Supramolecular aggregates,formed through the highly directional and reversible noncovalent assembly of building blocks,represent a cornerstone of modern materials science,enabling the creation of complex architectures...Supramolecular aggregates,formed through the highly directional and reversible noncovalent assembly of building blocks,represent a cornerstone of modern materials science,enabling the creation of complex architectures with emergent properties.Among the diverse molecular platforms available,resorcin[4]arene-derived cavitands have emerged as particularly powerful building units due to their intrinsic concave cavity,tunable geometry,and versatile functionalization capacity.This review highlights recent progress in the construction of functional supramolecular aggregates based on resorcin[4]arene cavitands,with a focus on their assembly strategies and wide-ranging applications.The review systematically covers several key types of aggregate systems:porous coordination aggregates(e.g.,metal-organic frameworks[MOFs])with stimuli-responsive properties,dynamic polymeric aggregates exhibiting self-healing behavior,sensing aggregates enabling differential detection,and therapeutic aggregates for combination therapy.These systems are unified by their exploitation of cavitands'unique host-vip chemistry and their ability to form well-defined superstructures through various noncovalent interactions.We emphasize how the precise manipulation of cavitand structure directs the assembly process and dictates the functional output of the resulting aggregates.Finally,we outline current challenges and future opportunities in this field,highlighting the potential of cavitand-based aggregates to enable next-generation technologies in sensing,catalysis,biomedicine,and energy materials.This review is expected to provide valuable insights and inspiration for researchers working in supramolecular chemistry and aggregate science.The construction of supramolecular aggregates triggered by macrocycles has become a thriving area of supramolecular chemistry.In this context,resorcinarene cavitands,a class of macrocyclic receptors with intrinsic cavities,have been drawn into the limelight because of their advantages,such as the concave-shaped structure,adjustable cavity size,favorable host-vip behavior,and ease of functionalization.They can induce organic and inorganic molecules to self-assemble into supramolecular aggregates through various bonding modes,including hydrophobic interactions,metal-ligand coordination,van der Waals forces,hydrogen bonding,electrostatic interactions,π-πstacking,and amphiphilic interactions.This minireview focuses on some representative resorcinarene cavitand-based assembly aggregates,including microporous MOFs,supramolecular polymers,sensor arrays,and multifunctional nanodrugs.Each section highlights recent advancements,structural characteristics,and functional applications of these aggregate systems.This review will provide useful information for researchers working on not only cavitand chemistry but also the chemistry of other macrocyclic hosts,and it will inspire new discoveries in the field of supramolecular assemblies and systems containing macrocyclic hosts.展开更多
Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need fo...Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.展开更多
Supramolecular prodrug vesicles(H-4⊃B-2@MB)with selective antibacterial activity have been successfully constructed.Specifically,a natural antibiotic prodrug(B-2)with glutathione(GSH)-responsiveness was synthesized.Th...Supramolecular prodrug vesicles(H-4⊃B-2@MB)with selective antibacterial activity have been successfully constructed.Specifically,a natural antibiotic prodrug(B-2)with glutathione(GSH)-responsiveness was synthesized.The hydrophobic interaction between B-2 and a novel water-soluble cavitand with deep cavity(H-4)resulted in the formation of a host-vip complex,which further self-assembled into supramolecular vesicles.The formed vesicles could effectively encapsulate the photosensitizer methylene blue(MB),enabling co-delivery of antibiotics and photosensitizers in the presence of GSH.Moreover,upon excitation at 630 nm,the photosensitizers generate reactive oxygen species(ROS),effectively eradicating E.coli through combined chemo-photodynamic therapy.Considering that GSH is predominantly present in Gram-negative bacteria such as E.coli,this strategy exhibits substantial potential for selectively inhibiting bacteria characterized by high GSH levels to regulate bacterial colony equilibrium.展开更多
Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecula...Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecular cyclization reactions of three vips with varying lengths within the well-defined nanocavities of cavitands in aqueous solution.Driven by hydrophobic effect,these vips were encapsulated within the dimeric capsules,adopting distinct conformations and orientations due to spatial constraints.Specifically,the shorter vip maintained an extended linear geometry,whereas the longer vips adopted a folded binding mode.Upon initiating the reaction,the terminal residue of the shorter vip displayed lower reactivity,while the longer vips,preorganized within the cavity,underwent efficient cyclization,resulting in significant differences in reaction kinetics.Furthermore,electrostatic potential fields played a critical role in modulating reaction rates,with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart,likely due to stabilization of the anionic transition state.This study provides an effective strategy for designing enzymemimetic nanoreactors through the utilization of well-defined nanospaces.展开更多
Compartmentalization in the biological world brings excellent efficiency and specificity to the formation of complex compounds,inspiring supramolecular chemists to continuously search for defined spaces that can mimic...Compartmentalization in the biological world brings excellent efficiency and specificity to the formation of complex compounds,inspiring supramolecular chemists to continuously search for defined spaces that can mimic such natural binding sites.Bowl-shaped cavitands built up from resorcinarenes(RA)present rigid and preorganized concave surfaces,which are capable of mimicking the molecular recognition properties of enzymes.The versatile scaffold of RA endows the cavitand with terrific variety and excellent binding behavior.This review provides a comprehensive overview over the structural modification to date in the high attention field of RA-based cavitands development.Different strategies for synthesizing diverse cavitands,such as small cavity cavitands,wider cavity cavitands,deep cavity cavitands,biscavitands,and asymmetric cavitands,are discussed in details.Furthermore,insights into their applications including catalysis,separations and sensing are provided.展开更多
A C-iso-butyl-cavitand bowl with trimethyl and methylol groups was isolated from the acetoxymethyl hydrolysis of mono-methylbromo-cavitand in THF. The molecular structure of the present cavitand compound was determi...A C-iso-butyl-cavitand bowl with trimethyl and methylol groups was isolated from the acetoxymethyl hydrolysis of mono-methylbromo-cavitand in THF. The molecular structure of the present cavitand compound was determined by single-crystal X-ray diffraction. The compound (C56H70N2O9) crystallizes in orthorhombic, space group Pnma with a = 19.5060(15), b = 19.8136(15), c = 12.9508(10) ?, V = 5005.3(7) ?3, Z = 4, Mr = 915.14, Dc = 1.214 g/cm3, F(000) = 1968, μ = 0.081 mm?1, S = 1.012, the final R = 0.0789 and wR = 0.1488 for 2298 observed reflections with I > 2σ(I) and 322 variable parameters. The structure exhibits a rigid bowl-cavity with an available functional hydroxyl group. The bowl of cavitand contains a CH3CN solvent molecule, and the depth of the bowl-shaped cavity is ca. 2.42 ?.展开更多
One goal of supramolecular chemistry is the creation of synthetic receptors that have a high affinity for hydrophilic molecules in water.We found that cavitands with upper rims extended by pyridyl groups coax hydrophi...One goal of supramolecular chemistry is the creation of synthetic receptors that have a high affinity for hydrophilic molecules in water.We found that cavitands with upper rims extended by pyridyl groups coax hydrophilic vips into the cavity where they are shielded from the aqueous environment.The ability of Pd(Ⅱ)to coordinate adjacent pyridyl groups leads to increased selectivity for highly hydrophilic solvent molecules such as acetone,1,4-dioxane and tetrahydrofuran in water.Analysis of the binding behavior indicated that metal-coordination restricts the container entrance,shrinks the effective cavity volume and increases the energetic barrier to vip exchange.展开更多
Binding of non-activated alkyl halides(2-20)in water-soluble cavitand(1)through supramolecular forces is here reported,with emphasis on the role of size and polarizability of the halogen atom in the formation of intra...Binding of non-activated alkyl halides(2-20)in water-soluble cavitand(1)through supramolecular forces is here reported,with emphasis on the role of size and polarizability of the halogen atom in the formation of intramolecular C-H hydrogen bonds in confined spaces.Rare reverse affinity in water(RI<RBr<RCl)is surprisingly observed for the more water-soluble short alkyl halides in dynamic open-ended containers.Competitive bindings and theoretical calculations confirm the unusual selectivity and the presence of C-H hydrogen bonds in non-activated systems for the first time,pointing out the importance and effect of subtle forces on molecular recognition in confined spaces.展开更多
