Gm. Janini et al., EFFECT OF ORGANIC-SOLVENTS ON SOLUTE MIGRATION AND SEPARATION IN CAPILLARY ZONE ELECTROPHORESIS, Chromatographia, 35(9-12), 1993, pp. 497-502
The effect of organic modifiers on mobility and selectivity in capilla
ry zone electrophoresis was investigated. Test solutes having differen
t functionalities were electropherographed at acidic and neutral pH wi
th aqueousorganic buffers. The results show that the electroosmotic mo
bility is mainly influenced by buffer viscosity. The role of the diele
ctric constant, zeta-potential and modifier-capillary wall interaction
s, which may be significant at trace levels of organic modifier, is ve
ry much diminished as the organic content is increased. Buffers having
equivalent viscosities generate similar electroosmotic mobilities irr
espective of the type and percentage of the organic modifier. Solute e
lectrophoretic mobility is affected similarly because of the identical
nature of the forces responsible for the electroosmotic and electroph
oretic flow phenomena. However, solute electrophoretic mobility is als
o influenced by the degree to which the organic modifier affects the e
quilibrium that generates the electrophoretically-active solute ions.
As a consequence, the order of elution of some solutes may change with
increasing buffer organic content. The separation of weakly-hydrophil
ic solutes is improved with increasing organic proportions. The separa
tion of dipeptides first improved with the addition of up to 15 % ACN,
then deteriorated with further increase of ACN proportion. An example
showing change in migration order and peak cross-over is presented an
d discussed.