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1
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Zhang W, Li Y, Zheng T, Xie Y, Dai X, Lee M. Fluorescence-switching 2-D sheet structure formed by self-assembly of cruciform aromatic amphiphiles. SOFT MATTER 2025; 21:1451-1454. [PMID: 39905892 DOI: 10.1039/d4sm01542h] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Subscribe] [Scholar Register] [Indexed: 02/06/2025]
Abstract
We report that aromatic amphiphiles based on cruciform aromatic segments self-assemble into 2-D sheet structures in aqueous environments. Notably, the aromatic amphiphile based on a pyrene unit generates fluorescence-switching 2-D sheet structures. In a pH-neutral condition, the sheets show strong excimer emission. However, upon lowering the pH the excimer emission is quenched due to loosely-packed pyrene units. Subsequent return of pH to a neutral condition leads to full recovery of the excimer emission, indicative of fully-reversible fluorescence emission switching.
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Affiliation(s)
- Wei Zhang
- College of Science, Shenyang University of Chemical Technology, Liaoning 110142, China.
- Department of Chemistry, State Key Lab of Molecular Engineering of Polymers, and Shanghai Key Lab of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China.
| | - Yongsheng Li
- Department of Chemistry, State Key Lab of Molecular Engineering of Polymers, and Shanghai Key Lab of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China.
| | - Tianyi Zheng
- Department of Chemistry, State Key Lab of Molecular Engineering of Polymers, and Shanghai Key Lab of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China.
| | - Ying Xie
- College of Science, Shenyang University of Chemical Technology, Liaoning 110142, China.
| | - Xianyin Dai
- Department of Chemistry, State Key Lab of Molecular Engineering of Polymers, and Shanghai Key Lab of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China.
- School of Chemistry and Pharmaceutical Engineering, Shandong First Medical University & Shandong Academy of Medical Sciences, Taian, 271016, China
| | - Myongsoo Lee
- Department of Chemistry, State Key Lab of Molecular Engineering of Polymers, and Shanghai Key Lab of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China.
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2
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Roithmeyer H, Bühler J, Blacque O, Tuncay I, Moehl T, Invernizzi C, Keller F, Iannuzzi M, Tilley SD. The Swiss Army Knife of Electrodes: Pillar[6]arene-Modified Electrodes for Molecular Electrocatalysis Over a Wide pH Range. Angew Chem Int Ed Engl 2025; 64:e202413144. [PMID: 39468829 DOI: 10.1002/anie.202413144] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 07/12/2024] [Indexed: 10/30/2024]
Abstract
Molecularly-modified electrode materials that maintain stability over a broad pH range are rare. Typically, each electrochemical transformation necessitates a specifically tuned system to achieve strong binding and high activity of the catalyst. Here, we report the functionalisation of mesoporous indium tin oxide (mITO) electrodes with the macrocyclic host molecule pillar[6]arene (PA[6]). These electrodes are stable within the pH range of 2.4-10.8 and can be equipped with electrochemically active ruthenium complexes through host-guest interactions to perform various oxidation reactions. Benzyl alcohol oxidation serves as a model reaction in acidic media, while ammonia oxidation is conducted to assess the systems performance under basic conditions. PA[6]-modified electrodes demonstrate catalytic activity for both reactions when complexed to different guest molecules and can be reused by reabsorption of the catalyst after its degradation. Furthermore, the system can be employed to perform subsequent reactions in electrolyte with varying pH, enabling the same electrode to be utilised in multiple different electrocatalytic reactions.
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Affiliation(s)
- Helena Roithmeyer
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
| | - Jan Bühler
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
| | - Olivier Blacque
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
| | - Isik Tuncay
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
| | - Thomas Moehl
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
| | - Cristiano Invernizzi
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
- Department of Science and High Technology, Insubria University and INSTM, 22100, Como, Italy
| | - Florian Keller
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
| | - Marcella Iannuzzi
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
| | - S David Tilley
- Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
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3
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Sharma CR, Mishra V, Agrawal Y. RP-HPLC Study of the Complexation of Acetamiprid, Imidacloprid and Carboxin Guest Molecules With Thiophosphorylated Calix [6] Arene in Dimethylformamide-Acetonitrile-Water Mobile Phase. J Chromatogr Sci 2024; 62:972-977. [PMID: 39377266 DOI: 10.1093/chromsci/bmae052] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 05/25/2023] [Revised: 08/09/2024] [Indexed: 10/09/2024]
Abstract
Reversed-phase high-performance liquid chromatography was used to study the host-guest complexation of thiophosphacalixarenes (TPC 1-3) with acetamiprid, imidacloprid and carboxin as guests. The Onyx Monolithic C 18 column (150 × 0.1 mm) and Phenomenex® were used with UV detection at 254 nm. The mobile phase consisted of dimethylformamide-acetonitrile-water. The association constant of the 1:1 guest-host complexes was determined from the relationship between the retention factor of the guest and concentration of the thiophosphacalix [6] arene host in the mobile phase. The stability constants are influenced by size, nature, position and quantity of substituents in the benzene ring of the calixarene skeleton. The detection limits for TPC 1, TPC 2 and TPC 3 are 0.95, 1.20 and 1.40 μg/mL, while the quantification limits are 2.85, 3.60 and 4.20 μg/mL for TPC 1, TPC 2 and TPC 3, respectively.
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Affiliation(s)
| | - Vijay Mishra
- Navdeep Chemical Pvt. Ltd, Ankleshwar, Gujarat-393002, India
| | - Yadvendra Agrawal
- L J Centre of Excellence, L J University, Ahmedabad-382210, Gujarat, India
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González-González JS, Martínez-Santos A, Emparán-Legaspi MJ, Pineda-Contreras A, Martínez-Martínez FJ, Flores-Alamo M, García-Ortega H. Molecular structure and selective theophylline complexation by conformational change of diethyl N,N'-(1,3-phenylene)dicarbamate. Acta Crystallogr C Struct Chem 2024; 80:190-199. [PMID: 38712545 DOI: 10.1107/s2053229624003358] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 03/21/2024] [Accepted: 04/16/2024] [Indexed: 05/08/2024] Open
Abstract
The receptor ability of diethyl N,N'-(1,3-phenylene)dicarbamate (1) to form host-guest complexes with theophylline (TEO) and caffeine (CAF) by mechanochemistry was evaluated. The formation of the 1-TEO complex (C12H16N2O4·C7H8N4O2) was preferred and involves the conformational change of one of the ethyl carbamate groups of 1 from the endo conformation to the exo conformation to allow the formation of intermolecular interactions. The formation of an N-H...O=C hydrogen bond between 1 and TEO triggers the conformational change of 1. CAF molecules are unable to form an N-H...O=C hydrogen bond with 1, making the conformational change and, therefore, the formation of the complex impossible. Conformational change and selective binding were monitored by IR spectroscopy, solid-state 13C nuclear magnetic resonance and single-crystal X-ray diffraction. The 1-TEO complex was characterized by IR spectroscopy, solid-state 13C nuclear magnetic resonance, powder X-ray diffraction and single-crystal X-ray diffraction.
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Affiliation(s)
- Juan Saulo González-González
- Instituto de Farmacobiología, Universidad de la Cañada, Carretera Teotitlán-San Antonio Nanahuatipán, km 1.7 s/n, Teotitlán de Flores Magón, Oaxaca 68540, Mexico
| | - Alfonso Martínez-Santos
- Instituto de Farmacobiología, Universidad de la Cañada, Carretera Teotitlán-San Antonio Nanahuatipán, km 1.7 s/n, Teotitlán de Flores Magón, Oaxaca 68540, Mexico
| | - María José Emparán-Legaspi
- Facultad de Ciencias Químicas, Universidad de Colima, km 9, Carretera Colima-Coquimatlán, Coquimatlán, Colima 28400, Mexico
| | - Armando Pineda-Contreras
- Facultad de Ciencias Químicas, Universidad de Colima, km 9, Carretera Colima-Coquimatlán, Coquimatlán, Colima 28400, Mexico
| | | | - Marcos Flores-Alamo
- Facultad de Química, Universidad Nacional Autónoma de México, Ciudad de México 04510, Mexico
| | - Hector García-Ortega
- Facultad de Química, Universidad Nacional Autónoma de México, Ciudad de México 04510, Mexico
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5
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Bartocci A, Dumont E. Situating the phosphonated calixarene-cytochrome C association by molecular dynamics simulations. J Chem Phys 2024; 160:105101. [PMID: 38465686 DOI: 10.1063/5.0198522] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [MESH Headings] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 01/18/2024] [Accepted: 02/20/2024] [Indexed: 03/12/2024] Open
Abstract
Protein-calixarenes binding plays an increasingly central role in many applications, spanning from molecular recognition to drug delivery strategies and protein inhibition. These ligands obey a specific bio-supramolecular chemistry, which can be revealed by computational approaches, such as molecular dynamics simulations. In this paper, we rely on all-atom, explicit-solvent molecular dynamics simulations to capture the electrostatically driven association of a phosphonated calix-[4]-arene with cytochome-C, which critically relies on surface-exposed paired lysines. Beyond two binding sites identified in direct agreement with the x-ray structure, the association has a larger structural impact on the protein dynamics. Then, our simulations allow a direct comparison to analogous calixarenes, namely, sulfonato, similarly reported as "molecular glue." Our work can contribute to a robust in silico predictive tool to assess binding sites for any given protein of interest for crystallization, with the specificity of a macromolecular cage whose endo/exo orientation plays a role in the binding.
