Jm. Zen et al., Mechanistic studies and sensitive determination of norepinephrine at a nafion/lead-ruthenium oxide pyrochlore chemically modified electrode, ELECTROANAL, 13(6), 2001, pp. 457-464
Nafion/Lead-ruthenium oxide pyrochlore (Pb2Ru1.75Pb0.25O7-y) chemically mod
ified electrode (NCME) exhibits excellent electrocatalytic response towards
the norepinephrine (NE) oxidation reaction. NE oxidation by CV studies sho
w the following main features: i) elechochemical oxidation of NE to o-quino
ne derivative (Al), ii) intramolecular cyclization of o-quinone derivative
to leucodopachrome derivative, iii) further oxidation to dopachrome (A2), a
nd iv) formation of polymeric melanine like products. Controlled product an
alysis using UV-visible spectroscopy gives evidence of the participation of
leucodopachrome derivative (lambda = 425 nm) intermediate. The electrocata
lytic oxidation process of Al is mediated by the electrochemically active R
u-VI present in the pyrochlore network. The electrocatalytic reaction follo
ws the Michaelis-Menten type kinetics, similar to an enzymatic mechanism. T
he determination of NE on the NCME was performed using square-cave voltamme
try. A linear calibration plot was obtained over 0-6 muM with a detection l
imit (3 sigma) of 7.44 nM. The NCR IE showed high stability and no marked i
nterference in the presence of glucose, ascorbic acid, and oxalic acid.