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Cucurbit[n]uril
JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

Cucurbit[n]uril-rotaxanes functionalized membranes with heterogeneous channel and regenerable surface for efficient and sustainable nanofiltration

Liang Ren,Jianxin Chen,Qing Lu,Jian Han,Jinsheng Liang,Hong Wu

Nanofiltration membranes with high permeability and antifouling ability is favor of efficient and sustainable separation. However, simultaneous enhancement of above performances faces formidable challenges. Herein, we present a facile method to obtain ultrapermeable antifouling nanofiltration membranes via surface binding binary complex of dihydroxyl viologen (HV 2+ ) axis molecule and cucurbit[n]uril (CB[n]) on the freshly prepared polyamide (PA) thin-film composite membranes in a rotaxane manner. CB[n]-rotaxanes feature three-dimensional hydrophilic structure and create heterogeneous channel in PA selective layer, which favors water transport resistance decrease. Meanwhile, CB[n]-rotaxanes as host molecules enhance superficial grafting ability of membranes towards guest-labelled antifouling materials through supramolecular recognition. Inspiringly, adopting stimuli-responsive guest, such as azobenzene , endows grafted antifouling layer with photo-activated regeneration capability, which further improves fouling reversibility of membranes. The optimal membrane exhibits a 3-fold increase of permeance, maintained Na 2 SO 4 rejection and enhanced antifouling properties compared to the pristine, which overmatches most of the state-of-the-art nanofiltration membranes. The proposed construction strategy may pave a novel avenue to develop ultrapermeable antifouling membranes for treating complex wastewater.

研究领域: 材料科学 · 环境工程
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Frontiers in Chemistry · 2023 · IF 5.5

Modulation of redox reactivity of resazurin through host-guest complexation with Cucurbit[n]uril (n = 7, 8)

Jia Liu,Su-Hang He,Hugues Lambert,Tung-Chun Lee

Resazurin (Alamar Blue, RZ) is a widely utilized fluorescent probe for biological sensing, whose fluorescent intensity can be modulated by changing its redox states; thereby, electrochemical reactivity of RZ is of significance when designing a sensing assay. Herein, we report novel two-way electrochemical reactivity modulation of RZ using host-guest complexation with rigid molecular containers cucurbit[ n ]uril (CB n , n = 7, 8). The complexation between CB n and RZ is confirmed by 1 H NMR measurements and supported by computational simulation, and the binding constants are determined via UV-vis titration. Notably, the voltametric data highlights that the redox reactivity of RZ can be activated or deactivated upon encapsulation by CB8 or CB7, respectively. This two-way reactivity modulation is hypothesized to be mediated by the difference in cavity volume that favors or hinders the approach of water molecules to the encapsulated reaction center during the reduction process. Despite the similar cavity size to CB, molecular containers such as cyclodextrins (CDs) exhibit considerably weaker modulation effects. Our approach can potentially be applied to other redox processes that involve proton transfer, and open new possibilities in supramolecular electrochemistry.

研究领域: 分析化学 · 超分子化学 · 生物传感
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DYES AND PIGMENTS · 2018 · IF 3.767

J-type dimer of Auramine O dye upon encapsulation in cucurbit[8]uril host showing intense excimer emission

Xiran Yang,Simin Liu

The host−guest interactions between Auramine O ( AuO ) dye and cucurbit[ n ]uril (CB[ n ], n  = 7, 8) were investigated in aqueous solution by 1 H NMR, UV/Vis, fluorescence spectroscopic techniques and single crystal diffraction. The results indicate the simultaneous formation of 1:1 and 2:1 inclusion complexes between CB[7] and AuO with two binding constants as 1.17 × 10 5  M −1 and 3.99 × 10 2  M −1 by UV/Vis spectroscopy titration (1.20 × 10 5  M −1 and 5.26 × 10 3  M −1 by fluorescence spectroscopy) in phosphate buffer (pH 7.4). And a 1:2 homoternary inclusion complex CB[8]· AuO 2 with binding constant as 2.95 × 10 9  M −2 (by fluorescence spectroscopy titration) is detected. Interestingly, the appearance of intense new broad emission band with big red-shift (100 nm) with respect to that of AuO proves the formation of excimer upon encapsulation of AuO molecules in CB[8]. Determination of single crystal structure of CB[8]· AuO 2 further discloses the existence of J-type dimer with intermolecular CH···π interactions between two included phenyl groups on AuO molecules. Upon host−guest complexation of AuO with CB[7] or CB[8], the p K a shifts of AuO were measured.