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Affiliation(s)
- Alessio Bartocci
- Department of Physics, University of Trento, Via Sommarive 14, I-38123 Trento, Italy
- INFN-TIFPA, Trento Institute for Fundamental Physics and Applications, Via Sommarive 14, I-38123 Trento, Italy
- Institut de Chimie de Strasbourg, UMR 7177, CNRS, Université de Strasbourg, Strasbourg Cedex 67083, France
| | - Elise Dumont
- Université Côte d'Azur, CNRS, Institut de Chimie de Nice, UMR 7272, 06108 Nice, France
- Institut Universitaire de France, 5 rue Descartes, 75005 Paris, France
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6
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Bartocci A, Pereira G, Cecchini M, Dumont E. Capturing the Recognition Dynamics of para-Sulfonato-calix[4]arenes by Cytochrome c: Toward a Quantitative Free Energy Assessment. J Chem Inf Model 2022; 62:6739-6748. [PMID: 36054284 DOI: 10.1021/acs.jcim.2c00483] [Citation(s) in RCA: 5] [Impact Index Per Article: 1.7] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 01/07/2023]
Abstract
Calix[n]arenes' selective recognition of protein surfaces covers a broad range of timely applications, from controlling protein assembly and crystallization to trapping partially disordered proteins. Here, the interaction of para-sulfonated calix-[4]-arenes with cytochrome c is investigated through all-atom, explicit water molecular dynamics simulations which allow characterization of two binding sites in quantitative agreement with experimental evidence. Free energy calculations based on the MM-PBSA and the attach-pull-release (APR) methods highlight key residues implicated in the recognition process and provide binding free energy results in quantitative agreement with isothermal titration calorimetry. Our study emphasizes the role of MD simulations to capture and describe the "walk" of sulfonated calix-[4]-arenes on the cytochrome c surface, with the arginine R13 as a pivotal interacting residue. Our MD investigation allows, through the quasi-harmonic multibasin (QHMB) method, probing an allosteric reinforcement of several per-residue interactions upon calixarene binding, which suggests a more complex mode of action of these supramolecular auxiliaries.
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Affiliation(s)
- Alessio Bartocci
- Laboratoire de Chimie, Ecole Normale Superieure de Lyon, F-69342 Lyon, France.,Institut de Chimie de Strasbourg, UMR 7177, CNRS, Université de Strasbourg, Strasbourg 67083, France
| | - Gilberto Pereira
- Institut de Chimie de Strasbourg, UMR 7177, CNRS, Université de Strasbourg, Strasbourg 67083, France.,Molecular Microbiology and Structural Biochemistry (MMSB, UMR 5086), CNRS & University of Lyon, 7 Passage du Vercors, 69007 Lyon, France
| | - Marco Cecchini
- Institut de Chimie de Strasbourg, UMR 7177, CNRS, Université de Strasbourg, Strasbourg 67083, France
| | - Elise Dumont
- Laboratoire de Chimie, Ecole Normale Superieure de Lyon, F-69342 Lyon, France.,Institut Universitaire de France, 5 rue Descartes, 75005 Paris, France
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7
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Wang Z, Sun C, Wang R. Macrocycle-Surfaced Polymer Nanocapsules: An Emerging Paradigm for Biomedical Applications. Bioconjug Chem 2022; 33:2254-2261. [PMID: 35436111 DOI: 10.1021/acs.bioconjchem.2c00102] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/29/2022]
Abstract
In the recent decade, macrocycle-surfaced polymer nanocapsules have been developed and studied as potential drug carriers. In particular, a unique group of these nanocapsules were constructed from a covalently self-assembled polymer network based on several classic macrocycles including cucurbituril, pillararene, and calixarene. The unique structure of these nanocapsules consists of a liquid or solid core and a shell laced with macrocycles in which the macrocycles not only act as the shell matrix of the nanocapsules but also allow further facile, modular functionalization via host-guest interactions with guest-tagged molecules. More interestingly, when a responsive cross-linker was introduced between the macrocycles, the payload inside the nanocapsules could be selectively released in the presence of typical hallmarks of certain diseases, which is of great interest for biomedical applications. In this Topical Review, macrocycle-surfaced polymer nanocapsules derived from covalently self-assembled polymer networks are introduced systemically with a focus on the molecular design and biomedical applications.
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Affiliation(s)
- Ziyi Wang
- State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macau SAR 999078, China
| | - Chen Sun
- State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macau SAR 999078, China
| | - Ruibing Wang
- State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macau SAR 999078, China.,Department of Pharmaceutical Sciences, Faculty of Health Sciences, University of Macau, Macau SAR 999078, China
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8
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Chen J, Hooley RJ, Zhong W. Applications of Synthetic Receptors in Bioanalysis and Drug Transport. Bioconjug Chem 2022; 33:2245-2253. [PMID: 35362963 DOI: 10.1021/acs.bioconjchem.2c00096] [Citation(s) in RCA: 7] [Impact Index Per Article: 2.3] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/29/2022]
Abstract
Synthetic receptors are powerful tools for molecular recognition. They can bind to guests with high selectivity and affinity, and their structures are tunable and diversified. These features, plus the relatively low cost and high simplicity in synthesis and modification, support the feasibility of array-based molecular analysis with synthetic receptors for improved selectivity in the recognition of a wide range of targets. More attractively, host-guest interaction is reversible and guest displacement allows biocompatible and gentle release of the host-bound molecules, simplifying the stimulation designs needed to control analyte sensing, enrichment, and transportation. Here, we highlight a few recent advancements in using synthetic receptors for molecular analysis and manipulation, with the focus on macrocyclic receptors and their applications in displacement sensing, separation, imaging, and drug transport.
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9
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Tavakkoli Yaraki M, Tukova A, Wang Y. Emerging SERS biosensors for the analysis of cells and extracellular vesicles. NANOSCALE 2022; 14:15242-15268. [PMID: 36218172 DOI: 10.1039/d2nr03005e] [Citation(s) in RCA: 28] [Impact Index Per Article: 9.3] [Reference Citation Analysis] [Abstract] [MESH Headings] [Track Full Text] [Subscribe] [Scholar Register] [Indexed: 06/16/2023]
Abstract
Cells and their derived extracellular vesicles (EVs) or exosomes contain unique molecular signatures that could be used as biomarkers for the detection of severe diseases such as cancer, as well as monitoring the treatment response. Revealing these molecular signatures requires developing non-invasive ultrasensitive tools to enable single molecule/cell-level detection using a small volume of sample with low signal-to-noise ratio background and multiplex capability. Surface-enhanced Raman scattering (SERS) can address the current limitations in studying cells and EVs through two main mechanisms: plasmon-enhanced electric field (the so-called electromagnetic mechanism (EM)), and chemical mechanism (CM). In this review, we first highlight these two SERS mechanisms and then discuss the nanomaterials that have been used to develop SERS biosensors based on each of the aforementioned mechanisms as well as the combination of these two mechanisms in order to take advantage of the synergic effect between electromagnetic enhancement and chemical enhancement. Then, we review the recent advances in designing label-aided and label-free SERS biosensors in both colloidal and planar systems to investigate the surface biomarkers on cancer cells and their derived EVs. Finally, we discuss perspectives of emerging SERS biosensors in future biomedical applications. We believe this review article will thus appeal to researchers in the field of nanobiotechnology including material sciences, biosensors, and biomedical fields.
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Affiliation(s)
- Mohammad Tavakkoli Yaraki
- School of Natural Sciences, Faculty of Science and Engineering, Macquarie University, Sydney, NSW 2109, Australia.
| | - Anastasiia Tukova
- School of Natural Sciences, Faculty of Science and Engineering, Macquarie University, Sydney, NSW 2109, Australia.
| | - Yuling Wang
- School of Natural Sciences, Faculty of Science and Engineering, Macquarie University, Sydney, NSW 2109, Australia.
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10
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Al-Saidi HM, Khan S. A Review on Organic Fluorimetric and Colorimetric Chemosensors for the Detection of Ag(I) Ions. Crit Rev Anal Chem 2022; 54:1810-1836. [PMID: 36251012 DOI: 10.1080/10408347.2022.2133561] [Citation(s) in RCA: 8] [Impact Index Per Article: 2.7] [Reference Citation Analysis] [Abstract] [Key Words] [MESH Headings] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 10/24/2022]
Abstract
Organic compounds display several electronic and structural features which enable their application in various fields, ranging from biological to non-biological. These compounds contain heteroatoms like sulfur, nitrogen and oxygen, which provide coordination sites to act as ligands in the field of coordination chemistry and are used as chemosensors to detect various metal ions. This review article covers different organic compounds including thiourea, Schiff base, pyridine, thiophene, coumarin, triazolyl pyrenes, imidazole, fluorescein, thiazole, tricarbocyanine, rhodanine, porphyrin, hydrazone, benzidine and other functional groups based chemosensors, that contain heteroatoms like sulfur, nitrogen and, oxygen for fluorimetric and colorimetric detection of Ag+ in different environmental, agricultural, and biological samples. Further, the sensing mechanism and performances of these chemosensors have been discussed, which could help the readers for the future design of highly efficient, selective, and sensitive chemosensors for the detection and determination of Ag+ ions.
