Medical stents have made significant strides in development,however,creating a single manufacturing material that combines size adjustability,robust strength,and degradability remains a major challenge.Here,we develop...Medical stents have made significant strides in development,however,creating a single manufacturing material that combines size adjustability,robust strength,and degradability remains a major challenge.Here,we developed an elastomer designed for stent fabrication,featuring excellent thermo-responsive shape memory and fast self-healing.This elastomer is produced through supramolecular inter-actions between liquid crystal moieties,which exhibit strong orientation,and a polymer backbone.These supramolecular interactions provide the elastomer with remarkable mechanical strength(10.46 MPa).Interestingly,the elastomer shows excellent mesocrystalline stability and cyclability,thanks to multiple non-covalent bonds,allowing the crosslinked liquid crystalline phase to maintain integrity at temper-atures up to 285℃.Impressively,the elastomer can respond to stress and temperature changes,fully reverting to its original shape in just 25.7±0.94 s.When configured as a helical stent,its macroscopic dimensions can be adjusted to mimic the size of blood vessels in vitro.The stent exhibits rapid responsiveness at 37℃,achieving complete self-expansion within 10 s.Furthermore,it demonstrates excellent degradability,with a weight loss of only 2.75%±0.31%after 70 d.This innovation paves the way for new possibilities in the use of medical stents,particularly for the long-term treatment of coronary heart disease.展开更多
Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges ...Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.展开更多
The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs).In this work,the electrochemical activity of...The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs).In this work,the electrochemical activity of H_(3)O^(+) is inhibited by the supramolecular host–vip complex composed of H_(3)O^(+) as vip and 18-crown-6 as host.The even Zn plating is induced by the host–vip complex electrostatic shielding layer on Zn anode,as detected by in-situ optical microscopy.The lamellar Zn is plated which profits from the improved Zn plating behavior.Density functional theory (DFT) calculation presents the stable structure of complex.The less produced H_(2) content is monitored online by a mass spectrometer during Zn plating/stripping,which indicates HER can be hampered by the host–vip behavior.Thus,the ZIBs with long life and high Coulombic efficiency are achieved via introducing 18-crown-6.The proposed host–vip supramolecular interaction is expected to facilitate the furthermore development of Zn batteries.展开更多
A calix[4]arene ligand assisted directβ-C-H arylation of tertiary aliphatic aldehydes has been developed via a Pd-catalyzed C(sp3)-H functionalization process.This strategy exhibited good functional group compatibili...A calix[4]arene ligand assisted directβ-C-H arylation of tertiary aliphatic aldehydes has been developed via a Pd-catalyzed C(sp3)-H functionalization process.This strategy exhibited good functional group compatibility and C-H bond site-selectivity.Mechanism studies have shown that both synergistic effect and cationic-πsupramolecular interaction between calixarene cavity and transition-metal catalytic center may play an important role in this catalytic cycle.This complementary method would be used in organic and medical chemistry due to the importance of tertiary aliphatic aldehydes.展开更多
Supramolecular chemistry has received considerable attention in host-vip recognition.The structureresponse relationship of host-vip recognition system is a meaningful issue.Herein,a series of tripodal nitrogen mus...Supramolecular chemistry has received considerable attention in host-vip recognition.The structureresponse relationship of host-vip recognition system is a meaningful issue.Herein,a series of tripodal nitrogen mustard derivatives(TMs)have been developed in this paper.By rationally design the intramolecular alkyl chain lengths of host,the host-vip binding model have been successfully tuned,which underwent a transformation fromπ-πto multiple hydrogen bonds.This process enhances the host-vip binding force and recognition efficiency.展开更多
Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(...Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(CB[8])as the host and terpyridine lanthanum ions metal complex as the vip,constructed by layer-by-layer self-assembly through supramolecular interaction.Moreover,nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior.In the tumor micro-environment,the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect.In addition,the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells.The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.展开更多
The rational design of dopant-free organic hole-transporting layer(HTL) materials is still a challenge for realizing high-efficient and stable p-i-n planar perovskite solar cells(pero-SCs). Here, we synthesized two π...The rational design of dopant-free organic hole-transporting layer(HTL) materials is still a challenge for realizing high-efficient and stable p-i-n planar perovskite solar cells(pero-SCs). Here, we synthesized two π-conjugated small-molecule HTL materials through tailoring the backbone and conjugated side chain to carefully control molecular conformation. The resultant BDT-TPAs Th containing a planar fused benzo[1,2-b:4,5-b′]dithiophene(BDT) core and a conjugated thiophene side chain showed the planar conformation. X-ray crystallography showed a favorable stacking model in solid states under the parallel-displaced π-πand additional S-π weak-bond supramolecular interactions, thus achieving an obviously increased hole mobility without dopants.As an HTL material in p-i-n planar pero-SCs, the marginal solubility of BDT-TPA-s Th enabled inverse diffusion into the perovskite precursor solution for assisting the subsequent perovskite film growth and passivating the uncoordinated Pb2+ ion defects. As a result, the planar p-i-n pero-SCs exhibited a champion power conversion efficiency(PCE) of 20.5% and enhanced moisture stability. Importantly, the BDT-TPA-s Th HTL material also showed weak thickness-photovoltaic dependence, and the pero-SCs with blade-coated BDT-TPA-s Th as a HTL achieved a 15.30% PCE for the 1-cm2 modularized device. This HTL material design strategy is expected to pave the way toward high-performance, dopant-free and printing large-area planar p-i-n pero-SCs.展开更多
