The ongoing development of small molecule drugs underscores the urgent need for novel excipients to formulate poorly soluble drug candidates.Cucurbit[7]uril(CB[7])possesses high binding affinities for a variety of mol...The ongoing development of small molecule drugs underscores the urgent need for novel excipients to formulate poorly soluble drug candidates.Cucurbit[7]uril(CB[7])possesses high binding affinities for a variety of molecular vips.However,its moderate water solubility limits broader application.Here we report the synthesis of three CB[7]derivatives M1-M3 by modifying an average of 4.2,5.5,and 5.9 sulfonatopropoxy groups onto their"equator"carbons.Compared to CB[7],their water-solubility increased by at least 26.6-,23.6-,and 19.2-fold,respectively,while the maximum tolerated doses(MTD)of M1 and M2 improved by 2.5-and 2.3-fold.Phase solubility diagram studies demonstrate that M1 and M2 significantly enhance the water-solubility of eighteen poorly soluble drugs.In vivo experiments in rat complete Freund's arthritis reveal that M1 not only improves the anti-inflammatory efficacy of indomethacin by up to 52%,but also substantially reduces its side effect of gastric ulcer.展开更多
The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration...The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration calorimetry(ITC) and X-ray crystallography. The data indicates that the Q[5]@4-AP complex exhibits exo binding, which is not observed in the other four host-vip complexes. Furthermore,X-ray crystallography clearly reveals how the Q[n]s bind with 4-AP to form complexes, for example Q[5]forms an outer-surface complex, whilst Q[6], TMe Q[6] and Q[7] formed 1:1 host and vip type complexes, and Q[8] formed a stable 1:2 ternary complex due to its large cavity, which can accommodate two 4-AP molecules.展开更多
Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]aren...Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]arene and 4-sulfocalix[6]arene using ^(1)H NMR spectroscopy and isothermal titration calorimetry(ITC),respectively.Moreover,solid fluorescent materials were prepared via the adsorption of fluorescent dyes by these porous supramolecular frameworks,which exhibit a selective response to certain volatile organic compounds.展开更多
With excellent biocompatibility and biodegradability,natural polysaccharides and their derivative s have exhibited great potential in constructing drug delivery ve hicles for tissue engineering and therapeutics.Cucurb...With excellent biocompatibility and biodegradability,natural polysaccharides and their derivative s have exhibited great potential in constructing drug delivery ve hicles for tissue engineering and therapeutics.Cucurbit[n]uril(CB[n])-mediated reversible crosslinking of polysaccharides possess intrinsic stimuliresponsiveness towards competitive vips and have been extensively investigated to fabricate various particles and hydrogels for multiple stimuli-re sponsive drug release by incorpo ration with other stimuli including photo,redox,and enzyme.Through host-vip interactions between CB[6]and aliphatic diamines,functional tags covalently connected with CB[6]can be readily anchored into polysaccharidebased hydrogels,realizing multiple functionalization.The rheological prope rty and drug release profile of polysaccharide-based supramolecular hydrogels can be facilely tuned through CB[8]-mediated dyna mic homo or hetero crosslinking of polysaccharides and/or other polymers.In this review,we introduce and summarize recent progress regarding polysaccharide-based supramolecular drug delivery systems mediated via host-vip interactions of CB[6]and CB[8],covering both bulk hydrogels and particular systems.At the end,possible utilization of CB[7]-based host-vip interactions in constructing polysaccharide-based drug delivery systems and future perspectives of this research direction are also discussed.展开更多
In order to reduce the impact of CdS photogenerated electron-hole recombination on its photocatalytic performance,a narrow band gap semiconductor MoS_(2) and organic macromolecular cucurbit[n]urils(Q[n])were used to m...In order to reduce the impact of CdS photogenerated electron-hole recombination on its photocatalytic performance,a narrow band gap semiconductor MoS_(2) and organic macromolecular cucurbit[n]urils(Q[n])were used to modify CdS.Q[n]/CdS-MoS_(2)(n=6,7,8)composite photocatalysts were synthesized by hydrothermal method.Infrared spectroscopy,X-ray diffraction,X-ray photoelectron spectroscopy,field emission scanning electron microscopy,ultraviolet-visible and photoluminescence spectrum were used to characterize the structure,morphology and optical properties of the products,and the catalytic degradation of the solutions of methylene blue,rhodamine B and crystal violet by Q[n]/CdS-MoS_(2) composite catalyst was investigated.The results showed that the Q[n]played a regulatory role on the growth and crystallization of CdS-MoS_(2) particles,Q[n]/CdS-MoS_(2)(n=6,7,8)formed flower clusters with petal-like leaves,the flower clusters of petal-like leaves increased the surface area and active sites of the catalyst,the Q[n]/CdS-MoS_(2) barrier width decreased,the electron-hole pair separation efficiency was improved in the Q[6]/Cds-MoS_(2).Q[n]makes the electron-hole pair to obtain better separation and migration.The Q[6]/CdS-MoS_(2) and Q[7]/CdS-MoS2 have good photocatalytic activity for methylene blue,and the catalytic process is based on hydroxyl radical principle.展开更多
Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected...Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected in their simple composition and preparation methods used for QSFs.The diversity of supramolecular organic frameworks(SOFs) is reflected in the synthesis methods and structural characteristics of the as-obtained QSFs,as well as the variety of structural directing agents and basic building blocks used to prepare QSFs.The modulability is reflected by the controllable channel size in the QSFs,which can be adjusted using different sizes of Q[n]s.In this work,the first re ported cucurbituril Q[6]was selected as the basic building block and three Q[6]-based su p ramolecular frameworks were obtained from aqueous HCl solutions in the presence of [CdCl_(4)]^(2-)respectively.The OSIQs are the main driving forces for the formation of these frameworks.This study shows the diversity of the QSFs.展开更多
