Cl. Wang et A. Mulchandani, FERROCENE-CONJUGATED POLYANILINE-MODIFIED ENZYME ELECTRODES FOR DETERMINATION OF PEROXIDES IN ORGANIC MEDIA, Analytical chemistry, 67(6), 1995, pp. 1109-1114
The development and characteristics of a reagentless amperometric orga
nic phase enzyme electrode (OPEE) employing covalently attached horser
adish peroxidase and an electrochemically deposited ferrocene-modified
polyaniline film on a glassy carbon electrode is reported, The covale
nt attachment of ferrocene to an electrochemically deposited insoluble
polymer film provided a mechanism of preventing the leaching of ferro
cene into the predominantly organic solvents, required for constructio
n of reagentless OPEE. Hydrodynamic voltammetry studies showed that th
e response of the OPEE to hydrogen peroxides increased at higher catho
dic potentials; however, interference due to molecular oxygen also inc
reased. Interference of molecular oxygen was minimized when the OPEE w
as operated at an applied potential of -50 mV (or less negative) vs Ag
/AgCl. The cathodic response of the OPEE was found to increase steeply
when the aqueous buffer content of the acetonitrile was increased fro
m 0% to 5% and then plateau with no further increase when the buffer c
ontent was increased to 30%. The dynamic properties of this enzyme ele
ctrode were exploited for the detection of micromolar concentrations o
f different peroxides in now injection analysis where the sensitivity
trend was lauroyl peroxide > hydrogen peroxide > 2-butanone peroxide >
cumene hydroperoxide > tert-butyl hydroperoxide. Applicability of the
enzyme electrode for measurement of peroxide in real sample was demon
strated.