Proteinaceous fibers based on spidroins have attracted widespread attention due to their lightweight and mechanically strong properties.Presently,mechanical modulation is mainly dependent on the ultrahigh molecular we...Proteinaceous fibers based on spidroins have attracted widespread attention due to their lightweight and mechanically strong properties.Presently,mechanical modulation is mainly dependent on the ultrahigh molecular weight of recombinant proteins.This makes it difficult to construct and express the target proteins.It is thus significant to develop alternative strategies for the fabrication of robust biological fibers.Herein,we demonstrate one new type of engineered protein fibers using electrostatic complexation of the cationic elastins and anionic dihydroxyphenylalanine surfactants.Interestingly,the mechanical performance of the resulting fibers can be modulated by multiple supramolecular interactions in the system including electrostatic force,hydrogen bonding,metal coordination,cation-πand other aromatic interactions.Consequently,significant alternation of the fibers’breaking strength(from 32 to 160 MPa),Young’s modulus(from 0.8 to 17 GPa),and toughness(from 1.2 to 99 MJ·m-3)has been achieved.Moreover,the fibers exhibit high plasticity;for example,the formation of different helical structures,and strong fluorescence after the introduction of Tb chelation.Therefore,this study offers new strategies for the mechanical regulation of engineered protein fibers.展开更多
The supramolecular interaction of gemfibrozil with β-cyclodextrin （β-CD） was studied by spectrofluorimetry. The mechanism of the inclusion was discussed by spectrofluoremetry, infrared spectrum and ^1H NMR spectru...The supramolecular interaction of gemfibrozil with β-cyclodextrin （β-CD） was studied by spectrofluorimetry. The mechanism of the inclusion was discussed by spectrofluoremetry, infrared spectrum and ^1H NMR spectrum. The results showed that a 1 ： 1 （β-CD ： gemfibrozil） complex was formed with an apparent association constant of 3.844 × 10^3 L·mol^-1. Based on the enhancement of the fluorescent intensity of gemfibrozil, a spectrofluorimetric method for the determination of gemfibrozil in bulk aqueous solution in the presence of β-CD was developed. The linear range was 3.30 ng·mL^- 1 -6.00 ug·mL^-1 with the detection limit of 0.980 ng·mL^-1. There was no interference from the excipients normally used in tablet composition and the serum main compositions. The proposed method was then successfully applied to the determination of gemfibrozil in capsules and serum.展开更多
Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements a...Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements are emerging to fabricate multifunctional coatings that effectively combat such microbially produced damage.However,rapid,reliable,and robust surface engineering remains challenging due to stability limitations and intricate anti-biofilm additive dynamics.Herein,a silver-capsule-conjugated polyurethane coating with high stability and antimicrobial efficacy in a cooperative manner is developed through controlled supramolecular self-assembly.Polyvinylpyrrolidone(PVP)-mediated molecule entanglement breaks through the incompatibility between polymeric components and nanomaterials,strengthening the dispersion and fixation of encapsulated silver nanoparticles.The facilitation and control of the nanoscale interfacial binding significantly suppresses the aggregation of inorganic nanoparticles and consequent microcracks development,giving rise to mechanical robustness and thermal stability of the hybrid coating under extreme conditions.A synergistic combination of exposed residues,electrostatic,and coordination interactions could readily integrate the resultant coating on virtually arbitrary material sur-faces.This composite coating exhibits broad-spectrum and high bactericidal efficiencies of 99.99% against Staphylococcus aureus and Escherichia coli,as well as excellent biofilm formation suppression.Moreover,our coating has robust resistance to microbial-influenced corrosion(MIC)and can even endure 720 h of salt spray.This study deciphers a general code for creating stable and durable nanohybrid coatings to mitigate microbially related risks.展开更多
A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains,driven...A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains,driven by CB[8]-encapsulation-enhanced donor-acceptor interaction.The as-formed supramolecular bottlebrush polymer has been characterized by -1H NMR titration experiment,UV-vis spectroscopy,DLS and 2D -1H NMR DOSY.展开更多
Photo-responsive mechanical actuator is a class of stimuli-responsive materials transferring light to mechanical energy through macroscopic transformation.To fabricate photo-responsive mechanical actuator,soft polymer...Photo-responsive mechanical actuator is a class of stimuli-responsive materials transferring light to mechanical energy through macroscopic transformation.To fabricate photo-responsive mechanical actuator,soft polymeric materials crosslinked with functional bridging structures are desired.Supramolecular interaction is a relatively common way to fabricate crosslinked materials due to its excellent self-assembly performance.And azobenzene and derivatives are ideal candidates of photo-responsive materials because of the unique photo-induced trans-cis isomerization.Here,a new kind of crosslinked materials based on supramolecular interaction between 4,4'-dihydroxyazobenzene and chitosan is reported.Under 355 nm irradiation,the macroscopic bending of polymeric materials occurs rapidly due to the photo-isomerization of 4,4-dihydroxyazobenzene.Meanwhile,the photo-responsive mechanical actuator can also lift weight which is up to 200 times that of the actuator itself,and convert energy from light to mechanical work efficiently.This report suggests a new kind of photo-responsive actuator based on supramolecular interaction and may be helpful to contribute a theoretical basis to the design and synthesis of photo-responsive mechanical actuator suitable for large-scale manufacturing industrialization in future.展开更多
