Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces
Autor: | V. V. Syakaev, Olga Babaeva, S. E. Solovieva, Igor S. Antipin, Ayrat Yakupov, Ekaterina Trushina, Sergey A. Katsyuba, Guliya Nizameeva, Tatiana P. Gerasimova, R. I. Nugmanov, A. A. Murav’ev, Sofiya L. Selektor |
---|---|
Jazyk: | angličtina |
Rok vydání: | 2021 |
Předmět: |
Magnetic Resonance Spectroscopy
Alkylation Molecular Conformation 01 natural sciences lcsh:Chemistry Coordination Complexes Crown Ethers Calixarene lcsh:QH301-705.5 Spectroscopy Langmuir monolayers Chemistry Air General Medicine Computer Science Applications Metals visual_art visual_art.visual_art_medium Selectivity surface potential Absorption spectroscopy Metal ions in aqueous solution Liquid-Liquid Extraction liquid-phase extraction Sulfides thiacalix[4]arene monocrowns 010402 general chemistry Catalysis Article Ion Inorganic Chemistry Metal Ion binding Phenols stomatognathic system UV/visible reflection–absorption spectroscopy Physical and Theoretical Chemistry Molecular Biology Ions 010405 organic chemistry Organic Chemistry Water Dynamic Light Scattering 0104 chemical sciences Crystallography ion binding lcsh:Biology (General) lcsh:QD1-999 Solvents Calcium Spectrophotometry Ultraviolet |
Zdroj: | International Journal of Molecular Sciences Volume 22 Issue 7 International Journal of Molecular Sciences, Vol 22, Iss 3535, p 3535 (2021) |
ISSN: | 1422-0067 1661-6596 |
DOI: | 10.3390/ijms22073535 |
Popis: | 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. |
Databáze: | OpenAIRE |
Externí odkaz: |