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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 11 ·1-10 · IF 5.3

Exploration of cucurbituril-mediated SERS plasmonic nanoarrays with sub-nanometer gaps

Teng Yuanjie,Li Xin,Chen Yingxin,Zhong Yi,Xu Pei,Shan Shengyan,Gunasekaran Sundaram

The uneven distribution of hotspots and the challenges associated with precise analyte localization within these hotspots present significant hurdles in the field of surface-enhanced Raman scattering (SERS). Here, at the water–oil interface, gold nanoparticles (AuNPs) interconnected by cucurbiturils[8] (CB[8]) with sub-nanometer gaps (AuNPs:CB[8]) were organized into plasmonic arrays. This arrangement was engineered to generate highly efficient hotspots. The CB[8] molecules, serving a dual role, not only facilitated the assembly of AuNPs with sub-nanometer (~ 1 nm) gaps to create intense plasmonic hotspots but also acted as molecular traps, enabling the precise localization of molecules within these hotspots. By comparing the enhancement effect of probe molecule on Au nanofilm, AuNPs:CB[8] colloids, and AuNPs:CB[8] nanofilm, it was found that the SERS intensity of the E1 characteristic peak in AuNPs:CB[8] nanofilm is five times higher than that on Au nanofilm, and more than 10 4 times higher than that of AuNPs:CB[8] colloids. The gaps are also accessible to different electronegativite molecules, such as estrone, p -aminoazobenzene, or methylene blue, which are captured at the plasmonic hotspots by the interaction of CB[8]. The method was employed for the practical detection of artificial antioxidant butylated hydroxyanisole (BHA), which has a weak Raman scattering cross-section, by coupling it with a reaction to enhance its SERS effect. The detection limit of BHA in soybean oil sample is 5.89 × 10 −8  mol/L, with the recovery range 85.1–115%. In conclusion, this hot-spot design and molecular capture approach will offer a highly effective method for detecting weak Raman scattering cross-section molecules and holds great promise for practical applications in the future. Graphical abstract

研究领域: 化学 · 纳米科技 · 分析化学
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Polymer Chemistry · 2013 ·Vol. 4 ·期 15 ·4192-4198 · IF 5.231

Supramolecular ternary polymer mediated by cucurbituril and cyclodextrin

Qian Wang,Yong Chen,Yu Liu

A novel supramolecular ternary polymer mediated by macrocyclic molecules cucurbit[8]uril (CB[8]) and cyclodextrin was successfully constructed, based on the CB[8]-stabilized charge-transfer (CT) interaction and cyclodextrin–adamantane host–guest interaction. Herein, we synthesized a naphthol-modified β-cyclodextrin (Np-β-CD) and an adamantane–viologen ditopic guest to obtain a ditopic host–guest complex with a preorientational donor–acceptor pair. Furthermore, after addition of CB[8] to the complex, the donor–acceptor pair of naphthol–viologen was encapsulated into the cavity of CB[8] leading to a linear supramolecular polymer which was well characterized by various methods, including DOSY, DLS, SEM, TEM and AFM. This work enriches the field of supramolecular polymers and provides a novel method to fabricate supramolecular architectures with multiple macrocyclic host molecules.

CAS / MDL: 2094-72-6 34626-51-2
研究领域: 超分子化学 · 材料科学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Polymerizable rotaxane of cucurbituril protecting dopamine based adhesive hydrogels

Yunpeng Gao,Xin Tian,Xueru Xiong,Yushi Wang,Wen Huang,Xuetao Shi,Yong-Guang Jia,Zhong-Kai Cui