CAS / MDL: 58543-17-2
研究领域: 化学 · 分子科学 · 超分子化学
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JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY · 2019 ·Vol. 95 ·期 3 ·207-213 · IF 1.429

Interaction of pesticide pyroquilon with two different cucurbit[n]uril

Fan Ying,Gao Ruihan,Jiang Yangming,Bian Bing,Tao Zhu,Wei Gang,Xiao Xin

In this work, we report a conceptual strategy for preventing pesticide degradation using cucurbit[n]uril to encapsulate pyroquilon (Pyn). The host–guest inclusion complexes of pyroquilon (Pyn) with CB[7] and CB[8] were prepared and characterized using 1 H NMR spectroscopy, quadrupole-time of flight mass spectrometry (Q-TOF), isothermal titration calorimetry (ITC) and UV absorbance spectrophotometry. The experimental results revealed that the entire Pyn molecule resides within the cavities of CB[7] and CB[8], forming 1:1 inclusion complexes between CB[n] and Pyn. Our study on the release of Pyn demonstrated that CB[n]@Pyn exhibit sustained- and slow-release properties. Moreover, CB[8] can effectively shield UV irradiation and thereby protect the Pyn from photodegradation. Therefore, CB[7]@Pyn and CB[8]@Pyn have great potential to be used as slow-release agents.

研究领域: 化学 · 材料科学 · 农业科学
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SUPRAMOLECULAR CHEMISTRY · 2015 · IF 2.394

Direct syntheses of a series of cucurbit[n]uril-anchored polyacrylamides

Bo Xiao,Ying Fan,Ning-Ning Ji,Xiao-Jie Cheng,Chuan-Zeng Wang,Jia-Jia Zhou,Sai-Feng Xue,Zhu Tao,Qian-Jiang Zhu

Using the one-pot, direct strategy reported by Su and co-workers, we have synthesised a series of cucurbit[n]urils (Q[n], n = 5–8) and alkyl-substituted cucurbit[6]urils (SQ[6]s) anchored on polymers. Acrylamide, as a typical monomer, was used to synthesise a series of Q[n]s (n = 5–8) and SQ[6]-anchored polyacrylamides (PAMs) using a persulfate salt as initiator and oxidant. The Q[n]s (n = 5–8) and SQ[6]-anchored PAM samples have been characterised by 1H NMR, 1H NMR titrations of probe guests, Fourier-transform infrared and thermogravimetric analyser. The results confirmed that PAM chains had been successfully grafted on the back of the Q[n]s (n = 5–8) and SQ[6]s through an in situ radical polymerisation approach. It was further confirmed that the hydrophobic cavities of the Q[n]s on the polymers were still freely accessible. This synthetic approach may be extended to a variety of Q[n]s that are difficult to functionalise.

CAS / MDL: 540-69-2
研究领域: 高分子化学 · 超分子化学
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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 11 ·4311-4318 · IF 3.288

Supramolecular assemblies controlled by cucurbit[n]uril size (n = 6, 7, 8 and 10)

Weitao Xu,Xinyu Deng,Xin Xiao,Bing Bian,Qing Chen,Scott J. Dalgarno,Zhu Tao,Carl Redshaw

A benzyl substituted 4-pyrrolidinopyridinium salt (G) with multiple active sites including benzyl, pyridinium and pyrrole groups has been synthesized. The interaction between G and a series of cucurbit[n]urils (TMeQ[6], Q[7], Q[8], Q[10]), has been studied both in aqueous solution and in the solid state. The binding interaction site between G and the Q[n] can be controlled by the size of the cavity of the Q[n]s. In the case of TMeQ[6], the benzyl is accommodated within the cavity, whilst for Q[7] and Q[8], the pyrrole ring and the benzyl are accommodated within the cavity of the Q[7/8], and the latter can shuttle on the guest G in a state of dynamic equilibrium. For the larger cavity of Q[10], the entire G molecule is located within the cavity of the Q[10].

CAS / MDL: 2456-81-7
研究领域: 化学 · 超分子化学 · 材料科学
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ISRAEL JOURNAL OF CHEMISTRY · 2018 · IF 2.607

Inclusion Complexes of Hymexazol with Three Different Cucurbit[n]uril: Preparation, and Physicochemical and Antifungal Characterization

Ying Fan,Rui-Han Gao,Xin Xiao,Zhu Tao

Graphical Host-guest inclusion complexes of hymexazol with three different cucurbit[ n ]uril, cucurbit[7]uril (Q[7]), hemimethyl-substituted cucurbit[6]uril (HHMeQ[6]), and twisted cucurbit[14]uril ( t Q[14]) have been investigated by means of 1 H NMR spectroscopy, quadrupole-time of flight mass spectrometry (Q-TOF), and isothermal titration calorimetry (ITC). 1 H NMR experimental results revealed that hymexazol resides within the respective cavities of the selected Q[ n ], and mass spectrometric experimental results revealed that it interacts with these three Q[ n ] through the formation of 1 : 1 inclusion complexes. ITC experimental results indicated moderate binding constants. In vitro assays showed that the complexation of hymexazol by the Q[ n ] increased its inhibitory effect on the mycelia growth of Botrytis cinerea Pers .