A series of sulfonatopropoxylated cucurbit[8]uril derivatives(SPECB8s)with water-solubility ranging from 344 mmol/L to 360 mmol/L have been prepared.One of the derivatives SPE_(5.5)CB8 bearing an average of 5.5 sulfon...A series of sulfonatopropoxylated cucurbit[8]uril derivatives(SPECB8s)with water-solubility ranging from 344 mmol/L to 360 mmol/L have been prepared.One of the derivatives SPE_(5.5)CB8 bearing an average of 5.5 sulfonatopropoxy side chains has been revealed to display high biocompatibility,with maximum tolerated dose being as high as 2500 mg/kg for mice.Phase solubility diagram investigations illustrate that SPE_(5.5)CB8 can solubilize eighteen poorly soluble drugs and,for fifteen of them including remdesivir,its solubilization efficiency is higher than that of Captisol,the most widely used β-cyclodextrin-derived excipient for drug formulation.Moreover,the improved solubilization for remdesivir,which is formulated by Captisol for clinical use,can lead to important increase of its antiviral activity as compared with Captisol.展开更多
The slightly water-soluble anticancer drug camptothecin(CPT) and its inclusion complexes with cucurbit[n = 7,8]uril(Q[n](n = 7,8)) were investigated.The formation of 1:2 complexes with Q[n](n = 7,8) in aqueous solutio...The slightly water-soluble anticancer drug camptothecin(CPT) and its inclusion complexes with cucurbit[n = 7,8]uril(Q[n](n = 7,8)) were investigated.The formation of 1:2 complexes with Q[n](n = 7,8) in aqueous solution was confirmed by fluorescence spectroscopy and the apparent stability constants were determined to be higher than 3.01 × 1012 L2/mol2.The solid inclusion complexes of CPT and Q[n](n = 7,8) were also prepared by the co-evaporation method and characterized by Fourier transformation-infrared spectroscopy,differential scanning calorimetry and powder X-ray diffraction.Aqueous solubility and dissolution studies indicate that the complexes exhibited significantly increased dissolution rates compared with the pure drug and physical mixtures.The potential of Q[7] or Q[8] for stabilizing lactone modality of CPT was investigated by the High Performance Liquid Chromatography(HPLC) method.The results reveal more than 63% CPT lactone form(active form) in CPT-Q[7] or Q[8] complexes compared to only 36% CPT lactone form in the absence of Q[7] or Q[8] after being incubated in the phosphate buffer solution(pH 7.4 at 37 °C) for 5h.展开更多
It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to pla...It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to play an insignificant role or only to provide a nonpolar microenvironment for hydrogen bonds.Herein,we report that hydrophobic cavity alone can also strongly bind neutral,highly hydrophilic molecules in water.We found that cucurbit[n]urils(n=7,8)bind 1,4-dioxane,crown ethers and monosaccharides in water with remarkable affinities.The best binding constant reaches 10^(7) M^(−1) for cucurbit[8]uril,which is higher than its binding affinities to common organic cations.Density functional theory(DFT)calculations and control experiments reveal that the hydrophobic effect is the major contributor to the binding through releasing the cavity water and/or properly occupying the weakly hydrated cavity.However,hydrophobic cavity still prefers nonpolar vips over polar vips with similar size and shape.展开更多
This investigation focuses on the utilization of cucurbit[6]uril(Q[6])as the host compound for the development of long-lasting afterglow materials.By strategically manipulating the outer surface interactions of Q[6],c...This investigation focuses on the utilization of cucurbit[6]uril(Q[6])as the host compound for the development of long-lasting afterglow materials.By strategically manipulating the outer surface interactions of Q[6],classical aggregation-caused quenching(ACQ)compounds such as fluorescein sodium(FluNa)and calcein sodium(CalNa)were transformed into afterglow materials with varying colors and durations upon exposure to ultraviolet light.This transformation was facilitated through a host-vip doping method combined with coordination with metal ions.Even at a reduced doping concentration of 5×10^(-5)wt%,the materials exhibit remarkable afterglow properties,lasting up to 2 s,with a phosphorescence lifetime of up to 150 ms.Moreover,by adjusting the concentration of the vip compound,the persistent luminescence color of the materials could be easily transitioned from orange to yellow and subsequently to green.These findings suggest that the developed afterglow materials hold significant potential for multilevel anti-counterfeiting and information encryption applications when exposed to ultraviolet light.The supramolecular assembly strategy,which relies on the outer surface interactions of cucurbit[n]uril,offers a simpler and more efficient approach to crafting multi-color luminescent materials.Additionally,this method opens avenues for enhancing the application potential of aggregation-caused quenching(ACQ)compounds in various technological domains.展开更多
Nor-seco-cucurbit[10]uril(ns-CB[10])is a kinetic product with unique structure.The single bridged methylene in its structure makes the molecular cavity of ns-CB[10]more deformable when compared to ordinary cucurbit[n]...Nor-seco-cucurbit[10]uril(ns-CB[10])is a kinetic product with unique structure.The single bridged methylene in its structure makes the molecular cavity of ns-CB[10]more deformable when compared to ordinary cucurbit[n]uril,reducing its structural stability.Repeated experiments showed that ns-CB[10]gradually cracks in an acidic solution and changes the specificity of cucurbit[5]uril(CB[5])and cucurbit[8]uril(CB[8])under more robust acidic solutions and when heated.A series of experiments were designed to study the transformation behavior of ns-CB[10].It was found that the concentration of ns-CB[10]was correlated with the content distribution of CB[5]and CB[8].This study explores the influencing factors and mechanisms of the transformation of ns-CB[10]to CB[5]and CB[8].The results are of great significance for the application of ns-CB[10],understanding the formation mechanism of cucurbit[n]urils.Furthermore,it provides a new pathway for synthesizing new cucurbit[n]urils.展开更多
