A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface....A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.展开更多
Exploring novel materials with excellent photothermal conversion capabilities for solar photothermal water evaporation is considered as an ideal strategy to simultaneously realize the direct and full use of the widely...Exploring novel materials with excellent photothermal conversion capabilities for solar photothermal water evaporation is considered as an ideal strategy to simultaneously realize the direct and full use of the widely distributed solar energy and alleviate the world's freshwater scarcity.Herein,an amphiphilic photothermal membrane is prepared through the self-assembly of hydrophilic heteropoly blue(HPB,H_(3)PMo_(12)O_(40))and hydrophobic surfactant(dioctadecyl dimethyl ammonium bromide,DODA).Benefiting from the synergistic effects of alternating functional hydrophilic HPB and hydrophobic DODA layers,the flexible membrane based on two-dimensional DODA-HPB self-assemblies(DODA-HPB/Nylon66)exhibits superior photothermal conversion properties,showing promising prospects in applications of solar desalination and wastewater treatment.展开更多
Molecular recognition directed self-assemblies from complementary molecular components, melamine and barbituric acid derivatives were studied by means of NMR, fluorescence, and TEM. It was found that both the process ...Molecular recognition directed self-assemblies from complementary molecular components, melamine and barbituric acid derivatives were studied by means of NMR, fluorescence, and TEM. It was found that both the process of the self-assembly and the morphologies of the result- ed self-assemblies could be mediated by modifying the structures of the molecular components used. The effect of the structures of the molecular components on the formation of the self-as- semblies was discussed in terms of intermolecular interactions.展开更多
The self-assembly characteristics of tetrathiafulvalene(TTF) derivatives molecules 1-3 at the 1-phenyloctane/HOPG(HOPG = highly oriented pyrolytic graphite) interface had been carefully studied by scanning tunneling m...The self-assembly characteristics of tetrathiafulvalene(TTF) derivatives molecules 1-3 at the 1-phenyloctane/HOPG(HOPG = highly oriented pyrolytic graphite) interface had been carefully studied by scanning tunneling microscopy(STM) method. The number of F atoms on the phenyl group had significantly affected the self-assembly structures. High-resolution STM images make clear the different assembly structures between the molecules 1-3, which attribute to the different F atom numbers and pyridine group in the molecule. Density functional theory(DFT) calculations have been performed to reveal the formation mechanism.展开更多
Two-dimensional self-assemblies of four partially fluorinated molecules, 1,4-bis（2,6-difluoropyridin-4-yl）benzene, 4,4＇-bis（2,6-difluoropyridin-4-yl）-1,1＇-biphenyl, 4,4＇-bis（2,6-difluoropyridin-4-yl）-1,1＇：4...Two-dimensional self-assemblies of four partially fluorinated molecules, 1,4-bis（2,6-difluoropyridin-4-yl）benzene, 4,4＇-bis（2,6-difluoropyridin-4-yl）-1,1＇-biphenyl, 4,4＇-bis（2,6-difluoropyridin-4-yl）-1,1＇：4＇,1＇-terphenyl and 4,4＇-bis（2,6-difluoropyridin-3-yl）-1,1＇-biphenyl, involving weak intermolecular C-H···F and C-H···N hydrogen bonds were systematically investigated on Au（111） with low-temperature scanning tunneling microscopy. The inter-molecular connecting modes and binding sites were closely related to the backbones of the building blocks, i.e., the molecule length determines its binding sites with neighboring molecules in the assemblies while the attaching positions of the N and F atoms dictate its approaching and docking angles. The experimental results demonstrate that multiple weak hydrogen bonds such as C-H···F and C-H···N can be efficiently applied to tune the molecular orientations and the self-assembly structures accordingly.展开更多
Manipulating the assembly,composition,and arrangement of metal atoms is a new concept to control the behavior,coordination environment,and electronic structure of metal atom catalytic systems and represents the develo...Manipulating the assembly,composition,and arrangement of metal atoms is a new concept to control the behavior,coordination environment,and electronic structure of metal atom catalytic systems and represents the development trend of next generation catalysts.Here,we report a method for anchoring copper atoms from individual atoms to the graphdiyne(GDY)surface and nucleating via atomic assembly manipulation under mild conditions,achieving step-by-step fabrication from atoms to clusters,tiny nanosheets,and larger atomic crystal arrangements,and achieving the selective and efficient C–C coupling during CO_(2)conversion.The new idea proposed in this work is to control the growth of the sp-C∼N-Cu structure interface,and produce zero-valent metal atoms,which leads to strong noninteger charge transfer between GDY and metal atoms.The distance between Cu atoms and the coordination environment of Cu metal atoms can be controlled by changing the catalyst structure,which promotes the selective adsorption of CO_(2)/intermediates and greatly activates C–C coupling to obtain C_(2)products.This new catalytic mechanism ensures excellent catalytic selectivity and stability of the catalysis process.In-situ infrared and X-ray absorption fine structure measurements demonstrate the formation and selective adsorption of*COH and*CO on Cu atoms,followed by C–C bond formation through a formyl-bicarbonate coupling pathway.Such a catalyst exhibits a high selectivity for CO_(2)-to-C_(2)conversion with a high C_(2)products Faradaic efficiency(FE)of 62.5%at a high current density of 178 mA cm^(−2)at ambient temperatures and pressures.The high FE and activity were maintained after the 100-h long-term stability test.展开更多