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Affiliation(s)
- Hamed M Al-Saidi
- Department of Chemistry, University College in Al-Jamoum, Umm Al-Qura University, Makkah, Saudi Arabia
| | - Sikandar Khan
- Department of Chemistry, University of Malakand, Khyber Pakhtunkhwa, Pakistan
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11
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Hadi H, Safari R. Synthesis and experimental/theoretical evaluation of an efficient Calix[4]arene based sensor for selective detection of Pt 2+ ion. Mol Phys 2022. [DOI: 10.1080/00268976.2022.2108516] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 10/15/2022]
Affiliation(s)
- Hamid Hadi
- Faculty of Science, Department of Chemistry (Physical Chemistry Group), University of Lorestan, Khorramabad, Iran
- Faculty of Science, Department of Chemistry (Physical Chemistry Group), University of Qom, Qom, Iran
| | - Reza Safari
- Faculty of Science, Department of Chemistry (Physical Chemistry Group), University of Qom, Qom, Iran
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12
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Simões JB, Leite da Silva D, Fernandes SA, de Fátima Â. Calix[n]arenes in Action: Recent Applications in Organocatalysis. European J Org Chem 2022. [DOI: 10.1002/ejoc.202200532] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/11/2022]
Affiliation(s)
| | | | | | - Ângelo de Fátima
- Universidade Federal de Minas Gerais Departamento de Química Av. Pres. Antônio Carlos, 6627, Pampulha 31270-901 Belo Horizonte BRAZIL
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13
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Rathod SL, Sharma VS, Sharma AS, Athar M, Shrivastav PS, Parekh HM. “Blue light-emitting Quinoline armed Thiacalix [4]arene 3D-scaffold: a Systematic Platform to construct Fluorescent Liquid Crystals with Bio-imaging Applications”. J Mol Struct 2022. [DOI: 10.1016/j.molstruc.2022.133830] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 10/16/2022]
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14
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Nag R, Rao CP. Calixarene-mediated host-guest interactions leading to supramolecular assemblies: visualization by microscopy. Chem Commun (Camb) 2022; 58:6044-6063. [PMID: 35510609 DOI: 10.1039/d2cc01850k] [Citation(s) in RCA: 5] [Impact Index Per Article: 1.7] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/24/2022]
Abstract
Host-guest chemistry, particularly of supramolecules, has been an intriguing topic for researchers for a long time due to its multiplicative applications ranging from chemical to biological to materials science. Supramolecules, such as calixarenes, are excellent host molecular systems due to their controllable cavity along with the ease of functionalization both at the lower and upper rims. The host-guest interactions involving calixarenes have been primarily studied using physical methods, such as absorption, fluorescence and nuclear magnetic resonance spectroscopy, isothermal titration calorimetry and mass spectrometry. The corresponding literature as disseminated through review articles triggered broadening of the spectrum of research. Depending upon the nature of the derivatization, the supramolecular conjugates of calixarenes have been shown to form different morphologies of micro and nanometric size as reported in the literature. Pertinent research performed in our own group was based on atomic force microscopy, transmission electron microscopy and scanning electron microscopy studies. The literature reveals that such morphologies are modified in the presence of guest species. Thus, the supramolecular host-guest complexation of calixarenes leading to the formation of various architectures has been studied using both spectroscopy and microscopy techniques to obtain complimentary data. However, there are no review articles that provide discussions on this exciting area of supramolecular science involving microscopy. Therefore, in the present article, for the first time, we have brought together the research reported in the literature during the past decade, including ours, in demonstrating the supramolecular architectures formed from the host-guest interactions extended by the conjugates of calixarenes, and their applications using microscopy. The scope of this article spans across various features of interaction in these systems: (i) in solution, (ii) at the air-water interface and (iii) on solid surfaces. The application domain includes sensing of organic explosives and drugs, exhibiting antibacterial activity, supramolecular self-assembly or co-assembly resulting in gels, micelles and vesicles, and the consequent aggregation-induced emission and a few others.
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Affiliation(s)
- Rahul Nag
- Department of Chemistry, Indian Institute of Technology Tirupati, Settipalli Post, Tirupati - 517506, Andhra Pradesh, India.
| | - Chebrolu Pulla Rao
- Department of Chemistry, Indian Institute of Technology Tirupati, Settipalli Post, Tirupati - 517506, Andhra Pradesh, India.
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15
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Liu WS, Li HY, Zhang HX, Han XY, Guo XC, Ding CH. Bridging chiral de- tert-butylcalix[4]arenes: Optical resolution based on column chromatography and structural characterization. OPEN CHEM 2022. [DOI: 10.1515/chem-2022-0130] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/15/2022] Open
Abstract
Abstract
As the third-generation supramolecular main structure, calixarenes, especially chiral calixarenes, have been applied to various fields. In this study, the bridging chiral de-tert-butylcalix[4]arene derivatives with an amide group attached to a chiral point was synthesized for the first time, which provided a new group for its structural derivation at the bridging chiral position. The racemic compound 2 was optically resolved by column chromatography on silica gel with the aid of the chiral auxiliary (1S)-(+)-10-camphorsulfonyl chloride, and finally a pair of optically pure bridging chiral de-tert-butylcalix[4]arene derivatives 4a and 4b were obtained. The results of experimental and calculated ECD showed that compounds 4a and 4b were a pair of enantiomers, and their absolute configurations were designated S and R, respectively. This study provides new idea for the derivatization of specific chiral groups based on bridging chiral calix[4]arenes and their chiral resolution.
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Affiliation(s)
- Wen-Shan Liu
- Department of Pharmacy, Shandong Key Laboratory of Clinical Applied Pharmacology, Affiliated Hospital of Weifang Medical University , Weifang 261041 , Shandong Province , China
| | - Hong-Ying Li
- Department of Pharmacy, Shandong Key Laboratory of Clinical Applied Pharmacology, Affiliated Hospital of Weifang Medical University , Weifang 261041 , Shandong Province , China
| | - Hai-Xia Zhang
- Department of Pharmacy, Shandong Key Laboratory of Clinical Applied Pharmacology, Affiliated Hospital of Weifang Medical University , Weifang 261041 , Shandong Province , China
| | - Xiu-Yuan Han
- Department of Pharmacy, Shandong Key Laboratory of Clinical Applied Pharmacology, Affiliated Hospital of Weifang Medical University , Weifang 261041 , Shandong Province , China
| | - Xi-Chun Guo
- Department of Pharmacy, Shandong Key Laboratory of Clinical Applied Pharmacology, Affiliated Hospital of Weifang Medical University , Weifang 261041 , Shandong Province , China
| | - Chuan-Hua Ding
- Department of Pharmacy, Shandong Key Laboratory of Clinical Applied Pharmacology, Affiliated Hospital of Weifang Medical University , Weifang 261041 , Shandong Province , China
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16
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Zhang KR, Hu M, Luo J, Ye F, Zhou TT, Yuan YX, Gao ML, Zheng YS. Pseudo-crown ether having AIE and PET effects from a TPE-CD conjugate for highly selective detection of mercury ions. CHINESE CHEM LETT 2022. [DOI: 10.1016/j.cclet.2021.08.072] [Citation(s) in RCA: 3] [Impact Index Per Article: 1.0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/16/2022]
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17
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Kim S, Jung JH, Lee SS, Park IH. Regioisomers of singly bridged calix[6]crown-6 and their heavy alkali metal complexes: a molecular baseball glove for caesium(I). IUCRJ 2022; 9:43-48. [PMID: 35059208 PMCID: PMC8733876 DOI: 10.1107/s2052252521010563] [Citation(s) in RCA: 2] [Impact Index Per Article: 0.7] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Subscribe] [Scholar Register] [Received: 08/19/2021] [Accepted: 10/12/2021] [Indexed: 05/30/2023]
Abstract
We report the formation of heavy alkali metal complexes of bicyclic host molecules including the caesium(I) complex that catches the central metal ion with the deep pocket of the host similar to a baseball glove. For this, three regioisomers of singly bridged calix[6]crown-6 [1,2-bridged (H4 L 1,2), 1,3-bridged (H4 L 1,3) and 1,4-bridged (H4 L 1,4)] have been synthesized by alkyl-ation of calix[6]arene with penta-ethyl-ene glycol di-tosyl-ate in the presence of M 2CO3 (M = Na, K, Rb and Cs). The larger the cation size of the metal carbonate, the higher the yield of the H4 L 1,4 isomer, indicating the size-based template effect. A combination of H4 L 1,2 and RbOH allowed isolation of the mononuclear rubidium(I) complex (1) in which the metal center is six-coordinated in a loose fashion, the remaining two oxygen donors in the crown loop and two phenols in the calix rim are uncoordinated. Notably, the complexation of H4 L 1,2 with CsOH yielded the mononuclear caesium(I) complex (2), in which all possible ten binding sites on the deep and good-fit pocket participate in coordination via high cooperativity between the crown loop and calix rim, similar to a baseball glove. In dipolar organic solution, the caesium(I) complex 2 remains intact. H4 L 1,4 afforded a dicesium(I) complex (3) and adjacent complexes are linked by intermolecular cation-π interactions, giving rise to a pseudo one-dimensional coordination polymer. These results provide insight into the metal carbonate-dependent synthesis of calix[6]crowns and the influence of regioisomers on caesium(I) complexation.
