Preconditions for reasonable detection sensitivity and for zone symmetry in electrophoretic separations of cluster...

Single-cage boron cluster anions with at least 11 cluster atoms, free of bonded functional groups that strongly absorb UV light, and their cobalt complexes have been the investigated compounds. Their UV-absorption spectra have absolute maxima between 200 and 215 nm. Corresponding molar extinction coefficients that are of the order of 10(3)-10(4) L mol(-1) cm(-1) indicate medium detection sensitivity. Its reaching requires elimination of background electrolytes that weaken the UV-light beam in any way. Frequently used carboxylic acids and zwitterionic Good's buffers cannot be used as buffering compounds from this reason. Freshly prepared 1 mM solutions of boron cluster compounds in aqueous sodium chloride, chosen as indifferent electrolyte, which contain 20-30% (v/v) of methanol or acetonitrile, give zones free of tailing. After storing in the fridge, zones of the compounds became pronouncedly tailed even if their solutions remain clear and free of precipitation, turbidity or opalescence. The tailing usually disappeared if the acetonitrile or the methanol concentration in samples was 40-60% (v/v) depending on the dissolved compound hydrophobicity. Solutions of extremely hydrophobic compounds, stored in the fridge, require mild heating to 30-40 degrees C for half an hour for the avoiding of the tailing. Permanent slow decrease in effective mobilites of boron cluster anions was found if background electrolytes contained acetonitrile and beta-cyclodextrin. Analogous decrease was not observed with organic anions. Constant mobilities of boron cluster anions have been reached if acetonitrile was replaced with methanol. Analyte zones were more symmetrical in background electrolytes buffered with sodium borate of pH 9 than in background electrolytes buffered with sodium phosphate of pH 7.