The assembly behaviors of two low-symmetric carboxylic acid molecules(50-(6-carboxynaphthalen-2-yl)-[1,10:30,100-triphenyl]-3,400,5-tricarboxylic acid(CTTA)and 30,50-bis(6-carboxynaphthalen-2-yl)-[1,10-biphenyl]-3,5-d...The assembly behaviors of two low-symmetric carboxylic acid molecules(50-(6-carboxynaphthalen-2-yl)-[1,10:30,100-triphenyl]-3,400,5-tricarboxylic acid(CTTA)and 30,50-bis(6-carboxynaphthalen-2-yl)-[1,10-biphenyl]-3,5-dicarboxylic acid(BCBDA))containing naphthalene rings on graphite surfaces have been investigated using scanning tunneling microscopy(STM).The transformation of nanostructures induced by the second components(EDA and PEBP-C4)have been also examined.Both CTTA and BCBDA molecules self-assemble at the 1-heptanoic acid(HA)/HOPG interface,forming porous network structures.The dimer represents the most elementary building unit due to the formation of double hydrogen bonds.Moreover,the flipping of naphthalene ring results in the isomerization of BCBDA molecule.The introduction of carboxylic acid derivative EDA disrupts the dimer,which subsequently undergoes a structural conformation to form a novel porous structure.Furthermore,upon the addition of pyridine derivative PEBP-C4,N–H⋯O hydrogen bonds are the dominant forces driving the three coassembled structures.We have also conducted density functional theory(DFT)calculations to determine the molecular conformation and analyze the mechanisms underlying the formation of nanostructures.展开更多
Rational design and precise regulation over the morphology, structure, and pore size of functional conducting mesoporous polymers with enriched active sites and shorten electron–ion transport pathway are extremely im...Rational design and precise regulation over the morphology, structure, and pore size of functional conducting mesoporous polymers with enriched active sites and shorten electron–ion transport pathway are extremely important for developing high-performance micro-supercapacitors (MSCs), but still remain a great challenge. Herein, a general dual-colloid interface co-assembly strategy is proposed to fabricate hollow mesoporous polypyrrole nano-bowls (mPPy-nbs) for high-energy-density solid-state planar MSCs. By simply adjusting the size of block copolymer micelles, the diameter of polystyrene nanospheres and the amount of pyrrole monomer, mesopore size of the shell, void and shell thickness of mPPy-nbs can be simultaneously controlled. Importantly, this strategy can be further utilized to synthesize other hollow mesoporous polymers, including poly(tris(4-aminophenyl)amine), poly(1,3,5-triaminobenzene) and their copolymers, demonstrative of excellent universality. The structurally optimized mPPy-nb exhibits high specific surface area of 122 m^(2) g^(−1)and large capacitance of 225 F g^(−1) at 1 mV s^(−1). Furthermore, the MSCs assembled by mPPy-nbs deliver impressive volumetric capacitance of 90 F cm^(−3) and energy density of 2.0 mWh cm^(−3), superior to the most reported polymers-based MSCs. Also, the fabricated MSCs present excellent flexibility with almost no capacitance decay under varying bending states, and robust serial/parallel self-integration for boosting voltage and capacitance output. Therefore, this work will inspire the new design of mesoporous conducting polymer materials toward high-performance microscale supercapacitive devices.展开更多
Co-assembly of ABC linear triblock copolymer/nanoparticle into bump-surface multicompartment hybrids in selective solvent was studied through self-consistent field theory （SCFT） simulation. Results from three-dimens...Co-assembly of ABC linear triblock copolymer/nanoparticle into bump-surface multicompartment hybrids in selective solvent was studied through self-consistent field theory （SCFT） simulation. Results from three-dimensional SCFT simulation showed that the hybrid morphology depended on the length and number of grafted chains, whereas the number and shape of bumps relied on nanoparticle size. Moreover, the simulation results showed that the length and number of grafted chains had equivalent effect on hybrid morphology. Calculated results indicated that entropy was a more important factor than enthalpy in the co-assembly.展开更多
The accumulation of extracellular senile plagues of amyloid β-proteins(Aβ) in the patient brain is one of most important facture in Alzheimer’s disease(AD), which is resulted from abnormal self-assembly of Aβpepti...The accumulation of extracellular senile plagues of amyloid β-proteins(Aβ) in the patient brain is one of most important facture in Alzheimer’s disease(AD), which is resulted from abnormal self-assembly of Aβpeptide. Nanoparticles show greatly potential for therapeutic studies due to the sophisticated surface which can mimic the functionality of protein. Herein, we design the bis(pyrene)-Lys-Leu-Val-Phe-PheGly-poly ethylene glycol(BP-KLVFFGPEG) based nanoparticles, which capture Aβthrough recognition and co-assembly of KLVFF. The resulting co-assemblies show different morphologies, such as large aggregates, nanoparticles and nanofibers corresponding to the different length chain of PEG, leading to different capture efficiencies. The co-assembly strategy shows a decrease of cytotoxicity, potentially for AD treatment.展开更多
The immune microenvironment induced by biomaterials played vital roles in bone regeneration.Hydroxyapatite(HA)and its ion-substituted derivates represent a large class of core inorganic materials for bone tissue engin...The immune microenvironment induced by biomaterials played vital roles in bone regeneration.Hydroxyapatite(HA)and its ion-substituted derivates represent a large class of core inorganic materials for bone tissue engineering.Although ion substitution was proved to be a potent way to grant HA more biological functions,few studies focused on the immunomodulatory properties of ion-doped HA.Herein,to explore the potential osteoimmunomodulatory effects of ion-doped HA,zinc and strontium co-assembled into HA through a collagen template biomimetic way(ZnSr-Col-HA)was successfully achieved.It was found that ZnSr-Col-HA could induce a favorable osteo-immune microenvironment by stimulating macrophages.Furthermore,ZnSr-Col-HA demonstrated a procedural promoting effect on osteogenic differentiation of bone marrow mesenchymal stem cells(BMSCs)in vitro.Specifically,the osteo-immune microenvironment acted as a dominant factor in promoting osteogenic gene expressions at the early stage through OSM signal pathway.Whereas the direct stimulating effects on BMSCs by Zn^(2+)/Sr^(2+) were more effectively at the later stage with Nfatc1/Maf and Wnt signals activated.In vivo study confirmed strong promoting effects of ZnSr-Col-HA on critical-sized cranial defect repair.The current study indicated that such a combined biomaterial design philosophy of dual ion-doping and biomimetic molecular co-assembly to endow HA applicable osteoimmunomodulatory characteristics might bring up a new cutting-edge concept for bone regeneration study.展开更多