The catechol moiety found within mussel proteins plays a pivotal role in enhancing their adhesive properties. Nonetheless, catechol compounds, such as dopamine (DOP) derivatives, are susceptible to oxidation, leading to the formation of q0uinone. This oxidation process poses a significant challenge in the development of DOP-based hydrogels, hampering their adhesion capabilities and hindering polymerization. To protect DOP moieties from oxidation, DOP and N-(3-aminopropyl)methacrylamide (AMA) moieties were grafted onto the side groups of biocompatible poly(glutamic acid) (PGA). Subsequently, the DOP unit, serving as a second guest, would be captured by a polymerizable rotaxane of cucurbituril (CB[n]), in which the host molecule CB[8] complexed with the first guest, polymerizable methyl viologen (MV), forming a protective function and dynamic cross-linking. Upon exposure to light curing, a composite network emerged through the synergy of covalent cross-linking and supramolecular host-guest complexation of DOP with CB[8]. The generated complexation between DOP and CB[8] could protect the DOP moieties, resulting in photocured hydrogels with exceptional adhesive strength and remarkable tensile capabilities. Moreover, 3D printing technology was used to create various models with these DOP-based hydrogels, demonstrating their promising applications in future.

研究领域: 材料科学 · 化学 · 生物医学工程 · 高分子科学
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CHEMISTRY-A EUROPEAN JOURNAL · 2012 ·Vol. 18 ·期 16 ·5087-5095 · IF 5.925

Cucurbituril-Modulated Supramolecular Assemblies: From Cyclic Oligomers to Linear Polymers

Hai Qian,Dong-Sheng Guo,Yu Liu

Employing bis( p -sulfonatocalix[4]arenes) (bisSC4A) and N ′, N ′′hexamethylenebis(1-methyl-4,4′-bipyridinium) (HBV 4+ ) as monomer building blocks, the assembly morphologies can be modulated by cucurbit[ n ]uril (CB[ n ]) ( n =7, 8), achieving the interesting topological conversion from cyclic oligomers to linear polymers. The binary supramolecular assembly fabricated by HBV 4+ and bisSC4A units, forms an oligomeric structure, which was characterized by NMR spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), dynamic light scattering (DLS), isothermal titration calorimetry (ITC), and gel permeation chromatography (GPC) experiments. The ternary supramolecular polymer participated by CB[8] is constructed on the basis of host–guest interactions by bisSC4A and the [2]pseudorotaxane HBV 4+ @CB[8], which is characterized by means of AFM, DLS, NMR spectroscopy, thermogravimetric analysis (TGA), UV/Vis spectroscopy, and elemental analysis. CB[ n ] plays vital roles in rigidifying the conformation of HBV 4+ , and reinforcing the host–guest inclusion of bisSC4A with HBV 4+ , which prompts the formation of a linear polymer. Moreover, the CB[8]-participated ternary assembly could disassemble into the molecular loop HBV 2+ @CB[8] and free bisSC4A after reduction of HBV 4+ to HBV 2+ , whereas the CB[7]-based assembly remained unchanged after the reduction. CB[8] not only controlled the topological conversion of the supramolecular assemblies, but also improved the redox-responsive assembly/disassembly property practically. Graphical Cucurbit[8]uril (blue) not only modulates the topology of supramolecular assemblies of bis( p -sulfonatocalix[4]arenes) (green) and hexamethylene-bridged bisviologen (orange; see figure), but also stimulates their switching between assembly and disassembly.

研究领域: 超分子化学 · 高分子科学 · 材料化学 · 纳米技术
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ANALYTICAL CHEMISTRY · 2017 · IF 6.32

Cucurbituril and Azide Cofunctionalized Graphene Oxide for Ultrasensitive Electro-Click Biosensing

