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JOURNAL OF MOLECULAR STRUCTURE · 2023 · IF 3.8

A cucurbit[8]uril-based fluorescent probe for the selective detection of pymetrozine

Pei-Hui Shan,Ding-Wu Pan,Li-Xia Chen,Timothy J. Prior,Carl Redshaw,Zhu Tao,Xin Xiao

Herein, we report a simple fluorescence-enhanced system for the selective recognition and determination of the insecticide pymetrozine. 1 H NMR spectroscopic data indicate that 1,2-bis(4-pyridyl)ethylene (BPE) is partially encapsulated in the cavity of the cucurbit[8]uril (Q[8]) in aqueous solution, forming a stable 1:2 host-guest inclusion complex. Good evidence is also provided by other characterization techniques including single crystal X-ray diffraction, UV–Vis and fluorescence spectroscopies. This host-guest inclusion complex shows weak fluorescence in aqueous solution. Interestingly, the addition of pymetrozine greatly enhanced the fluorescence of the host-guest inclusion complex. In contrast, no significant fluorescence enhancement was observed on addition of 10 other pesticides. The concentration of pymetrozine in aqueous solution was easily detected based on the linear relationship between fluorescence intensity and pymetrozine concentration. Therefore, this paper reports a new method to identify and determine pymetrozine by fluorescence enhancement.

研究领域: 分析化学 · 农药科学
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JOURNAL OF CHROMATOGRAPHY A · 2014 · IF 4.258

Separation performance of cucurbit[8]uril and its coordination complex with cadmium (II) in capillary gas chromatography

Tao Sun,Ningning Ji,Meiling Qi,Zhu Tao,Ruonong Fu

Here we report the investigation of using cucurbit[8]uril (CB8) and its coordination complex with cadmium (II) (CB8-Cd) as stationary phases for capillary gas chromatography (GC). The prepared capillary columns of CB8 and CB8-Cd stationary phases achieved column efficiency of 2200   plates/m and 1508   plates/m, respectively, and showed weak polarity based on the measured McReynolds constants. Their separation performance was investigated by GC separation of mixtures of different types while a commercial column was used for comparison. The CB8 stationary phase achieved high resolution for a wide range of analytes from nonpolar to polar while the CB8-Cd stationary phase exhibited good separation mainly for nonpolar to weak polar analytes. The CB stationary phases differ from the commercial one in terms of retention behaviors and resolving ability due to their different molecular interactions with analytes. Moreover, energy effect on the retention of analytes on CB8 and CB8-Cd stationary phases was examined, showing that retention on CB8 column was determined mainly by enthalpy change for polar analytes and by both enthalpy change and entropy change for weak polar analytes whereas retention on CB8-Cd column was mainly controlled by entropy change. This work demonstrates the great potential of CB8 and CB8-Cd stationary phases as a new type of GC stationary phases in GC analysis.

研究领域: 分析化学 · 材料科学
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JOURNAL OF MOLECULAR LIQUIDS · 2023 · IF 6

A cucurbit[8]uril-based supramolecular polymer constructed via outer surface interactions: Use as a sensor, in cellular imaging and beyond

Dan Yang,Yang Luo,Shang Wei Yuan,Li Xia Chen,Pei Hua Ma,Zhu Tao,Xin Xiao

In recent years, most of the constructions on cucurbit[ n ]uril-based supramolecular polymers have been based on host–guest chemistry, however, this limits the choice of host and guest. Herein, we present a newly designed supramolecular polymer, namely Q[8]@PEG-HPTS formed by utilizing outer surface Q[8] interactions. In aqueous solution, the supramolecular polymer Q[8]@PEG-HPTS was obtained quickly and simply by mixing Q[8] with PEG-HPTS, where after, a variety of characterization techniques were employed to confirm the structure of the Q[8]@PEG-HPTS. The ability of this system to selectively recognize metal ions as well as pesticide molecules was also investigated; selectivity was observed for Fe 3+ and paraquat. The biocompatibility and excellent fluorescence properties associated with the constituents of the supramolecular polymer allowed for the imaging of HeLa cells. This system could image and trace the nucleus through the cytoplasm, indicating that it could enter and internalize HeLa cells. Finally, by continuously adjusting the ratio between Q[8] and PEG-HPTS, a Q[8]@PEG-HPTS hydrogel was obtained. This hydrogel exhibited a stimulated temperature response, and opens up further possibilities for exploring the applications of such supramolecular polymers.

