Copolymers with super segregated structure of hydrophilic methoxy poly（ethylene glycol） （mPEG） and fluorophilic poly（1H,1H,2H,2H-perfluorodecyl acrylate） （PFA） were prepared. And just because of this super seg...Copolymers with super segregated structure of hydrophilic methoxy poly（ethylene glycol） （mPEG） and fluorophilic poly（1H,1H,2H,2H-perfluorodecyl acrylate） （PFA） were prepared. And just because of this super segregated structure which was resulted from the extremely strong incompatibility between the two blocks, several interesting self- assembly behaviors of the copolymers were displayed and studied under different conditions. Transmission electron microscope （TEM） showed that with the increase of PFA in the polymerization system, the incompatibility in this super segregated structure became stronger, and the self-assembly behavior changed from ball-like or rod-like to vesicles, and finally collapsed to sheet-like. The self-assembly behavior changed likewise when the initial concentration increased. And the interesting formation of these barrel-like and spindle-like vesicles was finally studied with different cooling speeds. It＇s finally found that with this super segregation structure, these new self-assembly morphology might be formed due to the extremely strong incompatibility between mPEG and PFA segments.展开更多
The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with th...The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.展开更多
N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A...N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.展开更多
We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B...We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B’blocks.The hydrogen bonding interactions are described by Yukawa potentials,where the hydrogen bonding donors and acceptors were modelled as two blocks smeared with opposite screened charges.The hierarchical microstructures with parallelly packed lamellae-in-lamellae(Lam)and 4.8.8 Archimedean tilting pattern(4.8.8)were observed at lower and higher hydrogen bonding density(θ),respectively.The hierarchy of Lam and 4.8.8 were demonstrated by the one-and two-dimensional density profiles and the underlying order of the large-length-scale and small-length-scale microstructures were also clarified.It was found that the 4.8.8 is favorable to the stronger hydrogen bonding density or interactions.Asθincreases,the microphase transition from Lam to 4.8.8 occurs atθ=0.34,which is mainly attributed to the optimization of the electrostatic energy and conformational entropy with sacrificing the interfacial energy.This work can provide a new strategy to understand the supramolecular self-assembly as well as the mechanism behind the formation of complex hierarchical microstructures.展开更多
The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN micr...The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN microgels) were synthesized by seed emulsion polymerization. The results obtained by dynamic laser light scattering( DLLS) show that the microgels have good pH /temperature dual sensitivities. The temperature sensitive component and the pH sensitive component inside the microgels have little interference with each other. The rheological properties of the concentrated PNIPAM /PAA IPN microgel dispersions as a function of temperature at pH 4. 0 or 7. 0 were investigated by viscometer,and the results displayed that only at pH 7. 0 the dispersions presented thermoreversible thickening behavior. Then the PNIPAM /PAA fibers were prepared by self-assembly of the PNIPAM /PAA IPN microgels in the ice-crystal templates formed by unidirectional liquid nitrogen freezing method. Field emission scanning electron microscopy( FESEM) images indicate that the PNIPAM /PAA fibers are rounded,randomly orientated and interweaved.展开更多
The self-assembly behavior of sphere-forming R_5C_（30）R_5 triblock copolymers within a planar slit is studied by performing dissipative particle dynamics simulations. A sequence of novel structures which are not obs...The self-assembly behavior of sphere-forming R_5C_（30）R_5 triblock copolymers within a planar slit is studied by performing dissipative particle dynamics simulations. A sequence of novel structures which are not observed in bulk are formed within slits, including wetting layers, island-like structure, parallel cylinders, perpendicular cylinders and crosscylindrical structures. Perpendicular cylinders are always formed before the increase in the layers of parallel cylinders. A phase diagram of the assembled structures with respective to the slit property and height is thus presented. The rod length is found to have a significant impact on the rod alignment, and a disordered-ordered transition of rod orientation occurs with an increase in the length of rod blocks. Some special structures, such as parallel half-cylinders and arrowhead-shaped morphology, are observed when the rod length increases to a certain extent. Our results show that the property and height of the slit and rod length all influence the self-assembly of rod-coil-rod triblock copolymers.展开更多
ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of...ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of linear ABCA tetrablock copolymers in a 2D space. The simulation was carried out under conditions of symmetrical compositions and interactions. We focus on the influence of chain length ratio of block A and interactions between block A and other blocks B and C on the self-assembly behavior of the copolymer system. The simulation results show that most of the structures self-assembled by the ABCA tetrablock copolymers are centrosymmetric, such as diblock-like lameUa phase, two kinds of lameUae with beads at interface, two kinds of hierarchical lamella phase, hexagonal honeycomb-like phase, lamella phase with mixed BC and hexagonal spheres with mixed BC. Furthermore, we find that a novel noncentrosymmetric Janus spheres can be obtained when the interaction between blocks B and C is strong, whereas a noncentrosymmetric lamella phase was obtained at weak interaction between blocks B and C. Phase diagrams for the ABCA tetrablock copolymers with different interaction strength between blocks B and C are constructed by comparing free energies of candidate ordered structures. In addition, studies on the metastable behavior of the system reveal that enthalpy plays an important role in the metastable behavior of the ABCA tetrablock copolymer system. Our work can provide useful guide for structure control of such kind of tetrablock copolymers in experiments.展开更多
In this paper,supra-amphiphilic compounds containing disaccharides and azobenzene ends have been constructed via dynamic covalent bond.It was found that the slight structural difference of the disaccharides made signi...In this paper,supra-amphiphilic compounds containing disaccharides and azobenzene ends have been constructed via dynamic covalent bond.It was found that the slight structural difference of the disaccharides made significant difference in the self-assembled morphologies.Namely,three kinds of azodisaccharide supra-amphiphiles were found to assemble into different morphologies,with the only difference in chemical structure from the disaccharides.More importantly,the structural difference between the disaccharides,including lactoside,maltoside and cellobioside was trivial.Molecular simulation revealed the packing of molecules was due to the different contribution from hydrogen bonds.The above results clearly indicated the contribution of saccharide packing,especially the related hydrogen bonding,to the final morphology of the assembled structures.展开更多
Well-defined P4VP-b-PBLG diblock polymer composed of poly (4-vinylpyridine) (P4VP) and poly (γ-benzyl-L-glutamate) (PBLG) was synthesized by click reaction with alkyne- and azide-functionalized homopolymers. Besides,...Well-defined P4VP-b-PBLG diblock polymer composed of poly (4-vinylpyridine) (P4VP) and poly (γ-benzyl-L-glutamate) (PBLG) was synthesized by click reaction with alkyne- and azide-functionalized homopolymers. Besides, P4VP blocks were synthesized by copper-mediated atom transfer radical polymerization (ATRP) with a chlorine-containing alkyne bifunctional initiator, and the azido-terminated PBLG homopolymers were synthesized by ring-opening polymerization (ROP) of γ-benzyl-L-glutamate with an amine-containing azide initiator. In addition, the synthesized P4VP-b-PBLG with different block ratios has been characterized by proton nuclear magnetic resonance (1H NMR), Gel permeation chromatograph (GPC) and fourier transform infrated spectroscopy (FT-IR). Then, the self-assembly behaviors of P4VP-b-PBLG have been studied by changing parameters like dripping speed and block ratio. The morphologies of self-assembly of spherical, disk-like and ellipsoid-like shape particles have been observed and analyzed by scanning electron microscopy (SEM). These results have provided guidelines for the design of macromolecular self-assembly.展开更多
Cholesteryl trimeric phenylene vinylene （ChoI-TPV） has been synthesized and characterized. The self- assembly behaviors of ChoI-TPV in THF/H20 system at different water content （water content： 40% and 80%） and di...Cholesteryl trimeric phenylene vinylene （ChoI-TPV） has been synthesized and characterized. The self- assembly behaviors of ChoI-TPV in THF/H20 system at different water content （water content： 40% and 80%） and different solute concentration （solute concentration： 1.0 ×10^-5 mol/L and saturated concentration） were studied using UV-vis spectrophotometry, photoluminescence spectrophotometry, and circular dichroism spectroscopy. Based on an analysis of the UV-vis and photoluminescence spectra, Chol-TPV shows the typical H-type aggregation at saturated concentration in 80% aqueous THF. However, ChoI-TPV shows the non-typical H-type aggregation under other conditions. The circular dichroism signal suggests that the Chol-TPV exists in the right handed helical architectures with high water content at a concentration of 1.0 × 10^-5 mol/L, and a helix inversion was found at saturated concentration.展开更多
