Anion-selective electrodes based on long-chain methyltrialkylammonium salts.

A new series of methyltrialkylammonium salts with an alkyl chain length (n) longer than the conventional methyltridodecylammonium (MTDDA, n = 12) has been developed, and these materials were examined for use as the ion-sensing component (ligand) in anion-selective electrodes (ISEs). Syntheses of the higher ammoniums with n = 16, 18, and 20 were carried out. In combination with an alcoholic plasticizer, the ammoniums with n = 12, 16, and 18 led to ISEs with fundamental characteristics, such as slope sensitivity, impedance, and time response, that were sufficient for practical applications. Compared with the conventional MTDDA, the ISEs based on the ligands of n = 16 and 18 showed marked improvement in chloride selectivity over both lipophilic and hydrophilic anions, deviating from the Hofmeister regime in some cases. Taking perchlorate as an example, the magnitude of the improvement was a factor of 20 for n = 16 and 15 for n = 18. When the new ISEs were applied to chloride analysis in blood serum, they improved the accuracy by a factor of 2-6. Therefore, the methyltrialkylammonium salts with alkyl chain lengths of 16 and 18 offer definite advantages over the conventional alternative and are strong candidates to become the standard compounds for use in future chloride ISEs.