A supramolecular assembly composed of perylene diimide derivative(PDI-nm)and nor-secocucurbit[10]uril(ns-Q[10])was designed.The excellent host-vip interaction between PDI-nm and nsQ[10]prevented the aggregation-caus...A supramolecular assembly composed of perylene diimide derivative(PDI-nm)and nor-secocucurbit[10]uril(ns-Q[10])was designed.The excellent host-vip interaction between PDI-nm and nsQ[10]prevented the aggregation-caused quenching(ACQ)effect of PDI-nm,resulting in a luminescent assembly.The addition of spermine to the PDI-nm/ns-Q[10]assembly restored the ACQ of PDI-nm due to the competitive binding of spermine to ns-Q[10],which released PDI-nm.The assembly based on this principle showed ultra-high sensitivity for the detection of spermine with a detection limit as low as7.84×10^(-7)mol/L in aqueous solution and 3.69×10^(-7)mol/L in plasma solution.Moreover,an artificial light-harvesting system based on this assembly was proposed,benefiting from its good luminescent performance.Nile red(Ni R)functioned as an acceptor loaded into assembly,and a highly efficient energy transfer process occurred from PDI-nm/ns-Q[10]to Ni R,with an efficiency up to 87%.展开更多
The cross-photodimerization often comes with the formation of undesired and competitive homophotodimer as side products.Herein,we report a series of highly selective[4+4]cross-photodimerization between anthracene and ...The cross-photodimerization often comes with the formation of undesired and competitive homophotodimer as side products.Herein,we report a series of highly selective[4+4]cross-photodimerization between anthracene and 4a-azoniaanthracene derivatives within a cucurbit[10]uril(CB[10])host in water.Heteroternary inclusion complexes were formed through encapsulation of donor(D1-D2,anthracene derivative)and acceptor(A1-A3,4a-azoniaanthracene derivatives)pairs in CB[10].In the presence of CB[10](1.0 equiv.),the[4+4]cross-photodimerization between D1 and A1/A2/A3 efficiently gave a single racemic cross-photodimer.Furthermore,the cross-photodimerization between 9-substituted anthracene D2 and A1/A3 was catalyzed by CB[10](0.1 equiv.)to quantitatively yield a cross-photodimer with high regioselectivity.Efficient formation of selective cross-photodimers could be attributed to the exclusive encapsulation of D-A hetero-vip pairs in CB[10]and the confinement effect of the CB[10]host cavity.Our study further proves host–vip complexation as a powerful strategy for cross-cycloaddition reactions with high efficiency.展开更多
Selective separation of amino acids and proteins is crucial in various areas of research,including proteomics,protein structure and function studies,protein purification and drug development,and biosensing and biodete...Selective separation of amino acids and proteins is crucial in various areas of research,including proteomics,protein structure and function studies,protein purification and drug development,and biosensing and biodetection.A nanocomposite film is formed by combining layer-by-layer self-assembled gold nanospheres(Au NPs)driven by cucurbit[7]uril(CB[7])and polymethyl methacrylate(PMMA)film.Due to the host-vip interactions,the selective transmission of l-tryptophan in the nanocomposite film is confirmed by the current-voltage measurements using a picoammeter.Furthermore,by adjusting the particle size of Au NPs to increase channel size,lysozyme containing multiple tryptophan residues can selectively pass through the nanocomposite film,indicating the high versatility and adaptability of the nanocomposite film.This study will provide a new direction for the selective separation of amino acids and proteins.展开更多
Pyridine(Py) and 3-methylpyridine(3-MP) are crucial intermediates in chemical industrial processes.Here,we provide a simple and energy-efficient approach for the isolation of Py and 3-MP by employing crystalline cucur...Pyridine(Py) and 3-methylpyridine(3-MP) are crucial intermediates in chemical industrial processes.Here,we provide a simple and energy-efficient approach for the isolation of Py and 3-MP by employing crystalline cucurbit[6]uril(Q[6]).The crystal exhibit high selectivity for Py from the mixture of Py and 3-MP in both vapor and liquid phases,with separation purities close to 100%.The selectivity is attributed to the varying stability of the host-vip complexes after the absorption of Py or 3-MP,as revealed by the single-crystal structure analysis.ITC experimental results and DFT calculations indicate that,compared to3-MP,Q[6] has a higher binding strength and lower binding energy with Py.In addition,pyridine can be removed from the Q[6] cavity through vacuum heating or organic solvent immersion,enabling Q[6]reuse via reversible vip loading.This method offers a promising approach for high-purity Py and 3-MP separation with significant economic and environmental benefits.展开更多
We report herein a new fluorescent probe for the selective recognition and determination of dodine among 20 different pesticides.This fluorescent probe was assembled through host-vip complexation between cucurbit[10...We report herein a new fluorescent probe for the selective recognition and determination of dodine among 20 different pesticides.This fluorescent probe was assembled through host-vip complexation between cucurbit[10]uril(Q[10]) and aminopropyl-1-pyrenebutanamide(PBA) and is designated as PBA@Q[10].Addition of dodine to PBA@Q[10] results in a dramatic enhancement of fluorescence intensity at 390 nm,accompanied by fluorescence quenching at 488 nm.On this basis,the detection limit is 6.78 × 10^(-7) mol/L.The response mechanism is a competitive interaction:dodine occupies the cavity of Q[10] and forces PBA to leave.展开更多
