Journal
ELECTROPHORESIS
Volume 42, Issue 7-8, Pages 910-919Publisher
WILEY
DOI: 10.1002/elps.202000298
Keywords
Acid dissociation constant; Capillary electrophoresis; Carboranes; Limiting ionic mobilities; Stokes hydrodynamic radii
Funding
- Czech Science Foundation [20-03899S]
- Czech Academy of Sciences [RVO 61388963]
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Capillary electrophoresis was used to determine the thermodynamic acidity constants (pK(a)) and ionic mobilities of two types of carboranes, showing that the sulfamidoalkyl and sulfonamidoalkyl groups have weak acidity in the range of 10.78-11.45. The study also found that the ionic mobilities and hydrodynamic radii of the carborane anions varied depending on their valence.
Capillary electrophoresis (CE) has been applied for determination of the thermodynamic acidity constants (pK(a)) of the sulfamidoalkyl and sulfonamidoalkyl groups, the actual and limiting ionic mobilities and hydrodynamic radii of important compounds, eight carborane-based inhibitors of carbonic anhydrases, which are potential new anticancer drugs. Two types of carboranes were investigated, (i) icosahedral cobalt bis(dicarbollide)(1-) ion with sulfamidoalkyl moieties, and (ii) 7,8-nido-dicarbaundecaborate with sulfonamidoalkyl side chains. First, the mixed acidity constants, pK(a)(mix), of the sulfamidoalkyl and sulfonamidoalkyl groups of the above carboranes and their actual ionic mobilities were determined by nonlinear regression analysis of the pH dependences of their effective electrophoretic mobility measured by capillary electrophoresis in the pH range 8.00-12.25, at constant ionic strength (25 mM), and constant temperature (25 degrees C). Second, the pK(a)(mix) were recalculated to the thermodynamic pK(a)s using the Debye-Huckel theory. The sulfamidoalkyl and sulfonamidoalkyl groups were found to be very weakly acidic with the pK(a)s in the range 10.78-11.45 depending on the type of carborane cluster and on the position and length of the alkyl chain on the carborane scaffold. These pK(a)s were in a good agreement with the pK(a)s (10.67-11.27) obtained by new program AnglerFish (freeware at ), which provides thermodynamic pK(a)s and limiting ionic mobilities directly from the raw CE data. The absolute values of the limiting ionic mobilities of univalent and divalent carborane anions were in the range 18.3-27.8 TU (Tiselius unit, 1 x 10(-9) m(2)/Vs), and 36.4-45.9 TU, respectively. The Stokes hydrodynamic radii of univalent and divalent carborane anions varied in the range 0.34-0.52 and 0.42-0.52 nm, respectively.
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