Electrochemical biosensors based on nanomaterials for aflatoxins detection: A review (2015-2021).

Due to their immunotoxicity, aflatoxins are considered as very important natural contaminants of a wide variety of agricultural products. Although conventional techniques such as high-performance liquid chromatography (HPLC) and gas chromatography (GC) combined with mass spectrometry (MS) have traditionally been used to detect such food contaminants, they are relatively expensive, laborious, and time consuming which limits their use for in field analysis at the so-called point-of-care (POC). Electrochemical biosensors are emerging devices that meet these expectations since they rely in reliable, simple, inexpensive, portable, selective, and easy-to-use analytical procedures and instruments that can be used by unskilled personnel outside the laboratory. In this context, in this review article we summarize and provide authoritative opinion on the use of electrochemical biosensors for aflatoxins of interest for food control. Even though previous reviews have rightly covered this issue, the continuous research and improvements in this field, mostly related to the use of novel nanomaterials, make an update much needed. For this reason, this review covers the most relevant approaches reported in the period 2015-2021, focusing for the first time on the use of nanomaterials for improving the biosensors performance. The principles of the different strategies developed are discussed, and some examples of relevant approaches are highlighted, together with future prospects and challenges.

Electrochemical (Bio)Sensors for Pesticides Detection Using Screen-Printed Electrodes.

Pesticides are among the most important contaminants in food, leading to important global health problems. While conventional techniques such as high-performance liquid chromatography (HPLC) and mass spectrometry (MS) have traditionally been utilized for the detection of such food contaminants, they are relatively expensive, time-consuming and labor intensive, limiting their use for point-of-care (POC) applications. Electrochemical (bio)sensors are emerging devices meeting such expectations, since they represent reliable, simple, cheap, portable, selective and easy to use analytical tools that can be used outside the laboratories by non-specialized personnel. Screen-printed electrodes (SPEs) stand out from the variety of transducers used in electrochemical (bio)sensing because of their small size, high integration, low cost and ability to measure in few microliters of sample. In this context, in this review article, we summarize and discuss about the use of SPEs as analytical tools in the development of (bio)sensors for pesticides of interest for food control. Finally, aspects related to the analytical performance of the developed (bio)sensors together with prospects for future improvements are discussed.

Direct competitive immunosensor for Imidacloprid pesticide detection on gold nanoparticle-modified electrodes.

A direct competitive immunosensor for the electrochemical determination of Imidacloprid (IMD) pesticide on gold nanoparticle-modified screen-printed carbon electrodes (AuNP-SPCE) is here reported for the first time. Self-obtained specific monoclonal antibodies are immobilized on the AuNP-SPCE taking advantage of the AuNPs biofunctionalization abilities. In our biosensor design, free IMD in the sample competes with IMD conjugated with horseradish peroxidase (IMD-HRP) for the recognition by the antibodies. After that, 3,3',5,5'-Tetramethylbenzidine (TMB) is enzymatically oxidized by HRP, followed by the oxidized TMB reduction back at the surface of the SPCE. This process gives an associated catalytic current (analytical signal) that is inversely proportional to the IMD amount. The main parameters affecting the analytical signal have been optimized, reaching a good precision (repeatability with a RSD of 6%), accuracy (relative error of 6%), stability (up to one month), selectivity and an excellent limit of detection (LOD of 22 pmol L-1), below the maximum levels allowed by the legislation, with a wide response range (50-10000 pmol L-1). The detection through antibodies also allows to have an excellent selectivity against other pesticides potentially present in real samples. Low matrix effects were found when analysing IMD in tap water and watermelon samples. The electrochemical immunosensor was also validated with HPLC-MS/MS, the reference method used in official laboratories for IMD analysis, through statistical tests. Our findings make the electrochemical immunosensor as an outstanding method for the rapid and sensitive determination of IMD at the point-of-use.

A monoclonal antibody-based immunosensor for the electrochemical detection of imidacloprid pesticide.

Imidacloprid (IMD) is one of the most used pesticides worldwide as a systemic insecticide as well as for pest control and seed treatment. The toxic and potential carcinogenic character of IMD makes its monitoring of great relevance in the field of agriculture and environment, so sensitive methodologies for in field analysis are strongly required. In this context, we have developed a competitive immunoassay for the determination of IMD using specific monoclonal antibodies followed by electrochemical detection on screen-printed carbon electrodes (SPCE). The optimized immunosensor exhibited a good reproducibility (RSD of 9%) and a logarithmic response in the range 50-10 000 pM of IMD, with an estimated detection limit (LOD) of 24 pM, which was below the maximum levels allowed by the legislation. High-Performance Liquid Chromatography-Mass Spectrometry-Mass Spectrometry (HPLC-MSMS) and Enzyme-Linked Immunosorbent Assay (ELISA) analysis were also performed for comparison purposes, where the electrochemical immunosensor exhibited a wider range of response and a lower detection limit. Matrix effects below 6.5% were obtained using tap water samples. All these characteristics make our electrochemical immunosensor a valid and advantageous tool for the in field determination of IMD.

Galvanostatic electrodeposition of copper nanoparticles on screen-printed carbon electrodes and their application for reducing sugars determination.

In this work, a novel method for the galvanostatic electrodeposition of copper nanoparticles on screen-printed carbon electrodes was developed. Nanoparticles of spherical morphology with sizes between 60 and 280nm were obtained. The electrocatalytic effect of these copper nanospheres towards the oxidation of different sugars was studied. Excellent analytical performance was obtained with the nanostructured sensor: low detection limits and wide linear ranges (1-10,000µM) were achieving for the different reducing sugars evaluated (glucose, fructose, arabinose, galactose, mannose, xylose) with very similar calibration slopes, which demonstrates the possibility of total sugar detection. The reproducibility of these sensors was 4.4% (intra-electrode) and 7.2% (inter-electrode). The stability of the nanostructured electrodes was at least 30 days, even using the same device on different days. Several real samples (honey, orange juice and normal and sugar-free soft drinks) were evaluated to study the reliability of the nanostructured sensor.