Intrinsic topological superconductors have garnered significant attention for their potential to harbor novel quantum phenomena.However,the limited availability of suitable material systems has hindered progress in th...Intrinsic topological superconductors have garnered significant attention for their potential to harbor novel quantum phenomena.However,the limited availability of suitable material systems has hindered progress in this field.Here,we present the synthesis and characterization of high-quality self-assembled SnS/TaS_(2)(SnTaS_(3))superlattice,which exhibits superconductivity alongside non-trivial band topology.Temperature-dependent magnetization susceptibility and electrical transport results confirm SnTaS_(3) as a type-Ⅱ superconductor with a critical transition temperature Tc of 3 K.Interestingly,this superconductivity can be turned off via an innovative solid proton gate technique,and a new superconducting state with a Tc of~2.3 K emerges when the gating voltage reaches-9.47 V.Heat capacity measurements reveal strong electronic correlations within this material,which is further supported by angle-resolved photoemission spectroscopy and first-principles calculations,underscoring the effect of topological flat bands and Van Hove singularity.Our research introduces a promising self-assembled material platform,adeptly positioned to delve into the quest for topological superconductors.展开更多
Large-area graphene films with defined uniformity,thickness and morphology are crucial for their applications in optoelectronic and photothermal devices.Herein,we demonstrate that oriented arrangement and ordered asse...Large-area graphene films with defined uniformity,thickness and morphology are crucial for their applications in optoelectronic and photothermal devices.Herein,we demonstrate that oriented arrangement and ordered assembly of graphene oxide(GO)nanosheets in solution films can be realized to obtain the high-quality and large-area reduced GO(rGO)films.The key to the success of this process primarily lies in the control of GO solution shear force direction with array capillaries,achieving oriented arrangement of GO nanosheets in the solution film.Secondly,the control of GO nanosheet concentration and solution viscosity during solvent evaporation of solution film is key to achieve the ordered and disordered assembly of GO,featuring the smooth and wrinkled structure rGO films,respectively.Subsequently,the resultant smooth rGO film with ordered assembly exhibits excellent thermal conductivity and electronic conductivity(over 1800 S·cm-1).Meanwhile,the wrinkled rGO film with disordered assembly can be used as a coating layer on Al current collectors,demonstrating anticorrosion properties and enhanced material adhesive stability.As a result,with such collectors,the high-voltage Li//NCM811 batteries show a 6-fold increase in cycle stability,and the lithium-sulfur batteries with high sulfur loading show a 3-fold increase in cycle stability.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
The goal of this investigation was to develop and demonstrate a polymer/paclitaxel selfassembly(PTX-SA) formulation. Polymer/PTX-SAs were screened based on smaller size of formulation using dynamic light scattering an...The goal of this investigation was to develop and demonstrate a polymer/paclitaxel selfassembly(PTX-SA) formulation. Polymer/PTX-SAs were screened based on smaller size of formulation using dynamic light scattering analysis. Additionally, fluorescence microscopy and flow cytometry studies exhibited that polyvinylpyrrolidone(PVP)-based PTX-SAs(PVP/PTX-SAs) had superior cellular internalization capability in MCF7 and MDA-MB-231 breast cancer cells. The optimized PVP/PTXSAs exhibited less toxicity to human red blood cells indicating a suitable formulation for reducing systemic toxicity. The formation of PVP and PTX self-assemblies was confirmed using fluorescence quenching and transmission electron microscopy which indicated that the PVP/PTX-SAs were spherical in shape with an average size range of 53.81 nm as detected by transmission electron microscopy(TEM).FTIR spectral analysis demonstrates incorporation of polymer and paclitaxel functional groups in PVP/PTX-SAs. Both proliferation(MTS) and clonogenic(colony formation) assays were used to validate superior anticancer activity of PVP/PTX-SAs in breast cancer cells over paclitaxel. Such superior anticancer activity was also demonstrated by downregulation of the expression of pro-survival protein(Bcl-x L), upregulation of apoptosis-associated proteins(Bid, Bax, cleaved caspase 7, and cleaved PARP)and β-tubulin stabilization. These results support the hypothesis that PVP/PTX-SAs improved paclitaxel delivery to cancer cells.展开更多
