Oymen Beste, Jalilzadeh Mitra, Yılmaz Fatma, Aşır Süleyman, Türkmen Deniz, Denizli Adil
Department of Gastronomy and Culinary Arts, Bahçeşehir Cyprus University, Mersin 10 Turkey, Nicosia 99010, Cyprus.
Department of Chemistry, Faculty of Science, Hacettepe University, Beytepe, Ankara 06800, Turkey.
Micromachines (Basel). 2023 Mar 23;14(4):707. doi: 10.3390/mi14040707.
Here, a molecular imprinting technique was employed to create an SPR-based nanosensor for the selective and sensitive detection of organophosphate-based coumaphos, a toxic insecticide/veterinary drug often used. To achieve this, UV polymerization was used to create polymeric nanofilms using -methacryloyl-l-cysteine methyl ester, ethylene glycol dimethacrylate, and 2-hydroxyethyl methacrylate, which are functional monomers, cross-linkers, and hydrophilicity enabling agents, respectively. Several methods, including scanning electron microscopy (SEM), atomic force microscopy (AFM), and contact angle (CA) analyses, were used to characterize the nanofilms. Using coumaphos-imprinted SPR (CIP-SPR) and non-imprinted SPR (NIP-SPR) nanosensor chips, the kinetic evaluations of coumaphos sensing were investigated. The created CIP-SPR nanosensor demonstrated high selectivity to the coumaphos molecule compared to similar competitor molecules, including diazinon, pirimiphos-methyl, pyridaphenthion, phosalone, -2,4(dimethylphenyl) formamide, 2,4-dimethylaniline, dimethoate, and phosmet. Additionally, there is a magnificent linear relationship for the concentration range of 0.1-250 ppb, with a low limit of detection (LOD) and limit of quantification (LOQ) of 0.001 and 0.003 ppb, respectively, and a high imprinting factor (I.F.4.4) for coumaphos. The Langmuir adsorption model is the best appropriate thermodynamic approach for the nanosensor. Intraday trials were performed three times with five repetitions to statistically evaluate the CIP-SPR nanosensor's reusability. Reusability investigations for the two weeks of interday analyses also indicated the three-dimensional stability of the CIP-SPR nanosensor. The remarkable reusability and reproducibility of the procedure are indicated by an RSD% result of less than 1.5. Therefore, it has been determined that the generated CIP-SPR nanosensors are highly selective, rapidly responsive, simple to use, reusable, and sensitive for coumaphos detection in an aqueous solution. An amino acid, which was used to detect coumaphos, included a CIP-SPR nanosensor manufactured without complicated coupling methods and labelling processes. Liquid chromatography with tandem mass spectrometry (LC/MS-MS) studies was performed for the validation studies of the SPR.
在此，采用分子印迹技术制备了一种基于表面等离子体共振（SPR）的纳米传感器，用于选择性和灵敏地检测有机磷酸酯类杀虫剂蝇毒磷，这是一种常用的有毒杀虫剂/兽药。为此，利用紫外光聚合反应，分别使用功能单体甲基丙烯酰-L-半胱氨酸甲酯、交联剂乙二醇二甲基丙烯酸酯和亲水性促进剂甲基丙烯酸2-羟乙酯制备聚合物纳米膜。采用多种方法对纳米膜进行表征，包括扫描电子显微镜（SEM）、原子力显微镜（AFM）和接触角（CA）分析。使用蝇毒磷印迹SPR（CIP-SPR）和非印迹SPR（NIP-SPR）纳米传感器芯片，对蝇毒磷传感进行了动力学评估。与包括二嗪农、甲基嘧啶磷、哒嗪硫磷、伏杀硫磷、N-2,4-（二甲基苯基）甲酰胺、2,4-二甲基苯胺、乐果和亚胺硫磷在内的类似竞争分子相比，所制备的CIP-SPR纳米传感器对蝇毒磷分子表现出高选择性。此外，在0.1-250 ppb的浓度范围内存在良好的线性关系，检测限（LOD）和定量限（LOQ）分别低至0.001和0.003 ppb，蝇毒磷的印迹因子（I.F.）高达4.4。朗缪尔吸附模型是最适合该纳米传感器的热力学方法。进行了日内试验，重复5次，共进行3次，以统计评估CIP-SPR纳米传感器的可重复使用性。日间分析为期两周的可重复使用性研究也表明了CIP-SPR纳米传感器的三维稳定性。该方法的RSD%结果小于1.5，表明其具有显著的可重复使用性和重现性。因此，可以确定所制备的CIP-SPR纳米传感器对水溶液中蝇毒磷的检测具有高选择性、快速响应、使用简单、可重复使用且灵敏的特点。用于检测蝇毒磷的氨基酸包括一种无需复杂偶联方法和标记过程制备的CIP-SPR纳米传感器。进行了液相色谱-串联质谱（LC/MS-MS）研究，以对SPR进行验证研究。