Peptide vaccine targeting tumor-specific antigens is a promising cancer treatment regimen.However,peptide vaccines are commonly low-immunogenic,leading to suboptimal antitumor T-cell responses.Current peptide vaccinat...Peptide vaccine targeting tumor-specific antigens is a promising cancer treatment regimen.However,peptide vaccines are commonly low-immunogenic,leading to suboptimal antitumor T-cell responses.Current peptide vaccination approaches are challenged by the variability of peptide physicochemical characters and vaccine formulations,flexibility,and the broad feasibility.Here,the supramolecular co-assembly of antigen epitope-conjugated peptides(ECPs)targeting CD8 or CD4 T-cell receptors was used to engineer a nanofibrious hydrogel vaccine platform.This approach provided precise and tunable loading of peptide antigens in nanofibers,which notably increased the antigen uptake,cross-presentation,and activation of dendritic cells(DCs).Immunization in mice indicated that the co-assembled peptide hydrogel did not induce local inflammation responses and elicited significantly promoted T-cell immunity by activating the MyD88-dependent NF-κB signaling pathway in DCs.Vaccination of mice using co-assembled peptide vaccine stimulated both enhanced CD8 and CD4 T cells against EG.7-OVA tumors without additional immunoadjuvants or delivery systems,and resulted in a more remarkable cancer immunotherapy efficacy,compared with free peptide vaccine or aluminum-adjuvanted peptide formulation.Altogether,peptide co-assembly demonstrated by three independent pairs of ECPs is a facile,customizable,and chemically defined approach for co-delivering peptide antigens in self-adjuvanting hydrogel vaccines that could induce stronger anticancer T-cell responses.展开更多
We demonstrated in this study that mixing two short peptide-based gelators with different aromatic capping groups would result in molecular hydrogels with enhanced mechanical property.We selected gelators of PTZ-GFFY ...We demonstrated in this study that mixing two short peptide-based gelators with different aromatic capping groups would result in molecular hydrogels with enhanced mechanical property.We selected gelators of PTZ-GFFY and Nap-GFFY for the study.Both PTZ-GFFY and Nap-GFFY could independently form molecular hydrogel by a heating-cooling process.However,the mechanical property of gels of PTZ-GFFY and Nap-GFFY was relatively weak with storage moduli(G')of about 500 and 150 Pa,respectively.A two-component gel of PTZ-GFFY and Nap-GFFY could also form by a heating-cooling process.Surprisingly,the G'value of the two-component gel was about 5000 Pa,which was at least ten times bigger than that of each single-component gel.This is a novel and simple strategy to improve the mechanical property of molecular hydrogels.展开更多
Bionanoparticles(BNPs),consisting of virus and virus-like assemblies,have attracted much attention in the biomedical field for their applications such as imaging and targeted drug delivery,owing to their well-defined ...Bionanoparticles(BNPs),consisting of virus and virus-like assemblies,have attracted much attention in the biomedical field for their applications such as imaging and targeted drug delivery,owing to their well-defined structures and well-controlled chemistries.BNPs-based core-shell structures provide a unique system for the investigation of biological interactions such as protein-protein and protein-carbohydrate interactions.However,it is still a challenge to prepare the BNPs-based core-shell structures.Herein,we describe(i) co-assembly method and(ii) template synthesis method in the development of polymer-BNPs core-shell structures.These two methods can be divided into three different systems.In system A,different polymers including poly(2-vinylpyridine)(P2VP),poly(4-vinylpyridine)(P4VP) and poly(ε-caprolactone)-block-poly(2-vinylpyridine)(PCL-b-P2VP) can form a raspberry-like structure with BNPs.In system B,polystyrene(PS) spheres end capped with free amine and BNPs can form a core-shell structure.In System C,layer-by-layer(LBL) method is used to prepare positive charged PS particles,which can be used as a template to form the core-shell structures with BNPs.These two methods may open a new way for preparing novel protein-based functional materials for potential applications in the biomedical field.展开更多
Long-lasting protective immune responses are expected following vaccination.However,most vaccines alone are inability to evoke an efficient protection.The combinatory administration of adjuvants with vaccines is criti...Long-lasting protective immune responses are expected following vaccination.However,most vaccines alone are inability to evoke an efficient protection.The combinatory administration of adjuvants with vaccines is critical for generating the enhanced immune responses.Herein,with biocompatible poly(4-vinylpyridine)(P4VP)as template,2.5 nm iron/molybdenum oxide cluster,{Mo_(72)Fe_(30)},is applied as an adjuvant to co-assemble with antigens of Mycobacterium bovis via hydrogen bonding at molecular scale.Molecular scale integration of the antigens and{Mo_(72)Fe_(30)}and their full exposure to body fluid media contribute to the augmentation of both humoral and cellular immune responses of the vaccines after inoculation in mice.Anti-inflammatory factor IL-10 gradually increases after 2 weeks followed by a final back to normal level by the 5th week.The balance between proinflammatory cytokines and anti-inflammatory factors suggests that immune system can be activated in the early stage of infection by the antigens carried by the supra-particles and secrete acute inflammatory factors for host defense and anti-inflammatory factors for immune protection.展开更多
Chiroptical materials with multicolor and signinvertible circularly polarized luminescence(CPL)are important for advanced optical devices and display technologies.Here,a general strategy is developed to generate CPL w...Chiroptical materials with multicolor and signinvertible circularly polarized luminescence(CPL)are important for advanced optical devices and display technologies.Here,a general strategy is developed to generate CPL with highly tunable emission bands and handedness through charge-transfer(CT)complexation and co-assembly of one chiral non-emissive tetranitrofluorene-based acceptor with various achiral purple to blue emissive donors.The resulting assemblies exhibit intense CPL with a rich array of colors(519-668 nm)and prominent dissymmetry factors(|glum|)in the range of 10^(-3)-10^(-2).Notably,the CPL sign can be readily inverted by slightly changing the molecular structure of achiral donors.Single-crystal analysis reveals that the donor and acceptor molecules are alternately and asymmetrically packed in a lamellar fashion through CT interactions,leading to efficient transfer of chirality.Furthermore,the refined packing is mediated by the intensity and manner of CT interactions,rendering an inversion of chirality.The chiral co-assembly not only occurs for planar achiral donor molecules,but is also accessible to nonplanar conjugated molecules such as[4]helicene derivatives.Thus,the CPL feature of the resulting products can be easily and broadly manipulated,aiming at advanced chiroptical systems.展开更多
Pure drug-assembled nanosystem provides a facile and promising solution for simple manufacturing of nanodrugs,whereas a lack of understanding of the underlying assembly mechanism and the inefficient and uncontrollable...Pure drug-assembled nanosystem provides a facile and promising solution for simple manufacturing of nanodrugs,whereas a lack of understanding of the underlying assembly mechanism and the inefficient and uncontrollable drug release still limits the development and application of this technology.Here,a simple and practical nanoassembly of DOX and DiR is constructed on basis of their co-assembly characteristics.Multiple interaction forces are found to drive the co-assembly process.Moreover,DOX release from the nanoassembly can bewell controlled by the acidic tumormicroenvironment and laser irradiation,resulting in favorable delivery efficiency of DiR and DOX in vitro and in vivo.As expected,the nanoassembly with high therapeutic safety completely eradicated the mice triple negative breast cancer cells(4T1)on BALB/c mice,owing to synergistic chemo-photothermal therapy.More interestingly,DiR and DOX synergistically induce immunogenic cell death(ICD)of tumor cells after treatment,enabling the mice to acquire immune memory against tumor growth and recurrence.Such a facile nanoassembly technique provides a novelmultimodal cancer treatment platform of chemotherapy/phototherapy/immunotherapy.展开更多
Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves c...Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves complex chemical synthesis steps or specific conditions which limits their practical applications. Herein, a new photoresponsive hydrogel is facilely prepared via co-assembly of two simple molecules, Fmoc-Phe-OH and Azp, without chemical synthesis. The co-assembly mechanism, morphology, and photoresponsiveness of(Fmoc-Phe-OH)-Azp hydrogel are investigated by circular dichroism(CD), ultraviolet-visible(UV-Vis), fluorescence, ~1 H nuclear magnetic resonance(~1 H-NMR), attenuated total internal reflection Fourier transform Infrared(ATR-FTIR) spectroscopy, and scanning electron microscopy(SEM). Furthermore, the enhanced release of encapsulated sulforhodamine B(SRB) dye molecules can be achieved via UV light irradiation. The enhanced dye release amount can be controlled by manipulating photoirradiation time. This study provides a facile way to prepare photoresponsive hydrogel which holds great potential for controllable drug release.展开更多
The hybrid structures of polystyrene-b-poly（ethylene oxide） （PS-b-PEO） block copolymer and inorganic nanoparticles with good stability and biocompatibility have potential applications in drug delivery and bioimagi...The hybrid structures of polystyrene-b-poly（ethylene oxide） （PS-b-PEO） block copolymer and inorganic nanoparticles with good stability and biocompatibility have potential applications in drug delivery and bioimaging. Spherical co-assemblies of PS120-b-PEO318 and oleylamine-capped CdS quantum dots （QDs） are produced successfully in this work by adding water to a mixed common solvent, such as N,N-dimethylmethanamide （DMF）/chloroform, DMF/tetrahydrofuran （THF）, or DMF/toluene. The energy dispersive X-ray （EDX） spectrum indicates that QDs are located at the interface between the core and shell of the spherical co-assemblies. The co-assembly process during water addition is traced by transmission electron microscopy （TEM） and turbidity measurement. Spherical co-assemblies are formed through budding from bilayers of the block copolymer and QDs. The morphology of the co-assemblies is related to the miscibility of the QD-dispersing solvents with water and the morphology changes from a spherical to a vesicle-like structure with DMF/toluene. Increasing THF content in the mixed solvent causes morphological transitions from spherical co-assemblies to multi-branched cylinders and micelles where QDs are located in the central core. Increasing chloroform content yields vesicle-like structures with protruding rods on the surface. The mechanism of the morphological transitions is also discussed in detail.展开更多
Photodynamic therapy(PDT)has shown great application potential in cancer treatment and the important manifestation of PDT in the inhibition of tumors is the activation of immunogenic cell death(ICD)effects.However,the...Photodynamic therapy(PDT)has shown great application potential in cancer treatment and the important manifestation of PDT in the inhibition of tumors is the activation of immunogenic cell death(ICD)effects.However,the strategy is limited in the innate hypoxic tumor microenvironment.There are two key elements for the realization of enhanced PDT:specific cellular uptake and release of the photosensitizer in the tumor,and a sufficient amount of oxygen to ensure photodynamic efficiency.Herein,self-oxygenated biomimetic nanoparticles(CS@M NPs)co-assembled by photosensitizer prodrug(Ce6-S-S-LA)and squalene(SQ)were engineered.In the treatment of triple negative breast cancer(TNBC),the oxygen carried by SQ can be converted to reactive oxygen species(ROS).Meanwhile,glutathione(GSH)consumption during transformation from Ce6-S-S-LA to chlorin e6(Ce6)avoided the depletion of ROS.The co-assembled(CS NPs)were encapsulated by homologous tumor cell membrane to improve the tumor targeting.The results showed that the ICD effect of CS@M NPs was confirmed by the significant release of calreticulin(CRT)and high mobility group protein B1(HMGB1),and it significantly activated the immune system by inhibiting the hypoxia inducible factor-1alpha(HIF-1α)-CD39-CD73-adenosine a2a receptor(A2AR)pathway,which not only promoted the maturation of dendritic cells(DC)and the presentation of tumor specific antigens,but also induced effective immune infiltration of tumors.Overall,the integrated nanoplatform implements the concept of multiple advantages of tumor targeting,reactive drug release,and synergistic photodynamic therapy-immunotherapy,which can achieve nearly 90%tumor suppression rate in orthotopic TNBC models.展开更多
The combination of diagnostic and therapeutic agents in the form of theranostic platforms to enhance tumor therapeutic efficacy is receiving increasing attention in recent years.However,simultaneous encapsulation,embe...The combination of diagnostic and therapeutic agents in the form of theranostic platforms to enhance tumor therapeutic efficacy is receiving increasing attention in recent years.However,simultaneous encapsulation,embedding or conjugation of various agents to traditional theranostic nanocarriers always require intricate synthetic process.Herein,a supramolecular drug-drug self-delivery nanosystem(DSDN)based on a newly developed aggregation-induced emission(AIE)photosensitizer(CBTM)and an anti-tumor tyroservaltide(YSV)was constructed for near-infrared(NIR)fluorescence imaging-guided photodynamic/chemotherapy of tumor.Transmission electron microscopy(TEM)and dynamic light scattering(DLS)confirmed that YSV and CBTM could co-assemble into YSV/CBTM nanoparticles,with regular round-shape morphology and homogeneous size.Inspiringly,YSV/CBTM nanoparticles could effectively overcome the aggregation-caused quenching(ACQ)effect,and enter CT26 tumor cells with a high NIR fluorescence emission,allowing preoperative diagnosis.Meanwhile,the as-prepared YSV/CBTM could efficiently generate reactive oxygen species(ROS)under NIR light irradiation,exhibiting photodynamic ablation of tumor cells.More importantly,the peptide drug of YSV not only improved the availability of CBTM nanoparticles,but also served as a toxic adjuvant to enhance the photodynamic therapy(PDT)efficacy of CBTM.In vitro and in vivo assays revealed that most of colorectal tumor cells and tumor tissues were thoroughly ablated by photodynamic-chemotherapy integrated nanoparticles,resulting in longer survival of tumor-bearing mice.Regarding the advantages of the YSV/CBTM nanosystem,we believe this research could offer valuable guidance for the design of nanodrugs with high performance for cancer theranostics.展开更多
