The Measurement of Mixed Potentials Using Platinum Decorated Nanoporous Gold Electrodes

Potentiometric redox sensing in solutions containing multiple redox molecules was evaluated using in-house constructed nanoporous gold (NPG)-platinum (Pt) and unmodified NPG electrodes. The NPG-Pt electrode was fabricated by electrodepositing Pt into the nanoporous framework of a chemically dealloyed NPG electrode. By varying the concentration of the Pt salt and the electrodeposition time, different amounts of Pt were introduced. Characterization by SEM shows the pore morphology doesn’t change with the addition of Pt and XPS indicates the electrodes contain ∼2.5–24 wt% Pt. Open-circuit potential (OCP) measurements in buffer and solutions containing ascorbic acid, cysteine, and/or uric acid show that the OCP shifts positive with the addition of Pt. These results are explained by an increase in the rate of the oxygen reduction reaction with the addition of Pt. The overall shape of the potentiometric titration curves generated from solutions containing one or more bioreagents is also highly dependent on the amount of Pt in the nanoporous electrode. Furthermore, the generation of OCP vs Log [bioreagent] from the results of the potentiometric experiments shows an ∼2-fold increase in sensitivity can result with the addition of Pt. These results indicate the promise that these electrodes have in potentiometric redox sensing.

Gravitational Dispersion Forces and Gravity Quantization

The parallel development of the theories of electrodynamical and gravitational dispersion forces reveals important differences. The former arose earlier than the formulation of quantum electrodynamics so that expressions for the unretarded, van der Waals forces were obtained by treating the field as classical. Even after the derivation of quantum electrodynamics, semiclassical considerations continued to play a critical role in the interpretation of the full results, including in the retarded regime. On the other hand, recent predictions about the existence of gravitational dispersion forces were obtained without any consideration that the gravitational field might be fundamentally classical. This is an interesting contrast, as several semiclassical theories of electrodynamical dispersion forces exist although the electromagnetic field is well known to be quantized, whereas no semiclassical theory of gravitational dispersion forces was ever developed although a full quantum theory of gravity is lacking. In the first part of this paper, we explore this evolutionary process from a historical point of view, stressing that the existence of a Casimir effect is insufficient to demonstrate that a field is quantized. In the second part of the paper, we show that the recently published results about gravitational dispersion forces can be obtained without quantizing the gravitational field. This is done first in the unretarded regime by means of Margenau’s treatment of multipole dispersion forces, also obtaining mixed potentials. These results are extended to the retarded regime by generalizing to the gravitational field the approach originally proposed by McLachlan. The paper closes with a discussion of experimental challenges and philosophical implications connected to gravitational dispersion forces.

Open-Circuit Voltage Comes from Non-Equilibrium Thermodynamics

Originally derived by Walther Nernst more than a century ago, the Nernst equation for the open-circuit voltage is a cornerstone in the analysis of electrochemical systems. Unfortunately, the assumptions behind its derivation are often overlooked in the literature, leading to incorrect forms of the equation when applied to complex systems (for example, those with ion-exchange membranes or involving mixed potentials). Such flaws can be avoided by applying a correct thermodynamic derivation independently of the form in which the electrochemical reactions are written. The proper derivation of the Nernst equation becomes important, for instance, in modeling of vanadium redox flow batteries or zinc-air batteries. The rigorous path towards the Nernst equation derivation starts in non-equilibrium thermodynamics.