The abundant intracellular glutathione(GSH)in cancer cells severely undermines the therapeutic efficacy of different treatments due to their role in protecting cancer cells from the associated oxidative stress.Develop...The abundant intracellular glutathione(GSH)in cancer cells severely undermines the therapeutic efficacy of different treatments due to their role in protecting cancer cells from the associated oxidative stress.Developing a highly integrated system to consume GSH would help to improve the therapeutic outcomes.In this study,supramolecular prodrug self-assemblies(SPSAs)with IR825 loaded inside were developed to consume GSH via two-pronged pathways while augmenting the therapeutic potency of chemo/photothermal treatment.SPSAs were prepared using water-soluble pillar[6]arene(WP[6])as host units and H_(2)O_(2)-responsive nitrogen mustard prodrug,chlorambucil-(phenylboronic acid pinacol ester)conjugates(Cb-BE),as the vips.When SPSAs were internalized by cancer cells,the generation of quinone methide(QM)from Cb-BE and singlet oxygen(^(1)O_(2))from irradiation-activated IR825 could consume GSH in a concerted way.As such,the therapeutic efficacies of the released chlorambucil and the accompanied hyperthermia were augmented toward synergistically inhibiting tumor growth.展开更多
Retinal degeneration is a main class of ocular diseases.So far,retinal progenitor cell(RPC)transplantation has been the most potential therapy for it,in which promoting RPCs neuronal differentiation remains an unmet c...Retinal degeneration is a main class of ocular diseases.So far,retinal progenitor cell(RPC)transplantation has been the most potential therapy for it,in which promoting RPCs neuronal differentiation remains an unmet challenge.To address this issue,innovatively designed L/D-phenylalanine based chiral nanofibers(LPG and DPG)are employed and it finds that chirality of fibers can efficiently regulate RPCs differentiation.qPCR,western blot,and immunofluorescence analysis show that right-handed helical DPG nanofibers significantly promote RPCs neuronal differentiation,whereas left-handed LPG nanofibers decrease this effect.These effects are mainly ascribed to the stereoselective interaction between chiral helical nanofibers and retinol-binding protein 4(RBP4,a key protein in the retinoic acid(RA)metabolic pathway).The findings of chirality-dependent neuronal differentiation provide new strategies for treatment of neurodegenerative diseases via optimizing differentiation of transplanted stem cells on chiral nanofibers.展开更多
Modulating the helicity of self-assemblies of conjugated molecules is important for their application in chiral electronics.In this communication,solvent effect has been investigated on how to modulate the helicity of...Modulating the helicity of self-assemblies of conjugated molecules is important for their application in chiral electronics.In this communication,solvent effect has been investigated on how to modulate the helicity of supramolecular assemblies of sugar-substituted perylenediimide(PTCDI-BAG)by using UV-Vis,circular dichroism spectroscopy and transmission electron microscopy.Left-handed helical nanowires are obtained in the mixed solvent system of both N,N-dimethylformamide/ethanol(DMF/ethanol)and N,N-dimethylacetamide/ethanol(DMAC/ethanol).As changing the solvents into dimethyl sulfoxide/ethanol(DMSO/ethanol),ethylene glycol/ethanol(EG/ethanol),or N-methyl-2-pyrrolidone/ethanol(NMP/ethanol),only right-handed heical nanowires are observed.The chirality of supramolecular structures can be tuned by the controlling of the polarity of the solvents.A theoretical calculation is carried out to explain the chiral optical inversion phenomena of PTCDI-BAG aggregates in different solvents,which reveals that reversed CD spectra is due to the difference of clockwise and anticlockwise rotation of the dimer.展开更多
Recently,nano theranostics,by integrating diagnostic and therapeutic functions into a nano system,have provided increasing opportunities for the design of personalized medicine in cancer.Among the construction method ...Recently,nano theranostics,by integrating diagnostic and therapeutic functions into a nano system,have provided increasing opportunities for the design of personalized medicine in cancer.Among the construction method of various theranostic nano systems,the design of single component nanoparticles which are composed of organic photosensitive dyes has become a promising approach to constructing multifunctional nano-theranostic systems,thanks to its unique advantages such as defined structure,100%loading,and high repeatability.Specifically,depending on the inherent photonic imaging and therapeutic properties of the photosensitive dyes,the multifunctional purpose which integrates theranostic effects and targeting abilities can be realized via reasonable molecular modification and supramolecular assembly.In this review,recent advances in the development of nanostructured self-assemblies of porphyrins,phthalocyanines,and boron-dipyrromethanes for theranostics are summarized.Emphasis on their design consideration and theranostic applications are presented.Additionally,prospects for clinical practice and potential challenges of this rapidly growing field are also provided.展开更多