CAS / MDL: 7722-84-1 7647-01-0
研究领域: 药理学 · 生物化学
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International Journal of Nanomedicine · 2024 · IF 6.6

Chlorogenic Acid-Cucurbit[n]uril Nanocomplex Delivery System: Synthesis and Evaluations for Potential Applications in Osteoporosis Medication

Yunqing Jiang,Haowen Qi,Mingjuan Wang,Kai Chen,Chen Chen,Haifeng Xie

Purpose Based on nanomedicine strategies, this study employed cucurbit[7]uril (Q[7]) as the macromolecular carrier to synthesize nanocomplex drug delivery system for chlorogenic acid (CGA). The nanocomplex drug delivery system is intended to overcome the unsatisfactory biocompatibility and bioavailability of CGA and realizing its potential role in long-term osteoporosis (OP) medication.Methods The nanocomplex was synthesized by the reflux stirring method. The chemical structure of the nanocomplex was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction analysis (XRD), UV-visible spectrophotometry (UV-vis), zeta potential analysis and transmission electronic microscope (TEM). The Cell Counting Kit-8 (CCK-8) assay, Live/Dead staining assay, and cytoskeleton staining were conducted to testify the biocompatibility of the nanocomplex. The release assay, Ferric Reducing Ability of Plasma (Frap) assay and Reactive oxygen species (ROS) staining were implemented to evaluate the release profile of CGA as well as its remaining antioxidative levels.Results CGA and Q[7] formed hydrogen bonding through an exclusion interaction, with the binding ratio more than 1:1. The nanocomplex had a crystalline and spherical-like structure and improved thermal stability. The nanocomplex demonstrated better biocompatibility than free CGA. The release profile of CGA from the nanocomplex was much steadier, and 70% of CGA was released in 5 days. The CGA released from the nanocomplex maintained its antioxidative properties at high levels and effectively eliminated the accumulated ROS in MC3T3-E1 cells under oxidative stress.Conclusion Q[7] has been demonstrated to be an ideal nanocarrier for CGA and the nanocomplex delivery system holds the potential for the long-term medication strategy of OP.

CAS / MDL: 327-97-9
研究领域: 药学 · 生物医学工程 · 纳米医学
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Coaxial electrospun nanofibrous substrates with tunable wettability for constructing cucurbit[n]uril-embedded organic solvent nanofiltration membranes

Qian Wang,Qin-Yuan He,Liu-Lin Zhao,Yue Wang,Rong Fang,Cong Luo,Wei-Tong Lu,Hong-Ya Jiang,Shi-Peng Sun,Xue-Li Cao

Solvent resistance and high perm-selectivity have always been the pursuit in organic solvent nanofiltration field. Insoluble polyimide nanofibrous membranes feature superior solvent resistance. However, its high hydrophobicity usually limits the uniform spread of the aqueous amine monomers during the interfacial polymerization process, resulting in the non-uniform reaction with the acyl chloride and the defective selective layer. Herein, coaxial electrospinning was employed to construct the core–shell nanofibrous substrates, in which aminated multi-walled carbon nanotubes were added to the shell layer. This strategy endowed the nanofibrous substrates with tunable wettability without sacrificing stability, which guaranteed the one-step construction of defect-free thin-film nanofibrous composite membranes via interfacial polymerization (IP). Further, cucurbit[6]uril was embedded into the polyamide network by coupling host–guest chemistry and IP, providing the wider solvent transport channels and achieving the four times enhanced methanol permeance (22.34 L·m −2 ·h −1 ·bar −1 ) without sacrificing the selectivity. The membrane shows application prospects for solvent recovery in chemical, pharmaceutical, and other fields. This work provides new thoughts for the design and modification of novel nanofiltration membranes.

研究领域: 材料科学 · 化学工程 · 膜技术
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ACS Omega · 2018 · IF 0

4-Sulfocalix[4]arene/Cucurbit[7]uril-Based Supramolecular Assemblies through the Outer Surface Interactions of Cucurbit[n]uril

Xiao Tian,Li Xia Chen,Yu Qing Yao,Kai Chen,Min-Dong Chen,Xi Zeng,Zhu Tao

Upon mixing of aqueous solutions of the freely soluble building blocks cucurbit[7]uril (Q[7]) and 4-sulfocalix[4]arene (SC[4]A), white microcrystals instantly separate in near-quantitative yield. The driving force for this assembly is suggested to be the outer-surface interaction of the Q[n]. Dynamic light scattering, scanning electron microscopy, and NMR (diffusion-ordered NMR spectroscopy) analyses have confirmed the supramolecular aggregation of Q[7] and SC[4]A. Titration 1H NMR spectroscopy and isothermal titration calorimetry have shown that the interaction ratio of Q[7] and SC[4]A is close to 3:1. Moreover, the Q[7]/SC[4]A-based supramolecular assembly can accommodate molecules of some volatile compounds or luminescent dyes. Thus, this work offers a simple and highly efficient means of preparing adsorbent or solid fluorescent materials.