The composite polymer electrolyte has been obtained via incorporating LiCUST-701(a new metal–organic rotaxane framework modified by Li+)into poly(ethylene oxide)(PEO)matrix and give a high ionic conductivity of 4.02&...The composite polymer electrolyte has been obtained via incorporating LiCUST-701(a new metal–organic rotaxane framework modified by Li+)into poly(ethylene oxide)(PEO)matrix and give a high ionic conductivity of 4.02×10^(−4)S/cm at 60℃.DFT calculations were used to visualize the possible diffusion pathway of Li+.The all-solid-state cell assembled with LiFePO_(4),composite polymer electrolyte and lithium metal foil delivered with excellent cycling capability and stability even under high current densities.展开更多
A linear supramolecular polymer with controllable features based on twisted cucurbit[14]uril(tQ[14])and cucurbit[8]uril(Q[8])was firstly fabricated via an effective self-sorting strategy.Herein we designed a monomer,1...A linear supramolecular polymer with controllable features based on twisted cucurbit[14]uril(tQ[14])and cucurbit[8]uril(Q[8])was firstly fabricated via an effective self-sorting strategy.Herein we designed a monomer,1–butyl–1?-(naphthalen-2-ylmethyl)-4,4?-bipyridinium bromide(BNB),that contains bipyridyl,aliphatic butyl and aromatic naphthyl groups,simultaneously.Two host molecules,tQ[14]and Q[8]were employed to develop an effective strategy for constructing a linear supramolecular polymer with con-trollable features.The alkyl groups on both sides of BNB could insert into the two cavities of tQ[14],the naphthyl part of BNB viaπ-πstacking in Q[8]cavity,serving as the driving force for supramolecular polymerization.Through self-sorting of the monomer,tQ[14]and Q[8],led to the formation of the linear supramolecular polymer.Depolymerization could be achieved by addition of adamantane hydrochloride(AH)which driven two BNB vip molecules out of the Q[8]cavity.This self-sorting strategy has great potential,not only for designing supramolecular polymer materials with different controllable structures through introduction of multiple functional groups,but also for broadening the application of twisted cucurbit[14]uril in supramolecular chemistry.展开更多
The insecticide cartap （CP） is non-fluorescent in aqueous solutions. This property makes its determination through direct fluorescent method difficult. In acidic medium and at room temperature, palmatine （PAL） can...The insecticide cartap （CP） is non-fluorescent in aqueous solutions. This property makes its determination through direct fluorescent method difficult. In acidic medium and at room temperature, palmatine （PAL） can react with cucurbit[7]uril （CB[7]） to form stable complexes, and the fluorescence intensity of the complex is greatly enhanced. Significant quenching of the fluorescence intensity of the CB[7]-PAL complex was observed with the addition of cartap. Based on the significant quenching of the supramolecular complex fluorescence intensity, a new spectrofluorimetric method with high sensitivity and selectivity was developed to determine cartap in aqueous solution. The fluorescence quenching values （AF） showed good linear relationship with cartap concentrations from 0.009 to 2.4 ~tg mL-~ with a detection limit 0.0029 ~tg mE-x. The proposed method had been successfully applied to the determination of cartap residues in grain and vegetable with recoveries of 87.4-103%. In addition, the association constants of the complexes formed between the host and the vip were determined. The competing reaction and the supramolecular interaction mechanisms between the cartap and PAL as they fight for occupancy of the CB[7] cavity were studied using spectrofluorimetry, xH NMR and molecular modeling calculations.展开更多
Sym-bis（benzimidazole）-2,2＇-ethylene cations act as a new axle template for threading cucurbit[6]uril derivatives on,forming[2]pseudorotaxane and[3]pseudorotaxane.These new complexes have been studied using 1 H NMR...Sym-bis（benzimidazole）-2,2＇-ethylene cations act as a new axle template for threading cucurbit[6]uril derivatives on,forming[2]pseudorotaxane and[3]pseudorotaxane.These new complexes have been studied using 1 H NMR,UV-vis absorption spectroscopy and X-ray analysis.Changes in the 1 H NMR spectra indicate that the two types of pseudorotaxane can be formed by varying the host concentration. UV-vis absorption titration experiments at different pH values demonstrate that interesting pK_a shifts of the bis-benzimidazole derivatives can be induced by the host-vip complexation.The associated constants were calculated to be 2.81×10^4 L/mol and 9.06×10^6 L/mol for the[2]pseudorotaxanes and ｜3]pseudorotaxanes,respectively.Furthermore,X-ray diffraction studies of the solid state structures provide unequivocal proof of the host concentration dependent pseudorotaxane,which is strongly in line with the evidences in solution.展开更多
基金National Natural Science Foundation of China(Nos.21921003 and 22201293)the National Key R&D Program of China(No.2023YFC3503400)for financial support。
文摘The ongoing development of small molecule drugs underscores the urgent need for novel excipients to formulate poorly soluble drug candidates.Cucurbit[7]uril(CB[7])possesses high binding affinities for a variety of molecular vips.However,its moderate water solubility limits broader application.Here we report the synthesis of three CB[7]derivatives M1-M3 by modifying an average of 4.2,5.5,and 5.9 sulfonatopropoxy groups onto their"equator"carbons.Compared to CB[7],their water-solubility increased by at least 26.6-,23.6-,and 19.2-fold,respectively,while the maximum tolerated doses(MTD)of M1 and M2 improved by 2.5-and 2.3-fold.Phase solubility diagram studies demonstrate that M1 and M2 significantly enhance the water-solubility of eighteen poorly soluble drugs.In vivo experiments in rat complete Freund's arthritis reveal that M1 not only improves the anti-inflammatory efficacy of indomethacin by up to 52%,but also substantially reduces its side effect of gastric ulcer.
