Text Box: CHIRAL SEPARATIONS Chiral Dynamic Chromatography Pushed to Its Extreme Low Temperature or High Speed Limits (Chiral DUHPLC): A Very Effective Tool in the Study of Stereolabile Compounds FRANCESCO GASPARRINI, ILARIA D’ACQUARICA, MARCO PIERINI, AND CLAUDIO VILLANI DIPARTIMENTO DI CHIMICA E TECNOLOGIE DEL FARMACO, SAPIENZA UNIVERSITÀ DI ROMA, ROMA (ITALY) Introduction The wide variety of chromatographic techniques developed and improved over the past three decades (Ward & Ward, 2010) allows analysts nowadays to address and resolve most problems related to the separation of molecular or ionic species, under both preparative and analytical conditions. Unusual and interesting examples of preparative separations have been performed for synthetic products, bioactive molecules extracted from biological sources and for racemates of chiral drugs. Typical analytical separations have been applied for the quantification of compounds in complex mixtures, the determination of enantiomeric excess of scalemic mixtures, and the identification of organic compounds by hyphenated chromatographic techniques (Wilkins, 1983; Holt et al., 1997; Ellis & Roberts, 1997; Guetens et al., 2002a; Guetens et al., 2002b). A peculiar and elegant application of chromatography has also been devoted to supramolecular chemistry where it allows calculating the thermodynamic stability of supramolecular adducts and the association constants of hostguest complexes. Moreover, chromatography has been recently used for the study of internal molecular dynamics of a range of stereochemically labile organic compounds and for the determination of kinetic parameters of the pertinent equilibrium (i.e., the reversible isomerization of one enantiomer into the other) (D’Acquarica et al., 2006). In this context, the implementation of highly efficient chromatographic techniques pushed to their extreme limits may represent a very effective tool to achieve thermodynamic and kinetic data (Krupcik et al., 2003; Katsanos et al., 1998; Wolf, 2005a; Wolf, 2008), when experimental conditions make the use of alternative methods difficult or impossible, such as dynamic nuclear magnetic resonance (DNMR) spectroscopy and batch-wise classical approaches.

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