Construction and evaluation of PVC and sol-gel sensor membranes based on Mn(III)TPP-Cl. Application to valproate determination in pharmaceutical preparations.

The construction and general performance of new valproate-selective electrodes based on manganese(III) tetraphenylporphyrin [Mn(III)TPP-Cl], as an ionophore, are presented. The ionophore was incorporated into PVC and ceramic membranes (sol-gel) based on methyltriethoxysilane. The influence of membrane composition and pH and the effect of lipophilic cationic and anionic additives in PVC membranes were investigated concerning their influence on the slope, response time, selectivity and lifetime of the electrodes. The PVC membrane without additive and the sol-gel membrane presented slopes and practical limits of detection of -60.8 mV dec(-1) and 5x10(-6) mol l(-1) and -60.3 mV dec(-1) and 1x10(-4) mol l(-1), respectively. The sol-gel membranes displayed higher selectivity for valproate when compared with PVC membranes. These two types of electrodes were coupled to a sequential-injection analysis (SIA) system for the direct determination of valproate in pharmaceutical formulations. The association of Mn(III)TPP-Cl with the sol-gel support inserted in a SIA system provided potentiometric sensors with an analytical range of 1x10(-3)-5x10(-2) mol l(-1), with a sample rate of 55 samples per hour and a sample and carrier consumption of 140 and 2,500 microl per determination, respectively.