基金supported by the Innovation Program for Highlevel Talents of Guizhou Province (No. 2016-5657)the University of Hull for support。
文摘The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration calorimetry(ITC) and X-ray crystallography. The data indicates that the Q[5]@4-AP complex exhibits exo binding, which is not observed in the other four host-vip complexes. Furthermore,X-ray crystallography clearly reveals how the Q[n]s bind with 4-AP to form complexes, for example Q[5]forms an outer-surface complex, whilst Q[6], TMe Q[6] and Q[7] formed 1:1 host and vip type complexes, and Q[8] formed a stable 1:2 ternary complex due to its large cavity, which can accommodate two 4-AP molecules.
基金the financial support of National Natural Science Foundation of China(Nos.51663005,21761007 and21871064)Science and Technology Plan Project of Guizhou Province(Nos.20175788 and 20185781)+2 种基金the Creative Research Groups of Guizhou Provincial Education Department(No.2017028)the Innovation Program for High-level Talents of Guizhou Province(No.20165657)“Chun-Hui” Fund of Chinese Ministry of Education(No.Z2017005)。
文摘Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]arene and 4-sulfocalix[6]arene using ^(1)H NMR spectroscopy and isothermal titration calorimetry(ITC),respectively.Moreover,solid fluorescent materials were prepared via the adsorption of fluorescent dyes by these porous supramolecular frameworks,which exhibit a selective response to certain volatile organic compounds.
基金supported by the National Natural Science Foundation of China(No.201872051)National Key Research and Development Plan(No.2017YFD0200306)Startup Research Fund of Nanjing University of Science and Technology(No.AE89991/163)。
文摘With excellent biocompatibility and biodegradability,natural polysaccharides and their derivative s have exhibited great potential in constructing drug delivery ve hicles for tissue engineering and therapeutics.Cucurbit[n]uril(CB[n])-mediated reversible crosslinking of polysaccharides possess intrinsic stimuliresponsiveness towards competitive vips and have been extensively investigated to fabricate various particles and hydrogels for multiple stimuli-re sponsive drug release by incorpo ration with other stimuli including photo,redox,and enzyme.Through host-vip interactions between CB[6]and aliphatic diamines,functional tags covalently connected with CB[6]can be readily anchored into polysaccharidebased hydrogels,realizing multiple functionalization.The rheological prope rty and drug release profile of polysaccharide-based supramolecular hydrogels can be facilely tuned through CB[8]-mediated dyna mic homo or hetero crosslinking of polysaccharides and/or other polymers.In this review,we introduce and summarize recent progress regarding polysaccharide-based supramolecular drug delivery systems mediated via host-vip interactions of CB[6]and CB[8],covering both bulk hydrogels and particular systems.At the end,possible utilization of CB[7]-based host-vip interactions in constructing polysaccharide-based drug delivery systems and future perspectives of this research direction are also discussed.
基金This work was supported by the National Natural Science Foundation of China(No.21871064)the National College Students’Innovative Training Program of China(No.2020053)+1 种基金the“Undergraduate Teaching Project”of Guizhou University(No.201936)the Student Research Training Foundation of Guizhou University,China(No.(2019)106).
文摘In order to reduce the impact of CdS photogenerated electron-hole recombination on its photocatalytic performance,a narrow band gap semiconductor MoS_(2) and organic macromolecular cucurbit[n]urils(Q[n])were used to modify CdS.Q[n]/CdS-MoS_(2)(n=6,7,8)composite photocatalysts were synthesized by hydrothermal method.Infrared spectroscopy,X-ray diffraction,X-ray photoelectron spectroscopy,field emission scanning electron microscopy,ultraviolet-visible and photoluminescence spectrum were used to characterize the structure,morphology and optical properties of the products,and the catalytic degradation of the solutions of methylene blue,rhodamine B and crystal violet by Q[n]/CdS-MoS_(2) composite catalyst was investigated.The results showed that the Q[n]played a regulatory role on the growth and crystallization of CdS-MoS_(2) particles,Q[n]/CdS-MoS_(2)(n=6,7,8)formed flower clusters with petal-like leaves,the flower clusters of petal-like leaves increased the surface area and active sites of the catalyst,the Q[n]/CdS-MoS_(2) barrier width decreased,the electron-hole pair separation efficiency was improved in the Q[6]/Cds-MoS_(2).Q[n]makes the electron-hole pair to obtain better separation and migration.The Q[6]/CdS-MoS_(2) and Q[7]/CdS-MoS2 have good photocatalytic activity for methylene blue,and the catalytic process is based on hydroxyl radical principle.
