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The principal importance of stereochemistry is in its significant influence upon biological activity. Racemic mixtures may introduce some biological side effects caused by the optical antipode in addition to the desired activity. Enantiomeric molecules arise when molecular substitutions in a molecule exhibit a different spatial orientation. The existence of enantiomers in nature is based upon the presence of an asymmetric carbon atom. Chirality can be classified with the help of different categories of isomers. In optimizing enantiomeric separations, most attention is directed to the choice of an appropriate chiral selector. Generally, this is the case in all enantiomeric separations, since there are no universally applicable chiral selectors available. Aside from the purely micellar systems for enantiomeric separations, cyclodextrins and crown ethers are the primary chiral selectors in CE.