Measurement/data-processing method to improve the ruggedness of membrane-based sensors: Application to amperometric oxygen sensor.

This paper describes alternative measurement and data-processing approaches that can reduce effects of experimental variables on results obtained with a membrane-based sensor for oxygen. In the new approaches, the membrane-based sensor is first equilibrated with the sample solution, after which a polarizing voltage is applied and current vs. time data are recorded as the response decays toward a steady-state condition. Current vs. time data are then processed by a fixed-time option and an integration option designed to determine the charge corresponding to the total amount of oxygen inside the membrane when a polarizing voltage is applied. The current measured at a fixed time and the total charge varied linearly with oxygen concentration between 0.05 and 0.26 mmol l(-1). Pooled relative standard deviations (N = 35) for the measurement/data-processing step were near 0.4% for the new pre-equilibrium options compared to a value of 0.3% for the steady-state option. Dependencies of the pre-equilibrium options on membrane thickness and stirring rate in the most sensitive regions were at least two orders of magnitude smaller than for the steady-state option.

Initial studies of a new approach to the design and use of enzyme-based reactor/sensor systems: amperometric system for glucose.

This paper describes the development and evaluation of a new approach to the design and use of enzyme-based reactor/sensor systems (so-called "enzyme electrodes"). In the new approach, the reactor/sensor design is such that the measured response corresponds to reaction of all substrate in a fixed volume of solution. The result is that equilibrium-based measurements can be made, which in turn should result in advantages such as extended linear ranges and reduced dependencies on experimental variables such as enzyme activity, temperature, activators, inhibitors, etc. The concept was implemented with a glucose oxidase/electron-mediator reactor system immobilized on a glassy-carbon electrode operated in an amperometric mode. The reactor/sensor system was used in a thin-layer (14 microns) cell such that the mean diffusion time of substrate (glucose) across the cell was very short (< 1 s) and the rate-limiting process was the chemical reaction at the reactor surface. In this way, it was possible to quantify the electrical charge corresponding to reaction of all the substrate in a fixed volume of solution perpendicular to the plane of the reactor system. Because the determined charge is dependent only on the total amount of substrate in the fixed volume, results exhibit linear range up to at least 2-fold the Michaelis constant and reduced dependency on pH relative to results obtained with steady-state responses from the same experimental system. A mathematical treatment is presented which yields equations that are consistent with time-dependent responses for current and charge and which provide a rational basis for several data-processing options evaluated.

Data-processing method to reduce error coefficients for membrane-based analytical systems. 1. Amperometric-based sensor evaluated for quantification of oxygen.

This paper describes the use of a predictive, curve-fitting method to reduce the effects of experimental variables on results obtained with membrane-based devices. Multipoint data from the transient regions of responses are used with suitable models and curve-fitting methods to predict the signal that would be measured for the system at equilibrium. The resulting equilibrium response usually is much less dependent on experimental variables than the transient responses used to predict it. The approach is evaluated for the membrane-based amperometric electrode for oxygen. Current vs time data are used to predict the equilibrium current expected when oxygen concentrations are the same on both sides of the membrane. Predicted equilibrium currents vary linearly with oxygen concentration. Relative to the more common steady-state method, the sensitivity of the predictive method is about 5-fold higher, the measurement time is about 17-fold shorter and the dependencies on membrane thickness and stirring rate are 125- and 8-fold lower, respectively. Pooled standard deviations (n = 40) correspond to uncertainties in oxygen concentration of about 0.009 mmol L-1.