Key Laboratory of Analytical Science and Technology of Hebei Province, College of Chemistry and Materials Science, Hebei University, Baoding 071002, P. R. China.
Key Laboratory of Interfacial Reaction & Sensing Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, P. R. China.
Anal Chem. 2023 Jul 25;95(29):11113-11123. doi: 10.1021/acs.analchem.3c02030. Epub 2023 Jul 10.
Organophosphate pesticides are used in agriculture due to their high effectiveness and low persistence in eradicating insects and pests. However, conventional detection methods encounter the limitation of undesired detection specificity. Thus, screening phosphonate-type organophosphate pesticides (OOPs) from their analogues, phosphorothioate organophosphate pesticides (SOPs), remains a challenge. Here, we reported a d-penicillamine@Ag/Cu nanocluster (DPA@Ag/Cu NCs)-based fluorescence assay to screen OOPs from 21 kinds of organophosphate pesticides, which can be used for logic sensing and information encryption. Acetylthiocholine chloride was enzymatically split by acetylcholinesterase (AChE) to produce thiocholine, which reduced the fluorescence of DPA@Ag/Cu NCs due to the transmission of electrons from DPA@Ag/Cu NCs donor to the thiol group acceptor. Impressively, OOPs acted as an AChE inhibitor and retained the high fluorescence of DPA@Ag/Cu NCs due to the stronger positive electricity of the phosphorus atom. Conversely, SOPs possessed weak toxicity to AChE, which led to low fluorescence intensity. By setting 21 kinds of organophosphate pesticides as the inputs and the fluorescence of the resulting products as the outputs, DPA@Ag/Cu NCs could serve as a fluorescent nanoneuron to construct Boolean logic tree and complex logic circuit for molecular computing. As a proof of concept, by converting the selective response patterns of DPA@Ag/Cu NCs into binary strings, molecular crypto-steganography for encoding, storing, and concealing information was successfully achieved. This study is expected to advance the progress and practical application of nanoclusters in the area of logic detection and information security while also enhancing the relationship between molecular sensors and the world of information.
有机磷农药由于其高效性和在消灭昆虫和害虫方面的低持久性而在农业中得到广泛应用。然而,传统的检测方法存在检测特异性不理想的问题。因此,从其类似物,即硫代磷酸酯有机磷农药(SOPs)中筛选膦酸型有机磷农药(OOPs)仍然是一个挑战。在这里,我们报道了一种基于 D-青霉胺@Ag/Cu 纳米团簇(DPA@Ag/Cu NCs)的荧光分析方法,用于从 21 种有机磷农药中筛选 OOPs,该方法可用于逻辑传感和信息加密。乙酰胆碱氯化物被乙酰胆碱酯酶(AChE)酶解生成硫代胆碱,由于电子从 DPA@Ag/Cu NCs 的供体传递到硫醇基团受体,DPA@Ag/Cu NCs 的荧光降低。令人印象深刻的是,OOPs 作为 AChE 抑制剂,由于磷原子的正电性更强,保留了 DPA@Ag/Cu NCs 的高荧光。相反,SOPs 对 AChE 的毒性较弱,导致荧光强度较低。通过将 21 种有机磷农药作为输入,将所得产物的荧光作为输出,DPA@Ag/Cu NCs 可以作为荧光纳米神经元来构建布尔逻辑树和复杂逻辑电路进行分子计算。作为概念验证,通过将 DPA@Ag/Cu NCs 的选择性响应模式转换为二进制字符串,成功实现了用于编码、存储和隐藏信息的分子密码隐写术。本研究有望推进纳米团簇在逻辑检测和信息安全领域的进展和实际应用,同时增强分子传感器与信息世界之间的联系。