A new ''push/pull'' model has been developed to explain synergistic ef
fects observed in a system in which a chiral stationary phase (CSP) is
used in combination with its homologous chiral mobile phase additive
(CMPA). The model predicts the beneficial CMPA enantiomer and the coun
terproductive CMPA enantiomer a priori. Thus, an (R)-CSP will obtain p
ositive synergism from a homologous (S)-CMPA and negative synergism fr
om a homologous (R)-CMPA. The reverse is true for an (S)-CSP. The impo
rtance of structural homology between the CSP and the CMPA is demonstr
ated. Furthermore, the analysis time is decreased relative to the use
of a CSP alone, because the retention time of the analyte peaks decrea
ses when the CMPAs are used. (C) 1993 Wiley-Liss, Inc.