The self-assembled structures of H_(3) BDA molecule with multiple meta-dicarboxylic groups and their stim-ulus responses to the vip molecules(COR and T4PT)are thoroughly investigated by scanning tunneling microscopy...The self-assembled structures of H_(3) BDA molecule with multiple meta-dicarboxylic groups and their stim-ulus responses to the vip molecules(COR and T4PT)are thoroughly investigated by scanning tunneling microscopy(STM).STM observations display that two kinds of nanostructures are fabricated by H3 BDA molecules through intermolecular hydrogen bonds,in which a linear structure is formed at a higher con-centration and a flower-like structure is obtained at a lower concentration.After the addition of COR and T4PT,H_(3) BDA appears different responsiveness resulting in different co-assembled structures,respectively.The linear structure is regulated into a flower-like structure by COR and COR molecules are trapped in the cavities.When the pyridine derivative(T4PT)is introduced,a new bicomponent porous structure emerges via the hydrogen bond formed between the carboxyl group and the pyridine.Furthermore,the deposition of additional COR to the H_(3) BDA/T4PT system results in the breakdown of the porous structure and the generation of H_(3) BDA/COR host-vip system.Combined with density functional theory(DFT)calculations and molecular dynamics(MD)simulations,the transformation phenomenon of bi-component nanostruc-ture induced by vip molecules is formulated.The results are expected to understand the modification effect of vip molecules on the host network,which is of great significance for the design and construc-tion of multi-component nanostructures and crystal engineering.展开更多
Glycyrrhizic acid(GA),as a traditional herbal,can self-assemble into helical nanofiber in the water.The formed helical nanostructures can be employed as scaffolds for asymmetric Diels-Alder reaction.Through co-assembl...Glycyrrhizic acid(GA),as a traditional herbal,can self-assemble into helical nanofiber in the water.The formed helical nanostructures can be employed as scaffolds for asymmetric Diels-Alder reaction.Through co-assembling with a series of achiral copper-ligands,the chirality of GA helical nanostructures can be transferred to catalytic site,and resulted assemblies showed moderated enantioselectivity toward catalysis of Diels-Alder reaction.展开更多
Biomimetics provides us a new perspective to understand complex biological process and strategy to fabricate functional materials. However,a great challenge still remains to design and fabricate biomimetic materials u...Biomimetics provides us a new perspective to understand complex biological process and strategy to fabricate functional materials. However,a great challenge still remains to design and fabricate biomimetic materials using a facile but effective method. Here, we develop a biomimetic light harvesting architecture based on one-step co-assembly of amphiphilic amino acid and porphyrin. Amphiphilic amino acid can self-assemble into nanofibers via π-stacking and hydrogen binding interactions. Negatively charged porphyrin adsorbs on the surface of the assembled nanofibers through electrostatic force, and the nanofibers further organize into porous urchin-like microspheres induced presumably by hydrophobic interaction. The assembled amphiphilic amino acid nanofibers work as a template to tune the organization of porphyrin with an architecture principle analogous to natural light harvesting complex. The co-assembled microspheres exhibit enhanced light capture due to the light reflection in the porous structure. Reaction center(platinum nanoparticles) can be effectively coupled with the light harvesting microspheres via photoreduction. After visible light illumination, hydrogen evolution occurs on the hybrid microspheres.展开更多
Mesoporous late-transition metal oxides have great potential in applications of energy,catalysis and chemical sensing due to their unique physical and chemical properties.However,their synthesis via the flexible and s...Mesoporous late-transition metal oxides have great potential in applications of energy,catalysis and chemical sensing due to their unique physical and chemical properties.However,their synthesis via the flexible and scalable soft-template method remain a great challenge,due to the weak organic-inorganic interaction between the frequently used surfactants(e.g.,Pluronic-type block copolymers) and metal oxide precursors,and the low crystallization temperature of metal oxides.In this study,ordered mesoporous NiO with dual mesopores,high surface area and well-interconnected crystalline porous frameworks have been successfully synthesized via the facile solvent evaporation-induced co-assembly(EICA) method,by using lab-made amphiphilic diblock copolymer polystyrene-b-poly(4-vinylpyridine)(PS-b-P4 VP) as both the structure-directing agent(the soft template) and macromolecular chelating agents for nickel species,THF as the solvent,and nickel acetylacetonate(Ni(acac)2) as inorganic precursor.Similarly,by using Ni(acac)2 and Fe(acac)3 as the binary precursors,ordered mesoporous Fedoped NiO materials can be obtained,which have bimodal mesopores of large mesopores(32.5 nm) and secondary mesopores(4.0-11.5 nm) in the nanocrystal-assembled walls,high specific surface areas(~74.8 m^2/g) and large pore value(~0.167 cm^3/g).The obtained mesoporous Fe-doped NiO based gas sensor showed superior ethanol sensing performances with good sensitivity,high selectivity and fast response-recovery dynamics.展开更多
The self-assembled behavior of an unsymmetric molecule(BCDTDA)with one imidazole group as center and benzoic acid group as functional group is studied,and the regulatory behaviors of coronene(COR)and three bipyridine ...The self-assembled behavior of an unsymmetric molecule(BCDTDA)with one imidazole group as center and benzoic acid group as functional group is studied,and the regulatory behaviors of coronene(COR)and three bipyridine derivatives(named BP,PEBP-C4 and PEBP-C8)on BCDTDA self-assembly structures are also investigated.Based on highly oriented pyrolytic graphite(HOPG)substrate,scanning tunneling microscopy(STM)is used to observe the variation of assembled behaviors at the solid-liquid interface.Because of the concentration effect,BCDTDA molecules can assemble into grids and Kagomés structures in the form of N–H…O hydrogen bonded dimers.BCDTDA molecules still maintain dimeric structures in the regulation of COR and BP molecules to BCDTDA self-assembly.However,PEBP-C4 and PEBP-C8 destroy the structure of the dimers,and form a variety of co-assembled structures with BCDTDA.Different vip molecules coordinate the host molecules differently,which makes the experiment more meaningful.Combined with density functional theory(DFT)calculation,the discovery of molecular interactions provides a promising strategy for the construction of functional nanostructures and devices.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22272039)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB36000000)+1 种基金the Youth Program of the Liaoning Education Department(No.LJKQZ20222280)the Jilin Chinese Academy of Sciences-Yanshen Technology Co.,Ltd.
文摘The assembly behaviors of two low-symmetric carboxylic acid molecules(50-(6-carboxynaphthalen-2-yl)-[1,10:30,100-triphenyl]-3,400,5-tricarboxylic acid(CTTA)and 30,50-bis(6-carboxynaphthalen-2-yl)-[1,10-biphenyl]-3,5-dicarboxylic acid(BCBDA))containing naphthalene rings on graphite surfaces have been investigated using scanning tunneling microscopy(STM).The transformation of nanostructures induced by the second components(EDA and PEBP-C4)have been also examined.Both CTTA and BCBDA molecules self-assemble at the 1-heptanoic acid(HA)/HOPG interface,forming porous network structures.The dimer represents the most elementary building unit due to the formation of double hydrogen bonds.Moreover,the flipping of naphthalene ring results in the isomerization of BCBDA molecule.The introduction of carboxylic acid derivative EDA disrupts the dimer,which subsequently undergoes a structural conformation to form a novel porous structure.Furthermore,upon the addition of pyridine derivative PEBP-C4,N–H⋯O hydrogen bonds are the dominant forces driving the three coassembled structures.We have also conducted density functional theory(DFT)calculations to determine the molecular conformation and analyze the mechanisms underlying the formation of nanostructures.