Tianxiang Wei,Tingting Dong,Hong Xing,Ying Liu,Zhihui Dai

To achieve high selectivity and sensitivity simultaneously in an electrochemical biosensing platform, cucurbituril and azide cofunctionalized graphene oxide, a new functional nanomaterial that acts as a go-between to connect the recognition element with amplified signal architecture, is developed in this work. The cucurbituril and azide cofunctionalized graphene oxide features a high specific surface area with abundant levels of the two types of functional groups. Specifically, it emerges as a powerful tool to link recognition elements with simplicity, high yield, rapidity, and highly selective reactivity through azide-alkynyl click chemistry. Moreover, it possesses many host molecules to interact with guest molecules (also signal molecules)-grafted branched ethylene imine polymer, through which the detection sensitivity can be greatly improved. Together with electro-click technology, a highly controllable, selective, and sensitive biosensing platform can be easily created. For VEGF165 protein detection, the electro-click assay has high selectivity and sensitivity; a dynamic detection range from 10 fg mL–1 to 1 ng mL–1 with a detection limit of 8 fg mL–1 was achieved. The electro-click biosensing strategy based on cucurbituril and azide cofunctionalized graphene oxide would have great promise for other target analytes with a broad range of applications.

CAS / MDL: 12093-10-6
研究领域: 生物传感器 · 纳米材料科学 · 分析化学
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DYES AND PIGMENTS · 2021 · IF 4.889

Cucurbituril-mediated AIE: An unconventional indicator displacement assay for ketamine detection

Kun Yan,Lancheng Wang,Huimin Zhou,Zhendong Hua,Peng Xu,Hui Xu,Youmei Wang,Bin Di,Chi Hu

Typical AIE luminogens with extensive π-electron conjugation are limited in use on account of their complex synthesis, high cost and environmental concerns. To this end, we report here a novel host-guest inclusion complex that is assembled from nonemissive ligands, and surprisingly exhibits notable AIE features in aqueous solution while maintaining good sensitivity for ketamine (KET) detection. Isothermal titration studies confirm that palmatine (PAL) binds to cucurbit[8]uril (Q8) in a 2:1 ratio with an equilibrium association constant of 1.75 × 10 11  M −2 , suggesting that the unconventional AIE effects can be attributed to the stacking of two PAL moieties inside a single Q8 cavity. Geometric constraints of the macrocycle result in dimeric coupling of PAL in the ground state with significant bathochromic shifts in absorption and emission, which can be readily excited to exhibit enhanced photoluminescence . The unusual upfield perturbation and broadening of Q8 signals in the 1 H NMR spectrum upon binding with PAL convey decisive information that Q8 not only serves as a molecular container, but also participates in the electron delocalization during the AIE events. Upon addition of KET, fluorescence was switched off through guest exchange to generate [email protected] as well as free PAL. The significant AIE characteristics of 2* [email protected] in combination with its specific molecular recognition towards KET gives rise to 5.0 ng/mL limit of detection with linear range from 16.8 to 500 ng/mL, and a pronounced selectivity over possible interfering substances in biological matrices. We demonstrate the first example of Q8-mediated AIE effects, where the photoluminescence of virtually nonemissive or feebly emissive ligands is remarkably intensified through clustering inside a macrocyclic host molecule, therefore offering great promise for further development into dedicated AIE-based sensors.

研究领域: 分析化学 · 超分子化学 · 材料科学 · 传感器与执行器
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DYES AND PIGMENTS · 2025 · IF 4.2

The coupling of magnetic separation of methamphetamine with cucurbituril-mediated fluorescence analysis

Xiaomei He,Bingtao Ren,Shan Xu,Lidan Tang,Hufeng Fang,Hao Yang,Dan Su,Bin Di,Kun Yan

Methamphetamine (MA) abuse still constantly increases in the world, which is seriously harmful for people's health. Cucurbituril-mediated sensors for detection of illicit drugs have received growing attention. However, urine samples contain inorganic salts with high concentration, which could disturb the interaction between cucurbituril host and fluorescence dye or target guest. Magnetic solid phase extraction (MSPE) technology exhibits excellent potential to remove impurity and ameliorate sensitivity for detection in complex biofluids. This work demonstrated a strategy for MA detection, in which MSPE was coupled with cucurbituril-mediated chemosensor to reduce interference of salts and overcome dilution issues in biological samples. The magnetic nanoparticles Fe 3 O 4 @polydopamine (PDA) were used as adsorbent and chemosensor 2∗proflavine@cucurbit[8]uril (2 PF@Q[8]) was applied for the fluorescence detection of MA. In the end, a linear range of 1.3–20 ng/mL and limit of detection of 0.4 ng/mL were achieved. Besides, the proposed method showed a pronounced selectivity in the presence of other illicit drugs. In general, we introduced an example focusing on coupling of MSPE with cucurbituril-mediated chemosensor, where small organic molecule MA was adsorbed and retained while inorganic salts were separated. This study underscores the potential of coupling MSPE with cucurbituril-mediated chemosensor in biological samples.