The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-drive...The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-driven self-assembly strategy by half-sandwich Cp^(*)Rh units was employed to construct diverse molecular links.The pyridyl ligand,adorned with thiophene moieties,assembles into[2]catenanes(2_(1)^(2)links),whereas the isoquinolinyl ligand produces molecular Borromean links(6_(2)^(3)links).Intriguingly,when utilizing extended bithiophene segments,the pyridyl ligand forms Borromean rings(6_(2)^(3)links),while isoquinolinyl counterparts produced a rare low-symmetry cyclic[3]catenane(6_(3)^(3)topology).The results were confirmed through single-crystal X-ray diffraction analysis,nuclear magnetic resonance(NMR)spectroscopy,and electrospray ionization time-of-flight mass spectrometry(ESI-TOF/MS)experiments.Synergistic π-π stacking,C-H···π interactions,and solvophobic effects governed the complex self-assembly system,with independent gradient model(IGM)analyses and solventaccessible surface area(SASA)calculations providing atomistic insights into the pathway selectivity of distinct topological links.展开更多
Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-...Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-C_(3)N_(4) suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m^(2)/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.展开更多
Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a s...Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a significant challenge and has not yet been reported.In this work,we develop a hydrogen bond self-assembly(HBSA)strategy that is triggered by the acidic tumor microenvironment to enable the photodynamic transition of tetra(4-carboxylphenyl)porphyrin(TCPP)PSs from type Ⅱ to type Ⅰ reactions.Upon self-assembly of TCPP monomers into TCPP assemblies(TCPP-ass),the generated reactive oxygen species shift from singlet oxygen to superoxide anions,which induces caspase-3/GSDME-mediated programmed pyroptosis,enabling rapid and complete solid tumor elimination with minimized adverse effects and enhanced therapeutic efficacy.Crucially,the HBSA process occurs exclusively within tumor cells,and this tumor-specific self-assembly strategy not only utilizes high tissue penetration of TCPP molecular-PSs,but also avoids phototoxicity caused by the formation and accumulation of TCPP-ass nano-PSs in normal tissue,providing an innovative approach for precise cancer therapy.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au...Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au nanoarrays via a liquid-liquid interface self-assembly method.The capacity of sandpaper to float directly on the cyclohexane-water interface allows nanoarrays to be formed directly on it,thereby minimizing stacking issues typically associated with nanoarray assemblies and significantly enhancing the sensitivity of S-fenvalerate detection.Moreover,the SERS sandpaper was reusable and portable due to its strong adhesion of the nanoarrays.Under optimized testing conditions,the developed SERS sandpaper method was capable of detecting S-fenvalerate,demonstrating a strong linear response within a concentration range of 10^(–7)–10^(3)μmol/L,with a limit of detection of 1.92×10^(−8)μmol/L.The analysis of spiked food samples containing S-fenvalerate using the developed SERS sandpaper afforded excellent recoveries(92.2%−109.7%).Additionally,the SERS sandpaper was successfully applied to quantify S-fenvalerate in real food samples,with results consistent with analyses conducted using gas chromatography.展开更多
Emerging evidence has established artesunate(ART)as a potent anticancer candidate,yet its clinical utility remains constrained by rapid clearance and limited bioavailability.To overcome these limitations,we developed ...Emerging evidence has established artesunate(ART)as a potent anticancer candidate,yet its clinical utility remains constrained by rapid clearance and limited bioavailability.To overcome these limitations,we developed fatty chain-driven self-assembling nanoassemblies(NAs)as an innovative therapeutic platform.In contrast to conventional prodrug-based self-assembled nanoassemblies(PBSANs),our ART conjugates(ART-R)activate antitumor effects without requiring responsive modules,substantially streamlining drug design.In this study,we investigated the assembly behavior,stability,and antitumor efficacy of ART-R conjugates with varying side chain lengths:short(ART-C4),medium(ART-C8,ART-C12),and long(ART-C14,ART-C18).To prolong systemic circulation and achieve tumor-selective release,we engineered reduction-responsive sp-ART-R NAs via 2-Distearoyl-sn-glycero-3-phosphoethanolamine-disulfide bond-polyethylene glycol 2000(DSPE-SS-PEG_(2K))modification.Following comprehensive evaluation,sp-ART-C14 NAs with the optimal side chain length were selected,which exhibit the most suitable octanol-water partition coefficient(logP),good assembly capability,stability,cytotoxicity,as well as optimal pharmacokinetic behavior and tumor accumulation ability.In the 4T1 breast tumor model,sp-ART-C14 NAs also demonstrated excellent therapeutic efficacy.This study overcomes the limitations of traditional PBSANs,eliminates dependence on response modules,and provides a new drug delivery solution for ART.展开更多
