Silylated-Acetylated Cyclodextrins as Chiral Sensors for the Enantiodiscrimination of Fluorinated Anesthetics
Silylated-acetylated cyclodextrin (CD) derivatives have recently been investigated, via nuclear magnetic resonance (NMR) spectroscopy, as chiral sensors for substrates that are endowed and devoid of fluorine atoms, and the importance of Si-F interaction in the discrimination phenomena has been asses...
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| Format: | Article |
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MDPI AG
2023-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/6/2804 |
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| author | Alessandra Recchimurzo Federica Balzano Gloria Uccello Barretta Luca Gherardi Milo Malanga Federica Aiello |
| author_facet | Alessandra Recchimurzo Federica Balzano Gloria Uccello Barretta Luca Gherardi Milo Malanga Federica Aiello |
| author_sort | Alessandra Recchimurzo |
| collection | DOAJ |
| description | Silylated-acetylated cyclodextrin (CD) derivatives have recently been investigated, via nuclear magnetic resonance (NMR) spectroscopy, as chiral sensors for substrates that are endowed and devoid of fluorine atoms, and the importance of Si-F interaction in the discrimination phenomena has been assessed. Here, the contributions of both superficial interactions and inclusion processes were further evaluated by extending the records to other chiral fluorinated substrates of interest for pharmaceutical applications. Non-equivalences were measured for both the <sup>1</sup>H and <sup>19</sup>F resonances in equimolar mixtures with the CDs; the promising results also supported the use of chiral sensors in <i>sub</i>-stoichiometric amounts. Finally, the occurrence of inclusion processes was evaluated by analyzing the intermolecular dipolar interactions by means of ROESY (Rotating-frame Overhauser Enhancement Spectroscopy) experiments. The study confirmed that the γCD derivative is the best chiral solvating agent for the fluorinated substrates investigated, likely due to the higher number of silyl moieties that can be involved in Si-F interactions. The contribution of inclusion processes to the enantiodiscrimination was also confirmed by comparison with the α- and β-analogues. Overall, the CD derivatives proved to be able to discriminate fluorinated substrates even when used in <i>sub</i>-stoichiometric amounts. |
| first_indexed | 2024-03-11T06:07:40Z |
| format | Article |
| id | doaj.art-b2805fd48492483390e107dcbd506b15 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T06:07:40Z |
| publishDate | 2023-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-b2805fd48492483390e107dcbd506b152023-11-17T12:55:25ZengMDPI AGMolecules1420-30492023-03-01286280410.3390/molecules28062804Silylated-Acetylated Cyclodextrins as Chiral Sensors for the Enantiodiscrimination of Fluorinated AnestheticsAlessandra Recchimurzo0Federica Balzano1Gloria Uccello Barretta2Luca Gherardi3Milo Malanga4Federica Aiello5Department of Chemistry and Industrial Chemistry, University of Pisa, via G. Moruzzi 13, 56124 Pisa, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, via G. Moruzzi 13, 56124 Pisa, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, via G. Moruzzi 13, 56124 Pisa, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, via G. Moruzzi 13, 56124 Pisa, ItalyCycloLab, Cyclodextrin R&D Ltd., Illatos út. 7, H-1097 Budapest, HungaryNational Research Council, Institute for Chemical and Physical Processes (CNR-IPCF), via G. Moruzzi 1, 56124 Pisa, ItalySilylated-acetylated cyclodextrin (CD) derivatives have recently been investigated, via nuclear magnetic resonance (NMR) spectroscopy, as chiral sensors for substrates that are endowed and devoid of fluorine atoms, and the importance of Si-F interaction in the discrimination phenomena has been assessed. Here, the contributions of both superficial interactions and inclusion processes were further evaluated by extending the records to other chiral fluorinated substrates of interest for pharmaceutical applications. Non-equivalences were measured for both the <sup>1</sup>H and <sup>19</sup>F resonances in equimolar mixtures with the CDs; the promising results also supported the use of chiral sensors in <i>sub</i>-stoichiometric amounts. Finally, the occurrence of inclusion processes was evaluated by analyzing the intermolecular dipolar interactions by means of ROESY (Rotating-frame Overhauser Enhancement Spectroscopy) experiments. The study confirmed that the γCD derivative is the best chiral solvating agent for the fluorinated substrates investigated, likely due to the higher number of silyl moieties that can be involved in Si-F interactions. The contribution of inclusion processes to the enantiodiscrimination was also confirmed by comparison with the α- and β-analogues. Overall, the CD derivatives proved to be able to discriminate fluorinated substrates even when used in <i>sub</i>-stoichiometric amounts.https://www.mdpi.com/1420-3049/28/6/2804NMRchiral solvating agentsROESYisofluranedesfluranehalothane |
| spellingShingle | Alessandra Recchimurzo Federica Balzano Gloria Uccello Barretta Luca Gherardi Milo Malanga Federica Aiello Silylated-Acetylated Cyclodextrins as Chiral Sensors for the Enantiodiscrimination of Fluorinated Anesthetics Molecules NMR chiral solvating agents ROESY isoflurane desflurane halothane |
| title | Silylated-Acetylated Cyclodextrins as Chiral Sensors for the Enantiodiscrimination of Fluorinated Anesthetics |
| title_full | Silylated-Acetylated Cyclodextrins as Chiral Sensors for the Enantiodiscrimination of Fluorinated Anesthetics |
| title_fullStr | Silylated-Acetylated Cyclodextrins as Chiral Sensors for the Enantiodiscrimination of Fluorinated Anesthetics |
| title_full_unstemmed | Silylated-Acetylated Cyclodextrins as Chiral Sensors for the Enantiodiscrimination of Fluorinated Anesthetics |
| title_short | Silylated-Acetylated Cyclodextrins as Chiral Sensors for the Enantiodiscrimination of Fluorinated Anesthetics |
| title_sort | silylated acetylated cyclodextrins as chiral sensors for the enantiodiscrimination of fluorinated anesthetics |
| topic | NMR chiral solvating agents ROESY isoflurane desflurane halothane |
| url | https://www.mdpi.com/1420-3049/28/6/2804 |
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