基金This work was financially supported by the Natural Science Foundation of China(Grant No.51773062,61831021,51872283,21805273,22075279,22005297,22005298)the China Postdoctoral Science Foundation(Project No.2019M661421)+9 种基金the National Key R@D Program of China(Grants 2016YBF0100100,2016YFA0200200)the Liaoning BaiQianWan Talents Program,Liaoning Revitalization Talents Program(Grant XLYC1807153)the Natural Science Foundation of Liaoning Province,Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science(Grant 20180510038)the Dalian Innovation Support Plan for High Level Talents(2019RT09)DICP(DICP ZZBS201708,DICP ZZBS201802,and DICP 1202032)the DICP&QIBEBT(Grant DICP&QjBEBT UN201702)the Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL180310,DNL180308,DNL201912,and DNL201915)We thank Yucen Li and Prof.Ming Hu(East China Normal University,China)for the kind help in nitrogen absorption-desorption isotherms measurementalso thank the Material structure analysis center and Multifunctional Platform for Innovation of East China Normal University(003,004,006)the Center for Advanced Electronic Materials and Devices(AEMD)of Shanghai Jiao Tong University.
文摘Rational design and precise regulation over the morphology, structure, and pore size of functional conducting mesoporous polymers with enriched active sites and shorten electron–ion transport pathway are extremely important for developing high-performance micro-supercapacitors (MSCs), but still remain a great challenge. Herein, a general dual-colloid interface co-assembly strategy is proposed to fabricate hollow mesoporous polypyrrole nano-bowls (mPPy-nbs) for high-energy-density solid-state planar MSCs. By simply adjusting the size of block copolymer micelles, the diameter of polystyrene nanospheres and the amount of pyrrole monomer, mesopore size of the shell, void and shell thickness of mPPy-nbs can be simultaneously controlled. Importantly, this strategy can be further utilized to synthesize other hollow mesoporous polymers, including poly(tris(4-aminophenyl)amine), poly(1,3,5-triaminobenzene) and their copolymers, demonstrative of excellent universality. The structurally optimized mPPy-nb exhibits high specific surface area of 122 m^(2) g^(−1)and large capacitance of 225 F g^(−1) at 1 mV s^(−1). Furthermore, the MSCs assembled by mPPy-nbs deliver impressive volumetric capacitance of 90 F cm^(−3) and energy density of 2.0 mWh cm^(−3), superior to the most reported polymers-based MSCs. Also, the fabricated MSCs present excellent flexibility with almost no capacitance decay under varying bending states, and robust serial/parallel self-integration for boosting voltage and capacitance output. Therefore, this work will inspire the new design of mesoporous conducting polymer materials toward high-performance microscale supercapacitive devices.
基金supported by the National Natural Science Foundation of China for General Program(No. 21274145)
文摘Co-assembly of ABC linear triblock copolymer/nanoparticle into bump-surface multicompartment hybrids in selective solvent was studied through self-consistent field theory （SCFT） simulation. Results from three-dimensional SCFT simulation showed that the hybrid morphology depended on the length and number of grafted chains, whereas the number and shape of bumps relied on nanoparticle size. Moreover, the simulation results showed that the length and number of grafted chains had equivalent effect on hybrid morphology. Calculated results indicated that entropy was a more important factor than enthalpy in the co-assembly.
基金supported by the National Natural Science Foundation of China(Nos.51573031,21374026 and 51573032)the National Science Fund for Distinguished Young Scholars(No.51725302)+2 种基金the Science Fund for Creative Research Groups of the National Natural Science Foundation of China(No.11621505)CAS Key Research Program for Frontier Sciences(No.QYZDJ-SSWSLH022)Key Project of Chinese Academy of Sciences in Cooperation with Foreign Enterprises(No.GJHZ1541)
文摘The accumulation of extracellular senile plagues of amyloid β-proteins(Aβ) in the patient brain is one of most important facture in Alzheimer’s disease(AD), which is resulted from abnormal self-assembly of Aβpeptide. Nanoparticles show greatly potential for therapeutic studies due to the sophisticated surface which can mimic the functionality of protein. Herein, we design the bis(pyrene)-Lys-Leu-Val-Phe-PheGly-poly ethylene glycol(BP-KLVFFGPEG) based nanoparticles, which capture Aβthrough recognition and co-assembly of KLVFF. The resulting co-assemblies show different morphologies, such as large aggregates, nanoparticles and nanofibers corresponding to the different length chain of PEG, leading to different capture efficiencies. The co-assembly strategy shows a decrease of cytotoxicity, potentially for AD treatment.
基金supported by National Key R&D Project(2018YFC1105701)of ChinaNational Natural Science Foundation of China(31870960,81801850)the Fundamental Research Funds for the Central Universities,HUST(2019kfyXMBZ021,2020kfyXJJS115).
文摘The immune microenvironment induced by biomaterials played vital roles in bone regeneration.Hydroxyapatite(HA)and its ion-substituted derivates represent a large class of core inorganic materials for bone tissue engineering.Although ion substitution was proved to be a potent way to grant HA more biological functions,few studies focused on the immunomodulatory properties of ion-doped HA.Herein,to explore the potential osteoimmunomodulatory effects of ion-doped HA,zinc and strontium co-assembled into HA through a collagen template biomimetic way(ZnSr-Col-HA)was successfully achieved.It was found that ZnSr-Col-HA could induce a favorable osteo-immune microenvironment by stimulating macrophages.Furthermore,ZnSr-Col-HA demonstrated a procedural promoting effect on osteogenic differentiation of bone marrow mesenchymal stem cells(BMSCs)in vitro.Specifically,the osteo-immune microenvironment acted as a dominant factor in promoting osteogenic gene expressions at the early stage through OSM signal pathway.Whereas the direct stimulating effects on BMSCs by Zn^(2+)/Sr^(2+) were more effectively at the later stage with Nfatc1/Maf and Wnt signals activated.In vivo study confirmed strong promoting effects of ZnSr-Col-HA on critical-sized cranial defect repair.The current study indicated that such a combined biomaterial design philosophy of dual ion-doping and biomimetic molecular co-assembly to endow HA applicable osteoimmunomodulatory characteristics might bring up a new cutting-edge concept for bone regeneration study.
基金the National Natural Science Foundation of China(No.31870950)China Postdoctoral Science Foundation(No.2019M660029)+1 种基金Non-profit Central Research Institute Fund of Chinese Academy of Medical Sciences(No.2018RC350017)Young Elite Scientists Sponsorship Program by Tianjin(TJSQNTJ-2018-01).