研究领域: 化学 · 材料科学 · 生物医学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2023 · IF 6.1

Supramolecular Fluorescence Sensor Array Based on Cucurbit[8]uril Complexes Used for the Detection of Multiplex Quaternary Ammonium Pesticides

Kai-Ni Wei,Ru-Pei Yang,Shu-Zhen Huang,Zhu Tao,Qing Tang,Ying Huang

The simultaneous detection of multiple quaternary ammonium pesticides (QAPs) in water is a challenge due to their high solubility in water and similar structures. In this paper, we have developed a quadruple-channel supramolecular fluorescence sensor array for the simultaneous analysis of five QAPs, including paraquat (PQ), diquat (DQ), difenzoquat (DFQ), mepiquat (MQ), and chlormequat (CQ). Not only were QAP samples of different concentrations (10, 50, and 300 μM) in water distinguished with 100% accuracy but also single QAP and binary QAP mixed samples (DFQ-DQ) were sensitively quantified. Our experimental interference study confirmed that the developed array has good anti-interference ability. The array can quickly identify five QAPs in river and tap water samples. In addition, it also qualitatively detected QAP residues in Chinese cabbage and wheat seedlings extract. This array has rich output signals, low cost, easy preparation, and simple technology, demonstrating great potential in environmental analysis.

CAS / MDL: 999-81-5 85-00-7
研究领域: 分析化学 · 环境科学
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JOURNAL OF CHEMICAL RESEARCH · 2019 · IF 0.67

Preparation and adsorption properties of a facile solid cucurbit[8]uril-based porous supramolecular assembly

Chunchun Chen,Weiwei Ge,Kai Chen,Zhu Tao,Yunqian Zhang,Qian Jiang Zhu

Cucurbit[8]uril (Q[8]) was used as the building block for the facile preparation of Q[8]-based supramolecular assemblies in aqueous HCl solutions (A). The Q[8]-based supramolecular assembly was constructed of Q[8] molecules held together through outer surface interactions of cucurbit[n]urils, and hydrogen bonding between latticed water molecules and portal carbonyl oxygens of Q[8]. The porous structure resulted in different adsorption properties for different fluorophore guests (FGs), including dyes and fused-ring compounds, and fluorescence enhancement or colour changes resulted in luminescent materials (FG@As). Moreover, some of the FG@A systems could selectively respond to certain volatile organic compounds, for which they can be used as solid sensors.

研究领域: 化学 · 材料科学 · 分析化学
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Chemistry-An Asian Journal · 2018 ·Vol. 14 ·期 1 ·235-242 · IF 3.692

A Study of the Interaction Between Cucurbit[8]uril and Alkyl-Substituted 4-Pyrrolidinopyridinium Salts

Weitao Xu,Jinglan Kan,Bo Yang,Timothy J. Prior,Bing Bian,Xin Xiao,Zhu Tao,Carl Redshaw

Graphical Can I have some pumpkin soup, please? In the host–guest complexes formed between cucurbit[8]uril and the alkyl-substituted 4-pyrrolidinopyridinium salts 4-(C 4 H 8 N)C 5 H 5 NRBr (R=Et, n -butyl, n -pentyl, n -dodecyl), the orientation of the guest molecule changes with the length of R. Solid state structures are different to those observed in solution, and for R= n -pentyl, there are two different interactions between Q[8] and the guest. The interaction between cucuribit[8]uril (Q[8]) and a series of 4-pyrrolidinopyridinium salts bearing aliphatic substituents at the pyridinium nitrogen, namely 4-(C 4 H 8 N)C 5 H 5 NRBr, where R=Et (g1), n -butyl (g2), n -pentyl (g3), n -hexyl (g4), n -octyl (g5), n -dodecyl (g6), has been studied in aqueous solution by 1 H NMR spectroscopy, electronic absorption spectroscopy, isothermal titration calorimetry and mass spectrometry. Single crystal X-ray diffraction revealed the structure of the host–guest complexes for g1, g2, g3, and g5. In each case, the Q[8] contains two guest molecules in a centrosymmetric dimer. The orientation of the guest molecule changes as the alkyl chain increases in length. Interestingly, in the solid state, the inclusion complexes identified are different from those observed in solution, and furthermore, in the case of g3, Q[8] exhibits two different interactions with the guest. In solution, the length of the alkyl chain plays a significant role in determining the type of host–guest interaction present.

