Enantiomer recognition solution effects

Enantiomeric recognition was clearly displayed in films spread from solution and films in equilibrium with their crystals, and was sharply dependent on the acidity of the subphase. Protonation of the amide group appeared to be necessary for spreading to stable monolayers. For example, the crystals of the racemate deposited on a 10n H2S04 solution at 25°C spread quickly to yield a film with an ESP of 7.7 dyn cm"1, while the single enantiomers spread only to a surface pressure of 3.9 dyn cm-1 (Table 1). Similar effects are observed at 15 and 35°C. The effect of stereochemistry on equilibrium spreading is even more pronounced at lower subphase acidities. On 6n sulfuric acid, the racemate spread to an equilibrium surface pressure of 4.9 dyn cm-1, while the enantiomeric systems spread to less than 1 dyn cm-1. 

Affinity liquid chromatography and chiral separations (enantiomer separations) require similar analyte properties. The solutes may have interactions through hydrogen-bonding, ligand formation, or Coulombic forces with the surface of stationary phase materials or the sites of additives however, the selectivity is controlled by the steric effects of the structures of the analyte molecules and the recognition molecules (chiral selectors). 

Enantiomeric resolution of solutes that fit within the molecular cavity, which is chiral, results in the formation of an inclusion complex (Ref. 169 and Fig. 4). In general, the enantiomers are separated on the basis of formation constants of the host-guest complexes. The enantiomer that forms the more stable complex has a greater migration time because of this effect. The chiral recognition mechanism for cyclodextrin enantioseparation has been discussed in several works (163-168). 

The critical point In the preceding Utopian prediction Is whether or not chiral coluonns can be devised which will Indeed efficiently and predictably separate the enantiomers of a wide array of solutes. Work conducted In our laboratory In Urbana leads us to believe that such Broad Spectrum CSP s are clearly possible, that their chiral recognition mechanisms can be discerned, and that an understanding of these mechanisms can be used for the rational design of still more effective CSP s (5-10). To support this belief, let us describe a simply prepared chiral chromatography column capable of separating the enantiomers of thousands of compounds of diverse functional types. 

When an enantiomer of CSA is used in the polymerization, such as R-CSA, it is possible to create chiral polyaniline nanofibers. Figure 7.20 shows the circular dichroism (CD) spectrum of a water dispersion of as-prepared R-CSA doped polyaniline nanofibers. The positive peak at 450 nm is characteristic of chiral polyaniline [66-70], and is consistent with water s effect on the direction of the CD signals previously observed [71]. The peak at 290 nm is due to excess R-CSA in the dispersion. Recently, Wang et al. discovered that highly chiral polyaniline nanofibers can be produced by incremental addition of the oxidant, ammonium peroxydisulfate, into aniline solution with aniline oligomers and concentrated chiral dopants (>5 M R- or S-CSA) [72]. Chiral polyaniline nanofibers are very interesting for chiral recognition studies [68]. 

---