郑学殷　黄嘉乐　许志彬　李瑞玲　曾广丰

摘      要：建立了超高效液相色譜-串联质谱法对食品接触用纸和纸板中异噻唑啉酮类杀菌剂含量进行快速测定。样品用甲醇重复提取后，旋转蒸发浓缩，甲醇复溶，同时以回收率为指标，结合响应曲面分析优化前处参数。以流动注射方式优化5种异噻唑啉酮类化合物的质谱参数，以电喷雾离子源正离子模式电离，结合多反应监测模式进行测定。5种异噻唑啉酮类化合物在5.0～200 μg·L^-1范围内标准曲线线性良好，相关系数r均大于0.998 9，平均回收率为82.1%～95.2%，方法检出限为5.0～10.0 μg·kg^-1，方法定量限为15.0～35.0 μg·kg^-1，相对标准偏差RSDs为5.15%～6.49%。该方法简单高效、回收率高、灵敏度高和重现性好均能达到分析测定要求，可用于食品接触用纸和纸板中异噻唑啉酮类杀菌剂的测定。

关  键  词：超高效液相色谱-串联质谱;食品接触用纸和纸板;异噻唑啉酮;杀菌剂;响应曲面优化

中图分类号：O657.63; TS762.6      文献标识码： A      文章编号： 1671-0460（2020）06-1253-05

Optimization of Determination Conditions of Isothiazolinone Fungicides Residues in Food Contact Paper by Response Surface Methodology

ZHENG Xue-yin¹， HUANG Jia-le¹， XU Zhi-bin¹， LI Rui-ling²， ZENG Guang-feng³

（1. National Quality Testing Center for Processed Food （Guangdong）， Guangzhou Inspection and Testing Certification Group Company， Guangzhou Guangdong 511447， China;

2. SGS-CSTC Standards Technical Services Co.， Ltd.， Guangzhou Guangdong 510000， China;

3. Guangdong Inspection and Quarantine Technology Center， Guangzhou Guangdong 510623， China）

Abstract： A method for determination of isothiazolinone fungicides in food contact paper and cardboard by ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） was established. Samples were extracted by methanol repeatedly， then rotary evaporation was carried out to concentrate the samples， finally the samples were redissolved by methanol. The recovery rate was used as an indicator to optimize the pre-processing parameters with the response surface analysis. The mass spectrometry parameters of five isothiazolinone compounds were optimized by flow injection under positive mode of the electron spray ionization （ESI +） ， data of the analytes were obtained with mass spectrometric multiple reaction monitoring （MRM） mode. Five isothiazolinone compounds exhibited good linearity with correlation coefficient（r>0.998 9） when the concentrations ranged from 5.0 to 200 μg/L. The average recoveries of three spike levels were 82.1%～95.2%， while the limits of detection and the limits of quantitation were ranged 5.0～10.0 μg·kg^-1 and 15.0～35.0 μg·kg^-1， respectively. The relative standard deviations （RSDs） were ranged 5.15%～6.49%. This method is easy to operate， and its recovery， sensitivity and reproducibility could achieve the requirements of determination for isothiazolinone fungicides in food contact paper and cardboard.

Key words： Ultra performance liquid chromatography-tandem mass spectrometry; Food contact paper and cardboard; Isothiazolinone; Fungicide; Response surface methodology

異噻唑啉酮类杀菌剂是一种高效的广谱杀菌剂，对细菌、真菌及藻类等具有很强的抑制和杀灭作用^[1-2]，由于其具有低毒，高效、广泛杀菌等特点，所以被优良的杀菌剂应用于农业、工业等生产领域的防霉防腐^[3]。但在工业生产的同时，环境的污染问题也成为首要关注的问题。由于其优越性，在工业生产的过程中也很容易出现滥用的情况，由于大量的排放，导致了水体中的残留^[4-5]。近年有研究报道显示，异噻唑啉酮类杀菌剂对人体皮肤会有过敏作用和炎症效应^[6-8]，对于食品接触用纸的生产工业，若出现滥用的情况，对食品安全和消费者的人身健康有可能会造成重大的威胁。……