Arnphiphilic cyclodextrin-calixarene conjugates 1 and 2 were synthesized from "click claemxstry, and tnelr sen-asscmuly uchaviors were investigated by transmission electron microscopy, and atomic force microscopy...Arnphiphilic cyclodextrin-calixarene conjugates 1 and 2 were synthesized from "click claemxstry, and tnelr sen-asscmuly uchaviors were investigated by transmission electron microscopy, and atomic force microscopy. The results obtained show that 1 and 2 can self-assemble to form distinctly different aggregations, and the morphology of aggregations critically relies on the polarity and hydrophilicity of the solvent.展开更多
Currently,enzyme-responsive nanomaterials have shown great promise in prognosis or diagnosis of disease biomarker.However,the great obstacle for conventional enzyme-responsive nanomaterials frequently lies in autofluo...Currently,enzyme-responsive nanomaterials have shown great promise in prognosis or diagnosis of disease biomarker.However,the great obstacle for conventional enzyme-responsive nanomaterials frequently lies in autofluorescence interference,poor monodispersity,uncontrollable size and morphology,low optical stability,and biotoxicity,which fundamentally impede their practical application in biological systems.To overcome these deficiencies,we proposed a novel strategy for reliable and precise detection of an enzyme disease biomarker,alkaline phosphatase(ALP),through lanthanide(Ln^(3+))nucleotide nanoparticles(LNNPs)with extremely improved monodispersity and uniformity,which were achieved by the coordination self-assembly between ATP and Ln^(3+)inside micellar nanoreactor.Specifically,for ATP-Ce/Tb LNNPs,highly improved photoluminescence(PL)emission of Tb^(3+)can be achieved via efficient Ce^(3+)sensitization.We demonstrated that ALP could specifically cleave the phosphorus–oxygen(P–O)bonds of ATP and result in the collapse of ATP-Ce/Tb scaffold,finally leading to the PL quenching of Tb^(3+).By taking advantage of time-resolved(TR)PL technique,the fabricated ATP-Ce/Tb LNNPs presented superior selectivity and sensitivity for the ALP bioassay in complicated serum samples,thus revealing the great potential of ATP-Ce/Tb LNNPs in the areas of ALP-related disease prognosis and diagnosis.展开更多
Hydrolysis reactions are capable of directing the non-equilibrium assembly of biomolecular scaffolds to realize sophisticated structures and functions in natural systems.However,utilizing the proper hydrolysis reactio...Hydrolysis reactions are capable of directing the non-equilibrium assembly of biomolecular scaffolds to realize sophisticated structures and functions in natural systems.However,utilizing the proper hydrolysis reactions to construct controlled assemblies with complex topologies is still an arduous challenge in artificial systems and needs to be addressed.Herein,we report a nitric oxide(NO)-triggered slow hydrolysis strategy for the controlled construction of biomimetic supramolecular toroids(STs),thus realizing their visualization of intermediate structures and regulation of geometry parameters.This presented protocol harnesses hydrolysis reactions to control of non-equilibrium self-assembly processes for the construction of self-assemblies with complex topologies successfully,which sheds light on how the hydrolysis reaction rate can modulate the kinetic pathway of assembly,thus realizing the artificial establishment of bio-inspired hierarchical structures.展开更多
The self-assembled nanoparticles(SAN)formed during the decoction process of traditional Chinese medicine(TCM)exhibit non-uniform particle sizes and a tendency for aggregation.Our group found that the p H-driven method...The self-assembled nanoparticles(SAN)formed during the decoction process of traditional Chinese medicine(TCM)exhibit non-uniform particle sizes and a tendency for aggregation.Our group found that the p H-driven method can improve the self-assembly phenomenon of Herpetospermum caudigerum Wall.,and the SAN exhibited uniform particle size and demonstrated good stability.In this paper,we analyzed the interactions between the main active compound,herpetrione(Her),and its main carrier,Herpetospermum caudigerum Wall.polysaccharide(HCWP),along with their self-assembly mechanisms under different p H values.The binding constants of Her and HCWP increase with rising p H,leading to the formation of Her-HCWP SAN with a smaller particle size,higher zeta potential,and improved thermal stability.While the contributions of hydrogen bonding and electrostatic attraction to the formation of Her-HCWP SAN increase with rising p H,the hydrophobic force consistently plays a dominant role.This study enhances our scientific understanding of the self-assembly phenomenon of TCM improved by p H driven method.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
基金The financial supports from the National Natural Science Foundation of China(NSFC,Nos.21773041 and 21327805)the National Basic Research Program of China(No.2016YFA0200700)。
文摘A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.
