Effect of alkali metal hydroxides on the enantioseparation of amines using di-O-isopropylidene-keto-L-gulonic acid as the selector in NACE.

The present work demonstrates the importance of the ionic composition in the BGE for enantioseparation. (-)-2,3:4,6-di-O-Isopropylidene-2-keto-L-gulonic acid ((-)-DIKGA) has been used as the chiral selector in methanolic and ethanolic BGEs. The influence of added alkali metal hydroxides on the EOF and the chiral separation of amines (atenolol, isoprenaline, pindolol and propranolol) have been studied. The ion-pair formation constants in ethanol were determined by precision conductometry for the enantiomers of pindolol with (-)-DIKGA, for Li(+), Na(+) and Cs(+) with (-)-DIKGA, and also for the corresponding alkali metal hydroxides. The effective mobilities and the enantiomeric mobility differences were affected by the type of alkali metal hydroxide (LiOH, NaOH, KOH, RbOH or CsOH) added to the BGE. The effective mobility and mobility difference were increased with decrease in solvated radius of the alkali metal cation. These differences could partly be correlated to the ion-pair formation constants of the alkali metal cations with the chiral selector, affecting the equilibrium concentration of the free selector. The electroosmosis was also affected by the alkali metal hydroxide added to the BGE. The cathodic electroosmosis decreased with decreasing solvated radius of the alkali metal cation added to the BGE. Interestingly, the cathodic EOF was even reversed, i.e. became anodic in the ethanolic BGEs containing KOH, RbOH or CsOH and the methanolic ones with RbOH and CsOH.

Transport properties and association behaviour of the zwitterionic drug 5-aminolevulinic acid in water. A precision conductometric study.

The behavior of the hydrochloride salt of 5-aminolevulinic acid (ALA-HCl) with respect to transport properties and dissociation in aqueous solution at 25 degrees C has been studied using precision conductometry within the concentration range 0.24-5.17mM. The conductivity data are interpreted according to elaborated conductance theory. The carboxyl group appears to be, in practice, undissociated. The dissociation constant, K(a), of the NH(3)(+) form of the amino acid molecules is determined to 6.78x10(-5) (molarity scale); pK(a)=4.17. The limiting molar conductivity of the ALA-H(+) ion, lambda(0)=33.5cm(2)Omega(-1)mol(-1); electric mobility u=3.47x10(-4)cm(2)V(-1)s(-1), is close to the electric mobilites of the acetate and benzoic ions.

Improvements of conductivity measurements of electrolyte solutions using a new conductometric cell design.

A new conductometric cell design, for precise conductance measurements, has been developed and tested using aqueous lidocaine hydrochloride as a model system. A small portion of a stock solution in the conductivity cell is diluted stepwise by pure solvent. The resistance of the cell is measured by means of a precision conductance bridge. Contrary to conventional technique in precision conductometry, the temperature is allowed to change during the measurements and corrected to the desired standard temperature. The temperature is determined using a thermistor immersed in the cell solution, which is agitated during the entire experiment. Using this new approach, significant improvements over conventional conductivity technique were observed. The time required for the measurements was considerably reduced, by a factor of at least ten. The amounts, especially of costly drugs, required in the measurements are also reduced. The pK(a) value obtained, 7.28, is close to the previously reported conductometrically determined average, 7.18. The precision of the single conductivity value is equally high, if not higher, as that obtained using conventional conductivity technique.