光谱学与光谱分析, 2020, 40 (3): 760, 网络出版: 2020-03-25   

纺织品中邻苯二甲酸酯的表面增强拉曼光谱快速检测

Rapid and Quantitative Detection of Phthalic Acid Ester in Textiles Using Surface-Enhanced Raman Spectroscopy
作者单位
1 厦门大学固体表面物理化学国家重点实验室, 化学化工学院, 福建 厦门 361005
2 深圳出入境检验检疫局工业品检测技术中心, 广东 深圳 518067
摘要
随着绿色纺织理念的不断深入, 国际上对于纺织品中的有毒有害化学品越来越重视。 纺织品中常用的邻苯二甲酸酯(PAEs)具有生殖毒性、 致突变和致癌性, 可通过空气、 水、 食物三大途径进入人体, 干扰人体的内分泌系统。 由于PAEs对生态系统和公共卫生环境潜在不利的影响, 近年来引起越来越多人们的关注。 目前, 检测PAEs的方法主要是色谱法和色-质联用法, 这些方法虽然灵敏度高, 但是存在着前处理繁琐复杂, 耗时久, 检测成本高, 需要专业技术人员等缺点, 不适合生产过程中的快速分析。 而其他方法如, 酶联免疫法等研究较少, 且存在样品基质干扰, 易出现假阳性等问题。 因此, 建立纺织品中邻苯二甲酸酯的快速分析技术具有重要意义。 表面增强拉曼光谱(SERS)作为一种分子振动光谱可提供丰富的分子结构信息, 具有极高的灵敏度, 广泛应用于食品安全、 环境监测和****等领域。 研究中提出并建立了一种结合便携式拉曼光谱仪, 利用SERS实现纺织品中邻苯二甲酸酯的快速定量检测方法。 首先利用水合肼将非水溶性的邻苯二甲酸酯类化合物转化为水溶性的邻苯二甲酰肼。 同时, 利用纳米金溶胶作为SERS基底, 使转化后的邻苯二甲酰肼吸附于金溶胶表面, 从而实现其拉曼信号的放大与检测。 结果表明, 通过这种方法, 可实现多种邻苯二甲酸酯的快速检测。 进一步研究还表明, 在5~150 mg·L-1范围内, 邻苯二甲酸酯浓度与其拉曼光谱强度呈线性关系, 线性方程为Y=139.04X+5 465.32, 相关系数为0.993 0, 检出限为5 mg·L-1。 利用该方法, 还实现了不同纺织品中多种邻苯二甲酸酯的快速检测, 加标回收率达80%以上, 且不受纺织品中其他成分的干扰。 所建立表面增强拉曼光谱检测方法操作简便、 成本低且结果准确, 适用于纺织品中邻苯二甲酸酯类增塑剂的快速定量检测。
Abstract
With the development of the concept of green textile, more and more attention has been paid to the toxic chemicals used in textiles. Phthalic acid esters (PAEs) having reproductive toxicity, mutagenicity and carcinogenicity, which are frequently used as plasticizers in textiles, will enter the human body via air, water and food and jeopardize human health. Therefore, theirpotential and adverse impacts on ecosystem functioning and onpublic health have aroused considerable and growing attentionin recent years. The determination of PAEs is largely based on chromatographic and chromatograph-mass spectrometer. These methods are sensitive, accurate, but have some limitations including high costs, long detection time, and the need of trained personnel. Other methods, such as ELISAs are less studied, which have some limitations including interference of matrix and false positives. Therefore, developing efficient method for the analysis of PAEs is of significant importance. Surface-enhanced Raman spectrum(SERS) can provide rich molecular structure information and has a very high sensitivity, which has been widely used in food safety, environmental monitoring and national security and other fields. In this paper, using a portable Raman spectrometer, a rapid and quantitative SERS method has been developed for the detection of PAEs. In this method, PAEs are first converted into phthalhydrazide, which is then adsorbed on the SERS substrates (Au sols). Using such a method, various PAEs can be rapidly detected. Furthermore, a good linear relationship between the concentration of PAEs and their Raman intensity has been obtained in the range of 5~150 mg·L-1. The linear regressionequation is Y=139.04X+5 465.32, with a correlation coefficient of 0.993 0 and a detection limit of 5 mg·L-1. Using such a method, various PAEs in textiles are quantitatively detected with a recovery of >80%. The work demonstrates that the SERS method developed here is very simple, cost-effective and accurate thus is suitable for the rapid detection of the total amount of PAEs in textiles.

黄艺伟, 林嘉盛, 谢堂堂, 温宝英, 李剑锋. 纺织品中邻苯二甲酸酯的表面增强拉曼光谱快速检测[J]. 光谱学与光谱分析, 2020, 40(3): 760. HUANG Yi-wei, LIN Jia-sheng, XIE Tang-tang, WEN Bao-ying, LI Jian-feng. Rapid and Quantitative Detection of Phthalic Acid Ester in Textiles Using Surface-Enhanced Raman Spectroscopy[J]. Spectroscopy and Spectral Analysis, 2020, 40(3): 760.

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