Complex emulsions,such as double emulsions and high-internal-phase emulsions,have shown great applications in the fields of drug delivery,sensing,catalysis,oil-water separation and self-healing materials.Their control...Complex emulsions,such as double emulsions and high-internal-phase emulsions,have shown great applications in the fields of drug delivery,sensing,catalysis,oil-water separation and self-healing materials.Their controllable preparation is at the forefront of interface and material science.Surfactants and polymers have been widely used as emulsifiers for building complex emulsions.Yet some inherent disadvantages exist including multi-step emulsifications and low production efficiency.Alternatively,supramolecular polymer emulsifier for complex emulsions via one-step emulsification is rising as a new strategy due to the ease of preparation.In this feature article,we review our recent progresses in using supramolecular polymer emulsifiers for the preparation of complex emulsions.Double emulsions and high-internal-phase emulsions are successfully prepared via one-step emulsification with the help of different supramolecular interactions including electrostatic,hydrogen bond,coordination interaction and dynamic covalent bond,which will be particularly emphasized in detail.In the end,a comprehensive prospect is given for the future development of this field.This article is expected to provide new inspirations for preparing complex emulsions via supramolecular routes.展开更多
A new mixed-ligand Mn（II）complex,namely [Mn（bipy）2（Huca）]·5H2O（1,bipy = 2,2＇-bipyridine,and H3uca = uracil-5-carboxylic acid）has been prepared and characterized by single-crystal X-ray diffraction,FT-IR ...A new mixed-ligand Mn（II）complex,namely [Mn（bipy）2（Huca）]·5H2O（1,bipy = 2,2＇-bipyridine,and H3uca = uracil-5-carboxylic acid）has been prepared and characterized by single-crystal X-ray diffraction,FT-IR spectroscopy and thermogravimetric analysis.It crystallizes in monoclinic,space group C2/c with a = 23.597（8）,b = 16.434（5）,c = 15.531（6）,β = 112.785（6）o,C25H28MnN6O9,Mr = 611.47,V = 5553（3）3,Z = 8,μ = 0.538,Dc = 1.463 g/cm3,F（000）= 2536,R = 0.0441 and wR = 0.1230 for all 5227 observed reflections（I 2σ（I））.The manganese（II）center is surrounded by three bidentate chelating ligands,and it displays a severely distorted octahedral geometry,with cis angles ranging from 72.14（6）to 109.78（6）o.Extensive intermolecular hydrogen bonds link the [Mn（bipy）2（Huca）] monomers and lattice water molecules to yield a three-dimensional supramolecular framework.TGA shows complete removal of all lattice water molecules above 270 ℃.展开更多
The construction of hydrogels with good mechanical properties and phosphorescent properties is full of challenges.Herein,we report a supramolecular phosphorescent hydrogel with long lifetime,high tensile strength and ...The construction of hydrogels with good mechanical properties and phosphorescent properties is full of challenges.Herein,we report a supramolecular phosphorescent hydrogel with long lifetime,high tensile strength and self-healing property,which can be easily constructed through in-situ thermalinitiated polymerization of isocyanatoethyl acrylate-modifiedβ-cyclodextrin(β-CD-DA)and acrylatemodified adamantane(Ad-DA),acrylic acid(AA),followed by the non-covalent association with carbon dots(CNDs).The lifetime of phosphorescent hydrogel can reach 1261 ms at room temperature,and the quantum yield is 11%.Importantly,through the efficient triplet to singlet Förster resonance energy transfer(TS-FRET),the phosphorescent hydrogel shows the good phosphorescence energy transfer property for organic dyes Rhodamine B and Eosin Y with the delayed fluorescence lifetime up to 730 ms and 585 ms as well as the energy transfer efficiency(Φ_(ET))up to 99.9%and 99.3%,respectively.Moreover,owing to the host-vip interactions betweenβ-CD-DA and Ad-DA,the three-dimensional cross-linked network phosphorescent hydrogel can be easily stretched to 18 times of its original length,and can achieve self-healing of the cut surfaces within 30 min.These results will expand the scope of phosphorescent materials and provide new ideas and opportunities for materials science.展开更多
Two new supramoleeular polymers [ M （2-NH2 py）2 （ox） ] [ M = Co （1）, Ni （2） ; 2-NH2py = 2-aminopyridine; ox = oxalate ] were hydrothermally synthesized and characterized by elemental analyses, IR and single-cr...Two new supramoleeular polymers [ M （2-NH2 py）2 （ox） ] [ M = Co （1）, Ni （2） ; 2-NH2py = 2-aminopyridine; ox = oxalate ] were hydrothermally synthesized and characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. The isomorphic compounds 1 and 2 both possess one-dimensional zigzag chain structures, which are composed of [ M （2-NH2 py）2 ]^2＋ units bridged by tetradentate oxalate ligands to form three-dimensional supramolecular network v/a the C-H…O hydrogen bonds and π-π stacking interactions. Compound 1 displays antiferromagnetie interaction.展开更多
Anion-π interactions as a new member of supramolecular weak interactions are still in the young stage,but they already attract considerable attentions. Now the concerns are shifting from recognition to construction o...Anion-π interactions as a new member of supramolecular weak interactions are still in the young stage,but they already attract considerable attentions. Now the concerns are shifting from recognition to construction of functional systems. In this review, the anion-π functional systems especially anion-πcatalysis and self-assembly were highlighted and summarized together with several solid and recent examples of host-vip recognition. These applications suggest that the great potential of these new interactions.展开更多