研究领域: 分析化学 · 生物医学工程 · 药物代谢 · 毒理学 · 分子识别 · 纳米医学 · 临床检验
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2020 · IF 3.232

pH-stimulus response dye-cucurbituril sensor for amino acids in aqueous solution

Mei-Xiang Yang,Qing Tang,Mei Yang,Qin Wang,Zhu Tao,Xin Xiao,Ying Huang

The host–guest inclusion complexes that comprise an inverted cucurbit[7]uril ( i Q[7]) and a quinoline derivative, 4-(4-dimethylaminostyryl) quinoline (DSQ) at different pHs were exploited as multiple supramolecular sensors to sense l -α-amino acids. DSQ complexation inside i Q[7] at different pHs leads to increased fluorescence and formation of different-colored i Q[7]-DSQ complexes. The enhanced fluorescence of DSQ after i Q[7] encapsulation may be attributed to limited dimethylamine rotation and the formation of a twisted internal charge transfer (TICT) state. The DSQ@ i Q[7] sensors have different affinities for l -α-amino acids at different pHs. Therefore, we propose a pH-stimulus response supramolecular sensor for the discrimination of structurally similar l -α-amino acids in aqueous solution.

研究领域: 分析化学 · 超分子化学
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AICHE JOURNAL · 2019 ·Vol. 66 ·期 4 ·e16879 · IF 3.463

The encouraging improvement of polyamide nanofiltration membrane by cucurbituril-based host–guest chemistry

Xue-Li Cao,Jia-Lin Guo,Jing Cai,Mei-Ling Liu,Susilo Japip,Weihong Xing,Shi-Peng Sun

The considerable performance enhancement of small molecule-sieving nanofiltration membrane has been achieved by the functional combination between host–guest chemistry and interfacial polymerization (IP) for the first time in this work. First, the water-insolubility of cucurbit[6]uril (CB6) was ameliorated by constructing host–guest complex (CB6-PIP) with piperazine. Second, the incorporation of water-soluble CB6-PIP in the selective layer via IP leads to the generation of not only the enlarged conventional polyamide network tunnels but also rotaxane tunnels. Such enrichment of solvent transport tunnels contributes to an amazing pure water permeability of 15.5–25.4 Lm −2 bar −1 h −1 , three times higher than that of traditional polyamide membranes, with a high R/MgSO 4 of 99.5–92.5%, perfect SO 4 2− /Cl − selectivity due to the electronegative contribution of CB6, as well as untapped potential in organic solvent nanofiltration. This work not only provides a fire-new strategy to design new type of NF materials but also promotes the application of CBs in many other fields.

研究领域: 材料科学 · 化学工程
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DESALINATION · 2022 · IF 11.211

Host-guest nanofiltration membranes having amino-complexed cucurbituril supramolecular channel for monovalent/divalent salts separation

