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.

Electrochemical sensors and biosensors are analytical tools, which are in continuous development with the aim of generating new analytical devices which are more reliable, cheaper, faster, sensitive, selective, and robust than others. In matrices related to agroalimentary, environmental, or health systems, natural or synthetic compounds occur which fulfil specific roles; some of them (such as mycotoxins or herbicides) may possess harmful properties, and others (such as antioxidants) beneficial ones. This imposes a challenge to develop new tools and analytical methodologies for their detection and quantification. This review summarises different aspects related to the development of electrochemical sensors and biosensors carried out in Argentina in the last ten years for application in agroalimentary, environmental, and health fields. The discussion focuses on the construction and development of electroanalytical methodologies for the determination of mycotoxins, herbicides, and natural and synthetic antioxidants. Studies based on the use of different electrode materials modified with micro/nanostructures, functional groups, and biomolecules, complemented by the use of chemometric tools, are explored. Results of the latest reports from research groups in Argentina are presented. The main goals are highlighted.

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.