基金the financial support of the National Natural Science Foundation of China(Nos.21761007,51663005 and 21871064)Science and Technology Plan Project of Guizhou Province(Nos.20175788 and 20185781)。
文摘Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected in their simple composition and preparation methods used for QSFs.The diversity of supramolecular organic frameworks(SOFs) is reflected in the synthesis methods and structural characteristics of the as-obtained QSFs,as well as the variety of structural directing agents and basic building blocks used to prepare QSFs.The modulability is reflected by the controllable channel size in the QSFs,which can be adjusted using different sizes of Q[n]s.In this work,the first re ported cucurbituril Q[6]was selected as the basic building block and three Q[6]-based su p ramolecular frameworks were obtained from aqueous HCl solutions in the presence of [CdCl_(4)]^(2-)respectively.The OSIQs are the main driving forces for the formation of these frameworks.This study shows the diversity of the QSFs.
基金supported by the National Natural Science Foundation of China(21921003 and 22201293)National Key R&D Program of China(2023YFC3503400).
文摘A series of sulfonatopropoxylated cucurbit[8]uril derivatives(SPECB8s)with water-solubility ranging from 344 mmol/L to 360 mmol/L have been prepared.One of the derivatives SPE_(5.5)CB8 bearing an average of 5.5 sulfonatopropoxy side chains has been revealed to display high biocompatibility,with maximum tolerated dose being as high as 2500 mg/kg for mice.Phase solubility diagram investigations illustrate that SPE_(5.5)CB8 can solubilize eighteen poorly soluble drugs and,for fifteen of them including remdesivir,its solubilization efficiency is higher than that of Captisol,the most widely used β-cyclodextrin-derived excipient for drug formulation.Moreover,the improved solubilization for remdesivir,which is formulated by Captisol for clinical use,can lead to important increase of its antiviral activity as compared with Captisol.
基金supported by the Talented Person Project of Guizhou University (2007016)Science and Technology Fund of Guizhou Province (20082294)Governor Foundations of Guizhou Province (200812)
文摘The slightly water-soluble anticancer drug camptothecin(CPT) and its inclusion complexes with cucurbit[n = 7,8]uril(Q[n](n = 7,8)) were investigated.The formation of 1:2 complexes with Q[n](n = 7,8) in aqueous solution was confirmed by fluorescence spectroscopy and the apparent stability constants were determined to be higher than 3.01 × 1012 L2/mol2.The solid inclusion complexes of CPT and Q[n](n = 7,8) were also prepared by the co-evaporation method and characterized by Fourier transformation-infrared spectroscopy,differential scanning calorimetry and powder X-ray diffraction.Aqueous solubility and dissolution studies indicate that the complexes exhibited significantly increased dissolution rates compared with the pure drug and physical mixtures.The potential of Q[7] or Q[8] for stabilizing lactone modality of CPT was investigated by the High Performance Liquid Chromatography(HPLC) method.The results reveal more than 63% CPT lactone form(active form) in CPT-Q[7] or Q[8] complexes compared to only 36% CPT lactone form in the absence of Q[7] or Q[8] after being incubated in the phosphate buffer solution(pH 7.4 at 37 °C) for 5h.
基金supported by the National Natural Science Foundation of China(22101125)Shenzhen Science and Technology Innovation Committee(JCYJ20180504165810828)+2 种基金Shenzhen“Pengcheng Scholar”Guangdong High-Level Personnel of Special Support Program(2019TX05C157)Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)。
文摘It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to play an insignificant role or only to provide a nonpolar microenvironment for hydrogen bonds.Herein,we report that hydrophobic cavity alone can also strongly bind neutral,highly hydrophilic molecules in water.We found that cucurbit[n]urils(n=7,8)bind 1,4-dioxane,crown ethers and monosaccharides in water with remarkable affinities.The best binding constant reaches 10^(7) M^(−1) for cucurbit[8]uril,which is higher than its binding affinities to common organic cations.Density functional theory(DFT)calculations and control experiments reveal that the hydrophobic effect is the major contributor to the binding through releasing the cavity water and/or properly occupying the weakly hydrated cavity.However,hydrophobic cavity still prefers nonpolar vips over polar vips with similar size and shape.
基金support of the National Natural Science Foundation of China(No.22361011)Guizhou Provincial Science and Technology Projects(No.ZK[2023]General 040)the Guizhou Provincial Key Laboratory Platform Project(No.ZSYS[2025]008)。
文摘This investigation focuses on the utilization of cucurbit[6]uril(Q[6])as the host compound for the development of long-lasting afterglow materials.By strategically manipulating the outer surface interactions of Q[6],classical aggregation-caused quenching(ACQ)compounds such as fluorescein sodium(FluNa)and calcein sodium(CalNa)were transformed into afterglow materials with varying colors and durations upon exposure to ultraviolet light.This transformation was facilitated through a host-vip doping method combined with coordination with metal ions.Even at a reduced doping concentration of 5×10^(-5)wt%,the materials exhibit remarkable afterglow properties,lasting up to 2 s,with a phosphorescence lifetime of up to 150 ms.Moreover,by adjusting the concentration of the vip compound,the persistent luminescence color of the materials could be easily transitioned from orange to yellow and subsequently to green.These findings suggest that the developed afterglow materials hold significant potential for multilevel anti-counterfeiting and information encryption applications when exposed to ultraviolet light.The supramolecular assembly strategy,which relies on the outer surface interactions of cucurbit[n]uril,offers a simpler and more efficient approach to crafting multi-color luminescent materials.Additionally,this method opens avenues for enhancing the application potential of aggregation-caused quenching(ACQ)compounds in various technological domains.