Ying Wang,Song Zhao,Zhiyuan Zha,Zhi Wang,Jixiao Wang

Nanofiltration (NF) is widely used in separation of ions with different sizes and charges. However, thin-film composite NF membrane is hard to reach satisfied selectivity for monovalent/divalent salts separation. Herein, a novel host-guest NF membrane was designed and fabricated with cucurbituril-polyethyleneimine (CB-PEI) complex, which provided a “ring-like” supramolecular channel. The results indicated that CB-PEI/PSf membrane showed attractive separation performance for monovalent/divalent salts separation, purification and desalination of small molecule solutions. The as-prepared CB-PEI/PSf membrane exhibited superior pure water permeability up to 25.6 L·m −2 ·h −1 ·bar −1 , and salt rejections of 97.4%, 90.6%, 41.9% and 12.4% to MgSO 4 , Na 2 SO 4 , MgCl 2 and NaCl, respectively. The monovalent/divalent selectivelies for NaCl/MgSO 4 and NaCl/Na 2 SO 4 reached up to 30.0 and 8.9, respectively. Besides, the CB-PEI/PSf membrane exhibited very high separation factors for medicine/NaCl and dye/NaCl mixtures. Moreover, NF membrane processes were designed and operated for monovalent/divalent mixed salt separation by using CB-PEI/PSf membrane. The NaCl with mass fraction above 98% was successfully recovered after the single-stage membrane separation of NaCl/MgSO 4 mixture and the two-stage membrane separation of NaCl/Na 2 SO 4 mixture. Therefore, this novel host-guest NF membranes and process design provide a valuable basis for the industrial application of monovalent/divalent salts separation.

研究领域: 膜科学 · 材料科学 · 化学工程 · 环境科学
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Natural ceramic clay and cucurbituril guest-host reconfiguration for smart light, humidity, solvent and temperature responsiveness

Dan Xiao,Xue-Min Yang,Jin-Xiang Lv,Meng-Ting Zheng,Qian-Ting Wang,Kathrin Harre

Aiming to endow natural minerals with fast, high-sensitivity, and controllable smart light, humidity, solvent and temperature responsiveness, a novel ceramic clay and cucurbituril (CB) guest-host system (MVCB) inspired by nature was self-assembled and rearranged via an ingenious and simple design successfully. For the first time, the multi-functional MVCB not only displayed a high intelligent multi-stimuli responsiveness as light, humidity, solvent, and temperature switches, but also had multiple selective molecular recognition responses because of different organic vapor with CB and asymmetrical bilayer clay. For instance, due to the factors of guest-host and slow release, the average response speed of self-assembled shuffling the MVCB in methanol was as high as 108°/s compared with bilayer film without CB (20°/s). Besides, the MVCB exhibited controllable swift movement and was bending for grabbing three times its own weight. Moreover, the ultra-wide operating temperature of the MVCB from was ranging −196 to 300 °C under extreme condition. More interestingly, the MVCB presented a unique and compliable self-driven, smart switch, shape memory, environmental awareness and soft robotic gripper owing to the asymmetrical swelling and supramolecular of the CB. This work not only brings a simple, cost-effective, large-scale, and efficient strategy for multi-functionalized natural minerals materials, but also opens potential applications for intelligent response, extremely resistant substances, energy conversion and soft robotics.

研究领域: 材料科学 · 化学 · 智能材料
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2020 ·Vol. 36 ·期 2 ·307-312 · IF 1.063

Ultrasensitive Detection of Hepatitis C Virus DNA Subtypes Based on Cucurbituril and Graphene Oxide Nano-composite

Jiang Ping,Li Yifei,Ju Ting,Cheng Wenbo,Xu Jianhua,Han Kun

Infectious of hepatitis C viruses(HCVs) lead to hepatic fibrosis, cirrhosis even hepatoma. Developing rapid and sensitive diagnostic method for HCV is of great importance. Based on the host-and-guest interaction between cucurbit[7]uril(CB[7]) and methylene blue(MB), a CB[7]-graphene nano-composite(CB[7]-N 3 -GO) is raised for the electrochemical detection of HCV DNA. The method is able to linearly detect the HCV nucleic acid in the range of 0.2–10 nmol/L with detection limit as low as 160.4 pmol/L. The proposed detection strategy is able to discriminate the 1b and 6k subtypes of HCV and has a prospective potential in the blood screen for HCV in clinical diagnosis.

研究领域: 病毒学 · 纳米技术 · 分子生物学 · 医学诊断
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