Combined Single-Crystal XRD,solution 13C and ^(195)Pt NMR,solid-state ^(195)Pt NMR and UV-vis measurements,together with comprehensive(TD)DFT calculations,are used to describe the supramolecular interactions and seque...Combined Single-Crystal XRD,solution 13C and ^(195)Pt NMR,solid-state ^(195)Pt NMR and UV-vis measurements,together with comprehensive(TD)DFT calculations,are used to describe the supramolecular interactions and sequential concerted structural transformation occurring in a{PPh4^(+);[Pt(CN)_(4)]^(2-);TCP;CH_(2)Cl_(2)}supramolecular system(TCP-tetracyanopyrazine).In the solid-state,a mixture of needle-like co-crystals first appears,(PPh_(4))_(2){[TCP][Pt(CN)_(4)]}(1)and(PPh_(4))_(2){[TCP][Pt(CN)_(4)]}·2CH_(2)Cl_(2)(2),and subsequent recrystallization leads to block-shaped co-crystals of(PPh_(4))_(2){[TCP]2[Pt(CN)_(4)]}·2CH_(2)Cl_(2)(3),wherein double{[Pt(CN)_(4)]^(2-);TCP}and triple{[Pt(CN)_(4)]^(2-);TCP;CH_(2)Cl_(2)}and{PPh4^(+);[Pt(CN)_(4)]^(2-);TCP}synthons present either in 1 or 2 are reproduced in 3.The structural pathway(1,2→3)is accompanied by a 1D-to-2D modular evolution of anion-πinteractions between[Pt(CN)_(4)]^(2-)andπ-acidic TCP that seems to be driven,as indicated by calculations,not by maximizing their strength but rather by optimizing other crystal interactions,e.g.between PPh4^(+)cations.Formation of the corresponding{[Pt(CN)_(4)]^(2-);π-acid}anion-πcontacts in solution is evidenced by 13C NMR shifts and by new low-energy electronic absorption in the visible region(UV-vis).Finally,a combined solution/solid-state ^(195)Pt NMR approach is used for the first time to shed light on the geometry and interactions involving such aggregates;it shows that the degree of trapping of[Pt(CN)_(4)]^(2-)near aπ-acidic surface can be monitored by ^(195)Pt NMR chemical shifts.The results give fresh insight into block arrangement tactics and characterization of hybrid organic-inorganic co-crystal salts,and into aggregation controlled properties.展开更多
Two novel ionic liquids,[Bzmim]Cl and[Bzmim][AuCl_(4)],were successfully synthesized and characterized by ^(1)H NMR spectroscopy,single crystal structure analysis and quantum mechanical calculations.Meanwhile,multiple...Two novel ionic liquids,[Bzmim]Cl and[Bzmim][AuCl_(4)],were successfully synthesized and characterized by ^(1)H NMR spectroscopy,single crystal structure analysis and quantum mechanical calculations.Meanwhile,multiple supramolecular interactions of[Bzmim][AuCl_(4)](hydrogen bonds,Cl…π,Au…π interactions and π-π stacking)were found between the N-methylimidazolium cation and AuCl_(4)^(-).Interestingly,the interactions made it easy for[Bzmim][AuCl_(4)]to form a 3D supramolecular structure.Thus,a series of N-methylimidazolium-based poly(ionic liquids)were synthesized to recover Au(Ⅲ)in aqueous solution.They show high adsorption capacity and excellent selectivity for tetrachloroaurate anions which can be used as solid phase extraction agents over a wide temperature range.Notably,the acid thiourea can desorb Au(Ⅲ)from polymeric ionic liquids(PILs),thus they also exhibit excellent recyclability.Among them,PS-b-PVBnMeImCl-5.9 has the highest efficiency for Au(Ⅲ)recovery after five adsorption-desorption cycles.Compared with the Raman spectroscopy results of gold-containing PS-b-PVBnMeImCl-5.9,1H NMR of[Bzmim][AuCl4]revealed that the Au(Ⅲ)recovery mechanism by polymeric ionic liquids was due to a combination of electrostatic interactions and multiple weak intermolecular interactions.展开更多
Thermoresponsive biotinylated dendronized copolymers carrying dendritic oligoethylene glycol（OEG）pendants were prepared via free radical polymerization,and their protein recognitions based on biotin-avidin interacti...Thermoresponsive biotinylated dendronized copolymers carrying dendritic oligoethylene glycol（OEG）pendants were prepared via free radical polymerization,and their protein recognitions based on biotin-avidin interaction investigated.Both first（PG1） and second generation（PG2） dendronized copolymers were designed to examine possible thickness effects on the interaction between biotin and avidin.Inherited from the outstanding thermoresponsive properties from OEG dendrons,these biotinylated cylindrical copolymers show characteristic thermoresponsive behavior which provides an envelope to capture avidin through switching temperatures above or below their phase transition temperatures（T_（cp）s）.Thus,the recognition of polymer-supported biotin with avidin was investigated with UV/vis spectroscopy and dynamic laser light scattering.In contrast to the case for PG1,the increased thickness for copolymer PG2 hinders partially and inhibits the recognition of biotin moieties with avidin either below or above its T_（cp）.This demonstrates the significant architecture effects from dendronized polymers on the biotin moieties to shift onto periphery of the collapsed aggregates,which should be a prerequisite for protein recognition.These kinds of novel thermoresponsive copolymers may pave a way for the interesting biological applications in areas such as reversible activity control of enzyme or proteins,and for controlled delivery of drugs or genes.展开更多
基金funded by the Natural Science Foundation of Liaoning Province(2024JH2/102600340&2024-BSLH-310)the support program for excellent young scholars at China Medical University.
文摘Medical stents have made significant strides in development,however,creating a single manufacturing material that combines size adjustability,robust strength,and degradability remains a major challenge.Here,we developed an elastomer designed for stent fabrication,featuring excellent thermo-responsive shape memory and fast self-healing.This elastomer is produced through supramolecular inter-actions between liquid crystal moieties,which exhibit strong orientation,and a polymer backbone.These supramolecular interactions provide the elastomer with remarkable mechanical strength(10.46 MPa).Interestingly,the elastomer shows excellent mesocrystalline stability and cyclability,thanks to multiple non-covalent bonds,allowing the crosslinked liquid crystalline phase to maintain integrity at temper-atures up to 285℃.Impressively,the elastomer can respond to stress and temperature changes,fully reverting to its original shape in just 25.7±0.94 s.When configured as a helical stent,its macroscopic dimensions can be adjusted to mimic the size of blood vessels in vitro.The stent exhibits rapid responsiveness at 37℃,achieving complete self-expansion within 10 s.Furthermore,it demonstrates excellent degradability,with a weight loss of only 2.75%±0.31%after 70 d.This innovation paves the way for new possibilities in the use of medical stents,particularly for the long-term treatment of coronary heart disease.
