| Title: |
Unravelling dispersion forces in liquid-phase enantioseparation. Part I: Impact of ferrocenyl versus phenyl groups |
| Authors: |
Sechi, Barbara; Dessì, Alessandro; Dallocchio, Roberto; Tsetskhladze, Nutsa; Chankvetadze, Bezhan; Pérez-Baeza, Mireia; Cossu, Sergio; Jibuti, Giorgi; Mamane, Victor; Peluso, Paola |
| Contributors: |
Sechi, Barbara; Dessì, Alessandro; Dallocchio, Roberto; Tsetskhladze, Nutsa; Chankvetadze, Bezhan; Pérez-Baeza, Mireia; Cossu, Sergio; Jibuti, Giorgi; Mamane, Victor; Peluso, Paola |
| Publication Year: |
2023 |
| Collection: |
Università Ca’ Foscari Venezia: ARCA (Archivio Istituzionale della Ricerca) |
| Subject Terms: |
Enantioseparation; Ferrocene; Molecular modeling; Noncovalent interaction; Polysaccharide-based chiral stationary phases; Settore CHEM-01/A - Chimica analitica |
| Description: |
Background: Highly ordered chiral secondary structures as well as multiple (tunable) recognition sites are the keys to success of polysaccharide carbamate-based chiral selectors in enantioseparation science. Hydrogen bonds (HBs), dipole-dipole, and & pi;-& pi; interactions are classically considered the most frequent noncovalent interactions underlying enantioselective recognition with these chiral selectors. Very recently, halogen, chalcogen and & pi;-hole bonds were also identified as interactions working in polysaccharide carbamate-based selectors to promote enantiomer distinction. On the contrary, the function of dispersion interactions in this field was not explored so far.Results: The enantioseparation of chiral ferrocenes featuring chiral axis or chiral plane as stereogenic elements was performed by comparing five polysaccharide carbamate-based chiral columns, with the aim to identify enantioseparation outcomes that could be reasonably determined by dispersion forces, making available a reliable experimental data set for future theoretical studies to confirm the heuristic hypothesis. The effects of mobile phase polarity and temperature on the enantioseparation were considered, and potential recognition sites on analytes and selectors were evaluated by electrostatic potential (V) analysis and molecular dynamics (MD). In this first part, the enantioseparation of 3,3 & PRIME;-dibromo-5,5 & PRIME;-bis-ferrocenylethynyl-4,4 & PRIME;-bipyridine bearing two ferrocenylethynyl units linked to an axially chiral core was performed and compared to that of the analyte featuring the same structural motif with two phenyl groups in place of the ferrocenyl moieties. The results of this study showed the superiority of the ferrocenyl compared to the phenyl group, as a structural element favouring enantiodifferentiation.Significance and novelty: Even if dispersion (London) forces have been envisaged acting in liquid-phase enantioseparations, focused studies to explore possible contributions of ... |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| Relation: |
info:eu-repo/semantics/altIdentifier/pmid/37709466; info:eu-repo/semantics/altIdentifier/wos/WOS:001065033100001; volume:1278; lastpage:341725; numberofpages:12; journal:ANALYTICA CHIMICA ACTA; https://hdl.handle.net/10278/5082428 |
| DOI: |
10.1016/j.aca.2023.341725 |
| Availability: |
https://hdl.handle.net/10278/5082428; https://doi.org/10.1016/j.aca.2023.341725 |
| Rights: |
info:eu-repo/semantics/openAccess |
| Accession Number: |
edsbas.7CE11E9 |
| Database: |
BASE |