CAS / MDL: 2456-81-7
研究领域: 化学 · 超分子化学
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ANALYTICAL CHEMISTRY · 2022 · IF 8.008

Teaching PCR for Simultaneous Sensing of Gene Transcription and Downstream Metabolites by Cucurbit[8]uril-Mediated Intervention of Polymerase Activity

Lancheng Wang,Mingjie Xu,Huimin Zhou,Kun Yan,Shiqi Duan,Dandan Xue,Youmei Wang,Bin Di,Chi Hu

The target of typical PCR analysis is restricted to nucleic acids. To this end, we report here a novel strategy to simultaneously detect genetic and metabolic markers using commercial PCR kits with cucurbit[8]urils (CB[8]) implemented to manipulate the activity of Taq DNA polymerase. CB[8] binds with the nonionic surfactants and displaces them from the polymerase surface, resulting in decreased enzyme activity. Meanwhile, the inhibited enzyme can be reversibly activated when spermine, the downstream metabolite of ornithine decarboxylase (ODC), is present in the sample, which competitively binds to CB[8] and recovers polymerase activity. CB[8] was implemented in conventional PCR kits not only to reduce false-positive results but also to extend the detection range of PCR technology. With this novel method to detect ODC in cell lysates containing both the nucleotides and intracellular metabolites, positive results were only observed in highly active HEK 293T cells, whereas silent cells treated with ODC inhibitor showed negative readouts, therefore providing a simple but elegant dual-modality PCR method for precision diagnosis.

研究领域: 分子生物学 · 生物技术 · 分析化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2021 · IF 8.128

Immuno-affinitive supramolecular magnetic nanoparticles incorporating cucurbit[8]uril-mediated ternary host-guest complexation structures for high-efficient small extracellular vesicle enrichment

Nanhang Zhu,Yujia Zhang,Jia Cheng,Yanchao Mao,Ke Kang,Guohao Li,Qiangying Yi,Yao Wu

Enriching small extracellular vesicles (sEVs) with undamaged structure and function is a pivotal step for further applications in biological and clinical fields. It has prompted researchers to explore a carrier material that can efficiently capture sEVs while also gently release the captured sEVs. Here, 1-adamantylamine (1-ADA) responsive immuno-affinitive supramolecular magnetic nanoparticles (ISM-NPs) incorporating ternary host-guest complexation structures mediated by CB[8] were proposed to achieved the goal. In particular, the ternary host-guest complexation was constructed by the host molecule (cucurbit[8]uril, CB[8]) mediated assembly of two guest molecules (naphthol and bipyridine), and served as a cleavable bridge to connect the magnetic core and peripheral antibody. These constructed ISM-NPs performed well in the applications of capturing sEVs with a high capture efficiency of 85.5%. Further, the CB[8]-mediated ternary host-guest complexation structures can be disassembled with addition of the 1-ADA. Thus, the sEVs recognized by the anti-CD63 were released competitively, with a decent release efficiency more than 82%. The released sEVs kept intact morphology and exhibited appropriate size distribution and concentration. This supramolecular magnetic system, with 1-ADA responsive ternary host-guest complexation structures, may contribute to efficient enrichment of any other biomarkers, likely cells, proteins, peptides, etc.

研究领域: 纳米技术 · 生物材料 · 生物医学工程 · 细胞生物学 · 分子生物学
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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Construction of a new supramolecular probe with turn-on mechanism for tricyclazole detection

Xueyang Xu,Hongli Zhang,Qingyuan Jiang,Qingyun Li,Zhu Tao,Dingwu Pan,Xin Xiao

A new supramolecular fluorescence “turn-on” probe ( QL 2 @Q[8]) based on quinolinium derivative ( QL ) and cucurbit[8]uril (Q[8]) was constructed by host-guest interaction to detect tricyclazole ( TC ). The probe was formed with a 1:2 interaction ratio between host and guest and confirmed by 1 H NMR, UV–vis spectroscopy, and fluorescent spectroscopy. QL 2 @Q[8] inclusion complex exhibited quenching fluorescence, while an enhanced fluorescence signal was observed obviously when gradually adding TC into the aqueous solution of QL 2 @Q[8]. It was noted that other pesticides tested in the probe system didn't cause any fluorescence enhancement, showing the probe could selectively respond to TC with no effects and afford a lower limit of detection of 1.5 × 10 −8  mol/L. The investigation on the fluorescence “turn-on” mechanism demonstrated that a QL molecule was squeezed out from the cavity of Q[8] and was replaced by a TC molecule to form a 1:1:1 ternary complex between TC , QL and Q[8], confirmed by UV–vis, 1 H NMR and isothermal titration calorimetry (ITC) experiments. The formation of ternary complex restricted intramolecular rotation of QL and promoted intramolecular charge transfer (ICT), hence, an obvious fluorescence enhancement was observed. The fluorescence “turn-on” probe system could be made into a smartphone model by which TC residue level was obtained by just reading the blue-red channel ratio values, and could also be utilized to detect the TC residues in real agricultural products, with clear fluorescence signals observed.