基金supported by the National Natural Science Foundation of China(22071020,22171041,22271043,22205034)Natural Science Foundation of Jilin Province Science and Technology Department(20220101045JC)the Fundamental Research Funds for the Central Universities(2412021QD008,2412022QD012)
文摘Exploring novel materials with excellent photothermal conversion capabilities for solar photothermal water evaporation is considered as an ideal strategy to simultaneously realize the direct and full use of the widely distributed solar energy and alleviate the world's freshwater scarcity.Herein,an amphiphilic photothermal membrane is prepared through the self-assembly of hydrophilic heteropoly blue(HPB,H_(3)PMo_(12)O_(40))and hydrophobic surfactant(dioctadecyl dimethyl ammonium bromide,DODA).Benefiting from the synergistic effects of alternating functional hydrophilic HPB and hydrophobic DODA layers,the flexible membrane based on two-dimensional DODA-HPB self-assemblies(DODA-HPB/Nylon66)exhibits superior photothermal conversion properties,showing promising prospects in applications of solar desalination and wastewater treatment.
基金the National Natural Science Foundation of China.
文摘Molecular recognition directed self-assemblies from complementary molecular components, melamine and barbituric acid derivatives were studied by means of NMR, fluorescence, and TEM. It was found that both the process of the self-assembly and the morphologies of the result- ed self-assemblies could be mediated by modifying the structures of the molecular components used. The effect of the structures of the molecular components on the formation of the self-as- semblies was discussed in terms of intermolecular interactions.
基金supported NSF of Zhejiang Province of China (Nos.Y20B020032,LY18B020016)the National Natural Science Foundation of China (Nos.21773041,21805144 and 21972031)the Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB36000000)。
文摘The self-assembly characteristics of tetrathiafulvalene(TTF) derivatives molecules 1-3 at the 1-phenyloctane/HOPG(HOPG = highly oriented pyrolytic graphite) interface had been carefully studied by scanning tunneling microscopy(STM) method. The number of F atoms on the phenyl group had significantly affected the self-assembly structures. High-resolution STM images make clear the different assembly structures between the molecules 1-3, which attribute to the different F atom numbers and pyridine group in the molecule. Density functional theory(DFT) calculations have been performed to reveal the formation mechanism.
基金supported by NSFC(Nos.21333001,21133001,21261130090),ChinaNRF CREATE-SPURc project(No.R-143-001-205-592),Singapore
文摘Two-dimensional self-assemblies of four partially fluorinated molecules, 1,4-bis（2,6-difluoropyridin-4-yl）benzene, 4,4＇-bis（2,6-difluoropyridin-4-yl）-1,1＇-biphenyl, 4,4＇-bis（2,6-difluoropyridin-4-yl）-1,1＇：4＇,1＇-terphenyl and 4,4＇-bis（2,6-difluoropyridin-3-yl）-1,1＇-biphenyl, involving weak intermolecular C-H···F and C-H···N hydrogen bonds were systematically investigated on Au（111） with low-temperature scanning tunneling microscopy. The inter-molecular connecting modes and binding sites were closely related to the backbones of the building blocks, i.e., the molecule length determines its binding sites with neighboring molecules in the assemblies while the attaching positions of the N and F atoms dictate its approaching and docking angles. The experimental results demonstrate that multiple weak hydrogen bonds such as C-H···F and C-H···N can be efficiently applied to tune the molecular orientations and the self-assembly structures accordingly.
基金supported by the Basic Science Center Project of the National Natural Science Foundation of China(grant no.22388101)the National Key Research and Development Project of China(grant nos.2022YFA1204500,2022YFA1204501,2022YFA1204503,and 2018YFA0703501)the Key Program of the Chinese Academy of Sciences(grant no.XDPB13).
文摘Manipulating the assembly,composition,and arrangement of metal atoms is a new concept to control the behavior,coordination environment,and electronic structure of metal atom catalytic systems and represents the development trend of next generation catalysts.Here,we report a method for anchoring copper atoms from individual atoms to the graphdiyne(GDY)surface and nucleating via atomic assembly manipulation under mild conditions,achieving step-by-step fabrication from atoms to clusters,tiny nanosheets,and larger atomic crystal arrangements,and achieving the selective and efficient C–C coupling during CO_(2)conversion.The new idea proposed in this work is to control the growth of the sp-C∼N-Cu structure interface,and produce zero-valent metal atoms,which leads to strong noninteger charge transfer between GDY and metal atoms.The distance between Cu atoms and the coordination environment of Cu metal atoms can be controlled by changing the catalyst structure,which promotes the selective adsorption of CO_(2)/intermediates and greatly activates C–C coupling to obtain C_(2)products.This new catalytic mechanism ensures excellent catalytic selectivity and stability of the catalysis process.In-situ infrared and X-ray absorption fine structure measurements demonstrate the formation and selective adsorption of*COH and*CO on Cu atoms,followed by C–C bond formation through a formyl-bicarbonate coupling pathway.Such a catalyst exhibits a high selectivity for CO_(2)-to-C_(2)conversion with a high C_(2)products Faradaic efficiency(FE)of 62.5%at a high current density of 178 mA cm^(−2)at ambient temperatures and pressures.The high FE and activity were maintained after the 100-h long-term stability test.
