Influence of (hydroxy)alkylamino substituents on enantioseparation ability of single-isomer amino-beta-cyclodextrin derivatives in chiral capillary electrophoresis.
A family of single-isomer amino-beta-cyclodextrin (amino-beta-CD) derivatives containing an amino or (hydroxy)alkylamino group in one of the primary positions has been synthesized. The steric effect and hydrogen bond forming ability of the different substituents on enantioseparation of acidic enantiomers has been studied by capillary electrophoresis (CE). Three enantiomeric model compounds (mandelic acid, cis-permethrinic acid, and cis-deltamethrinic acid) having significantly different apparent complex stability constants with beta-CD were applied in the experiments. Dependence of separation selectivity, resolution as well as mobility difference on chiral selector concentration (0.1-20 mM, pH 6.0) was investigated. Each amino-beta-CD showed higher enantioselectivity than the native beta-CD. One hydroxyalkyl group attached to the primary amino N-atom significantly increased both the enantioselectivity and the resolution compared to the primary amino-beta-CD, while two hydroxyalkyl moieties decreased them due to the predominance of steric hindrance. The value of the apparent complex stability constants obtained suited well the mobility difference model (by Wren). On the other hand, the optimum selector concentrations calculated according to the model were slightly lower than the experienced concentrations giving the maximum enantioresolution of enantiomers.
Iványi
Róbert
R
Cyclolab Cyclodextrin R & D. Laboratory Ltd., Budapest, Hungary. ivanyi@cyclolab.hu
Jicsinszky
László
L
Juvancz
Zoltán
Z
Roos
Natascha
N
Otta
Klára
K
Szejtli
József
J
D019075:Electrophoresis, Capillary / Q000379:methods*; D006860:Hydrogen Bonding; D008333:Mandelic Acids / Q000737:chemistry / Q000302:isolation & purification; D026023:Permethrin / Q000031:analogs & derivatives / Q000737:chemistry / Q000302:isolation & purification; D011722:Pyrethrins / Q000737:chemistry / Q000302:isolation & purification; D013237:Stereoisomerism; D047392:beta-Cyclodextrins / Q000737:chemistry* / Q000302:isolation & purification*
D008333:Mandelic Acids; D011722:Pyrethrins; D047392:beta-Cyclodextrins; D026023:Permethrin; C037938:mandelic acid