基金support from The Hong Kong Polytechnic University(U-CDCA)and Innovation and Technology Fund(ITS-322-23FP)。
文摘Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.
基金the partial financial support from the National Natural Science Foundation of China (22075171)。
文摘The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs).In this work,the electrochemical activity of H_(3)O^(+) is inhibited by the supramolecular host–vip complex composed of H_(3)O^(+) as vip and 18-crown-6 as host.The even Zn plating is induced by the host–vip complex electrostatic shielding layer on Zn anode,as detected by in-situ optical microscopy.The lamellar Zn is plated which profits from the improved Zn plating behavior.Density functional theory (DFT) calculation presents the stable structure of complex.The less produced H_(2) content is monitored online by a mass spectrometer during Zn plating/stripping,which indicates HER can be hampered by the host–vip behavior.Thus,the ZIBs with long life and high Coulombic efficiency are achieved via introducing 18-crown-6.The proposed host–vip supramolecular interaction is expected to facilitate the furthermore development of Zn batteries.
基金the financial support from the National Natural Science Foundation of China (Nos. 21572026, 21702019)Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX20_2525)+1 种基金Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou Universitythe analytical testing support from Analysis and Testing Center, NERC Biomass of Changzhou University
文摘A calix[4]arene ligand assisted directβ-C-H arylation of tertiary aliphatic aldehydes has been developed via a Pd-catalyzed C(sp3)-H functionalization process.This strategy exhibited good functional group compatibility and C-H bond site-selectivity.Mechanism studies have shown that both synergistic effect and cationic-πsupramolecular interaction between calixarene cavity and transition-metal catalytic center may play an important role in this catalytic cycle.This complementary method would be used in organic and medical chemistry due to the importance of tertiary aliphatic aldehydes.
基金the support from the National Natural Science Foundation of China(Nos.22165027,22061039,22001214)Key R&D program of Gansu Province(No.21YF5GA066)Gansu Provincial Department of Education:Excellent Postgraduate“Innovation Star”Project(No.2021CXZX-184)。
文摘Supramolecular chemistry has received considerable attention in host-vip recognition.The structureresponse relationship of host-vip recognition system is a meaningful issue.Herein,a series of tripodal nitrogen mustard derivatives(TMs)have been developed in this paper.By rationally design the intramolecular alkyl chain lengths of host,the host-vip binding model have been successfully tuned,which underwent a transformation fromπ-πto multiple hydrogen bonds.This process enhances the host-vip binding force and recognition efficiency.
基金supported by the National Natural Science Foundation of China(No.82273919)Natural Science Foundation of Heilongjiang Province(No.LH2024H013)China Postdoctoral Science Foundation(No.2022MD723781).
文摘Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(CB[8])as the host and terpyridine lanthanum ions metal complex as the vip,constructed by layer-by-layer self-assembly through supramolecular interaction.Moreover,nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior.In the tumor micro-environment,the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect.In addition,the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells.The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.
基金supported by the National Natural Science Foundation of China (51922074, 51673138, 51820105003)the Tang Scholar, the Priority Academic Program Development of Jiangsu Higher Education Institutions, Collaborative Innovation Center of Suzhou Nano Science and Technology, Collaborative Innovation Center for Newtype Urbanization and Social Governance of Jiangsu Province, National Key Research and Development Program 376 of China (2017YFA0207700)Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX18_2496)。
文摘The rational design of dopant-free organic hole-transporting layer(HTL) materials is still a challenge for realizing high-efficient and stable p-i-n planar perovskite solar cells(pero-SCs). Here, we synthesized two π-conjugated small-molecule HTL materials through tailoring the backbone and conjugated side chain to carefully control molecular conformation. The resultant BDT-TPAs Th containing a planar fused benzo[1,2-b:4,5-b′]dithiophene(BDT) core and a conjugated thiophene side chain showed the planar conformation. X-ray crystallography showed a favorable stacking model in solid states under the parallel-displaced π-πand additional S-π weak-bond supramolecular interactions, thus achieving an obviously increased hole mobility without dopants.As an HTL material in p-i-n planar pero-SCs, the marginal solubility of BDT-TPA-s Th enabled inverse diffusion into the perovskite precursor solution for assisting the subsequent perovskite film growth and passivating the uncoordinated Pb2+ ion defects. As a result, the planar p-i-n pero-SCs exhibited a champion power conversion efficiency(PCE) of 20.5% and enhanced moisture stability. Importantly, the BDT-TPA-s Th HTL material also showed weak thickness-photovoltaic dependence, and the pero-SCs with blade-coated BDT-TPA-s Th as a HTL achieved a 15.30% PCE for the 1-cm2 modularized device. This HTL material design strategy is expected to pave the way toward high-performance, dopant-free and printing large-area planar p-i-n pero-SCs.
基金supported by the National Key R&D Program of China(grant no.2018YFA0902600)the Scientific Instrument Developing Project of the Chinese Academy of Sciences(grant no.ZDKYYQ20180001)+2 种基金the National Natural Science Foundation of China(grant nos.21704099,21877104,21834007,and 21907088)K.C.Wong Education Foundation(grant no.GJTD-2018-09)Young Elite Scientists Sponsorship Program by CAST(grant no.2018QNRC001).