The mono-modified β-cyclodextrin derivative,6-O-(4-aminobenzoyl)-β-cyclodextrin(1) ,was synthesized and characterized. We compared its self-assembling behavior with structurally related β-cyclodextrin derivative,6-...The mono-modified β-cyclodextrin derivative,6-O-(4-aminobenzoyl)-β-cyclodextrin(1) ,was synthesized and characterized. We compared its self-assembling behavior with structurally related β-cyclodextrin derivative,6-O-(4-hydroxybenzoyl)-βcyclodextrin(2) ,in aqueous solution and in the solid state using NMR spectroscopy and single crystal X-ray structure analysis. The two complexes displayed different self-assembling behaviors.Complex 1 formed a head-to-tail helical columnar superstructure in which the substituent group penetrated deeply into the hydrophobic cavity of the adjacent β-cyclodextrin from the second side and aligned along the screw axis,whereas 2 exhibited a channel superstructure with a tail-to-tail dimer as the repeating motif.Further NMR studies in aqueous solution supported the result of the solid state.The influence of substituent groups on the self-assembly behavior was examined in mono-modified β-cyclodextrins by means of substituting an amino group for a hydroxyl group,which indicates that the weak intermolecular interaction is a critical factor in determining the self-assembling behavior.展开更多
Graphene derivatives,such as graphene oxide(GO)and reduced graphene oxide(RGO),have been widely used as promising two-dimensional nanoscale building blocks due to their fascinating properties,cost-effective production...Graphene derivatives,such as graphene oxide(GO)and reduced graphene oxide(RGO),have been widely used as promising two-dimensional nanoscale building blocks due to their fascinating properties,cost-effective production,and good processability.Understanding the intrinsic self-assembling,colloidal,and rheological features of graphene derivatives is of critical importance to establish the formation-structure-property relationship of graphene-based materials.This article reviews recent progresses in our studies of these interesting properties of graphene derivatives for developing high performance supercapacitors.The content is organized to include characteristics of the dispersions of graphene derivatives,self-assembly of nanosheets from liquid medium,colloidal behavior,rheological properties of the dispersions,processing methods based on the properties,and performance of the fabricated supercapacitors.GO and RGO nanosheets are proved to form different types of assembled structures with unique morphologies,such as ultrathin layer-by-layer films,porous aggregates,and nanoscrolls.The unique rheological properties of GO dispersions and hydrogels,feasible for both the traditional wet-processing and newly-developed technology like three-dimensional printing,are highlighted for their potential in structural manipulation and scalable fabrication of graphene-based devices.The research devoted to up-grading the performance of supercapacitors is presented in some details,which could be applicable for fabricating other graphene-based energy storage devices.Some challenges and perspectives in our point of view are given in the last part of this feature article.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
The self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin bothin solution and the solid state is comparatively studied by X-ray crystallography and ~1H NMRspectroscopy. The results obtained show that the ...The self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin bothin solution and the solid state is comparatively studied by X-ray crystallography and ~1H NMRspectroscopy. The results obtained show that the phenolic groups in the crystal 1 can successivelypenetrate into the adjacent β-cyclodextrin cavities from the secondary side to form head-to-taillinear polymeric su-pramolecule with a 2-fold screw axis. The self-assembly behavior also can bedetermined in D_2O solution, giving a self-association constant of 240 mol^(-1)·L. Using thepresent and previous structures reported for the relevant β-cyclodextrin derivatives, i.e.,mono(6-anilino-6-deoxy)-β-cyclodextrin, mono(6-phenylselenyl-6-deoxy)-β-cyclodextrin, andmono(6-phenylthio-6-deoxy)-β-cyclodextrin, we further reveal the factors governing the formationsof supramolecular assemblies.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.51173185 and 51303179)
文摘Copolymers with super segregated structure of hydrophilic methoxy poly（ethylene glycol） （mPEG） and fluorophilic poly（1H,1H,2H,2H-perfluorodecyl acrylate） （PFA） were prepared. And just because of this super segregated structure which was resulted from the extremely strong incompatibility between the two blocks, several interesting self- assembly behaviors of the copolymers were displayed and studied under different conditions. Transmission electron microscope （TEM） showed that with the increase of PFA in the polymerization system, the incompatibility in this super segregated structure became stronger, and the self-assembly behavior changed from ball-like or rod-like to vesicles, and finally collapsed to sheet-like. The self-assembly behavior changed likewise when the initial concentration increased. And the interesting formation of these barrel-like and spindle-like vesicles was finally studied with different cooling speeds. It＇s finally found that with this super segregation structure, these new self-assembly morphology might be formed due to the extremely strong incompatibility between mPEG and PFA segments.
