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Exploring the enantiorecognition mechanism of Cinchona alkaloid‐based zwitterionic chiral stationary phases and the basic trans‐paroxetine enantiomers

Sardella, Roccaldo, Macchiarulo, Antonio, Urbinati, Fabrizio, Ianni, Federica, Carotti, Andrea, Kohout, Michal, Lindner, Wolfgang, Péter, Antal, Ilisz, István
Journal of separation science 2018 v.41 no.6 pp. 1199-1207
Cinchona, enantiomers, energy, markets, moieties, quinidine, quinine, zwitterions
The enantiomers of trans‐paroxetine (the selectand) were separated on four chiral stationary phases incorporating either quinine [ZWIX(+), ZWIX(+A)] or quinidine [ZWIX(–), ZWIX(–A)] and (R,R)‐aminocyclohexanesulfonic acid [in ZWIX(–), and ZWIX(+A)] or (S,S)‐aminocyclohexanesulfonic acid [in ZWIX(+), and ZWIX(–A)] chiral selectors. The zwitterion nature of the phases is due to the presence of either (R,R)‐ or (S,S)‐aminocyclohexanesulfonic acid in the selector structure bearing the quinuclidine moiety. ZWIX(+) and ZWIX(–) phases are available on the market with the commercial names CHIRALPAK ZWIX(+) and CHIRALPAK ZWIX(–), respectively. With the aim of rationalizing the enantiomer elution order with the above chiral stationary phases, a molecular dynamic protocol was applied and two energetic parameters were initially measured: selectand conformational energy and selectand interaction energy. In the search for other descriptors allowing a better fitting with the experimental evidences, in the present work we consider an energetic parameter, defined as the selector conformational energy, which resulted to be relevant in the explanation of the experimental elution order in most of the cases. Very importantly, the computational data produced by the present study strongly support the outstanding role of the conformational energy of the chiral selector as it interacts with the analytes.