文摘Proteinaceous fibers based on spidroins have attracted widespread attention due to their lightweight and mechanically strong properties.Presently,mechanical modulation is mainly dependent on the ultrahigh molecular weight of recombinant proteins.This makes it difficult to construct and express the target proteins.It is thus significant to develop alternative strategies for the fabrication of robust biological fibers.Herein,we demonstrate one new type of engineered protein fibers using electrostatic complexation of the cationic elastins and anionic dihydroxyphenylalanine surfactants.Interestingly,the mechanical performance of the resulting fibers can be modulated by multiple supramolecular interactions in the system including electrostatic force,hydrogen bonding,metal coordination,cation-πand other aromatic interactions.Consequently,significant alternation of the fibers’breaking strength(from 32 to 160 MPa),Young’s modulus(from 0.8 to 17 GPa),and toughness(from 1.2 to 99 MJ·m-3)has been achieved.Moreover,the fibers exhibit high plasticity;for example,the formation of different helical structures,and strong fluorescence after the introduction of Tb chelation.Therefore,this study offers new strategies for the mechanical regulation of engineered protein fibers.
基金Project supported by the Program for New Century Excellent Talents in University （No. NCET-04-0651）, the National Natural Science Foundation of China （Nos. 20335030 and 20575036） and the Important Project of Natural Science Foundation of Shandong Province of China （No. Z2003B01）.
文摘The supramolecular interaction of gemfibrozil with β-cyclodextrin （β-CD） was studied by spectrofluorimetry. The mechanism of the inclusion was discussed by spectrofluoremetry, infrared spectrum and ^1H NMR spectrum. The results showed that a 1 ： 1 （β-CD ： gemfibrozil） complex was formed with an apparent association constant of 3.844 × 10^3 L·mol^-1. Based on the enhancement of the fluorescent intensity of gemfibrozil, a spectrofluorimetric method for the determination of gemfibrozil in bulk aqueous solution in the presence of β-CD was developed. The linear range was 3.30 ng·mL^- 1 -6.00 ug·mL^-1 with the detection limit of 0.980 ng·mL^-1. There was no interference from the excipients normally used in tablet composition and the serum main compositions. The proposed method was then successfully applied to the determination of gemfibrozil in capsules and serum.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB3808800,Dake Xu)the National Natural Science Foundation of China(Grant Nos.U2006219(Dake Xu),52301081(Xiangyu Li))+4 种基金the National Postdoctoral Program for Innovative Talents(Grant No.BX20220059,Xiangyu Li)the China Postdoctoral Science Foundation(Grant No.2022M720677,Xiangyu Li)the Liaoning Provincial Natural Science Foundation of China(Grant No.2023-BS-052,Xiangyu Li)the Fundamental Research Funds for the Central Universities(Grant No.N2302015,Xiangyu Li)the State Key Laboratory of Marine Coatings Funded Project(Grant No.2024020800027,Xiangyu Li).
文摘Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements are emerging to fabricate multifunctional coatings that effectively combat such microbially produced damage.However,rapid,reliable,and robust surface engineering remains challenging due to stability limitations and intricate anti-biofilm additive dynamics.Herein,a silver-capsule-conjugated polyurethane coating with high stability and antimicrobial efficacy in a cooperative manner is developed through controlled supramolecular self-assembly.Polyvinylpyrrolidone(PVP)-mediated molecule entanglement breaks through the incompatibility between polymeric components and nanomaterials,strengthening the dispersion and fixation of encapsulated silver nanoparticles.The facilitation and control of the nanoscale interfacial binding significantly suppresses the aggregation of inorganic nanoparticles and consequent microcracks development,giving rise to mechanical robustness and thermal stability of the hybrid coating under extreme conditions.A synergistic combination of exposed residues,electrostatic,and coordination interactions could readily integrate the resultant coating on virtually arbitrary material sur-faces.This composite coating exhibits broad-spectrum and high bactericidal efficiencies of 99.99% against Staphylococcus aureus and Escherichia coli,as well as excellent biofilm formation suppression.Moreover,our coating has robust resistance to microbial-influenced corrosion(MIC)and can even endure 720 h of salt spray.This study deciphers a general code for creating stable and durable nanohybrid coatings to mitigate microbially related risks.
基金the National Natural Science Foundation of China(No.21402228)for financial support
文摘A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains,driven by CB[8]-encapsulation-enhanced donor-acceptor interaction.The as-formed supramolecular bottlebrush polymer has been characterized by -1H NMR titration experiment,UV-vis spectroscopy,DLS and 2D -1H NMR DOSY.
基金supported by the National Natural Science Foundation of China(Nos.51703112,51673106)Natural Science Foundation of Shandong Province(Nos.ZR2017BEM040,ZR2016BQ28)+1 种基金Open Fund of the State Key Laboratory of Luminescent Materials and Devices(No.2017-skllmd-10,South China University of Technology)China Postdoctoral Science Foundation(No.2017M622152).
文摘Photo-responsive mechanical actuator is a class of stimuli-responsive materials transferring light to mechanical energy through macroscopic transformation.To fabricate photo-responsive mechanical actuator,soft polymeric materials crosslinked with functional bridging structures are desired.Supramolecular interaction is a relatively common way to fabricate crosslinked materials due to its excellent self-assembly performance.And azobenzene and derivatives are ideal candidates of photo-responsive materials because of the unique photo-induced trans-cis isomerization.Here,a new kind of crosslinked materials based on supramolecular interaction between 4,4'-dihydroxyazobenzene and chitosan is reported.Under 355 nm irradiation,the macroscopic bending of polymeric materials occurs rapidly due to the photo-isomerization of 4,4-dihydroxyazobenzene.Meanwhile,the photo-responsive mechanical actuator can also lift weight which is up to 200 times that of the actuator itself,and convert energy from light to mechanical work efficiently.This report suggests a new kind of photo-responsive actuator based on supramolecular interaction and may be helpful to contribute a theoretical basis to the design and synthesis of photo-responsive mechanical actuator suitable for large-scale manufacturing industrialization in future.