基金supported by Innovation Program for Quantum Science and Technology(No.2021ZD0302800)the National Natural Science Foundation of China(Nos.52373309 and 12004357)+2 种基金the National Key R&D Program of China(No.2023YFA1610100)the financial support from U.S.Department of Energy Office of Science-The Basic Energy Sciences program(DOE-BES)(No.DE-FG02-04ER46148)the financial support from the National Natural Science Foundation of China(No.12574210).
文摘Intrinsic topological superconductors have garnered significant attention for their potential to harbor novel quantum phenomena.However,the limited availability of suitable material systems has hindered progress in this field.Here,we present the synthesis and characterization of high-quality self-assembled SnS/TaS_(2)(SnTaS_(3))superlattice,which exhibits superconductivity alongside non-trivial band topology.Temperature-dependent magnetization susceptibility and electrical transport results confirm SnTaS_(3) as a type-Ⅱ superconductor with a critical transition temperature Tc of 3 K.Interestingly,this superconductivity can be turned off via an innovative solid proton gate technique,and a new superconducting state with a Tc of~2.3 K emerges when the gating voltage reaches-9.47 V.Heat capacity measurements reveal strong electronic correlations within this material,which is further supported by angle-resolved photoemission spectroscopy and first-principles calculations,underscoring the effect of topological flat bands and Van Hove singularity.Our research introduces a promising self-assembled material platform,adeptly positioned to delve into the quest for topological superconductors.
基金the National Natural Science Foundation of China(No.U22A20437)Joint Fund of Science and Technology R&D Plan of Henan Province(No.222301420005)Program for Innovative Research Team(in Science and Technology)in University of Henan Province(No.24IRTSTHN001)for financial support.
文摘Large-area graphene films with defined uniformity,thickness and morphology are crucial for their applications in optoelectronic and photothermal devices.Herein,we demonstrate that oriented arrangement and ordered assembly of graphene oxide(GO)nanosheets in solution films can be realized to obtain the high-quality and large-area reduced GO(rGO)films.The key to the success of this process primarily lies in the control of GO solution shear force direction with array capillaries,achieving oriented arrangement of GO nanosheets in the solution film.Secondly,the control of GO nanosheet concentration and solution viscosity during solvent evaporation of solution film is key to achieve the ordered and disordered assembly of GO,featuring the smooth and wrinkled structure rGO films,respectively.Subsequently,the resultant smooth rGO film with ordered assembly exhibits excellent thermal conductivity and electronic conductivity(over 1800 S·cm-1).Meanwhile,the wrinkled rGO film with disordered assembly can be used as a coating layer on Al current collectors,demonstrating anticorrosion properties and enhanced material adhesive stability.As a result,with such collectors,the high-voltage Li//NCM811 batteries show a 6-fold increase in cycle stability,and the lithium-sulfur batteries with high sulfur loading show a 3-fold increase in cycle stability.
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performed under National Institute of Health/National Cancer Center's Career Development Award K22 CA174841,R15 CA 213232CORNET-UTHSC,Start-up by the College of Pharmacy,UTHSC to Murali M.Yallapu+1 种基金gratefully acknowledge the National Institutes of Health Research Project Grant Program (R01 CA210192,R01 CA206069,and CA204552) to Subhash C.ChauhanUTHSC-College of Pharmacy-Dean's Seed Grant support to Murali M.Yallapu,Meena Jaggi and Subhash C.Chauhan
文摘The goal of this investigation was to develop and demonstrate a polymer/paclitaxel selfassembly(PTX-SA) formulation. Polymer/PTX-SAs were screened based on smaller size of formulation using dynamic light scattering analysis. Additionally, fluorescence microscopy and flow cytometry studies exhibited that polyvinylpyrrolidone(PVP)-based PTX-SAs(PVP/PTX-SAs) had superior cellular internalization capability in MCF7 and MDA-MB-231 breast cancer cells. The optimized PVP/PTXSAs exhibited less toxicity to human red blood cells indicating a suitable formulation for reducing systemic toxicity. The formation of PVP and PTX self-assemblies was confirmed using fluorescence quenching and transmission electron microscopy which indicated that the PVP/PTX-SAs were spherical in shape with an average size range of 53.81 nm as detected by transmission electron microscopy(TEM).FTIR spectral analysis demonstrates incorporation of polymer and paclitaxel functional groups in PVP/PTX-SAs. Both proliferation(MTS) and clonogenic(colony formation) assays were used to validate superior anticancer activity of PVP/PTX-SAs in breast cancer cells over paclitaxel. Such superior anticancer activity was also demonstrated by downregulation of the expression of pro-survival protein(Bcl-x L), upregulation of apoptosis-associated proteins(Bid, Bax, cleaved caspase 7, and cleaved PARP)and β-tubulin stabilization. These results support the hypothesis that PVP/PTX-SAs improved paclitaxel delivery to cancer cells.
