Avoiding Potential Pitfalls in Designing Wired Glucose Biosensors.

Glucose sensing has been studied for more than half a century, leading many to believe that further progress comes mainly from engineering efforts. Our society requires robust, reliable, compact, and easy-to-use sensing solutions for decentralized applications such as wearables, and engineering solutions are essential. However, true progress is only possible by understanding and improving the underlying working principles and fundamental limitations. This Perspective discusses the delicate relationship between the observed current and glucose concentration when using wired enzyme biosensors. Some of the potential pitfalls often encountered in the recent literature are discussed. These include the need to suppress the influence of enzyme turnover kinetics on the sensor signal and the undesired faradaic charging of the electron transfer mediator that gives a continuously decaying baseline signal. These fundamental issues must be carefully evaluated and resolved for the realization of continuously operating enzyme biosensor systems.

Correction: A submersible probe with in-line calibration and a symmetrical reference element for continuous direct nitrate concentration measurements.

Correction for 'A submersible probe with in-line calibration and a symmetrical reference element for continuous direct nitrate concentration measurements' by Tara Forrest et al., Environ. Sci.: Processes Impacts, 2023, 25, 519-530, https://doi.org/10.1039/D2EM00341D.

A submersible probe with in-line calibration and a symmetrical reference element for continuous direct nitrate concentration measurements.

Current methods to monitor nitrate levels in freshwater systems are outdated because they require expensive equipment and manpower. Punctual sampling on the field or at a fixed measuring station is still the accepted monitoring procedure and fails to provide real-time estimation of nitrate levels. Continuous information is of crucial importance to evaluate the health of natural aquatic systems, which can strongly suffer from a nitrogen imbalance. We present here a nitrate-selective potentiometric probe to measure the analyte continuously without requiring maintenance or high-power consumption. Owing to a simple design where the sensors are located directly in contact with the sample, the need for constant pump usage is eliminated, requiring just 0.7 mW power per day instead of 184 mW per day and per pump. It is estimated that with this power consumption, the setup can easily run for more than 97 h on four simple Li-ion batteries. A simple in-line one-point calibration step was implemented to allow for drift correction. At the same time, a symmetrical design was used involving a second nitrate probe as a reference electrode placed in the calibrant compartment. This, combined with an in situ calibration step, allows one to quantify nitrate ion concentrations directly, instead of yielding activities. The dependence on ion activity was removed by using the analysed sample spiked with nitrate as the calibrant. This results in essentially the same activity coefficients and additionally reduces junction potentials to a fraction of a millivolt. In addition, a symmetrical reference element served to compensate for fluctuations caused by environmental factors (temperature, convection, etc.) to achieve improved stability and signal reproducibility compared to a traditional Ag/AgCl based reference electrode. The final prototype was deployed in the Arve River in Geneva for 75 h without requiring any intervention. The nitrate levels measured using the symmetrical reference element over this period were estimated at 44.0 ± 3.5 M and agreed well with the values obtained with ion chromatography (38.2 ± 2.1 µM) used as the reference method. Thanks to a modular sensing head the potentiometric sensors can be easily exchanged, making it possible to quantify other types of analytes and leading the way to a new monitoring strategy.

Unconditioned Symmetric Solid-Contact Electrodes for Potentiometric Sensing.

In potentiometric sensing, the preparation of the electrodes preceding a measurement is often the most time-consuming step. Eliminating the conditioning process can significantly speed up the preparation procedure, but it can also compromise the need for proper pre-equilibration of the membrane. We propose here a symmetric setup to address this challenge with an identical indicator and reference elements measured against each other, thereby compensating for potential drift. This strategy allows one to achieve potentiometric measurements using non-conditioned all-solid-state ion-selective electrodes for the detection of nitrate and potassium ions with Nernstian response slopes and detection ranges identical to those of conventional systems. To establish symmetry, a set of solid-contact ion-selective electrodes placed in a reference cell is measured against a set of identical electrodes in a sample cell. By subtracting the potentials between the two cells, potential instabilities not directly relevant to the measuring sample are eliminated, giving minimal potential drifts and stable 5-day potential responses. The E0 value of the nitrate-selective electrodes in the symmetric setup had a standard deviation of just 3 mV for the 5-day period in contrast to 19 mV in the asymmetric system, clearly demonstrating the influence of the conditioning step which is almost eliminated in the former system. During the 20 h potential monitoring experiments, the drift dropped to below 0.3 mV/min in less than 6 min, as opposed to an average time of 35 min for the asymmetric system. The applicability of the proposed setup was successfully demonstrated with the measurement of nitrate in a river water sample, where a potential drift lower than 0.1 mV/min was reached in less than 5 min of first contact with solution.