基金supported by the National Natural Science Foundation of China(22078211)the China Postdoctoral Science Foundation(2022M721115).
文摘The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.
基金Shanghai Natural Science Foundation,China(No.13ZR1400700)The Program for Innovative Research Team in University,China(No.IRT1221)
文摘N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.
基金financially supported by the Natural Science Foundation of Shanghai(No.21ZR1402800)the Fundamental Research Funds for the Central Universities(No.2232020D-11)+1 种基金the China Postdoctoral Science Foundation(No.2021M690597)the Open Project Program of Fujian Provincial Key Laboratory of Textiles Inspection Technology(Fujian Fiber Inspection Center)(Nos.2020-MXJ-04)。
文摘We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B’blocks.The hydrogen bonding interactions are described by Yukawa potentials,where the hydrogen bonding donors and acceptors were modelled as two blocks smeared with opposite screened charges.The hierarchical microstructures with parallelly packed lamellae-in-lamellae(Lam)and 4.8.8 Archimedean tilting pattern(4.8.8)were observed at lower and higher hydrogen bonding density(θ),respectively.The hierarchy of Lam and 4.8.8 were demonstrated by the one-and two-dimensional density profiles and the underlying order of the large-length-scale and small-length-scale microstructures were also clarified.It was found that the 4.8.8 is favorable to the stronger hydrogen bonding density or interactions.Asθincreases,the microphase transition from Lam to 4.8.8 occurs atθ=0.34,which is mainly attributed to the optimization of the electrostatic energy and conformational entropy with sacrificing the interfacial energy.This work can provide a new strategy to understand the supramolecular self-assembly as well as the mechanism behind the formation of complex hierarchical microstructures.
基金National Natural Science Foundations of China(Nos.51073033,51373030)the Fundamental Research Funds for the Central Universities,China(No.2232014D3-43)
文摘The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN microgels) were synthesized by seed emulsion polymerization. The results obtained by dynamic laser light scattering( DLLS) show that the microgels have good pH /temperature dual sensitivities. The temperature sensitive component and the pH sensitive component inside the microgels have little interference with each other. The rheological properties of the concentrated PNIPAM /PAA IPN microgel dispersions as a function of temperature at pH 4. 0 or 7. 0 were investigated by viscometer,and the results displayed that only at pH 7. 0 the dispersions presented thermoreversible thickening behavior. Then the PNIPAM /PAA fibers were prepared by self-assembly of the PNIPAM /PAA IPN microgels in the ice-crystal templates formed by unidirectional liquid nitrogen freezing method. Field emission scanning electron microscopy( FESEM) images indicate that the PNIPAM /PAA fibers are rounded,randomly orientated and interweaved.
基金financially supported by the National Natural Science Foundation of China(No.21574117)
文摘The self-assembly behavior of sphere-forming R_5C_（30）R_5 triblock copolymers within a planar slit is studied by performing dissipative particle dynamics simulations. A sequence of novel structures which are not observed in bulk are formed within slits, including wetting layers, island-like structure, parallel cylinders, perpendicular cylinders and crosscylindrical structures. Perpendicular cylinders are always formed before the increase in the layers of parallel cylinders. A phase diagram of the assembled structures with respective to the slit property and height is thus presented. The rod length is found to have a significant impact on the rod alignment, and a disordered-ordered transition of rod orientation occurs with an increase in the length of rod blocks. Some special structures, such as parallel half-cylinders and arrowhead-shaped morphology, are observed when the rod length increases to a certain extent. Our results show that the property and height of the slit and rod length all influence the self-assembly of rod-coil-rod triblock copolymers.
