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Unravelling dispersion forces in liquid-phase enantioseparation. Part III: Interplay between dispersion, repulsion, and hydrophobic forces in the enantioseparation of planar chiral 3-substituted-1-iodoethynylferrocenes

Title: Unravelling dispersion forces in liquid-phase enantioseparation. Part III: Interplay between dispersion, repulsion, and hydrophobic forces in the enantioseparation of planar chiral 3-substituted-1-iodoethynylferrocenes
Authors: Sechi, Barbara; Dessì, Alessandro; Dallocchio, Roberto; Jorbenadze, Saba; Tchanturia, Natia; Chankvetadze, Bezhan; Cossu, Sergio; Matarashvili, Iza; Mamane, Victor; Peluso, Paola
Contributors: Istituto di chimica biomolecolare Padova, Italy (ICB); National Research Council of Italy; University of Venice Ca’ Foscari = Université de Venise Ca’ Foscari = Università Ca’ Foscari di Venezia; Institut de Chimie de Strasbourg (IC); Université de Strasbourg (UNISTRA)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS); ANR-21-CE07-0014,ASYMHOLE,Catalyse Asymétrique Induites par des Trous Sigma(2021)
Source: ISSN: 0003-2670 ; Analytica Chimica Acta ; https://hal.science/hal-05354500 ; Analytica Chimica Acta, 2025, 1382, pp.344853. ⟨10.1016/j.aca.2025.344853⟩.
Publisher Information: CCSD; Elsevier Masson
Publication Year: 2025
Subject Terms: Enantioseparation; High-performance liquid chromatography; Planar chiral ferrocenes; Noncovalent interactions; Polysaccharide-based chiral stationary phases; Enantioseparation High-performance liquid chromatography Planar chiral ferrocenes Noncovalent interactions Polysaccharide-based chiral stationary phases; Enantioseparation High-performance liquid chromatography Planar chiral ferrocenes Noncovalent interactions Polysaccharide; [CHIM]Chemical Sciences
Description: International audience ; Background -The detection of dispersion forces in enantioselective liquid chromatography (LC) is rather challenging because selectand, selector and mobile phase molecules may participate in multiple types of intra-and intermolecular noncovalent interactions of different strength. In this frame, the LC system can be used as a tool to evaluate the impact of changing the structures of selectand, chiral selector and separation medium, through fast analytical screenings. In the last few years, we studied the enantioseparations of chiral compounds containing the ethynylferrocene moiety as a test probe to identify dispersion forces in LC by using amylose carbamate-based CSPs. Results -The results of the study have been reported in a series of three papers. In Part II, we confirmed that the high affinity observed for the second eluted (Rp)-enantiomer of the 1-(iodoethynyl)-3phenylferrocene toward amylose phenylcarbamate-based selectors could be reasonably based on dispersion forces. In the present Part III of the series, we focus on the impact of changing the 3-aryl substituent of 1-(iodoethynyl)-3-arylferrocenes on the enantioseparation, considering the 1-(iodoethynyl)-3-phenylferrocene as reference for comparison. On this basis, the enantioseparations of seven planar chiral ferrocenes were performed and compared by using amylose-based CSPs. n-Hexane-based mixtures, polar organic solvents and aqueous organic mixtures were used with the aim of evaluate the impact of mobile phases of different polarity on the enantioseparations. The results of the chromatographic analyses confirmed the high and unique affinity of the second eluted (Rp)-enantiomer of the 1-(iodoethynyl)-3-(4t-butyl)phenylferrocene toward the amylose-based CSPs. Significance -By using 1-(iodoethynyl)-3-arylferrocenes as test probes, this study confirmed that dispersion forces may turn steric repulsion into attraction with a strength depending on the structure of the 3-aryl group and on mobile phase polarizability. Furthermore, the ...
Document Type: article in journal/newspaper
Language: English
DOI: 10.1016/j.aca.2025.344853
Availability: https://hal.science/hal-05354500; https://hal.science/hal-05354500v1/document; https://hal.science/hal-05354500v1/file/Anal%20Chim%20Acta.pdf; https://doi.org/10.1016/j.aca.2025.344853
Rights: https://creativecommons.org/licenses/by/4.0/ ; info:eu-repo/semantics/OpenAccess
Accession Number: edsbas.FC8BD18F
Database: BASE