Potentiometric Evaluation of Solvent Polymeric Carbonate-Selective Membranes Based on Molecular Tweezer-Type Neutral Carriers

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Abstract
Potentiometric properties of the ion-selective electrodes) based on highly plasticized PVC membranes doped with the carbonate-selective cholic acid (CA) derivatives have been measured. The carbonate-selective neutral carriers have been prepared by coupling one to three trifluoroacetobenzoyl (TFAB) groups to a cholic acid derivative which has three hydroxyl linkers lining on the C3, C7, and C12 positions of its rigid steroidal ring structure. The membranes based on cholic acid derivatives with two TFABs [3,7-bis(TFAB)CA, 3,12-bis(TFAB)CA, and 7,12-bis(TFAB)CA] exhibited remarkably improved carbonate selectivity, indicating that the bis(TFAB)CAs behave like molecular tweezers for the carbonate ion. For example, 3,12-bis(TFAB)CA resulted in 10−300-fold-enhanced carbonate selectivity over other anions (e.g., salicylate, ClO4-, SCN-, HPO42-, NO3-, NO2-, Br-, and Cl-) compared to that of the neutral carriers with a single TFAB group. The distances between the carbonate binding centers of bis(TFAB)CAs, i.e., the carbonyl carbons of the two TFAB groups, are in the 7.3−7.9-Å range at the AM1 level semiempirical calculation, which is too far for the carbonate ion to form direct covalent bonding. The fast atom bombardment mass spectra of bis(TFAB)CAs show that significant fractions of the compounds are either mono- or dihydrated before complexing the carbonate ion. These findings seem to suggest that bis(TFAB)CAs recognize the incoming carbonate ion by forming both covalent and hydrogen bonding between the hydrated and unhydrated TFAB groups. The analytical utility of the carbonate-selective electrode based on 3,12-bis(TFAB)CA has been demonstrated by measuring the total carbon dioxide in human serum in the presence of lipophilic anion interferents, e.g., salicylate.