文摘Peptide vaccine targeting tumor-specific antigens is a promising cancer treatment regimen.However,peptide vaccines are commonly low-immunogenic,leading to suboptimal antitumor T-cell responses.Current peptide vaccination approaches are challenged by the variability of peptide physicochemical characters and vaccine formulations,flexibility,and the broad feasibility.Here,the supramolecular co-assembly of antigen epitope-conjugated peptides(ECPs)targeting CD8 or CD4 T-cell receptors was used to engineer a nanofibrious hydrogel vaccine platform.This approach provided precise and tunable loading of peptide antigens in nanofibers,which notably increased the antigen uptake,cross-presentation,and activation of dendritic cells(DCs).Immunization in mice indicated that the co-assembled peptide hydrogel did not induce local inflammation responses and elicited significantly promoted T-cell immunity by activating the MyD88-dependent NF-κB signaling pathway in DCs.Vaccination of mice using co-assembled peptide vaccine stimulated both enhanced CD8 and CD4 T cells against EG.7-OVA tumors without additional immunoadjuvants or delivery systems,and resulted in a more remarkable cancer immunotherapy efficacy,compared with free peptide vaccine or aluminum-adjuvanted peptide formulation.Altogether,peptide co-assembly demonstrated by three independent pairs of ECPs is a facile,customizable,and chemically defined approach for co-delivering peptide antigens in self-adjuvanting hydrogel vaccines that could induce stronger anticancer T-cell responses.
基金This work is supported by the National Natural Science Foundation of China(Nos.51173060 and 51203078).
文摘We demonstrated in this study that mixing two short peptide-based gelators with different aromatic capping groups would result in molecular hydrogels with enhanced mechanical property.We selected gelators of PTZ-GFFY and Nap-GFFY for the study.Both PTZ-GFFY and Nap-GFFY could independently form molecular hydrogel by a heating-cooling process.However,the mechanical property of gels of PTZ-GFFY and Nap-GFFY was relatively weak with storage moduli(G')of about 500 and 150 Pa,respectively.A two-component gel of PTZ-GFFY and Nap-GFFY could also form by a heating-cooling process.Surprisingly,the G'value of the two-component gel was about 5000 Pa,which was at least ten times bigger than that of each single-component gel.This is a novel and simple strategy to improve the mechanical property of molecular hydrogels.
基金support from the US NSF CAREER program,US DoD (W911NF-09-1-0236),the Alfred P. Sloan Scholarship, the Camille Dreyfus Teacher Scholar Award, DoD-BCRP,and the W.M.Keck Foundation
文摘Bionanoparticles(BNPs),consisting of virus and virus-like assemblies,have attracted much attention in the biomedical field for their applications such as imaging and targeted drug delivery,owing to their well-defined structures and well-controlled chemistries.BNPs-based core-shell structures provide a unique system for the investigation of biological interactions such as protein-protein and protein-carbohydrate interactions.However,it is still a challenge to prepare the BNPs-based core-shell structures.Herein,we describe(i) co-assembly method and(ii) template synthesis method in the development of polymer-BNPs core-shell structures.These two methods can be divided into three different systems.In system A,different polymers including poly(2-vinylpyridine)(P2VP),poly(4-vinylpyridine)(P4VP) and poly(ε-caprolactone)-block-poly(2-vinylpyridine)(PCL-b-P2VP) can form a raspberry-like structure with BNPs.In system B,polystyrene(PS) spheres end capped with free amine and BNPs can form a core-shell structure.In System C,layer-by-layer(LBL) method is used to prepare positive charged PS particles,which can be used as a template to form the core-shell structures with BNPs.These two methods may open a new way for preparing novel protein-based functional materials for potential applications in the biomedical field.
基金The work was supported financially by the National Natural Science Foundation of China(Nos.22101086,21961142018,and 51873067)the Natural Science Foundation of Guangdong Province(Nos.2021A1515012024 and 2021A1515010271).
文摘Long-lasting protective immune responses are expected following vaccination.However,most vaccines alone are inability to evoke an efficient protection.The combinatory administration of adjuvants with vaccines is critical for generating the enhanced immune responses.Herein,with biocompatible poly(4-vinylpyridine)(P4VP)as template,2.5 nm iron/molybdenum oxide cluster,{Mo_(72)Fe_(30)},is applied as an adjuvant to co-assemble with antigens of Mycobacterium bovis via hydrogen bonding at molecular scale.Molecular scale integration of the antigens and{Mo_(72)Fe_(30)}and their full exposure to body fluid media contribute to the augmentation of both humoral and cellular immune responses of the vaccines after inoculation in mice.Anti-inflammatory factor IL-10 gradually increases after 2 weeks followed by a final back to normal level by the 5th week.The balance between proinflammatory cytokines and anti-inflammatory factors suggests that immune system can be activated in the early stage of infection by the antigens carried by the supra-particles and secrete acute inflammatory factors for host defense and anti-inflammatory factors for immune protection.
基金This work was financially supported by the National Key R&D Program of China(grant no.2020YFA0908100)the National Natural Science Foundation of China(grant nos.92056110 and 22075180)+2 种基金the Innovation Program of Shanghai Municipal Education Commission(grant no.202101070002E00084)the Science and Technology Commission of Shanghai Municipality(grant nos.20JC1415000 and 21XD1421900)the China Postdoctoral Science Foundation(grant no.2019M661480).
文摘Chiroptical materials with multicolor and signinvertible circularly polarized luminescence(CPL)are important for advanced optical devices and display technologies.Here,a general strategy is developed to generate CPL with highly tunable emission bands and handedness through charge-transfer(CT)complexation and co-assembly of one chiral non-emissive tetranitrofluorene-based acceptor with various achiral purple to blue emissive donors.The resulting assemblies exhibit intense CPL with a rich array of colors(519-668 nm)and prominent dissymmetry factors(|glum|)in the range of 10^(-3)-10^(-2).Notably,the CPL sign can be readily inverted by slightly changing the molecular structure of achiral donors.Single-crystal analysis reveals that the donor and acceptor molecules are alternately and asymmetrically packed in a lamellar fashion through CT interactions,leading to efficient transfer of chirality.Furthermore,the refined packing is mediated by the intensity and manner of CT interactions,rendering an inversion of chirality.The chiral co-assembly not only occurs for planar achiral donor molecules,but is also accessible to nonplanar conjugated molecules such as[4]helicene derivatives.Thus,the CPL feature of the resulting products can be easily and broadly manipulated,aiming at advanced chiroptical systems.
