Abstract

The combination of the generic mobile technology and inherent stability, versatility and cost-effectiveness of the synthetic receptors allows producing optical sensors for potentially any analyte of interest, and, therefore, to qualify as a platform technology for a fast routine analysis of a large number of contaminated samples. To support this statement, we present here a novel miniature sensor based on a combination of molecularly imprinted polymer (MIP) membranes and a smartphone, which could be used for the point-of-care detection of an important food contaminant, oestrogen-like toxin zearalenone associated with Fusarium contamination of cereals. The detection is based on registration of natural fluorescence of zearalenone using a digital smartphone camera after it binds to the sensor recognition element. The recorded image is further processed using a mobile application. It shows here a first example of the zearalenone-specific MIP membranes synthesised in situ using “dummy template”-based approach with cyclododecyl 2, 4-dihydroxybenzoate as the template and 1-allylpiperazine as a functional monomer. The novel smartphone sensor system based on optimized MIP membranes provides zearalenone detection in cereal samples within the range of 1–10 µg mL−1 demonstrating a detection limit of 1 µg mL−1 in a direct sensing mode. In order to reach the level of sensitivity required for practical application, a competitive sensing mode is also developed. It is based on application of a highly-fluorescent structural analogue of zearalenone (2-[(pyrene-l-carbonyl) amino]ethyl 2,4-dihydroxybenzoate) which is capable to compete with the target mycotoxin for the binding to zearalenone-selective sites in the membrane’s structure. The competitive mode increases 100 times the sensor’s sensitivity and allows detecting zearalenone at 10 ng mL−1. The linear dynamic range in this case comprised 10–100 ng mL−1. The sensor system is tested and found effective for zearalenone detection in maize, wheat and rye flour samples both spiked and naturally contaminated. The developed MIP membrane-based smartphone sensor system is an example of a novel, inexpensive tool for food quality analysis, which is portable and can be used for the “field” measurements and easily translated into the practice.

Highlights

  • Microscopic fungal species affiliated to genus Fusarium cause a number of the dangerous and widespread diseases in cereals: head blight of wheat, barley, and rice as well as ear rot disease of maize

  • It is widely recognized that template molecules used for the molecularly imprinted polymer (MIP) synthesis cannot be fully extracted from the resulting polymer due to extremely high levels of cross-linking that are typical for this type of materials

  • Zearalenone-selective free-standing molecularly imprinted polymer membranes were synthesized in situ and their composition was optimized taking into account the chemical structure of the functional monomer and its molecular ratio with the dummy template

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Summary

Introduction

Microscopic fungal species affiliated to genus Fusarium cause a number of the dangerous and widespread diseases in cereals: head blight of wheat, barley, and rice as well as ear rot disease of maize. Fusarium contamination causes significant harvest losses and results in accumulation of mycotoxins produced by Fusarium spp. as secondary metabolites in grain, which makes it dangerous for consumption for both humans and animals. Zearalenone is considered as the most toxic secondary metabolite produced by species. F. graminearum and F. culmorum possessing strong oestrogen-like, endocrine-disrupting, carcinogenic and toxic effects [2]. A number of neurotoxic, hepatotoxic and hemotoxic effects are typical for zearalenone [4]. Zearalenone contamination is often revealed in cereals, nuts, spices and vine, causing significant losses for agriculture [5,6]

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