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Affiliation(s)
- Seulgi Kim
- Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea
| | - Jong Hwa Jung
- Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea
| | - Shim Sung Lee
- Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea
| | - In-Hyeok Park
- Graduate School of Analytical Science and Technology (GRAST), Chungnam National University, Daejeon 34134, Republic of Korea
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18
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Quaglio D, Polli F, Del Plato C, Cianfoni G, Tortora C, Mazzei F, Botta B, Calcaterra A, Ghirga F. Calixarene: a versatile scaffold for the development of highly sensitive biosensors. Supramol Chem 2021. [DOI: 10.1080/10610278.2021.2011283] [Citation(s) in RCA: 1] [Impact Index Per Article: 0.3] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Submit a Manuscript] [Subscribe] [Scholar Register] [Indexed: 10/19/2022]
Affiliation(s)
- Deborah Quaglio
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
| | - Francesca Polli
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
| | - Cristina Del Plato
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
- Center for Life Nano- & Neuro-Science@Sapienza, Italian Institute of Technology, Rome, Italy
| | - Gabriele Cianfoni
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
- Center for Life Nano- & Neuro-Science@Sapienza, Italian Institute of Technology, Rome, Italy
| | - Carola Tortora
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
| | - Franco Mazzei
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
| | - Bruno Botta
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
| | - Andrea Calcaterra
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
| | - Francesca Ghirga
- Department of Chemistry and Technology of Drugs, Sapienza - University of Rome, Rome, Italy
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19
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Sun C, Du S, Zhang T, Han J. A Novel Calix[4]Crown-Based 1,3,4-Oxadiazole as a Fluorescent Chemosensor for Copper(II) Ion Detection. Front Chem 2021; 9:766442. [PMID: 34869207 PMCID: PMC8632693 DOI: 10.3389/fchem.2021.766442] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 08/29/2021] [Accepted: 10/18/2021] [Indexed: 11/13/2022] Open
Abstract
The synthesis and characterization of a novel florescent chemosensor 1 with two different types of cationic binding sites have been reported in this work, which is a calix[4]crown derivative in 1,3-alternate conformation bearing two 2-phenyl-5-(4-dimethylaminopyenyl)-1,3,4-oxadiazole units. The recognition behaviors of 1 in dichloromethane/acetonitrile solution to alkali metal ions (Na+ and K+), alkaline earth metal ions (Mg2+ and Ca2+), and transition metal ions (Co2+, Ni2+, Zn2+, Cd2+, Cu2+, Mn2+, and Ag+) have been investigated by UV-Vis and fluorescence spectra. The fluorescence of 1 might be quenched selectively by Cu2+ due to the photo-induced electron transfer mechanism, and the quenched emission from 1 could be partly revived by the addition of Ca2+ or Mg2+; thus, the receptor 1 might be worked as an on-off switchable fluorescent chemosensor triggered by metal ion exchange.
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Affiliation(s)
| | | | | | - Jie Han
- Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Energy), College of Chemistry, Nankai University, Tianjin, China
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20
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Guan T, Cheng M, Zeng L, Chen X, Xie Y, Lei Z, Ruan Q, Wang J, Cui S, Sun Y, Li H. Engineering the Redox-Driven Channel for Precisely Regulating Nanoconfined Glutathione Identification and Transport. ACS APPLIED MATERIALS & INTERFACES 2021; 13:49137-49145. [PMID: 34623797 DOI: 10.1021/acsami.1c12061] [Citation(s) in RCA: 6] [Impact Index Per Article: 1.5] [Reference Citation Analysis] [Abstract] [Key Words] [MESH Headings] [Track Full Text] [Subscribe] [Scholar Register] [Indexed: 06/13/2023]
Abstract
Bioinspired artificial nanochannels for molecular and ionic transport have extensive applications. However, it is still a huge challenge to achieve an intelligent transport system with high selectivity/efficiency and controllability. Inspired by glutathione transport across the plasma membrane via redox regulation, we herein designed and fabricated a redox-reactive artificial nanochannel based on the host-guest chemical strategy. The nanochannel platform achieved high selectivity/efficiency for the identification and transmission of glutathione in the confined space. In addition, this nanochannel can switch between the ON and OFF states through the redox reaction. This redox-regulated system can provide a potential application for detection/binding of biological analytes and redox-controlled drug release.
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Affiliation(s)
- Tianpei Guan
- Department 2 of Gastroentestinal Surgery, Affiliated Cancer Hospital and Institute of Guangzhou Medical University, Guangzhou 510095, P. R. China
| | - Ming Cheng
- Key Laboratory of Pesticide and Chemical Biology (CCNU), Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
| | - Lisi Zeng
- Department 2 of Gastroentestinal Surgery, Affiliated Cancer Hospital and Institute of Guangzhou Medical University, Guangzhou 510095, P. R. China
| | - Xiaoya Chen
- Key Laboratory of Pesticide and Chemical Biology (CCNU), Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
| | - Yuan Xie
- Guangdong Provincial Key Laboratory of Radioactive and Rare Resource Utilization, Shaoguan 512026, P. R. China
| | - Ziying Lei
- Department 2 of Gastroentestinal Surgery, Affiliated Cancer Hospital and Institute of Guangzhou Medical University, Guangzhou 510095, P. R. China
| | - Qiang Ruan
- Department 2 of Gastroentestinal Surgery, Affiliated Cancer Hospital and Institute of Guangzhou Medical University, Guangzhou 510095, P. R. China
| | - Jin Wang
- Department 2 of Gastroentestinal Surgery, Affiliated Cancer Hospital and Institute of Guangzhou Medical University, Guangzhou 510095, P. R. China
| | - Shuzhong Cui
- Department 2 of Gastroentestinal Surgery, Affiliated Cancer Hospital and Institute of Guangzhou Medical University, Guangzhou 510095, P. R. China
| | - Yao Sun
- Key Laboratory of Pesticide and Chemical Biology (CCNU), Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
| | - Haibing Li
- Key Laboratory of Pesticide and Chemical Biology (CCNU), Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
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21
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Xu J, Zhang Y, Zhang J, Li Y, Li B, Qiu H, Zhang P, Yin S. Constructing a triangular metallacycle with salen-Al and its application to a catalytic cyanosilylation reaction. Chem Commun (Camb) 2021; 57:10399-10402. [PMID: 34542548 DOI: 10.1039/d1cc04577f] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/21/2022]
Abstract
A triangular metallosalen-based metallacycle was constructed in quantitative yield by the self-assembly of a 180° bis(pyridyl)salen-Al complex and a 60° diplatinum(II) acceptor in a 1 : 1 stoichiometric ratio. This metallacycle was then successfully used to cyanosilylate a wide range of benzaldehydes with trimethylsilyl cyanide.
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Affiliation(s)
- Jun Xu
- College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China.
| | - Yueyue Zhang
- College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China.
| | - Jinjin Zhang
- College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China.
| | - Yang Li
- College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China.
| | - Bo Li
- College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China.
| | - Huayu Qiu
- College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China.
| | - Pengfei Zhang
- College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China.
| | - Shouchun Yin
- College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. China.
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22
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Cheignon C, Heurté M, Knighton RC, Kassir AA, Lecointre A, Nonat A, Boos A, Christine C, Asfari Z, Charbonnière LJ. Investigation of the Supramolecular Assembly of Luminescent Lanthanide Nanoparticles Surface Functionalized by
p‐
Sulfonato‐Calix[4]arenes with Charged Aromatic Compounds. Eur J Inorg Chem 2021. [DOI: 10.1002/ejic.202100546] [Citation(s) in RCA: 2] [Impact Index Per Article: 0.5] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 01/14/2023]
Affiliation(s)
- Clémence Cheignon
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Margaux Heurté
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Richard C. Knighton
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Ali A. Kassir
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Alexandre Lecointre
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Aline Nonat
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Anne Boos
- Equipe de Reconnaissance et Procédés de Séparation Moléculaire (RePSeM) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS, Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Câline Christine
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Zouhair Asfari
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
| | - Loïc J. Charbonnière
- Equipe de Synthèse Pour l'Analyse (SynPA) Institut Pluridisciplinaire Hubert Curien (IPHC), UMR 7178, CNRS,Université de Strasbourg, ECPM 25 rue Becquerel 67087 Strasbourg Cedex France
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23
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Schlüter D, Korsching KR, Azov VA. Lower‐Rim‐Modified Calix[4]arene‐Pyrrolotetrathiafulvalene Molecular Tweezers. European J Org Chem 2021. [DOI: 10.1002/ejoc.202100676] [Citation(s) in RCA: 1] [Impact Index Per Article: 0.3] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/08/2022]
Affiliation(s)
- Dirk Schlüter
- Department of Chemistry University of Bremen Leobener Str. NW 2 C 28359 Bremen Germany
| | - Kai R. Korsching
- Molecular Sensory Systems Center of Advanced European Studies and Research 53175 Bonn Germany
| | - Vladimir A. Azov
- Department of Chemistry University of the Free State P.O. Box 339 9300 Bloemfontein South Africa
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24
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Immobilization of molecular catalysts on electrode surfaces using host-guest interactions. Nat Chem 2021; 13:523-529. [PMID: 33767362 DOI: 10.1038/s41557-021-00652-y] [Citation(s) in RCA: 34] [Impact Index Per Article: 8.5] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 04/14/2020] [Accepted: 02/05/2021] [Indexed: 01/31/2023]
Abstract
Anchoring molecular catalysts on electrode surfaces combines the high selectivity and activity of molecular systems with the practicality of heterogeneous systems. Molecular catalysts, however, are far less stable than traditional heterogeneous electrocatalysts, and therefore a method to easily replace anchored molecular catalysts that have degraded could make such electrosynthetic systems more attractive. Here we applied a non-covalent 'click' chemistry approach to reversibly bind molecular electrocatalysts to electrode surfaces through host-guest complexation with surface-anchored cyclodextrins. The host-guest interaction is remarkably strong and enables the flow of electrons between the electrode and the guest catalyst. Electrosynthesis in both organic and aqueous media was demonstrated on metal oxide electrodes, with stability on the order of hours. The catalytic surfaces can be recycled by controlled release of the guest from the host cavities and the readsorption of fresh guest.
