We summarize the application of multivariate optimization for the construction of electrochemical biosensors. The introduction provides an overview of electrochemical biosensing, which is classified into catalytic-based and affinity-based biosensors, and discusses the most recent published works in each category. We then explore the relevance of electrochemical biosensors for food safety analysis, taking into account analytes of different natures. Then, we describe the chemometrics tools used in the construction of electrochemical sensors/biosensors and provide examples from the literature. Finally, we carefully discuss the construction of electrochemical biosensors based on design of experiments, including the advantages, disadvantages, and future perspectives of using multivariate optimization in this field. The discussion section offers a comprehensive analysis of these topics.

A novel, simple, rapid, and non-expensive analytical method based on square wave voltammogram at Pt-microelectrode coupled with partial least square multivariate calibration was used for the simultaneous quantitation of thymol (THY) and carvacrol (CAR) in thyme and oregano essential oils. Results demonstrated that the multivariate calibration method successfully exploited the first-order advantage, rendering highly satisfactory quantitative figures (average recoveries not statistically different than 100%). Moreover, the results agree well with those obtained from the official analytical method. Last, the method’s environmental sustainability was asserted using the AGREE metric, highlighting its eco-friendly nature. More importantly, the proposed analytical procedure does not require previous sample preparation or electrode surface modification. The results underscore the suitability of the method for determining THY and CAR in essential oils at low concentrations (LOD ~ 7.6 µM) with REP% below 5.6%, meeting the requirements of the green analytical chemistry.

In this work, we designed a novel and simple electrochemical approach for the determination of daidzein antioxidant (Dz) in peanut oil samples. The Dz determination was based on anodic stripping linear voltammetry using screen-printed graphene electrodes (SPGEs) activated in acidic media, where a strong adsorption of Dz on activated graphene was obtained. In this regard, electroanalytical parameters such as the scan rate, supporting electrolyte, pH, and accumulation step were optimized to ensure the best conditions for the selective and sensitive Dz quantification. The electrochemical method developed for the determination of Dz exhibits a linear behavior of the anodic peak current in the concentration range from 0.05 to 1 μM, with a limit of detection of 0.012 μM. The electrochemical sensor demonstrated to the capacity to quantify Dz in peanut oil samples at low concentrations without the necessity of an extensive sample pretreatment. Therefore, the electrochemical method proposed can be used as a new portable analytical tool for the in situ quality control of peanut oil samples.