基金financially supported by the National Natural Science Foundation of China(No.21474107)
文摘ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of linear ABCA tetrablock copolymers in a 2D space. The simulation was carried out under conditions of symmetrical compositions and interactions. We focus on the influence of chain length ratio of block A and interactions between block A and other blocks B and C on the self-assembly behavior of the copolymer system. The simulation results show that most of the structures self-assembled by the ABCA tetrablock copolymers are centrosymmetric, such as diblock-like lameUa phase, two kinds of lameUae with beads at interface, two kinds of hierarchical lamella phase, hexagonal honeycomb-like phase, lamella phase with mixed BC and hexagonal spheres with mixed BC. Furthermore, we find that a novel noncentrosymmetric Janus spheres can be obtained when the interaction between blocks B and C is strong, whereas a noncentrosymmetric lamella phase was obtained at weak interaction between blocks B and C. Phase diagrams for the ABCA tetrablock copolymers with different interaction strength between blocks B and C are constructed by comparing free energies of candidate ordered structures. In addition, studies on the metastable behavior of the system reveal that enthalpy plays an important role in the metastable behavior of the ABCA tetrablock copolymer system. Our work can provide useful guide for structure control of such kind of tetrablock copolymers in experiments.
基金the National Natural Science Foundation of China(NSFC,Nos.52125303,51721002,91956127 and 21975047)for financial supportthe National Natural Science Foundation of China(NSFC,Nos.21674114 and 91956127)for financial support+1 种基金supported by the Shanghai Municipal Science and Technology Major Project(No.2018SHZDZX01)ZJ Lab。
文摘In this paper,supra-amphiphilic compounds containing disaccharides and azobenzene ends have been constructed via dynamic covalent bond.It was found that the slight structural difference of the disaccharides made significant difference in the self-assembled morphologies.Namely,three kinds of azodisaccharide supra-amphiphiles were found to assemble into different morphologies,with the only difference in chemical structure from the disaccharides.More importantly,the structural difference between the disaccharides,including lactoside,maltoside and cellobioside was trivial.Molecular simulation revealed the packing of molecules was due to the different contribution from hydrogen bonds.The above results clearly indicated the contribution of saccharide packing,especially the related hydrogen bonding,to the final morphology of the assembled structures.
文摘Well-defined P4VP-b-PBLG diblock polymer composed of poly (4-vinylpyridine) (P4VP) and poly (γ-benzyl-L-glutamate) (PBLG) was synthesized by click reaction with alkyne- and azide-functionalized homopolymers. Besides, P4VP blocks were synthesized by copper-mediated atom transfer radical polymerization (ATRP) with a chlorine-containing alkyne bifunctional initiator, and the azido-terminated PBLG homopolymers were synthesized by ring-opening polymerization (ROP) of γ-benzyl-L-glutamate with an amine-containing azide initiator. In addition, the synthesized P4VP-b-PBLG with different block ratios has been characterized by proton nuclear magnetic resonance (1H NMR), Gel permeation chromatograph (GPC) and fourier transform infrated spectroscopy (FT-IR). Then, the self-assembly behaviors of P4VP-b-PBLG have been studied by changing parameters like dripping speed and block ratio. The morphologies of self-assembly of spherical, disk-like and ellipsoid-like shape particles have been observed and analyzed by scanning electron microscopy (SEM). These results have provided guidelines for the design of macromolecular self-assembly.
基金supported by the National Science Foundation of China(No.51173155)the Hebei Province Science Foundation of China(No.F2011203160)
文摘Cholesteryl trimeric phenylene vinylene （ChoI-TPV） has been synthesized and characterized. The self- assembly behaviors of ChoI-TPV in THF/H20 system at different water content （water content： 40% and 80%） and different solute concentration （solute concentration： 1.0 ×10^-5 mol/L and saturated concentration） were studied using UV-vis spectrophotometry, photoluminescence spectrophotometry, and circular dichroism spectroscopy. Based on an analysis of the UV-vis and photoluminescence spectra, Chol-TPV shows the typical H-type aggregation at saturated concentration in 80% aqueous THF. However, ChoI-TPV shows the non-typical H-type aggregation under other conditions. The circular dichroism signal suggests that the Chol-TPV exists in the right handed helical architectures with high water content at a concentration of 1.0 × 10^-5 mol/L, and a helix inversion was found at saturated concentration.