Tetra-bromo-methyl-resorcin[4]arene cavitands were synthesized and C-2 position amine functionalized to obtain C-propyl-o-toluidine-methyl-resorcin[4]arene cavitand 4, and the crystal containing one solvate molecule o...Tetra-bromo-methyl-resorcin[4]arene cavitands were synthesized and C-2 position amine functionalized to obtain C-propyl-o-toluidine-methyl-resorcin[4]arene cavitand 4, and the crystal containing one solvate molecule of ethanol was obtained in a dichloromethane-ethanol solvent system, its structure crystallized in the monoclinic space group P2<sub>1</sub>/n, with a = 12.521(3) Å, b = 21.738(6) Å, c = 25.353(6) Å, α = 90˚, β = 102.372(4)˚, γ = 90˚, and Z = 4. The compound was determined by single-crystal X-ray diffraction and characterized by <sup>1</sup>H NMR, FT-IR and elemental analyses.展开更多
The use of a metallo cavitand for the selective sequestration of n-alkanes from their mixtures with isooctane is described.Competition experiments and NMR spectroscopy are used to show the preference of a water-solubl...The use of a metallo cavitand for the selective sequestration of n-alkanes from their mixtures with isooctane is described.Competition experiments and NMR spectroscopy are used to show the preference of a water-soluble cavitand host for vips that are hydro-phobic and have narrow or flat shapes.The host showed selectivity for trans 1,4-dimethylcyclohexane over the cis-isomers.The sep-arations of n-alkanes from isooctane by gas/liquid adsorption and a liquid/liquid extraction are detailed.展开更多
基金supported by the National Natural Science Foundation of China(22322107,22301174,and 22571190)the Shanghai Scientific and Technological Committee(22010500300).
文摘Supramolecular aggregates,formed through the highly directional and reversible noncovalent assembly of building blocks,represent a cornerstone of modern materials science,enabling the creation of complex architectures with emergent properties.Among the diverse molecular platforms available,resorcin[4]arene-derived cavitands have emerged as particularly powerful building units due to their intrinsic concave cavity,tunable geometry,and versatile functionalization capacity.This review highlights recent progress in the construction of functional supramolecular aggregates based on resorcin[4]arene cavitands,with a focus on their assembly strategies and wide-ranging applications.The review systematically covers several key types of aggregate systems:porous coordination aggregates(e.g.,metal-organic frameworks[MOFs])with stimuli-responsive properties,dynamic polymeric aggregates exhibiting self-healing behavior,sensing aggregates enabling differential detection,and therapeutic aggregates for combination therapy.These systems are unified by their exploitation of cavitands'unique host-vip chemistry and their ability to form well-defined superstructures through various noncovalent interactions.We emphasize how the precise manipulation of cavitand structure directs the assembly process and dictates the functional output of the resulting aggregates.Finally,we outline current challenges and future opportunities in this field,highlighting the potential of cavitand-based aggregates to enable next-generation technologies in sensing,catalysis,biomedicine,and energy materials.This review is expected to provide valuable insights and inspiration for researchers working in supramolecular chemistry and aggregate science.The construction of supramolecular aggregates triggered by macrocycles has become a thriving area of supramolecular chemistry.In this context,resorcinarene cavitands,a class of macrocyclic receptors with intrinsic cavities,have been drawn into the limelight because of their advantages,such as the concave-shaped structure,adjustable cavity size,favorable host-vip behavior,and ease of functionalization.They can induce organic and inorganic molecules to self-assemble into supramolecular aggregates through various bonding modes,including hydrophobic interactions,metal-ligand coordination,van der Waals forces,hydrogen bonding,electrostatic interactions,π-πstacking,and amphiphilic interactions.This minireview focuses on some representative resorcinarene cavitand-based assembly aggregates,including microporous MOFs,supramolecular polymers,sensor arrays,and multifunctional nanodrugs.Each section highlights recent advancements,structural characteristics,and functional applications of these aggregate systems.This review will provide useful information for researchers working on not only cavitand chemistry but also the chemistry of other macrocyclic hosts,and it will inspire new discoveries in the field of supramolecular assemblies and systems containing macrocyclic hosts.