研究领域: 化学 · 超分子化学 · 材料科学
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ANALYTICAL CHEMISTRY · 2026 · IF 7.3

Cucurbit[n]uril (n = 6 and 7)-Based High Affinity Enrichment of Basic Peptides Containing Multiple K/R Residues via Supramolecular Affinity Chromatography

Ruizhi Tang,Shujuan Ma,Quan Bai,Yangyang Bian,Zichao Tang,Junjie Ou

Host–guest interactions by artificially synthesized macrocyclic molecules, such as cucurbit[n]uril (CB[n], n refers to the number of glycoluril units), exhibited comparable affinity to natural biological interactions, offering orthogonal selectivities. These unique high-affinity interactions are crucial in bioseparation, particularly in the separation of complex biomacromolecules. However, to date, the application of supramolecular systems in bioseparation remains insufficient and challenging. In this work, a site-specific host–guest interaction-based method by CB[6] and CB[7] was developed for the selective enrichment of basic peptides, and their recognition for basic lysine/arginine (K/R) residues exhibited distinct selectivity. Although they both exhibited affinity to basic peptides, CB[6] tended to bind to peptides containing multiple K/R residues, while CB[7] preferred to adsorb peptides containing both phenylalanine residues and basic K/R residues. This difference was attributed to their distinct cavity sizes. Furthermore, CB[6]-containing monolith was employed for the enrichment of basic peptides from mouse liver sample digested with Staphylococcus aureus protease V8 (Glu-C). It is noteworthy that basic peptides containing 3–4 K/R residues can be successfully enriched, whereas those with more than 5 K/R residues cannot be effectively eluted. It was also observed that 1043 unique peptides were newly identified from 2.5 μg of mouse liver after the capture of basic peptides, with a markable increase in the identification coverage (31%). These newly identified peptides are generally more acidic and shorter than those depleted by CB[6], with median isoelectric point (pI) values of 5.8 and 7.0 and median lengths of 10 and 16 amino acids, respectively.

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JOURNAL OF CHROMATOGRAPHY A · 2022 · IF 4.601

Cucurbit(n)uril-functionalized magnetic composite for the dispersive solid-phase extraction of perfluoroalkyl and polyfluoroalkyl substances in environmental samples with determination by ultra-high performance liquid chromatography coupled to Orbitrap high-resolution mass spectrometry

Zhenzhen Huang,Peng Liu,Xia Lin,Yudong Xing,Yan Zhou,Yuehua Luo,Hian Kee Lee

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) have raised serious public health concerns because of their potential adverse effects in humans as revealed by toxicological and epidemiological research. However, routine monitoring of PFASs is still challenging due to their trace levels in various environmental and biological matrices. In this study, magnetic composite materials based on iron (II, III) oxide (Fe 3 O 4) with surface functionalization by cucurbit(n)uril (CB(n)) (Fe 3 O 4 @CB(n)) ( n  = 6, 7, 8), were prepared and evaluated as new adsorbents for the magnetic solid-phase extraction of nine PFASs in lake water, tap water and fish muscle samples. The Fe 3 O 4 @CB(n) was characterized to examine their surface morphologies, sizes magnetism and thermal stability. Featuring good aqueous solution dispersibility, the macrocyclic structure of Fe 3 O 4 @CB(n) was also endowed with strong host-guest interactions, allowing extraction and enrichment capability towards the PFASs in complex matrices. MSPE using Fe 3 O 4 @CB(7) combination with ultra-high performance liquid chromatography coupled to Orbitrap high-resolution mass spectrometry, gave satisfactory quantitative analytical performance with low limits of detection of 0.004–0.04 µg L − 1 and limits of quantification of 0.005–0.1 µg L − 1 , linearities ranging from 0.01 to 10 µg L − 1 with high coefficients of determination (R 2 ≥ 0.993), and enrichment factors (15–76) for the nine target PFASs. The method proved to be effective for the enrichment and analysis of trace levels of PFASs in genuine environmental water and fish muscle samples, indicating that Fe 3 O 4 @CB(7) has promising applicability as an adsorbent for these contaminants.

研究领域: 环境科学 · 分析化学 · 材料科学
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