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25
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Structural Insights into the Host-Guest Complexation between β-Cyclodextrin and Bio-Conjugatable Adamantane Derivatives. Molecules 2021; 26:molecules26092412. [PMID: 33919170 PMCID: PMC8122645 DOI: 10.3390/molecules26092412] [Citation(s) in RCA: 9] [Impact Index Per Article: 2.3] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 01/26/2021] [Revised: 04/06/2021] [Accepted: 04/14/2021] [Indexed: 11/20/2022] Open
Abstract
Understanding the host–guest chemistry of α-/β-/γ- cyclodextrins (CDs) and a wide range of organic species are fundamentally attractive, and are finding broad contemporary applications toward developing efficient drug delivery systems. With the widely used β-CD as the host, we herein demonstrate that its inclusion behaviors toward an array of six simple and bio-conjugatable adamantane derivatives, namely, 1-adamantanol (adm-1-OH), 2-adamantanol (adm-2-OH), adamantan-1-amine (adm-1-NH2), 1-adamantanecarboxylic acid (adm-1-COOH), 1,3-adamantanedicarboxylic acid (adm-1,3-diCOOH), and 2-[3-(carboxymethyl)-1-adamantyl]acetic acid (adm-1,3-diCH2COOH), offer inclusion adducts with diverse adamantane-to-CD ratios and spatial guest locations. In all six cases, β-CD crystallizes as a pair supported by face-to-face hydrogen bonding between hydroxyl groups on C2 and C3 and their adjacent equivalents, giving rise to a truncated-cone-shaped cavity to accommodate one, two, or three adamantane derivatives. These inclusion complexes can be terminated as (adm-1-OH)2⊂CD2 (1, 2:2), (adm-2-OH)3⊂CD2 (2, 3:2), (adm-1-NH2)3⊂CD2 (3, 3:2), (adm-1-COOH)2⊂CD2 (4, 2:2), (adm-1,3-diCOOH)⊂CD2 (5, 1:2), and (adm-1,3-diCH2COOH)⊂CD2 (6, 1:2). This work may shed light on the design of nanomedicine with hierarchical structures, mediated by delicate cyclodextrin-based hosts and adamantane-appended drugs as the guests.
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26
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Chen GY, Sun YB, Shi PC, Liu T, Li ZH, Luo SH, Wang XC, Cao XY, Ren B, Liu GK, Yang LL, Tian ZQ. Revealing unconventional host-guest complexation at nanostructured interface by surface-enhanced Raman spectroscopy. LIGHT, SCIENCE & APPLICATIONS 2021; 10:85. [PMID: 33875636 PMCID: PMC8055983 DOI: 10.1038/s41377-021-00526-5] [Citation(s) in RCA: 15] [Impact Index Per Article: 3.8] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Figures] [Subscribe] [Scholar Register] [Received: 10/28/2020] [Revised: 03/20/2021] [Accepted: 03/31/2021] [Indexed: 06/12/2023]
Abstract
Interfacial host-guest complexation offers a versatile way to functionalize nanomaterials. However, the complicated interfacial environment and trace amounts of components present at the interface make the study of interfacial complexation very difficult. Herein, taking the advantages of near-single-molecule level sensitivity and molecular fingerprint of surface-enhanced Raman spectroscopy (SERS), we reveal that a cooperative effect between cucurbit[7]uril (CB[7]) and methyl viologen (MV2+2I-) in aggregating Au NPs originates from the cooperative adsorption of halide counter anions I-, MV2+, and CB[7] on Au NPs surface. Moreover, similar SERS peak shifts in the control experiments using CB[n]s but with smaller cavity sizes suggested the occurrence of the same guest complexations among CB[5], CB[6], and CB[7] with MV2+. Hence, an unconventional exclusive complexation model is proposed between CB[7] and MV2+ on the surface of Au NPs, distinct from the well-known 1:1 inclusion complexation model in aqueous solutions. In summary, new insights into the fundamental understanding of host-guest interactions at nanostructured interfaces were obtained by SERS, which might be useful for applications related to host-guest chemistry in engineered nanomaterials.
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Affiliation(s)
- Gan-Yu Chen
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
| | - Yi-Bin Sun
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
| | - Pei-Chen Shi
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
| | - Tao Liu
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
- State Key Laboratory of Marine Environmental Science, Fujian Provincial Key Laboratory for Coastal Ecology and Environmental Studies, Center for Marine Environmental Chemistry & Toxicology, College of the Environment and Ecology, Xiamen University, Xiamen, 361102, China
| | - Zhi-Hao Li
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
| | - Si-Heng Luo
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
- State Key Laboratory of Marine Environmental Science, Fujian Provincial Key Laboratory for Coastal Ecology and Environmental Studies, Center for Marine Environmental Chemistry & Toxicology, College of the Environment and Ecology, Xiamen University, Xiamen, 361102, China
| | - Xin-Chang Wang
- School of Electronic Science and Engineering (National Model Microelectronics College), Xiamen University, Xiamen, 361005, China
| | - Xiao-Yu Cao
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
- Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, 361005, China
| | - Bin Ren
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
| | - Guo-Kun Liu
- State Key Laboratory of Marine Environmental Science, Fujian Provincial Key Laboratory for Coastal Ecology and Environmental Studies, Center for Marine Environmental Chemistry & Toxicology, College of the Environment and Ecology, Xiamen University, Xiamen, 361102, China.
| | - Liu-Lin Yang
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
| | - Zhong-Qun Tian
- State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
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27
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Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid-Liquid and 2D-Confined Interfaces. Int J Mol Sci 2021; 22:ijms22073535. [PMID: 33805474 PMCID: PMC8038083 DOI: 10.3390/ijms22073535] [Citation(s) in RCA: 3] [Impact Index Per Article: 0.8] [Reference Citation Analysis] [Abstract] [Key Words] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 03/11/2021] [Revised: 03/23/2021] [Accepted: 03/25/2021] [Indexed: 11/23/2022] Open
Abstract
Understanding the interaction of ions with organic receptors in confined space is of fundamental importance and could advance nanoelectronics and sensor design. In this work, metal ion complexation of conformationally varied thiacalix[4]monocrowns bearing lower-rim hydroxy (type I), dodecyloxy (type II), or methoxy (type III) fragments was evaluated. At the liquid–liquid interface, alkylated thiacalixcrowns-5(6) selectively extract alkali metal ions according to the induced-fit concept, whereas crown-4 receptors were ineffective due to distortion of the crown-ether cavity, as predicted by quantum-chemical calculations. In type-I ligands, alkali-metal ion extraction by the solvent-accessible crown-ether cavity was prevented, which resulted in competitive Ag+ extraction by sulfide bridges. Surprisingly, amphiphilic type-I/II conjugates moderately extracted other metal ions, which was attributed to calixarene aggregation in salt aqueous phase and supported by dynamic light scattering measurements. Cation–monolayer interactions at the air–water interface were monitored by surface pressure/potential measurements and UV/visible reflection–absorption spectroscopy. Topology-varied selectivity was evidenced, towards Sr2+ (crown-4), K+ (crown-5), and Ag+ (crown-6) in type-I receptors and Na+ (crown-4), Ca2+ (crown-5), and Cs+ (crown-6) in type-II receptors. Nuclear magnetic resonance and electronic absorption spectroscopy revealed exocyclic coordination in type-I ligands and cation–π interactions in type-II ligands.