基金financially supported by the National Natural Science Foundation of China(Nos.21674127,21422407 and 51373197)
文摘Complex emulsions,such as double emulsions and high-internal-phase emulsions,have shown great applications in the fields of drug delivery,sensing,catalysis,oil-water separation and self-healing materials.Their controllable preparation is at the forefront of interface and material science.Surfactants and polymers have been widely used as emulsifiers for building complex emulsions.Yet some inherent disadvantages exist including multi-step emulsifications and low production efficiency.Alternatively,supramolecular polymer emulsifier for complex emulsions via one-step emulsification is rising as a new strategy due to the ease of preparation.In this feature article,we review our recent progresses in using supramolecular polymer emulsifiers for the preparation of complex emulsions.Double emulsions and high-internal-phase emulsions are successfully prepared via one-step emulsification with the help of different supramolecular interactions including electrostatic,hydrogen bond,coordination interaction and dynamic covalent bond,which will be particularly emphasized in detail.In the end,a comprehensive prospect is given for the future development of this field.This article is expected to provide new inspirations for preparing complex emulsions via supramolecular routes.
基金supported by the NNSFC (Nos.20973172 and 21071145)the 973 Program (No.2009CB220009)the NSF of Fujian Province (Nos.2008J0175 and 2007F3112)
文摘A new mixed-ligand Mn（II）complex,namely [Mn（bipy）2（Huca）]·5H2O（1,bipy = 2,2＇-bipyridine,and H3uca = uracil-5-carboxylic acid）has been prepared and characterized by single-crystal X-ray diffraction,FT-IR spectroscopy and thermogravimetric analysis.It crystallizes in monoclinic,space group C2/c with a = 23.597（8）,b = 16.434（5）,c = 15.531（6）,β = 112.785（6）o,C25H28MnN6O9,Mr = 611.47,V = 5553（3）3,Z = 8,μ = 0.538,Dc = 1.463 g/cm3,F（000）= 2536,R = 0.0441 and wR = 0.1230 for all 5227 observed reflections（I 2σ（I））.The manganese（II）center is surrounded by three bidentate chelating ligands,and it displays a severely distorted octahedral geometry,with cis angles ranging from 72.14（6）to 109.78（6）o.Extensive intermolecular hydrogen bonds link the [Mn（bipy）2（Huca）] monomers and lattice water molecules to yield a three-dimensional supramolecular framework.TGA shows complete removal of all lattice water molecules above 270 ℃.
基金National Natural Science Foundation of China(NNSFC,No.22131008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support.
文摘The construction of hydrogels with good mechanical properties and phosphorescent properties is full of challenges.Herein,we report a supramolecular phosphorescent hydrogel with long lifetime,high tensile strength and self-healing property,which can be easily constructed through in-situ thermalinitiated polymerization of isocyanatoethyl acrylate-modifiedβ-cyclodextrin(β-CD-DA)and acrylatemodified adamantane(Ad-DA),acrylic acid(AA),followed by the non-covalent association with carbon dots(CNDs).The lifetime of phosphorescent hydrogel can reach 1261 ms at room temperature,and the quantum yield is 11%.Importantly,through the efficient triplet to singlet Förster resonance energy transfer(TS-FRET),the phosphorescent hydrogel shows the good phosphorescence energy transfer property for organic dyes Rhodamine B and Eosin Y with the delayed fluorescence lifetime up to 730 ms and 585 ms as well as the energy transfer efficiency(Φ_(ET))up to 99.9%and 99.3%,respectively.Moreover,owing to the host-vip interactions betweenβ-CD-DA and Ad-DA,the three-dimensional cross-linked network phosphorescent hydrogel can be easily stretched to 18 times of its original length,and can achieve self-healing of the cut surfaces within 30 min.These results will expand the scope of phosphorescent materials and provide new ideas and opportunities for materials science.
基金Supported by the National Natural Science Foundation of China(Nos.20571032 and 20333070).
文摘Two new supramoleeular polymers [ M （2-NH2 py）2 （ox） ] [ M = Co （1）, Ni （2） ; 2-NH2py = 2-aminopyridine; ox = oxalate ] were hydrothermally synthesized and characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. The isomorphic compounds 1 and 2 both possess one-dimensional zigzag chain structures, which are composed of [ M （2-NH2 py）2 ]^2＋ units bridged by tetradentate oxalate ligands to form three-dimensional supramolecular network v/a the C-H…O hydrogen bonds and π-π stacking interactions. Compound 1 displays antiferromagnetie interaction.
基金supported by the National Natural Science Foundation of China(No. 21604046)the National Young Thousand Talents ProgramShandong Provincial Natural Science Foundation, China (No. ZR2016XJ004)
文摘Anion-π interactions as a new member of supramolecular weak interactions are still in the young stage,but they already attract considerable attentions. Now the concerns are shifting from recognition to construction of functional systems. In this review, the anion-π functional systems especially anion-πcatalysis and self-assembly were highlighted and summarized together with several solid and recent examples of host-vip recognition. These applications suggest that the great potential of these new interactions.