基金supported by the Department of Chemistry,Fudan Universitythe National Natural Science Foundation of China(22031003,21720102004)the Shanghai Science Technology Committee(19DZ2270100)。
文摘The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-driven self-assembly strategy by half-sandwich Cp^(*)Rh units was employed to construct diverse molecular links.The pyridyl ligand,adorned with thiophene moieties,assembles into[2]catenanes(2_(1)^(2)links),whereas the isoquinolinyl ligand produces molecular Borromean links(6_(2)^(3)links).Intriguingly,when utilizing extended bithiophene segments,the pyridyl ligand forms Borromean rings(6_(2)^(3)links),while isoquinolinyl counterparts produced a rare low-symmetry cyclic[3]catenane(6_(3)^(3)topology).The results were confirmed through single-crystal X-ray diffraction analysis,nuclear magnetic resonance(NMR)spectroscopy,and electrospray ionization time-of-flight mass spectrometry(ESI-TOF/MS)experiments.Synergistic π-π stacking,C-H···π interactions,and solvophobic effects governed the complex self-assembly system,with independent gradient model(IGM)analyses and solventaccessible surface area(SASA)calculations providing atomistic insights into the pathway selectivity of distinct topological links.
文摘Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-C_(3)N_(4) suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m^(2)/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.
基金supported by the National Natural Science Foundation of China(22176058)the Science and Technology Commission of Shanghai Municipality(24DX1400200,23ZR1416100,25ZR1401082)+1 种基金the Program of Introducing Talents of Discipline to Universities(B16017)the Fundamental Research Funds for the Central Universities(222201717003)。
文摘Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a significant challenge and has not yet been reported.In this work,we develop a hydrogen bond self-assembly(HBSA)strategy that is triggered by the acidic tumor microenvironment to enable the photodynamic transition of tetra(4-carboxylphenyl)porphyrin(TCPP)PSs from type Ⅱ to type Ⅰ reactions.Upon self-assembly of TCPP monomers into TCPP assemblies(TCPP-ass),the generated reactive oxygen species shift from singlet oxygen to superoxide anions,which induces caspase-3/GSDME-mediated programmed pyroptosis,enabling rapid and complete solid tumor elimination with minimized adverse effects and enhanced therapeutic efficacy.Crucially,the HBSA process occurs exclusively within tumor cells,and this tumor-specific self-assembly strategy not only utilizes high tissue penetration of TCPP molecular-PSs,but also avoids phototoxicity caused by the formation and accumulation of TCPP-ass nano-PSs in normal tissue,providing an innovative approach for precise cancer therapy.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金financially supported by the Key R&D Program of Shandong Province,China(2023CXGC010712).
文摘Herein,a reusable and portable surface-enhanced Raman spectroscopy(SERS)sandpaper was successfully synthesized for the sensitive detection of S-fenvalerate in foods.Commercial sandpapers were decorated with Ag@SiO2@Au nanoarrays via a liquid-liquid interface self-assembly method.The capacity of sandpaper to float directly on the cyclohexane-water interface allows nanoarrays to be formed directly on it,thereby minimizing stacking issues typically associated with nanoarray assemblies and significantly enhancing the sensitivity of S-fenvalerate detection.Moreover,the SERS sandpaper was reusable and portable due to its strong adhesion of the nanoarrays.Under optimized testing conditions,the developed SERS sandpaper method was capable of detecting S-fenvalerate,demonstrating a strong linear response within a concentration range of 10^(–7)–10^(3)μmol/L,with a limit of detection of 1.92×10^(−8)μmol/L.The analysis of spiked food samples containing S-fenvalerate using the developed SERS sandpaper afforded excellent recoveries(92.2%−109.7%).Additionally,the SERS sandpaper was successfully applied to quantify S-fenvalerate in real food samples,with results consistent with analyses conducted using gas chromatography.
基金supported by the Liaoning Revitalization Talents Program(No.XLYC2403107)the Excellent Youth Science Foundation of Liaoning Province(No.2024JH3/10200046)+1 种基金the National Natural Science Foundation of China(No.82204317)the Basic Scientific Research Project of Liaoning Provincial Department of Education(No.LJ212410163015).