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28
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Cai Y, Yan X, Wang S, Zhu Z, Cen M, Ou C, Zhao Q, Yan Q, Wang J, Yao Y. Pillar[5]arene-Based 3D Hybrid Supramolecular Polymer for Green Catalysis in Water. Inorg Chem 2021; 60:2883-2887. [PMID: 33570384 DOI: 10.1021/acs.inorgchem.0c03645] [Citation(s) in RCA: 21] [Impact Index Per Article: 5.3] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/13/2022]
Abstract
Pillar[n]arene-based supramolecular polymers have attracted great interest because of their tunable morphologies and external stimuli responsiveness. However, most of the investigations of supramolecular polymers previously reported were focused on their formation and transformation, and investigations on their applications are rare. Herein, we designed and prepared hybrid polymeric materials by incorporating Pd nanoparticles into a supramolecular polymer, constructed from a pillar[5]arene dimer and a three-arm guest. The obtained hybrid polymer was fully characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy-energy-dispersive X-ray mapping, and X-ray diffraction technologies. Importantly, the hybrid supramolecular polymeric materials exhibited desirable catalytic activity for reductions of toxic nitroaromatics and C-C bond-forming Suzuki-Miyaura reaction in aqueous solution.
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Affiliation(s)
- Yan Cai
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Xin Yan
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Siyuan Wang
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Zhiwen Zhu
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Moupan Cen
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Changjin Ou
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Qin Zhao
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Qian Yan
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Jin Wang
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
| | - Yong Yao
- School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019, P. R. China
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30
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Shuai X, Cai Z, Zhao X, Chen Y, Zhang Q, Ma Z, Hu J, Sun T, Hu S. A New Stationary Phase for Capillary Gas Chromatography: Calix[4]resorcinarene Functionalized with Imidazolium Cationic Units. Chromatographia 2021. [DOI: 10.1007/s10337-021-04018-x] [Citation(s) in RCA: 3] [Impact Index Per Article: 0.8] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/20/2022]
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31
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Zhang R, Huang J, Chen K, Boussouar I, Chen X, Fan Y, Sun Y, Li H. Highly Efficient Ionic Gating of Solid-State Nanosensors by the Reversible Interaction between Pillar[6]arene-AuNPs and Azobenzene. Anal Chem 2021; 93:3280-3286. [PMID: 33528247 DOI: 10.1021/acs.analchem.0c05241] [Citation(s) in RCA: 11] [Impact Index Per Article: 2.8] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/13/2022]
Abstract
By mimicking nature, various artificial nanofluidic platforms have been widely applied in a range of scientific fields. However, their low performance in terms of gating efficiency (<25) still hinders their practical applications. Herein, we present a highly efficient ionic gating nanosensor by fusing the merits of host-guest chemistry and Au nanoparticles (AuNPs). Based on this strategy, the pillar[6]arene (WP6)-functionalized AuNPs facilely regulated an azobenzene (AZO)-modified nanosensor with an excellent ion rectification ratio (∼22.2) and gating efficiency (∼89.5). More importantly, this gating nanosensor system also demonstrated promising stability and recyclability under conditions of alternative irradiation of visible and ultraviolet light. These excellent results would significantly help in expanding the utilization of artificial nanosensors for controllable drug delivery and biosensors.
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Affiliation(s)
- Ruiping Zhang
- The Affiliated Bethune Hospital of Shanxi Medical University, Taiyuan 030001, P. R. China
| | - Jinmei Huang
- Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), Nanjing University of Information Science & Technology, Nanjing 210044, China.,Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China
| | - Kai Chen
- Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), Nanjing University of Information Science & Technology, Nanjing 210044, China
| | - Imene Boussouar
- Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China
| | - Xiaoya Chen
- The State Key Laboratory of Fine Chemicals, Dalian University of Technology, Liaoning 116024, China
| | - Yifan Fan
- Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China.,Guangdong Provincial Key Laboratory of Radioactive and Rare Resource Utilization, Shaoguan 512026, China
| | - Yao Sun
- Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China
| | - Haibing Li
- Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China
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32
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Shaban A, Eddaif L. Comparative Study of a Sensing Platform via Functionalized Calix[4]resorcinarene Ionophores on QCM Resonator as Sensing Materials for Detection of Heavy Metal Ions in Aqueous Environments. ELECTROANAL 2021. [DOI: 10.1002/elan.202060331] [Citation(s) in RCA: 1] [Impact Index Per Article: 0.3] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 01/25/2023]
Affiliation(s)
- Abdul Shaban
- Functional Interfaces Research Group, Institute of Materials and Environmental Chemistry Research Centre for Natural Sciences, Bp. Hungary
| | - Larbi Eddaif
- Functional Interfaces Research Group, Institute of Materials and Environmental Chemistry Research Centre for Natural Sciences, Bp. Hungary
- Doctoral School of Material Sciences and Technologies Óbuda University, Faculty of Light Industry and Environmental Engineering, Bp. Hungary
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33
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Limsakul P, Charupanit K, Moonla C, Jeerapan I. Advances in emergent biological recognition elements and bioelectronics for diagnosing COVID-19. EMERGENT MATERIALS 2021; 4:231-247. [PMID: 33718775 PMCID: PMC7937783 DOI: 10.1007/s42247-021-00175-9] [Citation(s) in RCA: 6] [Impact Index Per Article: 1.5] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Subscribe] [Scholar Register] [Received: 01/04/2021] [Accepted: 01/26/2021] [Indexed: 05/04/2023]
Abstract
Coronaviruses pose a serious threat to public health. Tremendous efforts are dedicated to advance reliable and effective detection of coronaviruses. Currently, the coronavirus disease 2019 (COVID-19) diagnosis mainly relies on the detection of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) genetic materials by using reverse transcription-polymerase chain reaction (RT-PCR) assay. However, simpler and more rapid and reliable alternatives are needed to meet high demand during the pandemic. Biosensor-based diagnosis approaches become alternatives for selectively and rapidly detecting virus particles because of their biorecognition elements consisting of biomaterials that are specific to virus biomarkers. Here, we summarize biorecognition materials, including antibodies and antibody-like molecules, that are designed to recognize SARS-CoV-2 biomarkers and the advances of recently developed biosensors for COVID-19 diagnosis. The design of biorecognition materials or layers is crucial to maximize biosensing performances, such as high selectivity and sensitivity of virus detection. Additionally, the recent representative achievements in developing bioelectronics for sensing coronavirus are included. This review includes scholarly articles, mainly published in 2020 and early 2021. In addition to capturing the fast development in the fields of applied materials and biodiagnosis, the outlook of this rapidly evolving technology is summarized. Early diagnosis of COVID-19 could help prevent the spread of this contagious disease and provide significant information to medical teams to treat patients.
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Affiliation(s)
- Praopim Limsakul
- Division of Physical Science, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla, 90112 Thailand
- Center of Excellence for Trace Analysis and Biosensor, Prince of Songkla University, Hat Yai, Songkhla, 90112 Thailand
| | - Krit Charupanit
- Department of Biomedical Sciences and Biomedical Engineering, Faculty of Medicine, Prince of Songkla University, Hat Yai, Songkhla, 90110 Thailand
| | - Chochanon Moonla
- School of Chemistry, Institute of Science, Suranaree University of Technology, 111, University Avenue, Nakhon Ratchasima, 30000 Thailand
| | - Itthipon Jeerapan
- Division of Physical Science, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla, 90112 Thailand
- Center of Excellence for Trace Analysis and Biosensor, Prince of Songkla University, Hat Yai, Songkhla, 90112 Thailand
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34
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Saini M, Ghosh S, Kumar V, Roy P, Sadhu KK. Selective Release of Doxorubicin from Cucurbit[8]uril Stabilized Gold Supra-Pyramid Host at pH of Small Intestine. Chemistry 2020; 26:15150-15158. [PMID: 32463129 DOI: 10.1002/chem.202002048] [Citation(s) in RCA: 2] [Impact Index Per Article: 0.4] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 04/27/2020] [Indexed: 12/14/2022]
Abstract
Gold supra-pyramid structures were obtained by the addition of acidic solution of cucurbit[8]uril (CB[8]) to an aqueous solution of citrate stabilized gold nanoparticles (AuNP). The reaction resulted in the precipitation of supra-pyramid from the solution after just 1 min of shaking. Microscopic images confirmed formation of the supra-pyramid. The stepwise structural transformation towards the supra-pyramid was examined with variable concentrations of CB[8] to AuNP solution. Anionic counter parts of these acids (Br- , NO3 - , SO4 2- and Cl- ) controlled the size of the synthesized supra-pyramids. These supra-pyramid hosts showed uptake of three anticancer drugs: oral drugs etoposide, prednisolone and intravenous drug doxorubicin. Releases of drugs from these hosts were emulated at acidic stomach pH, basic small intestinal pH and in the presence of human serum albumin (HSA). The specific release of doxorubicin was confirmed at small intestinal pH 7.4. Poor release of drugs in presence of CB[8] specific guest 1-adamantanamine confirmed the role of the supra-pyramid as the exclusive host. The release of doxorubicin from the supra-pyramid at pH 7.4 was confirmed by fluorescence microscopic imaging with prostate cancer DU-145 cell line.