基金supported by the National Science Center in Poland(grant OPUS 8,UMO 2014/15/B/ST5/02098)E.Kuzniak acknowledges the fellowship within the project no.POWR.03.02.00-00-I013/16.J.Hooper is grateful for the financial support from the Ministry of Science and Higher Education in Poland(Outstanding Young Scientist scholarship)+2 种基金R.Podgajny and S.Ferlay acknowledge the support from French Government and the French Embassy in Poland(the BGF Fellowship)Measurements were carried out with the equipment purchased thanks to the support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program(contract no.POIG.02.01.00-12-023/08)the PL-Grid Infrastructure and the ACC Cyfronet AGH(Krakow,Poland)for computational resources.
文摘Combined Single-Crystal XRD,solution 13C and ^(195)Pt NMR,solid-state ^(195)Pt NMR and UV-vis measurements,together with comprehensive(TD)DFT calculations,are used to describe the supramolecular interactions and sequential concerted structural transformation occurring in a{PPh4^(+);[Pt(CN)_(4)]^(2-);TCP;CH_(2)Cl_(2)}supramolecular system(TCP-tetracyanopyrazine).In the solid-state,a mixture of needle-like co-crystals first appears,(PPh_(4))_(2){[TCP][Pt(CN)_(4)]}(1)and(PPh_(4))_(2){[TCP][Pt(CN)_(4)]}·2CH_(2)Cl_(2)(2),and subsequent recrystallization leads to block-shaped co-crystals of(PPh_(4))_(2){[TCP]2[Pt(CN)_(4)]}·2CH_(2)Cl_(2)(3),wherein double{[Pt(CN)_(4)]^(2-);TCP}and triple{[Pt(CN)_(4)]^(2-);TCP;CH_(2)Cl_(2)}and{PPh4^(+);[Pt(CN)_(4)]^(2-);TCP}synthons present either in 1 or 2 are reproduced in 3.The structural pathway(1,2→3)is accompanied by a 1D-to-2D modular evolution of anion-πinteractions between[Pt(CN)_(4)]^(2-)andπ-acidic TCP that seems to be driven,as indicated by calculations,not by maximizing their strength but rather by optimizing other crystal interactions,e.g.between PPh4^(+)cations.Formation of the corresponding{[Pt(CN)_(4)]^(2-);π-acid}anion-πcontacts in solution is evidenced by 13C NMR shifts and by new low-energy electronic absorption in the visible region(UV-vis).Finally,a combined solution/solid-state ^(195)Pt NMR approach is used for the first time to shed light on the geometry and interactions involving such aggregates;it shows that the degree of trapping of[Pt(CN)_(4)]^(2-)near aπ-acidic surface can be monitored by ^(195)Pt NMR chemical shifts.The results give fresh insight into block arrangement tactics and characterization of hybrid organic-inorganic co-crystal salts,and into aggregation controlled properties.
基金supported by the National Natural Science Foundation of China(Grant 51474118).
文摘Two novel ionic liquids,[Bzmim]Cl and[Bzmim][AuCl_(4)],were successfully synthesized and characterized by ^(1)H NMR spectroscopy,single crystal structure analysis and quantum mechanical calculations.Meanwhile,multiple supramolecular interactions of[Bzmim][AuCl_(4)](hydrogen bonds,Cl…π,Au…π interactions and π-π stacking)were found between the N-methylimidazolium cation and AuCl_(4)^(-).Interestingly,the interactions made it easy for[Bzmim][AuCl_(4)]to form a 3D supramolecular structure.Thus,a series of N-methylimidazolium-based poly(ionic liquids)were synthesized to recover Au(Ⅲ)in aqueous solution.They show high adsorption capacity and excellent selectivity for tetrachloroaurate anions which can be used as solid phase extraction agents over a wide temperature range.Notably,the acid thiourea can desorb Au(Ⅲ)from polymeric ionic liquids(PILs),thus they also exhibit excellent recyclability.Among them,PS-b-PVBnMeImCl-5.9 has the highest efficiency for Au(Ⅲ)recovery after five adsorption-desorption cycles.Compared with the Raman spectroscopy results of gold-containing PS-b-PVBnMeImCl-5.9,1H NMR of[Bzmim][AuCl4]revealed that the Au(Ⅲ)recovery mechanism by polymeric ionic liquids was due to a combination of electrostatic interactions and multiple weak intermolecular interactions.
基金the National Natural Science Foundation of China(Nos.21374058,21474060 and 21574078)the Ph.D. Programs Foundation of Ministry of Education of China(No 201331081100166)the Shanghai Rising-Star Program(No.16QA1401800)
文摘Thermoresponsive biotinylated dendronized copolymers carrying dendritic oligoethylene glycol（OEG）pendants were prepared via free radical polymerization,and their protein recognitions based on biotin-avidin interaction investigated.Both first（PG1） and second generation（PG2） dendronized copolymers were designed to examine possible thickness effects on the interaction between biotin and avidin.Inherited from the outstanding thermoresponsive properties from OEG dendrons,these biotinylated cylindrical copolymers show characteristic thermoresponsive behavior which provides an envelope to capture avidin through switching temperatures above or below their phase transition temperatures（T_（cp）s）.Thus,the recognition of polymer-supported biotin with avidin was investigated with UV/vis spectroscopy and dynamic laser light scattering.In contrast to the case for PG1,the increased thickness for copolymer PG2 hinders partially and inhibits the recognition of biotin moieties with avidin either below or above its T_（cp）.This demonstrates the significant architecture effects from dendronized polymers on the biotin moieties to shift onto periphery of the collapsed aggregates,which should be a prerequisite for protein recognition.These kinds of novel thermoresponsive copolymers may pave a way for the interesting biological applications in areas such as reversible activity control of enzyme or proteins,and for controlled delivery of drugs or genes.
