Sa. Kuzdzal et al., A STUDY OF DENDRIMER-SOLUTE INTERACTIONS VIA ELECTROKINETIC CHROMATOGRAPHY, Journal of the American Chemical Society, 119(9), 1997, pp. 2255-2261
Polyacid cascade dendrimers (generations 1-4) are used as a pseudostat
ionary phase for electrokinetic capillary chromatography to separate m
ixtures of neutral species. Separation of a homologous series of molec
ules allow the capacity factors and distribution coefficients to be ca
lculated, which in turn allow the standard enthalpy, entropy, and Gibb
s free energy for solubilization to be evaluated by van't Hoff analysi
s. Comparison of these values to analogous values measured for sodium
dodecyl sulfate (SDS) micelles suggests fundamental differences in the
thermodynamic quantities associated with solubilization. As the size
of the polyacid dendrimer increases, entropy becomes the driving force
for solubilization, and enthalpy is disfavored. Gibb's free energy va
lues are negative for: all of the dendrimer/analyte interactions inves
tigated. The capacity factor is found to increase linearly with increa
sing concentrations of dendrimer. Thermodynamic parameters are evaluat
ed for several small molecules to show that the technique is not limit
ed to molecules that are part of a homologous series.