基金supported by the National Natural Science Foundation of China(Nos.22322107,22101169 and 22071144)by Shanghai Scientific and Technological Committee(No.22010500300).
文摘Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.
基金supported by the National Natural Science Foundation of China(No.22271154)Natural Science Foundation of Jiangsu Province(No.BK20211179)+3 种基金Innovation Support Program of Jiangsu Province(No.BZ2023055)Fundamental Research Funds for the Central Universities(No.NS2023033)China Postdoctoral Science Foundation(No.2023M731658)Achievement Transformation Project of Qinghai Province(No.2021-SF-145).
文摘Supramolecular prodrug vesicles(H-4⊃B-2@MB)with selective antibacterial activity have been successfully constructed.Specifically,a natural antibiotic prodrug(B-2)with glutathione(GSH)-responsiveness was synthesized.The hydrophobic interaction between B-2 and a novel water-soluble cavitand with deep cavity(H-4)resulted in the formation of a host-vip complex,which further self-assembled into supramolecular vesicles.The formed vesicles could effectively encapsulate the photosensitizer methylene blue(MB),enabling co-delivery of antibiotics and photosensitizers in the presence of GSH.Moreover,upon excitation at 630 nm,the photosensitizers generate reactive oxygen species(ROS),effectively eradicating E.coli through combined chemo-photodynamic therapy.Considering that GSH is predominantly present in Gram-negative bacteria such as E.coli,this strategy exhibits substantial potential for selectively inhibiting bacteria characterized by high GSH levels to regulate bacterial colony equilibrium.
基金funded by the National Natural Science Foundation of China(Nos.22271154,M-0411)the China Postdoctoral Science Foundation(No.2023M731658)+2 种基金the Science Fund for Distinguished Young Scholars of Jiangsu Province(No.BK20240078)the Innovation Support Program of Jiangsu Province(No.BZ2023055)the High-Performance Computing Platform of Peking Uniersity。
文摘Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecular cyclization reactions of three vips with varying lengths within the well-defined nanocavities of cavitands in aqueous solution.Driven by hydrophobic effect,these vips were encapsulated within the dimeric capsules,adopting distinct conformations and orientations due to spatial constraints.Specifically,the shorter vip maintained an extended linear geometry,whereas the longer vips adopted a folded binding mode.Upon initiating the reaction,the terminal residue of the shorter vip displayed lower reactivity,while the longer vips,preorganized within the cavity,underwent efficient cyclization,resulting in significant differences in reaction kinetics.Furthermore,electrostatic potential fields played a critical role in modulating reaction rates,with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart,likely due to stabilization of the anionic transition state.This study provides an effective strategy for designing enzymemimetic nanoreactors through the utilization of well-defined nanospaces.
基金supported by the Natural Science Foundation of Jiangsu Province(Nos.BK20200432,BK20211179)National Natural Science Foundation of China(Nos.22271154,M-0411)the Fundamental Research Funds for the Central Universities(No.NG2022003).
文摘Compartmentalization in the biological world brings excellent efficiency and specificity to the formation of complex compounds,inspiring supramolecular chemists to continuously search for defined spaces that can mimic such natural binding sites.Bowl-shaped cavitands built up from resorcinarenes(RA)present rigid and preorganized concave surfaces,which are capable of mimicking the molecular recognition properties of enzymes.The versatile scaffold of RA endows the cavitand with terrific variety and excellent binding behavior.This review provides a comprehensive overview over the structural modification to date in the high attention field of RA-based cavitands development.Different strategies for synthesizing diverse cavitands,such as small cavity cavitands,wider cavity cavitands,deep cavity cavitands,biscavitands,and asymmetric cavitands,are discussed in details.Furthermore,insights into their applications including catalysis,separations and sensing are provided.
