved in 1D FM chains,followed by a self-assembly process driving the assembly of 1D FM chains into an antiferromagnet.These constituent 1D FM chains become decoupled by external perturbations,such as heat,pressure,strain,etc.,thereby realizing the read-data operation of information.We anticipate that this antiferromagnet,composed of 1D FM chains,can be realized not only in the 1D to 2D system,but also is expected to expand to 2D to three-dimensional(3D)system,and even 1D to 3D system.
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.