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Affiliation(s)
- Meenaxi Saini
- Department of Chemistry, Indian Institution of Technology Roorkee, Roorkee, 247667, Uttarakhand, India
| | - Souvik Ghosh
- Department of Biotechnology, Indian Institution of Technology Roorkee, Roorkee, 247667, Uttarakhand, India
| | - Viney Kumar
- Department of Biotechnology, Indian Institution of Technology Roorkee, Roorkee, 247667, Uttarakhand, India
| | - Partha Roy
- Department of Biotechnology, Indian Institution of Technology Roorkee, Roorkee, 247667, Uttarakhand, India
| | - Kalyan K Sadhu
- Department of Chemistry, Indian Institution of Technology Roorkee, Roorkee, 247667, Uttarakhand, India
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35
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Xiong YL, Yu MY, Guo TT, Yang J, Ma JF. A Nanosized Propeller-like Polyoxometalate-linked Copper(I)-Resorcin[4]arene for Efficient Catalysis. Inorg Chem 2020; 59:15402-15409. [DOI: 10.1021/acs.inorgchem.0c02404] [Citation(s) in RCA: 12] [Impact Index Per Article: 2.4] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/17/2022]
Affiliation(s)
- Yan-Ling Xiong
- Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, China
| | - Ming-Yue Yu
- Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, China
| | - Ting-Ting Guo
- Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, China
| | - Jin Yang
- Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, China
| | - Jian-Fang Ma
- Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, China
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36
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Garnier L, Bonal C, Malfreyt P. Free‐energy calculations of the host–guest association in grafted supramolecular assemblies. J Comput Chem 2020. [DOI: 10.1002/jcc.26382] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/05/2022]
Affiliation(s)
- Ludovic Garnier
- Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont‐Ferrand Clermont‐Ferrand France
| | - Christine Bonal
- Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont‐Ferrand Clermont‐Ferrand France
| | - Patrice Malfreyt
- Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont‐Ferrand Clermont‐Ferrand France
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37
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Ashwin BCMA, Shanmugavelan P, Muthu Mareeswaran P. Electrochemical aspects of cyclodextrin, calixarene and cucurbituril inclusion complexes. J INCL PHENOM MACRO 2020. [DOI: 10.1007/s10847-020-01028-4] [Citation(s) in RCA: 2] [Impact Index Per Article: 0.4] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 01/17/2023]
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38
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Separation performance of p-nitro-octadecyloxy-calix[8]arene as stationary phases for capillary gas chromatography. Microchem J 2020. [DOI: 10.1016/j.microc.2020.105124] [Citation(s) in RCA: 8] [Impact Index Per Article: 1.6] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 01/13/2023]
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39
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Uttam B, Jahan I, Sen S, Rao CP. Coumarin-Calix[4]arene Conjugate-Anchored SiO 2 Nanoparticles as an Ultrasensor Material for Fe 3+ to Work in Water, in Serum, and in Biological Cells. ACS OMEGA 2020; 5:21288-21299. [PMID: 32875265 PMCID: PMC7450711 DOI: 10.1021/acsomega.0c03373] [Citation(s) in RCA: 3] [Impact Index Per Article: 0.6] [Reference Citation Analysis] [Abstract] [Track Full Text] [Subscribe] [Scholar Register] [Received: 07/14/2020] [Accepted: 07/28/2020] [Indexed: 05/05/2023]
Abstract
A coumarin-appended calixarene derivative ( CouC4A ) and a hybrid material generated by covalently linking this onto a silica surface ( CouC4A@SiO 2 ) were synthesized and were characterized by various analytical, spectroscopy, and microscopy methods. Both these materials are capable of sensing Fe3+ with greater sensitivity and selectivity. The sensitivity is enhanced by 30,000 fold on going from a simple solution phase to the silica surface with the limit of Fe3+ detection being 1.75 ± 0.4 pM when CouC4A@SiO 2 is used, and the sensing is partially reversible with phosphates, while it is completely reversible with adenosine 5'-triphosphate (ATP). While the calix precursor, CouC4A , has a limitation to work in water, anchoring this onto SiO2 endowed it with the benefit of its use in water as well as in buffer and thereby extends its application toward Fe3+ sensing even in the biorelevant medium such as fetal bovine serum and human serum. The hybrid material is biocompatible and shows ∼90% cell viability in the case of MDA-MB231 and 3T3 cell lines. CouC4A@SiO 2 functions as a reversible sensor for Fe3+ with the use of ATP in vitro as well as in biological cells. Thus, the inorganic-organic hybrid material, such as, CouC4A@SiO 2 , is an indispensable material for sensitive and selective detection of Fe3+ in a picomolar range in solution and in nanomolar to micromolar range in biorelevant fluids and biological cells, respectively.
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Affiliation(s)
- Bhawna Uttam
- Department
of Chemistry, Indian Institute of Technology
Bombay, Powai, Mumbai 400 076, India
| | - Iffat Jahan
- Department
of Biosciences & Bioengineering, Indian
Institute of Technology Bombay, Powai, Mumbai 400 076, India
| | - Shamik Sen
- Department
of Biosciences & Bioengineering, Indian
Institute of Technology Bombay, Powai, Mumbai 400 076, India
| | - Chebrolu Pulla Rao
- Department
of Chemistry, Indian Institute of Technology
Tirupati, Settipalli Post, Tirupati 517 506, Andhra Pradesh, India
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40
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Mutihac RC, Bunaciu AA, Buschmann HJ, Mutihac L. A brief overview on supramolecular analytical chemistry of cucurbit[n]urils and hemicucurbit[n]urils. J INCL PHENOM MACRO 2020. [DOI: 10.1007/s10847-020-01019-5] [Citation(s) in RCA: 1] [Impact Index Per Article: 0.2] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/26/2022]
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41
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Senthilkumaran M, Saravanan C, Ashwin BCMA, Shanmugavelan P, Muthu Mareeswaran P, Prakash M. Inclusion induced water solubility and binding investigation of acenaphthene-1,2-dione with p-sulfonatocalix[4]arene. J INCL PHENOM MACRO 2020. [DOI: 10.1007/s10847-020-01017-7] [Citation(s) in RCA: 1] [Impact Index Per Article: 0.2] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 10/22/2022]
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42
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Garnier L, Bonal C, Malfreyt P. Molecular Description of Grafted Supramolecular Assemblies on Gold Surfaces: Effect of Grafting Points and Chain Lengths. ACS OMEGA 2020; 5:16628-16634. [PMID: 32685829 PMCID: PMC7365550 DOI: 10.1021/acsomega.0c01453] [Citation(s) in RCA: 2] [Impact Index Per Article: 0.4] [Reference Citation Analysis] [Abstract] [Track Full Text] [Figures] [Subscribe] [Scholar Register] [Received: 03/31/2020] [Accepted: 06/23/2020] [Indexed: 06/11/2023]
Abstract
The association of 4 aminoazobenzene (4AA) with two different water-soluble hosts, β-cyclodextrins (β-CD) and calixarenesulfonates (CnS), was studied in heterogeneous conditions using molecular simulations. This situation is achieved by immobilization of macrocycles onto a gold Au(111) surface. Several factors that can influence the binding properties are investigated here through the chain length of alkylthiols spacer of the surface-immobilized host and the number of attachment points to the surface. A conformational change of β-CD as a function of the chain length is evidenced upon grafting on the gold surface, whereas CnS does not show any changes. It is then possible to tune the thermodynamic properties of β-CD by changing the grafted chain length and forming a larger hydrophobic region. The mechanisms of insertion of guests into the cavities are similar to those obtained in a homogeneous system. 4AA is included longitudinally in the β-CD cavity, and it interacts rather with the sulfonate groups of the CnS located at the outer edge of the cavity.
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Affiliation(s)
- Ludovic Garnier
- Université Clermont Auvergne,
CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, F63000 Clermont-Ferrand, France
| | - Christine Bonal
- Université Clermont Auvergne,
CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, F63000 Clermont-Ferrand, France
| | - Patrice Malfreyt
- Université Clermont Auvergne,
CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, F63000 Clermont-Ferrand, France
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43
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Macrocyclic Arenes Functionalized with BODIPY: Rising Stars among Chemosensors and Smart Materials. CHEMOSENSORS 2020. [DOI: 10.3390/chemosensors8030051] [Citation(s) in RCA: 8] [Impact Index Per Article: 1.6] [Reference Citation Analysis] [Abstract] [Track Full Text] [Subscribe] [Scholar Register] [Indexed: 12/11/2022]
Abstract
Macrocycles play a crucial role in supramolecular chemistry and the family of macrocyclic arenes represents one of the most important types of hosts. Among them, calixarenes, resorcinarenes and pillararenes are the most commonly encountered macrocyclic arenes, and they have received considerable attention. Boron-dipyrromethene (BODIPY) dyes are fascinating compounds with multiple functionalization sites and outstanding luminescence properties including high fluorescence quantum yields, large molar absorption coefficients and remarkable photo- and chemical stability. The combination of macrocyclic arenes and BODIPY dyes has been demonstrated to be an effective strategy to construct chemosensors for various guests and smart materials with tailored properties. Herein, we firstly summarize the recent advances made so far in macrocyclic arenes substituted with BODIPY. This review only focuses on the three macrocyclic arenes of calixarenes, resorcinarenes and pillararenes, as there are no other macrocyclic arenes substituted BODIPY units at the present time. Hopefully, this review will not only afford a guide and useful information for those who are interested in developing novel chemosensors and smart materials, but also inspire new opportunities in this field.