基金This project was supported by the Key Scientific Research Foundation of State Education Ministry of China (No. 204067)
文摘A C-iso-butyl-cavitand bowl with trimethyl and methylol groups was isolated from the acetoxymethyl hydrolysis of mono-methylbromo-cavitand in THF. The molecular structure of the present cavitand compound was determined by single-crystal X-ray diffraction. The compound (C56H70N2O9) crystallizes in orthorhombic, space group Pnma with a = 19.5060(15), b = 19.8136(15), c = 12.9508(10) ?, V = 5005.3(7) ?3, Z = 4, Mr = 915.14, Dc = 1.214 g/cm3, F(000) = 1968, μ = 0.081 mm?1, S = 1.012, the final R = 0.0789 and wR = 0.1488 for 2298 observed reflections with I > 2σ(I) and 322 variable parameters. The structure exhibits a rigid bowl-cavity with an available functional hydroxyl group. The bowl of cavitand contains a CH3CN solvent molecule, and the depth of the bowl-shaped cavity is ca. 2.42 ?.
基金supported by the National Natural Science Foundation of China(Nos.22071144 and 21801164)Shanghai University(No.13-G210-20-201)the Program for Professor of Special Appointment(Dongfang Scholarship)of the Shanghai Education Committee。
文摘One goal of supramolecular chemistry is the creation of synthetic receptors that have a high affinity for hydrophilic molecules in water.We found that cavitands with upper rims extended by pyridyl groups coax hydrophilic vips into the cavity where they are shielded from the aqueous environment.The ability of Pd(Ⅱ)to coordinate adjacent pyridyl groups leads to increased selectivity for highly hydrophilic solvent molecules such as acetone,1,4-dioxane and tetrahydrofuran in water.Analysis of the binding behavior indicated that metal-coordination restricts the container entrance,shrinks the effective cavity volume and increases the energetic barrier to vip exchange.
基金supported by the National Natural Science Foundation of China(Nos.22071144 and 21801164)Shanghai Scientific and Technological Committee(No.22010500300)the Program for Professor of Special Appointment(Dongfang Scholaship)of the Shanghai Education Committee。
文摘Binding of non-activated alkyl halides(2-20)in water-soluble cavitand(1)through supramolecular forces is here reported,with emphasis on the role of size and polarizability of the halogen atom in the formation of intramolecular C-H hydrogen bonds in confined spaces.Rare reverse affinity in water(RI<RBr<RCl)is surprisingly observed for the more water-soluble short alkyl halides in dynamic open-ended containers.Competitive bindings and theoretical calculations confirm the unusual selectivity and the presence of C-H hydrogen bonds in non-activated systems for the first time,pointing out the importance and effect of subtle forces on molecular recognition in confined spaces.
文摘Tetra-bromo-methyl-resorcin[4]arene cavitands were synthesized and C-2 position amine functionalized to obtain C-propyl-o-toluidine-methyl-resorcin[4]arene cavitand 4, and the crystal containing one solvate molecule of ethanol was obtained in a dichloromethane-ethanol solvent system, its structure crystallized in the monoclinic space group P2<sub>1</sub>/n, with a = 12.521(3) Å, b = 21.738(6) Å, c = 25.353(6) Å, α = 90˚, β = 102.372(4)˚, γ = 90˚, and Z = 4. The compound was determined by single-crystal X-ray diffraction and characterized by <sup>1</sup>H NMR, FT-IR and elemental analyses.
基金the National Natural Science Foundation of China(Nos.21801164 and 22071144)Shanghai University(N.13-G210-20-201).Dr.Yang Yu thanks the Program for Professor of Special Appointment(Dongfang Scholarship)of the Shanghai Education Committee.
文摘The use of a metallo cavitand for the selective sequestration of n-alkanes from their mixtures with isooctane is described.Competition experiments and NMR spectroscopy are used to show the preference of a water-soluble cavitand host for vips that are hydro-phobic and have narrow or flat shapes.The host showed selectivity for trans 1,4-dimethylcyclohexane over the cis-isomers.The sep-arations of n-alkanes from isooctane by gas/liquid adsorption and a liquid/liquid extraction are detailed.