基金This work was supported by the National Natural Science Foundation of China(Nos.21801162,22277011,and 22107019)National Key Research&Development Program of China(No.2020YFA0210800)+1 种基金National Science Basic Research Plan in Shaanxi Province of China(No.2023-JC-QN-0150)the Major Project of Science and Technology of Fujian Province(No.2020HZ06006).
文摘The abundant intracellular glutathione(GSH)in cancer cells severely undermines the therapeutic efficacy of different treatments due to their role in protecting cancer cells from the associated oxidative stress.Developing a highly integrated system to consume GSH would help to improve the therapeutic outcomes.In this study,supramolecular prodrug self-assemblies(SPSAs)with IR825 loaded inside were developed to consume GSH via two-pronged pathways while augmenting the therapeutic potency of chemo/photothermal treatment.SPSAs were prepared using water-soluble pillar[6]arene(WP[6])as host units and H_(2)O_(2)-responsive nitrogen mustard prodrug,chlorambucil-(phenylboronic acid pinacol ester)conjugates(Cb-BE),as the vips.When SPSAs were internalized by cancer cells,the generation of quinone methide(QM)from Cb-BE and singlet oxygen(^(1)O_(2))from irradiation-activated IR825 could consume GSH in a concerted way.As such,the therapeutic efficacies of the released chlorambucil and the accompanied hyperthermia were augmented toward synergistically inhibiting tumor growth.
基金the HE images.This research was funded by the National Nature Science Foundation of China(NSFC 51833006)the National Key R&D Program of China(2018YFC1106100,2018YFC1106101)+3 种基金SJTU Trans-med Awards Research(WF540162603)the Innovation Program of Shanghai Municipal Education Commission(201701070002E00061)the Shanghai Municipal Commission of Health and Family Planning(201840073)the Science and Technology Commission of Shanghai(17DZ2260100).
文摘Retinal degeneration is a main class of ocular diseases.So far,retinal progenitor cell(RPC)transplantation has been the most potential therapy for it,in which promoting RPCs neuronal differentiation remains an unmet challenge.To address this issue,innovatively designed L/D-phenylalanine based chiral nanofibers(LPG and DPG)are employed and it finds that chirality of fibers can efficiently regulate RPCs differentiation.qPCR,western blot,and immunofluorescence analysis show that right-handed helical DPG nanofibers significantly promote RPCs neuronal differentiation,whereas left-handed LPG nanofibers decrease this effect.These effects are mainly ascribed to the stereoselective interaction between chiral helical nanofibers and retinol-binding protein 4(RBP4,a key protein in the retinoic acid(RA)metabolic pathway).The findings of chirality-dependent neuronal differentiation provide new strategies for treatment of neurodegenerative diseases via optimizing differentiation of transplanted stem cells on chiral nanofibers.
基金supported by the National Natural Science Foundation of China (Grant Nos.91027031 and 21125420)the Ministry of Science and Technology of China (Grant No.2011CB932300)the Chinese Academy of Sciences.
文摘Modulating the helicity of self-assemblies of conjugated molecules is important for their application in chiral electronics.In this communication,solvent effect has been investigated on how to modulate the helicity of supramolecular assemblies of sugar-substituted perylenediimide(PTCDI-BAG)by using UV-Vis,circular dichroism spectroscopy and transmission electron microscopy.Left-handed helical nanowires are obtained in the mixed solvent system of both N,N-dimethylformamide/ethanol(DMF/ethanol)and N,N-dimethylacetamide/ethanol(DMAC/ethanol).As changing the solvents into dimethyl sulfoxide/ethanol(DMSO/ethanol),ethylene glycol/ethanol(EG/ethanol),or N-methyl-2-pyrrolidone/ethanol(NMP/ethanol),only right-handed heical nanowires are observed.The chirality of supramolecular structures can be tuned by the controlling of the polarity of the solvents.A theoretical calculation is carried out to explain the chiral optical inversion phenomena of PTCDI-BAG aggregates in different solvents,which reveals that reversed CD spectra is due to the difference of clockwise and anticlockwise rotation of the dimer.
