基于制备接枝型分子印迹膜构建农药电位型电化学传感器及其检测性能研究

基于分子设计,以氯甲基化聚砜(CMPSF)为基膜,阴离子单体对苯乙烯磺酸钠(SSS)为功能单体,N,N'-亚甲基双丙烯酰胺(MBA)为交联剂,在表面引发体系-NH2/S2O2-8的作用下,采用"接枝聚合与分子印迹同步进行"的分子表面印迹新技术,制备了接枝型农药抗蚜威分子印迹膜(MIM)。采用红外光谱(FITR)和光学显微镜(OM)对该分子印迹膜进行表征,通过等温结合实验与竞争吸附实验,考察了抗蚜威分子印迹膜的分子识别性能与机理。以该印迹膜作为敏感膜,构建了抗蚜威电位型传感器,并对其检测性能进行了考察。结果表明,所制备的接枝型印迹膜对模板抗蚜威分子具有特异的识别选择性和优良的结合亲和性,结合容量高达92μg/cm2,相对于分子结构与抗蚜威相似的阿特拉津,印迹膜对抗蚜威的选择性系数为4.537。在p H 4.0的水介质中,传感器膜电极的电位响应与抗蚜威浓度对数在1.0×10-6~1.0×10-3mol/L范围内呈良好的线性关系(r=0.999 9),其检出限为2.5×10-8mol/L;以抗蚜威分子印迹膜为敏感膜所构建的电位型传感器,其构建过程简捷,检测灵敏准确,电位响应快速(t10 s)。     

Chemiluminometric Determination of the Pesticide Pirimicarb by a Flow Injection Analysis Assembly

Abstract

A flow injection (FI) method is described for the determination of pirimicarb. It was found that an enhanced chemiluminescence (CL) signal is obtained when employing the luminol–H₂O₂–horseradish peroxidase (HRP) system. Under the optimum experimental conditions, the enhanced CL intensity was linear with the concentration 4.25–30.75 ng mL^?1 (r = 0.997, n = 8) with a relative standard deviation of 0.99%, containing 12.75 ng mL^?1 (n = 8). The limit of detection of the investigated compound was 0.12 ng mL^?1. The method shows a moderate selectivity against other pesticides (Amitrole, Atrazine, 2,4,5-T, Dichlorprop, and Metamidophos).The proposed method was sensitive, simple, rapid, and successfully applied to the determination of pirimicarb when it is applied in freshwater; the mean recoveries were 98.3–118.5%.     

流动注射化学发光法测定抗蚜威

在多聚磷酸钠介质中,抗蚜威能显著增强RhB-Cu2 -H2O2体系的化学发光强度。基于此,结合流动注射技术,建立了测定抗蚜威的流动注射化学发光新方法。该法的检出限为58μg/L(3σ);线性范围为0.1~10 mg/L;对1.0 mg/L的抗蚜威连续平行测定11次,其相对标准偏差(RSD)为2.8%。该方法灵敏、简单、快速。用于农田水、乌江水、长江水以及自来水中抗蚜威含量的测定,回收率为95.5%~100.9%,结果令人满意。     

Accelerated ZnMoO4 photocatalytic degradation of pirimicarb under UV light mediated by peroxymonosulfate

This paper reports the optimized synthesis of zinc molybdates by the hydrothermal method and the combination of ZnMoO₄ and peroxymonosulfate (PMS) under UV irradiation for the degradation of pirimicarb. The as‐prepared ZnMoO₄ photocatalyst was characterized using X‐ray diffraction, scanning electron microscopy, X‐ray photoelectron spectroscopy and UV–visible diffuse reflectance spectroscopy. The effects of operational parameters in the ZnMoO₄/PMS/UV system were evaluated and the results indicated the highest performance is achieved with pH = 9.0, 1 mM PMS and 1 g l^?1 ZnMoO₄. The degradation efficiency of pirimicarb was 98% after 3 h in the photocatalytic process. A photodegradation mechanism is proposed based on scavenger and electron spin resonance studies to decide the main active species and by using chromatography–mass spectrometry to identify the major intermediates. Pirimicarb degradation is found to be mainly driven by holes and ?O₂^? radicals, with the contribution of ?OH and SO₄^?? radicals enhancing the process in the tested catalytic system. The mechanism is proposed involving two routes, dealkylation and decarbamoylation. Lastly, the zinc molybdate photocatalyst is shown to be stable, reusable and efficient in the removal of pirimicarb from real water samples in the presence of PMS, demonstrating potential application in the treatment of contaminated and/or environmental water.