Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces
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...
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2021-03-01
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| Series: | International Journal of Molecular Sciences |
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| author | Anton Muravev Ayrat Yakupov Tatiana Gerasimova Ramil Nugmanov Ekaterina Trushina Olga Babaeva Guliya Nizameeva Viktor Syakaev Sergey Katsyuba Sofiya Selektor Svetlana Solovieva Igor Antipin |
| author_facet | Anton Muravev Ayrat Yakupov Tatiana Gerasimova Ramil Nugmanov Ekaterina Trushina Olga Babaeva Guliya Nizameeva Viktor Syakaev Sergey Katsyuba Sofiya Selektor Svetlana Solovieva Igor Antipin |
| author_sort | Anton Muravev |
| collection | DOAJ |
| description | 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<sup>+</sup> 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 Sr<sup>2+</sup> (crown-4), K<sup>+</sup> (crown-5), and Ag<sup>+</sup> (crown-6) in type-I receptors and Na<sup>+</sup> (crown-4), Ca<sup>2+</sup> (crown-5), and Cs<sup>+</sup> (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. |
| first_indexed | 2024-03-10T12:48:44Z |
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| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-10T12:48:44Z |
| publishDate | 2021-03-01 |
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| series | International Journal of Molecular Sciences |
| spelling | doaj.art-cfff4123785441128027ab78bca848162023-11-21T13:17:16ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672021-03-01227353510.3390/ijms22073535Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined InterfacesAnton Muravev0Ayrat Yakupov1Tatiana Gerasimova2Ramil Nugmanov3Ekaterina Trushina4Olga Babaeva5Guliya Nizameeva6Viktor Syakaev7Sergey Katsyuba8Sofiya Selektor9Svetlana Solovieva10Igor Antipin11FRC Kazan Scientific Center, Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan, RussiaButlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya Str. 18, 420008 Kazan, RussiaFRC Kazan Scientific Center, Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan, RussiaButlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya Str. 18, 420008 Kazan, RussiaSchool of Chemistry, University of Glasgow, University Avenue, Glasgow G12 8QQ, UKFRC Kazan Scientific Center, Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan, RussiaDepartment of Physics, Kazan National Research Technological University, Karl Marx Str. 68, 420015 Kazan, RussiaFRC Kazan Scientific Center, Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan, RussiaFRC Kazan Scientific Center, Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan, RussiaFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr. 31, 119071 Moscow, RussiaButlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya Str. 18, 420008 Kazan, RussiaButlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya Str. 18, 420008 Kazan, RussiaUnderstanding 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<sup>+</sup> 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 Sr<sup>2+</sup> (crown-4), K<sup>+</sup> (crown-5), and Ag<sup>+</sup> (crown-6) in type-I receptors and Na<sup>+</sup> (crown-4), Ca<sup>2+</sup> (crown-5), and Cs<sup>+</sup> (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.https://www.mdpi.com/1422-0067/22/7/3535thiacalix[4]arene monocrownsLangmuir monolayersliquid-phase extractionion bindingsurface potentialUV/visible reflection–absorption spectroscopy |
| spellingShingle | Anton Muravev Ayrat Yakupov Tatiana Gerasimova Ramil Nugmanov Ekaterina Trushina Olga Babaeva Guliya Nizameeva Viktor Syakaev Sergey Katsyuba Sofiya Selektor Svetlana Solovieva Igor Antipin Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces International Journal of Molecular Sciences thiacalix[4]arene monocrowns Langmuir monolayers liquid-phase extraction ion binding surface potential UV/visible reflection–absorption spectroscopy |
| title | Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces |
| title_full | Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces |
| title_fullStr | Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces |
| title_full_unstemmed | Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces |
| title_short | Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces |
| title_sort | switching ion binding selectivity of thiacalix 4 arene monocrowns at liquid liquid and 2d confined interfaces |
| topic | thiacalix[4]arene monocrowns Langmuir monolayers liquid-phase extraction ion binding surface potential UV/visible reflection–absorption spectroscopy |
| url | https://www.mdpi.com/1422-0067/22/7/3535 |
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