Potentiometric redox measurements were made in solutions of increasing biological complexity starting with buffer solutions containing either potassium ferri/ferrocyanide or ascorbic acid and finishing with plasma and blood. When the concentration of ferri/ferrocyanide was high (∼0.2 mM), both biofouled planar and nanoporous gold electrodes gave Nernstian slopes of 55-59 mV. However, at or below a critical concentration (≤ 0.1 mM), ∼20% loss in sensitivity was observed at planar gold in contrast to nanoporous gold where Nernstian behavior was retained. For ascorbic acid, a Nernst slope of −41 mV was observed at biofouled nanoporous gold electrodes. In contrast, biofouled planar gold electrodes failed to give any potentiometric redox response. At all concentrations studied, cyclic voltammetric measurements on biofouled electrodes revealed significant impairment of faradaic electroactivity at planar gold electrodes while no impairment was shown at nanoporous gold. These results indicate that nanoporous gold is an ideal electrode material to use when making both potentiometric and cyclic voltammetric measurements, particularly in complex solutions containing relatively low concentrations of redox molecules. As proof of concept, the redox potential of plasma and blood has been measured using nanoporous and planar gold electrodes and their values compared. Potentiometry is a technologically simple and inexpensive approach to obtain important information about the redox state of a system and/or the concentration of ions in solution.1,2 The measurement itself is simple in that all that is needed is a high impedance voltammeter, a stable reference electrode, and a suitable indicating electrode. In contrast to voltammetric measurements, no current flows, and the concentration of the redox species in solution does not change nor does the indicating electrode surface become altered as a potential is not applied. Likely the most popular potentiometric measurement is the measurement of pH using an ion-selective electrode that incorporates a thin membrane responsive to the activity of protons in solution.
3For the work described herein, the indicating electrode is an inert metallic redox electrode that is purposely designed to be nonselective and will 'ideally' respond to all redox active species in solution able to exchange electrons with the metallic surface.1,2 When the indicator electrode is immersed in solution, it will equilibrate electrochemically with the dissolved redox species and a potential will develop at its surface. The measured potential is governed by factors such as (1) the redox species present, (2) their concentrations (activities), and (3) the rate of electron exchange with the electrode.2,4,5 Such redox measurements have been used to characterize the redox state of solutions with a complex matrix including milk, cheese, sludge, water and biological systems. [6][7][8][9][10][11][12][13] An important and often neglected factor in the measurement of redox potential is the nature of the electrode surface, pa...