S. Rapicault et al., RENEWABLE PERFLUOROSULFONATED IONOMER CARBON-PASTE ELECTRODE FOR COMPETITIVE HOMOGENEOUS ELECTROCHEMICAL IMMUNOASSAYS USING A REDOX CATIONIC LABELED HAPTEN, Analytical chemistry, 68(5), 1996, pp. 930-935
A Nafion-loaded carbon paste electrode (CPE) was prepared and its squa
re wave voltammetric response at a fresh surface was optimized using (
ferrocenylmethyl)trimethylammonium iodide (1) as a model of a cation t
hat accumulates irreversibly. Low current responses could be obtained
reproducibly without preconditioning at a CPE loaded with 1-octanol an
d neutralized Nafion. Use of the former made the method more sensitive
, and use of the latter gave lower background currents and stable anal
ytical response over a long period of Nafion-loaded CPE use. Under opt
imized conditions and using a 5 min accumulation period, the modified
electrode gave a linear current response over the range of 5 nM to 1.5
mu M 1, a detection limit of 5 nM 1 and a relative standard deviation
of 5% for 0.5 mu M 1. Using these optimized conditions, the competiti
ve homogeneous immunoassay of phenytoin as a model hapten was carried
out with cobaltocenium-labeled phenytoin as tracer. Clinical serum sam
ples (5 mu L) of phenytoin at therapeutic concentrations (20-80 mu M)
could be analyzed using this method.