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.

Neonicotinoids are systemic insecticides used in agriculture. In particular, imidacloprid (IM) and thiamethoxam (TM) have selective toxicity to insects, and they have been implicated in the steep decline of the global honeybee population, specifically in colony collapse disorder (CCD). Some scientific reports have shown that a significant amount of honey worldwide contains traces of neonicotinoids, at levels strong enough to cause damage to bees. Therefore, the development of portable and low-cost sensor devices to permit rapid detection of these neonicotinoids in the field (in situ) is of great importance. The main goal of this work was the development of an electrochemical method, for the first time, to simultaneously determine IM and TM, which can occur in honey samples from Argentina. The electrochemical sensor was based on a pretreated glassy carbon electrode (GCE) using square wave voltammetry (SWV) as the analytical technique. All parameters involved in the response were optimized using a central composite design. The SWV response was modeled using the artificial neural network (ANN) algorithm. Recovery experiments were performed with spiked honey samples, yielding recovery values from 90% to 107% without pretreatment of the samples. The proposed method is presented as a very good and simple alternative for determining IM and TM in Argentina honeys samples.