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44
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Shalaeva Y, Morozova JE, Gubaidullin A, Saifina A, Shumatbaeva A, Nizameev I, Kadirov M, Ovsyannikov A, Antipin I. Photocatalytic properties of supramolecular nanoassociates based on gold and platinum nanoparticles, capped by amphiphilic calix[4]resorcinarenes, towards organic dyes. Colloids Surf A Physicochem Eng Asp 2020. [DOI: 10.1016/j.colsurfa.2020.124700] [Citation(s) in RCA: 6] [Impact Index Per Article: 1.2] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 10/24/2022]
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45
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Colorimetric and electrochemical sensing of As(III) using calix[4]pyrrole capped gold nanoparticles and evaluation of its cytotoxic activity. J INCL PHENOM MACRO 2020. [DOI: 10.1007/s10847-020-01005-x] [Citation(s) in RCA: 3] [Impact Index Per Article: 0.6] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 02/06/2023]
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46
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Luo GG, Guo QL, Wang Z, Sun CF, Lin JQ, Sun D. New protective ligands for atomically precise silver nanoclusters. Dalton Trans 2020; 49:5406-5415. [PMID: 32243489 DOI: 10.1039/d0dt00477d] [Citation(s) in RCA: 29] [Impact Index Per Article: 5.8] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/14/2022]
Abstract
Atomically precise silver nanoclusters (NCs) have emerged as a hot topic attracting immense research interest. Protecting ligands are needed for direct capping on cluster surfaces in order to prevent aggregation and to stabilize NCs. It has been demonstrated that protective ligands are critical to determining the sizes, structures and properties of silver NCs. The past decades have witnessed conventionally used organic ligands (thiolates/selenols, phosphines and alkynyls) and inorganic ligands (chalcogens and halogens) being extensively used to passivate NC surfaces. However, only in the most recent years have new-type protecting ligands beyond the conventional ones begun to be introduced in the protecting sphere of new functional silver NCs. The present Frontier article covers the most recent examples of some new protective agents for well-defined silver NCs. We describe four classes of novel silver NCs stabilized by newly-developed surface ligands, namely, nitrogen-donor organic ligands, oxygen-donor inorganic ligands, metalloligands and macrocyclic hosts, paying attention to the synthesis, structures and properties of these silver NCs. This Frontier article will hopefully attract more cluster scientists to explore more freshly ligated atomically precise silver NCs with novel structures and properties in the years ahead. The literature survey in this review is based on publications up to February 2020. Some suggestions for future directions in this field are also given.
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Affiliation(s)
- Geng-Geng Luo
- Key Laboratory of Environmental Friendly Function Materials Ministry of Education, College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, P. R. China.
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47
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Wu L, Han C, Wang Z, Wu X, Su F, Li M, Zhang Q, Jing X. Porphyrin-Based Organoplatinum(II) Metallacycles With Enhanced Photooxidization Reactivity. Front Chem 2020; 8:262. [PMID: 32411659 PMCID: PMC7199493 DOI: 10.3389/fchem.2020.00262] [Citation(s) in RCA: 3] [Impact Index Per Article: 0.6] [Reference Citation Analysis] [Abstract] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 02/17/2020] [Accepted: 03/18/2020] [Indexed: 02/05/2023] Open
Abstract
In recent years, metal coordination macrocycles have obtained great interests due to the fact that they combined the rich host-guest properties of macro-cyclic hosts and the unique optical properties of the organic ligands. In this work, we constructed two porphyrin-based organoplatinum(II) metallacycles (MC1 and MC2) through coordination-driven self-assembly. 1H NMR, 31P NMR, and HRMS technologies were used to characterize the structures of MC1 and MC2. Interestingly, MC1 and MC2 can be used as catalysts for photooxidization under light irradiation with higher efficiency compared with the porphyrin ligand only. We hope that the coordination-driven self-assembly strategy can provide an efficient method to construct photo-active materials.
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Affiliation(s)
- Lintao Wu
- Department of Chemistry, Changzhi University, Changzhi, China
| | - Chun Han
- Department of Chemistry, Changzhi University, Changzhi, China
| | - Zhijun Wang
- Department of Chemistry, Changzhi University, Changzhi, China
| | - Xi Wu
- Department of Chemistry, Changzhi University, Changzhi, China
| | - Feng Su
- Department of Chemistry, Changzhi University, Changzhi, China
| | - Mengyao Li
- Department of Chemistry, Changzhi University, Changzhi, China
| | - Qingyang Zhang
- State Key Laboratory of Bioactive Substances and Function of Natural Medicine, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, China
- *Correspondence: Qingyang Zhang
| | - Xiaobi Jing
- School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, China
- Xiaobi Jing
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48
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Shah A. A Novel Electrochemical Nanosensor for the Simultaneous Sensing of Two Toxic Food Dyes. ACS OMEGA 2020; 5:6187-6193. [PMID: 32226903 PMCID: PMC7098044 DOI: 10.1021/acsomega.0c00354] [Citation(s) in RCA: 21] [Impact Index Per Article: 4.2] [Reference Citation Analysis] [Abstract] [Track Full Text] [Figures] [Subscribe] [Scholar Register] [Received: 01/24/2020] [Accepted: 03/04/2020] [Indexed: 06/10/2023]
Abstract
This work reports for the first time the preparation and performance of a nanosensor for the simultaneous detection of metanil yellow and fast green, which are toxic food dyes. For the development of this sensitive platform, the surface of a glassy carbon electrode (GCE) was modified with calixarene and gold nanoparticles. The sensing ability of the designed nanosensor (calix8/Au NPs/GCE) was tested by cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy. The influence of a number of parameters was investigated for optimizing the conditions to achieve the best response of the target analytes. Due to the synergistic activity of calix[8]arene and Au nanoparticles, the calix8/Au NPs/GCE nanocomposite was found to significantly enhance the signals of the selected food dyes in comparison to bare GCE. Under optimized conditions, limits of detection for metanil yellow and fast green were found to be 9.8 and 19.7 nM, respectively, at the calix8/Au NPs/GCE. The designed sensing platform also demonstrated figures of merit when applied for the sensing of food dyes in real water and juice samples. Moreover, high percent recovery, reproducibility, and stability suggested applicability of the designed electrochemical platform for real sample analysis.
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Affiliation(s)
- Afzal Shah
- Department
of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan
- Department
of Chemistry, College of Science, University
of Bahrain, Sakhir, P.O Box 32038, The Kingdom of Bahrain
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49
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Jiang P, Li Y, Ju T, Cheng W, Xu J, Han K. Ultrasensitive Detection of Hepatitis C Virus DNA Subtypes Based on Cucurbituril and Graphene Oxide Nano-composite. Chem Res Chin Univ 2020. [DOI: 10.1007/s40242-020-9111-8] [Citation(s) in RCA: 6] [Impact Index Per Article: 1.2] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/30/2022]
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50
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Guo H, Zhang R, Han Y, Wang J, Yan C. A p-tert-Tutyldihomooxacalix[4]arene Based Soft Gel for Sustained Drug Release in Water. Front Chem 2020; 8:33. [PMID: 32181237 PMCID: PMC7059609 DOI: 10.3389/fchem.2020.00033] [Citation(s) in RCA: 3] [Impact Index Per Article: 0.6] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 11/19/2019] [Accepted: 01/09/2020] [Indexed: 12/15/2022] Open
Abstract
P-tert-butyldihomooxacalix[4]arene is a well-known calix[4]arene analog in which one CH2 bridge is replaced by one -O- group. Thus, dihomooxacalix[4]arene has a slightly larger cavity than that of calix[4]arene and usually possesses a more flexible cone conformation, and the bridged oxygen atom might provide additional binding sites. Here, we synthesized a new functional p-tert-butyldihomooxacalix[4]arene 1 through Ugi reaction with good yield (70%), starting from condensed p-tert-butyldihomooxacalix[4]arene O-alkoxy-substituted benzaldehydes, benzoic acid, benzylamine, and cyclohexyl isocyanide. Proton nuclear magnetic resonance spectroscopy (1H NMR), 13C NMR, IR, and diffusion-ordered 1H NMR spectroscopy (DOSY) methods were used to characterize the structure of 1. Then soft gel was prepared by adding 1 into cyclohexane directly. It shows remarkable thermoreversibility and can be demonstrated for several cycles. As is revealed by scanning electron microscopy (SEM) images, xerogel showed highly interconnected and homogeneous porous network structures, and hence, the gel is suitable for storage and controlled release.
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Affiliation(s)
- Hao Guo
- School of Chemistry and Chemical Engineer, Yangzhou University, Yangzhou, China.,School of Chemistry and Chemical Engineer, Nantong University, Nantong, China
| | - Runmiao Zhang
- School of Chemistry and Chemical Engineer, Yangzhou University, Yangzhou, China.,School of Chemistry and Chemical Engineer, Nantong University, Nantong, China
| | - Ying Han
- School of Chemistry and Chemical Engineer, Yangzhou University, Yangzhou, China
| | - Jin Wang
- School of Chemistry and Chemical Engineer, Nantong University, Nantong, China
| | - Chaoguo Yan
- School of Chemistry and Chemical Engineer, Yangzhou University, Yangzhou, China
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