This work describes the development of a new selective photocontrollable molecularly imprinted-based sorbent for the selective enrichment/pre-concentration of dimethoate from spiked olive oil samples. To achieve this goal an improved molecularly imprinted strategy relying on the embedding of a functional monomer containing an azobenzene chromophore as light-responsive element, on the crosslinked tridimensional molecular imprinted network, has been assessed. To address the mechanisms underlying template recognition and uptake/release of the analyte from the functional imprinted material, computational studies using a quantum chemical approach, have been explored. This new functional sorbent provides a straightforward controllable uptake/release of the target template using light as the stimuli tool, which is highly advantageous due to light manipulation characteristics, such as superior clean, precision and remote controllable properties. In general, this work will contribute to the implementation of a photoswitchable analytical methodology that proves to be suitable for the selective isolation and further quantification of dimethoate from olive oil matrices at levels similar to the maximum residues limits imposed by the legislation. The limits of detection, calculated based on 3σ, was 1.6 mgL-1 and the limit of quantification, based on 10σ, was 5.2 mgL-1. The implemented sample preparation shows high reproducibility and recoveries (93.3 ± 0.4%).

中文翻译：

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从橄榄油中选择性富集乐果的光可切换“主客体”方法

这项工作描述了一种新的选择性光控分子印迹吸附剂的开发，用于选择性富集/预浓缩加标橄榄油样品中的乐果。为了实现这一目标，已经评估了一种改进的分子印迹策略，该策略依赖于在交联的三维分子印迹网络上嵌入含有偶氮苯发色团作为光响应元素的功能单体。为了解决模板识别和从功能印迹材料中吸收/释放分析物的机制，已经探索了使用量子化学方法的计算研究。这种新的功能性吸附剂使用光作为刺激工具，提供了一种直接可控的目标模板的吸收/释放，由于光操纵特性，例如卓越的清洁、精确和远程控制特性，这是非常有利的。总的来说，这项工作将有助于实施光开关分析方法，该方法证明适用于从橄榄油基质中选择性分离和进一步量化乐果，其水平类似于立法规定的最大残留限量。基于 3σ 计算的检测限为 1.6 mgL-1，基于 10σ 的定量限为 5.2 mgL-1。实施的样品制备显示出高重现性和回收率 (93.3 ± 0.4%)。这项工作将有助于实施光开关分析方法，该方法被证明适用于从橄榄油基质中选择性分离和进一步量化乐果，其水平与立法规定的最大残留限量相似。基于 3σ 计算的检测限为 1.6 mgL-1，基于 10σ 的定量限为 5.2 mgL-1。实施的样品制备显示出高重现性和回收率 (93.3 ± 0.4%)。这项工作将有助于实施光开关分析方法，该方法被证明适用于从橄榄油基质中选择性分离和进一步量化乐果，其水平与立法规定的最大残留限量相似。基于 3σ 计算的检测限为 1.6 mgL-1，基于 10σ 的定量限为 5.2 mgL-1。实施的样品制备显示出高重现性和回收率 (93.3 ± 0.4%)。