文摘Emerging evidence has established artesunate(ART)as a potent anticancer candidate,yet its clinical utility remains constrained by rapid clearance and limited bioavailability.To overcome these limitations,we developed fatty chain-driven self-assembling nanoassemblies(NAs)as an innovative therapeutic platform.In contrast to conventional prodrug-based self-assembled nanoassemblies(PBSANs),our ART conjugates(ART-R)activate antitumor effects without requiring responsive modules,substantially streamlining drug design.In this study,we investigated the assembly behavior,stability,and antitumor efficacy of ART-R conjugates with varying side chain lengths:short(ART-C4),medium(ART-C8,ART-C12),and long(ART-C14,ART-C18).To prolong systemic circulation and achieve tumor-selective release,we engineered reduction-responsive sp-ART-R NAs via 2-Distearoyl-sn-glycero-3-phosphoethanolamine-disulfide bond-polyethylene glycol 2000(DSPE-SS-PEG_(2K))modification.Following comprehensive evaluation,sp-ART-C14 NAs with the optimal side chain length were selected,which exhibit the most suitable octanol-water partition coefficient(logP),good assembly capability,stability,cytotoxicity,as well as optimal pharmacokinetic behavior and tumor accumulation ability.In the 4T1 breast tumor model,sp-ART-C14 NAs also demonstrated excellent therapeutic efficacy.This study overcomes the limitations of traditional PBSANs,eliminates dependence on response modules,and provides a new drug delivery solution for ART.
基金supported by the National Natural Science Foundation of China(20704031)Tianjin Natural Science Fund(09JCYBJC06300)Science Fund of Tianjin Education Committee(20060515)
文摘The mono-modified β-cyclodextrin derivative,6-O-(4-aminobenzoyl)-β-cyclodextrin(1) ,was synthesized and characterized. We compared its self-assembling behavior with structurally related β-cyclodextrin derivative,6-O-(4-hydroxybenzoyl)-βcyclodextrin(2) ,in aqueous solution and in the solid state using NMR spectroscopy and single crystal X-ray structure analysis. The two complexes displayed different self-assembling behaviors.Complex 1 formed a head-to-tail helical columnar superstructure in which the substituent group penetrated deeply into the hydrophobic cavity of the adjacent β-cyclodextrin from the second side and aligned along the screw axis,whereas 2 exhibited a channel superstructure with a tail-to-tail dimer as the repeating motif.Further NMR studies in aqueous solution supported the result of the solid state.The influence of substituent groups on the self-assembly behavior was examined in mono-modified β-cyclodextrins by means of substituting an amino group for a hydroxyl group,which indicates that the weak intermolecular interaction is a critical factor in determining the self-assembling behavior.
基金supported by the National Basic Research Program of China(973 Program,No.2012CB933402).
文摘Graphene derivatives,such as graphene oxide(GO)and reduced graphene oxide(RGO),have been widely used as promising two-dimensional nanoscale building blocks due to their fascinating properties,cost-effective production,and good processability.Understanding the intrinsic self-assembling,colloidal,and rheological features of graphene derivatives is of critical importance to establish the formation-structure-property relationship of graphene-based materials.This article reviews recent progresses in our studies of these interesting properties of graphene derivatives for developing high performance supercapacitors.The content is organized to include characteristics of the dispersions of graphene derivatives,self-assembly of nanosheets from liquid medium,colloidal behavior,rheological properties of the dispersions,processing methods based on the properties,and performance of the fabricated supercapacitors.GO and RGO nanosheets are proved to form different types of assembled structures with unique morphologies,such as ultrathin layer-by-layer films,porous aggregates,and nanoscrolls.The unique rheological properties of GO dispersions and hydrogels,feasible for both the traditional wet-processing and newly-developed technology like three-dimensional printing,are highlighted for their potential in structural manipulation and scalable fabrication of graphene-based devices.The research devoted to up-grading the performance of supercapacitors is presented in some details,which could be applicable for fabricating other graphene-based energy storage devices.Some challenges and perspectives in our point of view are given in the last part of this feature article.
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.
基金This work was supported by the National Natural Science Foundation of China (Grant Nos.90306009, 20272028, and 20421202) the Tianjin Natural Science Foundation (Grant No. 043604411).
文摘The self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin bothin solution and the solid state is comparatively studied by X-ray crystallography and ~1H NMRspectroscopy. The results obtained show that the phenolic groups in the crystal 1 can successivelypenetrate into the adjacent β-cyclodextrin cavities from the secondary side to form head-to-taillinear polymeric su-pramolecule with a 2-fold screw axis. The self-assembly behavior also can bedetermined in D_2O solution, giving a self-association constant of 240 mol^(-1)·L. Using thepresent and previous structures reported for the relevant β-cyclodextrin derivatives, i.e.,mono(6-anilino-6-deoxy)-β-cyclodextrin, mono(6-phenylselenyl-6-deoxy)-β-cyclodextrin, andmono(6-phenylthio-6-deoxy)-β-cyclodextrin, we further reveal the factors governing the formationsof supramolecular assemblies.