研究领域: 分析化学 · 超分子化学 · 环境监测 · 荧光传感 · 农药检测
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ANALYTICA CHIMICA ACTA · 2020 · IF 5.977

Amino acid recognition by a fluorescent chemosensor based on cucurbit[8]uril and acridine hydrochloride

Weitao Xu,Huaming Feng,Weiwei Zhao,Chunhua Huang,Carl Redshaw,Zhu Tao,Xin Xiao

A new fluorescent chemosensor comprised of cucurbit[8]uril (Q[8]) and acridine hydrochloride (AC) has been designed and utilized for the recognition of amino acids . The AC was encapsulated by the Q[8] cavity and formed a 1:2 host-guest inclusion complex both in solution (aqueous) and in the solid-state. Whilst free AC is known to be strongly fluorescent, this strong fluorescence was quenched in the inclusion complex Q [8]-AC. This non-fluorescent complex Q[8]-AC was capable of serving as a fluorescence “off-on” probe, and was able to recognize either L -Phe or L -Trp via the competitive interaction between L -Phe or L -Trp. Moreover, the pH responsive nature of the probe allowed for the detection of basic amino acids, namely L -Arg, L -His, or L -Lys). As a result, a fluorescence method for the detection of five amino acids using a single system has been developed.

CAS / MDL: 260-94-6
研究领域: 化学 · 分析化学 · 材料科学 · 生物化学
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ACS Applied Bio Materials · 2024 · IF 4.6

Tunable Fluorescence, Morphology, and Antibacterial Behaviors of Conjugated Oligomers via Host–Guest Supramolecular Self-Assembly

Qian Zhang,Hui Li,Yuetong Kang,Qianling Cui,Hean Zhang,Lidong Li

Host–guest supramolecular self-assembly has become one facile but efficient way to regulate the optical properties of conjugated oligomers and construct promising photofunctional materials. Herein, we design two linear conjugated oligomers terminated with two or four pyridinium moieties, which show different 1:1 ‘head-to-tail’ binding patterns with cucurbit[8]uril (CB[8]) to form host–guest supramolecules. After being encapsulated in the hydrophobic cavity of the CB[8] host, the fluorescence emission of the conjugated oligomers undergoes significant changes, resulting in tunable fluorescence color with enhanced quantum yields. Triggered by the aggregation of supramolecules, the regular or rigid binding modes lead to the formation of cuboids and spheroids in nanoscale, respectively. Due to the macrocyclic-confinement effect, the light-driven reactive oxygen species (ROS) production of the host–guest complex is increased significantly, thereby improving the photodynamic antibacterial performance toward Staphylococcus aureus (S. aureus).

研究领域: 材料科学 · 化学 · 纳米技术 · 生物医学工程
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ACS Applied Materials & Interfaces · 2018 · IF 8.097

Cucurbit[8]uril-Based Giant Supramolecular Vesicles: Highly Stable, Versatile Carriers for Photoresponsive and Targeted Drug Delivery

Cuihua Hu,Ningning Ma,Fei Li,Yu Fang,Yao Liu,Linlu Zhao,Shanpeng Qiao,Xiumei Li,Xiaojia Jiang,Tiezhu Li,Fangzhong Shen,Yibing Huang,Quan Luo,Junqiu Liu

Highly stable giant supramolecular vesicles were constructed by hierarchical self-assembly of cucurbit[8]uril (CB[8])-based supra-amphiphiles for photoresponsive and targeted intracellular drug delivery. These smart vesicles can encapsulate the model drugs with high loading efficiencies and then release them by manipulating photoswitchable CB[8] heteroternary complexation to regulate the formation and dissociation of supra-amphiphiles that cause dramatic morphological changes of the assemblies to achieve remote optically controlled drug delivery. More importantly, the confocal microscopy analysis, cellular uptake experiment, and cell viability assay have shown that the giant vesicles are able to maintain the structural integrity and stability within actual cellular environments and exhibit obvious advantages for intracellular drug delivery such as low toxicity, easy surface modification for tumor-targeting selectivity, and rapid internalization into different human cancer cell lines. A synergistic mechanism that integrates multiple pathways including energy-dependent endocytosis, macropinocytosis, cholesterol-dependent endocytosis, and microtubule-related endocytosis was determined to facilitate the internalization process. Moreover, cytotoxicity experiments and flow cytometric analysis have demonstrated that the doxorubicin hydrochloride-loaded vesicles exhibited a significant therapeutic effect for tumor cells upon UV light irradiation, which makes the photoresponsive system more promising for potential applications in pharmaceutically relevant fields.

研究领域: 药学 · 纳米技术 · 生物医学工程 · 材料科学 · 药物递送系统 · 光化学
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