基金financially supported by the Liaoning Revitalization Talents Program (no. XLYC1907129)the National Natural Science Foundation of China (no. 82161138029)+1 种基金the Excellent Youth Science Foundation of Liaoning Province (no. 2020-YQ-06)the China Postdoctoral Science Foundation (no. 2020M670794 and no. 2021MD703858)
文摘Pure drug-assembled nanosystem provides a facile and promising solution for simple manufacturing of nanodrugs,whereas a lack of understanding of the underlying assembly mechanism and the inefficient and uncontrollable drug release still limits the development and application of this technology.Here,a simple and practical nanoassembly of DOX and DiR is constructed on basis of their co-assembly characteristics.Multiple interaction forces are found to drive the co-assembly process.Moreover,DOX release from the nanoassembly can bewell controlled by the acidic tumormicroenvironment and laser irradiation,resulting in favorable delivery efficiency of DiR and DOX in vitro and in vivo.As expected,the nanoassembly with high therapeutic safety completely eradicated the mice triple negative breast cancer cells(4T1)on BALB/c mice,owing to synergistic chemo-photothermal therapy.More interestingly,DiR and DOX synergistically induce immunogenic cell death(ICD)of tumor cells after treatment,enabling the mice to acquire immune memory against tumor growth and recurrence.Such a facile nanoassembly technique provides a novelmultimodal cancer treatment platform of chemotherapy/phototherapy/immunotherapy.
基金financially supported by the Alexander von Humboldt Foundation(postdoc stipend to X.Q.Dou)the European Research Council(No.279202)the National Natural Science Foundation of China(Nos.51833006 and 51573092)
文摘Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves complex chemical synthesis steps or specific conditions which limits their practical applications. Herein, a new photoresponsive hydrogel is facilely prepared via co-assembly of two simple molecules, Fmoc-Phe-OH and Azp, without chemical synthesis. The co-assembly mechanism, morphology, and photoresponsiveness of(Fmoc-Phe-OH)-Azp hydrogel are investigated by circular dichroism(CD), ultraviolet-visible(UV-Vis), fluorescence, ~1 H nuclear magnetic resonance(~1 H-NMR), attenuated total internal reflection Fourier transform Infrared(ATR-FTIR) spectroscopy, and scanning electron microscopy(SEM). Furthermore, the enhanced release of encapsulated sulforhodamine B(SRB) dye molecules can be achieved via UV light irradiation. The enhanced dye release amount can be controlled by manipulating photoirradiation time. This study provides a facile way to prepare photoresponsive hydrogel which holds great potential for controllable drug release.
基金financially supported by the National Natural Science Foundation of China(No.21274145)
文摘The hybrid structures of polystyrene-b-poly（ethylene oxide） （PS-b-PEO） block copolymer and inorganic nanoparticles with good stability and biocompatibility have potential applications in drug delivery and bioimaging. Spherical co-assemblies of PS120-b-PEO318 and oleylamine-capped CdS quantum dots （QDs） are produced successfully in this work by adding water to a mixed common solvent, such as N,N-dimethylmethanamide （DMF）/chloroform, DMF/tetrahydrofuran （THF）, or DMF/toluene. The energy dispersive X-ray （EDX） spectrum indicates that QDs are located at the interface between the core and shell of the spherical co-assemblies. The co-assembly process during water addition is traced by transmission electron microscopy （TEM） and turbidity measurement. Spherical co-assemblies are formed through budding from bilayers of the block copolymer and QDs. The morphology of the co-assemblies is related to the miscibility of the QD-dispersing solvents with water and the morphology changes from a spherical to a vesicle-like structure with DMF/toluene. Increasing THF content in the mixed solvent causes morphological transitions from spherical co-assemblies to multi-branched cylinders and micelles where QDs are located in the central core. Increasing chloroform content yields vesicle-like structures with protruding rods on the surface. The mechanism of the morphological transitions is also discussed in detail.
基金supported by the Guangdong Nature Resource Center(No.(2020)037)Natural Science Foundation of Guangdong Province(Nos.22019A1515011498 and 2019A1515011619)+2 种基金Basic and Applied Basic Research Foundation of Guangdong Province(No.2020B1515120063)National Natural Science Foundation of China(No.81803877)supported by the China Postdoctoral Science Foundation(No.2022M721535)。
文摘Photodynamic therapy(PDT)has shown great application potential in cancer treatment and the important manifestation of PDT in the inhibition of tumors is the activation of immunogenic cell death(ICD)effects.However,the strategy is limited in the innate hypoxic tumor microenvironment.There are two key elements for the realization of enhanced PDT:specific cellular uptake and release of the photosensitizer in the tumor,and a sufficient amount of oxygen to ensure photodynamic efficiency.Herein,self-oxygenated biomimetic nanoparticles(CS@M NPs)co-assembled by photosensitizer prodrug(Ce6-S-S-LA)and squalene(SQ)were engineered.In the treatment of triple negative breast cancer(TNBC),the oxygen carried by SQ can be converted to reactive oxygen species(ROS).Meanwhile,glutathione(GSH)consumption during transformation from Ce6-S-S-LA to chlorin e6(Ce6)avoided the depletion of ROS.The co-assembled(CS NPs)were encapsulated by homologous tumor cell membrane to improve the tumor targeting.The results showed that the ICD effect of CS@M NPs was confirmed by the significant release of calreticulin(CRT)and high mobility group protein B1(HMGB1),and it significantly activated the immune system by inhibiting the hypoxia inducible factor-1alpha(HIF-1α)-CD39-CD73-adenosine a2a receptor(A2AR)pathway,which not only promoted the maturation of dendritic cells(DC)and the presentation of tumor specific antigens,but also induced effective immune infiltration of tumors.Overall,the integrated nanoplatform implements the concept of multiple advantages of tumor targeting,reactive drug release,and synergistic photodynamic therapy-immunotherapy,which can achieve nearly 90%tumor suppression rate in orthotopic TNBC models.
基金financially supported by Natural Science Foundation of China(Nos.52173295,52273313,22377152,52202357)the Fundamental Research Funds for the Central Universities,South-Central Minzu University(Nos.CZQ23036,CZY22005)the Knowledge Innovation Program of Wuhan-Basic Research(No.2023020201010150)。
文摘The combination of diagnostic and therapeutic agents in the form of theranostic platforms to enhance tumor therapeutic efficacy is receiving increasing attention in recent years.However,simultaneous encapsulation,embedding or conjugation of various agents to traditional theranostic nanocarriers always require intricate synthetic process.Herein,a supramolecular drug-drug self-delivery nanosystem(DSDN)based on a newly developed aggregation-induced emission(AIE)photosensitizer(CBTM)and an anti-tumor tyroservaltide(YSV)was constructed for near-infrared(NIR)fluorescence imaging-guided photodynamic/chemotherapy of tumor.Transmission electron microscopy(TEM)and dynamic light scattering(DLS)confirmed that YSV and CBTM could co-assemble into YSV/CBTM nanoparticles,with regular round-shape morphology and homogeneous size.Inspiringly,YSV/CBTM nanoparticles could effectively overcome the aggregation-caused quenching(ACQ)effect,and enter CT26 tumor cells with a high NIR fluorescence emission,allowing preoperative diagnosis.Meanwhile,the as-prepared YSV/CBTM could efficiently generate reactive oxygen species(ROS)under NIR light irradiation,exhibiting photodynamic ablation of tumor cells.More importantly,the peptide drug of YSV not only improved the availability of CBTM nanoparticles,but also served as a toxic adjuvant to enhance the photodynamic therapy(PDT)efficacy of CBTM.In vitro and in vivo assays revealed that most of colorectal tumor cells and tumor tissues were thoroughly ablated by photodynamic-chemotherapy integrated nanoparticles,resulting in longer survival of tumor-bearing mice.Regarding the advantages of the YSV/CBTM nanosystem,we believe this research could offer valuable guidance for the design of nanodrugs with high performance for cancer theranostics.