基金financial support of National Natural Science Foundation of China(No.22161010)。
文摘Nor-seco-cucurbit[10]uril(ns-CB[10])is a kinetic product with unique structure.The single bridged methylene in its structure makes the molecular cavity of ns-CB[10]more deformable when compared to ordinary cucurbit[n]uril,reducing its structural stability.Repeated experiments showed that ns-CB[10]gradually cracks in an acidic solution and changes the specificity of cucurbit[5]uril(CB[5])and cucurbit[8]uril(CB[8])under more robust acidic solutions and when heated.A series of experiments were designed to study the transformation behavior of ns-CB[10].It was found that the concentration of ns-CB[10]was correlated with the content distribution of CB[5]and CB[8].This study explores the influencing factors and mechanisms of the transformation of ns-CB[10]to CB[5]and CB[8].The results are of great significance for the application of ns-CB[10],understanding the formation mechanism of cucurbit[n]urils.Furthermore,it provides a new pathway for synthesizing new cucurbit[n]urils.
基金support of the National Natural Science Foundation of China(No.22361011)。
文摘A supramolecular assembly composed of perylene diimide derivative(PDI-nm)and nor-secocucurbit[10]uril(ns-Q[10])was designed.The excellent host-vip interaction between PDI-nm and nsQ[10]prevented the aggregation-caused quenching(ACQ)effect of PDI-nm,resulting in a luminescent assembly.The addition of spermine to the PDI-nm/ns-Q[10]assembly restored the ACQ of PDI-nm due to the competitive binding of spermine to ns-Q[10],which released PDI-nm.The assembly based on this principle showed ultra-high sensitivity for the detection of spermine with a detection limit as low as7.84×10^(-7)mol/L in aqueous solution and 3.69×10^(-7)mol/L in plasma solution.Moreover,an artificial light-harvesting system based on this assembly was proposed,benefiting from its good luminescent performance.Nile red(Ni R)functioned as an acceptor loaded into assembly,and a highly efficient energy transfer process occurred from PDI-nm/ns-Q[10]to Ni R,with an efficiency up to 87%.
基金financially supported by the National Natural Science Foundation of China(No.21871216)。
文摘The cross-photodimerization often comes with the formation of undesired and competitive homophotodimer as side products.Herein,we report a series of highly selective[4+4]cross-photodimerization between anthracene and 4a-azoniaanthracene derivatives within a cucurbit[10]uril(CB[10])host in water.Heteroternary inclusion complexes were formed through encapsulation of donor(D1-D2,anthracene derivative)and acceptor(A1-A3,4a-azoniaanthracene derivatives)pairs in CB[10].In the presence of CB[10](1.0 equiv.),the[4+4]cross-photodimerization between D1 and A1/A2/A3 efficiently gave a single racemic cross-photodimer.Furthermore,the cross-photodimerization between 9-substituted anthracene D2 and A1/A3 was catalyzed by CB[10](0.1 equiv.)to quantitatively yield a cross-photodimer with high regioselectivity.Efficient formation of selective cross-photodimers could be attributed to the exclusive encapsulation of D-A hetero-vip pairs in CB[10]and the confinement effect of the CB[10]host cavity.Our study further proves host–vip complexation as a powerful strategy for cross-cycloaddition reactions with high efficiency.
基金financially supported by National Natural Science Foundation of China(Nos.22371086,22071074,21772055)the National Key Research and Development Program(No.2021YFA0716702)+3 种基金the 111 Project(No.B17019)the China Postdoctoral Science Foundation(No.2020 M672388)Self-determined research funds of CCNU from the colleges’basic research and operation of MOE,National Natural Science Foundation of China(No.22006055)the State Key Laboratory of Environmental Chemistry and Ecotoxicology,RCEES,CAS(No.KF2017-4)。
文摘Selective separation of amino acids and proteins is crucial in various areas of research,including proteomics,protein structure and function studies,protein purification and drug development,and biosensing and biodetection.A nanocomposite film is formed by combining layer-by-layer self-assembled gold nanospheres(Au NPs)driven by cucurbit[7]uril(CB[7])and polymethyl methacrylate(PMMA)film.Due to the host-vip interactions,the selective transmission of l-tryptophan in the nanocomposite film is confirmed by the current-voltage measurements using a picoammeter.Furthermore,by adjusting the particle size of Au NPs to increase channel size,lysozyme containing multiple tryptophan residues can selectively pass through the nanocomposite film,indicating the high versatility and adaptability of the nanocomposite film.This study will provide a new direction for the selective separation of amino acids and proteins.
基金supported by the Guizhou Provincial Basic Research Program(Natural Science) Youth Guidance(Nos.[2024]110,[2024]378)Science and Technology Innovation Team of Natural Science Foundation of Guizhou Province(No.CXTD[2023]005)+3 种基金Science and Technology Innovation Team of Higher Education Department of Guizhou Province(No.QJJ[2023]053)Natural Science Special of Guizhou University(No.202137)Guizhou Provincial Key Laboratory Platform Project(No.ZSYS[2025]008)PhD Foundation of Guizhou University(No.[2021]83)。
文摘Pyridine(Py) and 3-methylpyridine(3-MP) are crucial intermediates in chemical industrial processes.Here,we provide a simple and energy-efficient approach for the isolation of Py and 3-MP by employing crystalline cucurbit[6]uril(Q[6]).The crystal exhibit high selectivity for Py from the mixture of Py and 3-MP in both vapor and liquid phases,with separation purities close to 100%.The selectivity is attributed to the varying stability of the host-vip complexes after the absorption of Py or 3-MP,as revealed by the single-crystal structure analysis.ITC experimental results and DFT calculations indicate that,compared to3-MP,Q[6] has a higher binding strength and lower binding energy with Py.In addition,pyridine can be removed from the Q[6] cavity through vacuum heating or organic solvent immersion,enabling Q[6]reuse via reversible vip loading.This method offers a promising approach for high-purity Py and 3-MP separation with significant economic and environmental benefits.