基金supported by the National Natural Science Foundation of China(Grant Nos.22078066 and 22178065)
文摘Recently,nano theranostics,by integrating diagnostic and therapeutic functions into a nano system,have provided increasing opportunities for the design of personalized medicine in cancer.Among the construction method of various theranostic nano systems,the design of single component nanoparticles which are composed of organic photosensitive dyes has become a promising approach to constructing multifunctional nano-theranostic systems,thanks to its unique advantages such as defined structure,100%loading,and high repeatability.Specifically,depending on the inherent photonic imaging and therapeutic properties of the photosensitive dyes,the multifunctional purpose which integrates theranostic effects and targeting abilities can be realized via reasonable molecular modification and supramolecular assembly.In this review,recent advances in the development of nanostructured self-assemblies of porphyrins,phthalocyanines,and boron-dipyrromethanes for theranostics are summarized.Emphasis on their design consideration and theranostic applications are presented.Additionally,prospects for clinical practice and potential challenges of this rapidly growing field are also provided.
基金supported by the National Basic Research Program of China (973 Program, 2011CB932500)National Natural Science Foundation of China (20932004)
文摘Arnphiphilic cyclodextrin-calixarene conjugates 1 and 2 were synthesized from "click claemxstry, and tnelr sen-asscmuly uchaviors were investigated by transmission electron microscopy, and atomic force microscopy. The results obtained show that 1 and 2 can self-assemble to form distinctly different aggregations, and the morphology of aggregations critically relies on the polarity and hydrophilicity of the solvent.
基金supported by the National Key R&D Program of China(No.2022YFB3503700)the National Natural Science Foundation of China(NSFC)(Nos.22135008,U22A20398,and 22275190)+1 种基金the Natural Science Foundation of Fujian Province(Nos.2021L3024,2021Y0067)the Open Fund of State Key Laboratory of Structural Chemistry(No.20210023).
文摘Currently,enzyme-responsive nanomaterials have shown great promise in prognosis or diagnosis of disease biomarker.However,the great obstacle for conventional enzyme-responsive nanomaterials frequently lies in autofluorescence interference,poor monodispersity,uncontrollable size and morphology,low optical stability,and biotoxicity,which fundamentally impede their practical application in biological systems.To overcome these deficiencies,we proposed a novel strategy for reliable and precise detection of an enzyme disease biomarker,alkaline phosphatase(ALP),through lanthanide(Ln^(3+))nucleotide nanoparticles(LNNPs)with extremely improved monodispersity and uniformity,which were achieved by the coordination self-assembly between ATP and Ln^(3+)inside micellar nanoreactor.Specifically,for ATP-Ce/Tb LNNPs,highly improved photoluminescence(PL)emission of Tb^(3+)can be achieved via efficient Ce^(3+)sensitization.We demonstrated that ALP could specifically cleave the phosphorus–oxygen(P–O)bonds of ATP and result in the collapse of ATP-Ce/Tb scaffold,finally leading to the PL quenching of Tb^(3+).By taking advantage of time-resolved(TR)PL technique,the fabricated ATP-Ce/Tb LNNPs presented superior selectivity and sensitivity for the ALP bioassay in complicated serum samples,thus revealing the great potential of ATP-Ce/Tb LNNPs in the areas of ALP-related disease prognosis and diagnosis.
基金supported by the National Science Foundation of China(22071197,22022107,82304889)。
文摘Hydrolysis reactions are capable of directing the non-equilibrium assembly of biomolecular scaffolds to realize sophisticated structures and functions in natural systems.However,utilizing the proper hydrolysis reactions to construct controlled assemblies with complex topologies is still an arduous challenge in artificial systems and needs to be addressed.Herein,we report a nitric oxide(NO)-triggered slow hydrolysis strategy for the controlled construction of biomimetic supramolecular toroids(STs),thus realizing their visualization of intermediate structures and regulation of geometry parameters.This presented protocol harnesses hydrolysis reactions to control of non-equilibrium self-assembly processes for the construction of self-assemblies with complex topologies successfully,which sheds light on how the hydrolysis reaction rate can modulate the kinetic pathway of assembly,thus realizing the artificial establishment of bio-inspired hierarchical structures.
基金supported by the National Natural Science Foundation of China(Nos.81873092,82174074)。
文摘The self-assembled nanoparticles(SAN)formed during the decoction process of traditional Chinese medicine(TCM)exhibit non-uniform particle sizes and a tendency for aggregation.Our group found that the p H-driven method can improve the self-assembly phenomenon of Herpetospermum caudigerum Wall.,and the SAN exhibited uniform particle size and demonstrated good stability.In this paper,we analyzed the interactions between the main active compound,herpetrione(Her),and its main carrier,Herpetospermum caudigerum Wall.polysaccharide(HCWP),along with their self-assembly mechanisms under different p H values.The binding constants of Her and HCWP increase with rising p H,leading to the formation of Her-HCWP SAN with a smaller particle size,higher zeta potential,and improved thermal stability.While the contributions of hydrogen bonding and electrostatic attraction to the formation of Her-HCWP SAN increase with rising p H,the hydrophobic force consistently plays a dominant role.This study enhances our scientific understanding of the self-assembly phenomenon of TCM improved by p H driven method.
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.
