Potentiometric quantitation of general local anesthetics with a new highly sensitive membrane sensor

The detection of local anesthetic drugs is of great importance in the analysis of pharmaceutical, clinical and forensic samples. This paper reports a simple and sensitive potentiometric assay suitable for detecting general local anesthetics (LAs) of two types, namely: amino ester-anesthetics (procaine) and amino amide-anesthetics (lidocaine, articaine). As a detector, a new highly sensitive sensor based on a poly(vinyl chloride)-matrix membrane incorporating ion-pair complexes of protonated procaine with 2-[bis-octadecyl-sulfonic)-closo-decaborate is used. To improve the analytical characteristics of the sensor, the tetradodecylammonium - 2-[bis-octadecyl-sulfonic)-closo-decaborate associate as a lipophilic additive is proposed. The procedures for the synthesis of both electroactive membrane components are described. The dependence of potential response characteristics of the potentiometric system on the membrane composition, local anesthetic properties, and pH of the sample solutions is discussed. The difference in sensitivity and selectivity of the sensor was found to be responsible for the lipophilic property and pKa values of local anesthetic molecules. The developed sensor exhibited a near Nernstian response to cationic forms of procaine and some other anesthetics of higher lipophility, in particular lidocaine and articaine, over a wide linear concentration range. The limit of detection was varied from 2 x 10-8 to 5 x 10-7 mu M, and it is the lowest value among the early published potentiometric analogs. The proposed method was successfully applied to the analysis of pharmaceutical formulations and spiked enzyme-free urine samples containing LAs at low concentration levels (0.5-100 mu g mL-1). The recovery range (n = 5) was 98.0-101.5%, and the relative standard deviation was no more than 5.0%.