基金support from the National Natural Science Foundation of China(No.22172055)the Natural Science Foundation of Guangdong Province(Nos.2023B1515040026,2022A1515011892)the Basic and Applied Basic Research Program of Guangzhou City(Nos.202002030083,202102080443)is gratefully acknowledged.
文摘The self-assembled structures of H_(3) BDA molecule with multiple meta-dicarboxylic groups and their stim-ulus responses to the vip molecules(COR and T4PT)are thoroughly investigated by scanning tunneling microscopy(STM).STM observations display that two kinds of nanostructures are fabricated by H3 BDA molecules through intermolecular hydrogen bonds,in which a linear structure is formed at a higher con-centration and a flower-like structure is obtained at a lower concentration.After the addition of COR and T4PT,H_(3) BDA appears different responsiveness resulting in different co-assembled structures,respectively.The linear structure is regulated into a flower-like structure by COR and COR molecules are trapped in the cavities.When the pyridine derivative(T4PT)is introduced,a new bicomponent porous structure emerges via the hydrogen bond formed between the carboxyl group and the pyridine.Furthermore,the deposition of additional COR to the H_(3) BDA/T4PT system results in the breakdown of the porous structure and the generation of H_(3) BDA/COR host-vip system.Combined with density functional theory(DFT)calculations and molecular dynamics(MD)simulations,the transformation phenomenon of bi-component nanostruc-ture induced by vip molecules is formulated.The results are expected to understand the modification effect of vip molecules on the host network,which is of great significance for the design and construc-tion of multi-component nanostructures and crystal engineering.
基金the National Natural Science Foundation of China(Nos.21861132002,21773043)Chinese Academy of Sciences(Nos.XDB12020200,QYZDJ-SSW-SLH044)for the financial support
文摘Glycyrrhizic acid(GA),as a traditional herbal,can self-assemble into helical nanofiber in the water.The formed helical nanostructures can be employed as scaffolds for asymmetric Diels-Alder reaction.Through co-assembling with a series of achiral copper-ligands,the chirality of GA helical nanostructures can be transferred to catalytic site,and resulted assemblies showed moderated enantioselectivity toward catalysis of Diels-Alder reaction.
基金financial support from the National Natural Science Foundation of China(Project Nos.21522307,21473208,91434103 and 21473153)the Talent Fund of the Recruitment Program of Global Youth Expertsthe Chinese Academy of Sciences
文摘Biomimetics provides us a new perspective to understand complex biological process and strategy to fabricate functional materials. However,a great challenge still remains to design and fabricate biomimetic materials using a facile but effective method. Here, we develop a biomimetic light harvesting architecture based on one-step co-assembly of amphiphilic amino acid and porphyrin. Amphiphilic amino acid can self-assemble into nanofibers via π-stacking and hydrogen binding interactions. Negatively charged porphyrin adsorbs on the surface of the assembled nanofibers through electrostatic force, and the nanofibers further organize into porous urchin-like microspheres induced presumably by hydrophobic interaction. The assembled amphiphilic amino acid nanofibers work as a template to tune the organization of porphyrin with an architecture principle analogous to natural light harvesting complex. The co-assembled microspheres exhibit enhanced light capture due to the light reflection in the porous structure. Reaction center(platinum nanoparticles) can be effectively coupled with the light harvesting microspheres via photoreduction. After visible light illumination, hydrogen evolution occurs on the hybrid microspheres.
基金supported by the NSF of China(Nos.51372041, 51422202,21673048,21875044,51822202 and 51772050)Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (No.17JC1400100)+4 种基金Youth Top-notch Talent Support Program of ChinaShanghai Rising-Star Program(No. 18QA1400100)Youth Top-notch Talent Support Program of ShanghaiDHU distinguished Young Professor Programthe Fundamental Research Funds for the Central Universities
文摘Mesoporous late-transition metal oxides have great potential in applications of energy,catalysis and chemical sensing due to their unique physical and chemical properties.However,their synthesis via the flexible and scalable soft-template method remain a great challenge,due to the weak organic-inorganic interaction between the frequently used surfactants(e.g.,Pluronic-type block copolymers) and metal oxide precursors,and the low crystallization temperature of metal oxides.In this study,ordered mesoporous NiO with dual mesopores,high surface area and well-interconnected crystalline porous frameworks have been successfully synthesized via the facile solvent evaporation-induced co-assembly(EICA) method,by using lab-made amphiphilic diblock copolymer polystyrene-b-poly(4-vinylpyridine)(PS-b-P4 VP) as both the structure-directing agent(the soft template) and macromolecular chelating agents for nickel species,THF as the solvent,and nickel acetylacetonate(Ni(acac)2) as inorganic precursor.Similarly,by using Ni(acac)2 and Fe(acac)3 as the binary precursors,ordered mesoporous Fedoped NiO materials can be obtained,which have bimodal mesopores of large mesopores(32.5 nm) and secondary mesopores(4.0-11.5 nm) in the nanocrystal-assembled walls,high specific surface areas(~74.8 m^2/g) and large pore value(~0.167 cm^3/g).The obtained mesoporous Fe-doped NiO based gas sensor showed superior ethanol sensing performances with good sensitivity,high selectivity and fast response-recovery dynamics.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21972031,12064026 and 22272039)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB36000000)Jilin Chinese Academy of Sciences-Yanshen Technology Co.,Ltd.
文摘The self-assembled behavior of an unsymmetric molecule(BCDTDA)with one imidazole group as center and benzoic acid group as functional group is studied,and the regulatory behaviors of coronene(COR)and three bipyridine derivatives(named BP,PEBP-C4 and PEBP-C8)on BCDTDA self-assembly structures are also investigated.Based on highly oriented pyrolytic graphite(HOPG)substrate,scanning tunneling microscopy(STM)is used to observe the variation of assembled behaviors at the solid-liquid interface.Because of the concentration effect,BCDTDA molecules can assemble into grids and Kagomés structures in the form of N–H…O hydrogen bonded dimers.BCDTDA molecules still maintain dimeric structures in the regulation of COR and BP molecules to BCDTDA self-assembly.However,PEBP-C4 and PEBP-C8 destroy the structure of the dimers,and form a variety of co-assembled structures with BCDTDA.Different vip molecules coordinate the host molecules differently,which makes the experiment more meaningful.Combined with density functional theory(DFT)calculation,the discovery of molecular interactions provides a promising strategy for the construction of functional nanostructures and devices.