基金the National Natural Science Foundation of China(No.21861011)the Major Program for Creative Research Groups ofGuizhou Provincial Education Department(No.2017-028)+1 种基金the Innovation Program for High-level Talents of Guizhou Province(No.2016-5657)the Science and Technology Fund of Guizhou Province(Nos.2016-1030,2018-5781)are gratefully acknowledged for financial support。
文摘We report herein a new fluorescent probe for the selective recognition and determination of dodine among 20 different pesticides.This fluorescent probe was assembled through host-vip complexation between cucurbit[10]uril(Q[10]) and aminopropyl-1-pyrenebutanamide(PBA) and is designated as PBA@Q[10].Addition of dodine to PBA@Q[10] results in a dramatic enhancement of fluorescence intensity at 390 nm,accompanied by fluorescence quenching at 488 nm.On this basis,the detection limit is 6.78 × 10^(-7) mol/L.The response mechanism is a competitive interaction:dodine occupies the cavity of Q[10] and forces PBA to leave.
基金the National Natural Science Foundation of China(Nos.U1973201 and 22271023).
文摘The composite polymer electrolyte has been obtained via incorporating LiCUST-701(a new metal–organic rotaxane framework modified by Li+)into poly(ethylene oxide)(PEO)matrix and give a high ionic conductivity of 4.02×10^(−4)S/cm at 60℃.DFT calculations were used to visualize the possible diffusion pathway of Li+.The all-solid-state cell assembled with LiFePO_(4),composite polymer electrolyte and lithium metal foil delivered with excellent cycling capability and stability even under high current densities.
基金supported by the National Natural Science Foundation of China (Nos. 21861011, 21871064)the Innovation Program for High-level Talents of Guizhou Province (No. 2016–5657)the Graduate scientific research Fund of Guizhou Province (No. YJSCXJH-2019–011)
文摘A linear supramolecular polymer with controllable features based on twisted cucurbit[14]uril(tQ[14])and cucurbit[8]uril(Q[8])was firstly fabricated via an effective self-sorting strategy.Herein we designed a monomer,1–butyl–1?-(naphthalen-2-ylmethyl)-4,4?-bipyridinium bromide(BNB),that contains bipyridyl,aliphatic butyl and aromatic naphthyl groups,simultaneously.Two host molecules,tQ[14]and Q[8]were employed to develop an effective strategy for constructing a linear supramolecular polymer with con-trollable features.The alkyl groups on both sides of BNB could insert into the two cavities of tQ[14],the naphthyl part of BNB viaπ-πstacking in Q[8]cavity,serving as the driving force for supramolecular polymerization.Through self-sorting of the monomer,tQ[14]and Q[8],led to the formation of the linear supramolecular polymer.Depolymerization could be achieved by addition of adamantane hydrochloride(AH)which driven two BNB vip molecules out of the Q[8]cavity.This self-sorting strategy has great potential,not only for designing supramolecular polymer materials with different controllable structures through introduction of multiple functional groups,but also for broadening the application of twisted cucurbit[14]uril in supramolecular chemistry.
基金supported by the Research Fund for the Doctoral Program of Higher Education of China(20091404110001)
文摘The insecticide cartap （CP） is non-fluorescent in aqueous solutions. This property makes its determination through direct fluorescent method difficult. In acidic medium and at room temperature, palmatine （PAL） can react with cucurbit[7]uril （CB[7]） to form stable complexes, and the fluorescence intensity of the complex is greatly enhanced. Significant quenching of the fluorescence intensity of the CB[7]-PAL complex was observed with the addition of cartap. Based on the significant quenching of the supramolecular complex fluorescence intensity, a new spectrofluorimetric method with high sensitivity and selectivity was developed to determine cartap in aqueous solution. The fluorescence quenching values （AF） showed good linear relationship with cartap concentrations from 0.009 to 2.4 ~tg mL-~ with a detection limit 0.0029 ~tg mE-x. The proposed method had been successfully applied to the determination of cartap residues in grain and vegetable with recoveries of 87.4-103%. In addition, the association constants of the complexes formed between the host and the vip were determined. The competing reaction and the supramolecular interaction mechanisms between the cartap and PAL as they fight for occupancy of the CB[7] cavity were studied using spectrofluorimetry, xH NMR and molecular modeling calculations.
基金supported by the National Natural Science Foundation of China(No,21272045)the Natural Science Foundation of Guizhou Province and Guizhou Universitythe "Chun-Hui" Funds of the Chinese Ministry of Education are gratefully acknowledged
文摘Sym-bis（benzimidazole）-2,2＇-ethylene cations act as a new axle template for threading cucurbit[6]uril derivatives on,forming[2]pseudorotaxane and[3]pseudorotaxane.These new complexes have been studied using 1 H NMR,UV-vis absorption spectroscopy and X-ray analysis.Changes in the 1 H NMR spectra indicate that the two types of pseudorotaxane can be formed by varying the host concentration. UV-vis absorption titration experiments at different pH values demonstrate that interesting pK_a shifts of the bis-benzimidazole derivatives can be induced by the host-vip complexation.The associated constants were calculated to be 2.81×10^4 L/mol and 9.06×10^6 L/mol for the[2]pseudorotaxanes and ｜3]pseudorotaxanes,respectively.Furthermore,X-ray diffraction studies of the solid state structures provide unequivocal proof of the host concentration dependent pseudorotaxane,which is strongly in line with the evidences in solution.
