建立了基于高效液相色谱法-紫外检测器(high-performance liquid chromatography -ultraviolet detector,HPLC-UVD)检测松脂酸铜在火龙果、豇豆和杧果3种果蔬中的农药残留的分析方法。果蔬样品在加入盐酸衍生后,使用石油醚超声提取,提取液蒸干后使用乙腈定容,通过HPLC-UVD对样品进行定量测定,选择静电场轨道阱高分辨质谱仪对松脂酸铜转化为松脂酸进行确证分析。结果表明,松脂酸铜的相关系数R2为0.999 6,平均回收率在77%～108%,相对标准偏差均小于5%,线性关系良好,该方法的检出限为0.03 mg/kg,定量限为0.1 mg/kg。该方法简便、准确、快速,可满足果蔬中松脂酸铜残留检测灵敏度和准确度的要求,其他果蔬样品中的松脂酸铜残留也可参照该方法进行分析。
An analytical method based on high-performance liquid chromatography-ultraviolet detector (HPLC-UVD) was established to determine the residues of copper abietate in mango, pitaya, and cowpea. The sample was extracted with hydrochloric acid and petroleum ether, which was ultrasonicated. The extracted supernatant was evaporated to dryness, and then dissolved with acetonitrile, the HPLC-UVD was used to quantitatively determine the sample. The copper abietate in the samples was acidified with hydrochloric acid and changed to abietic acid and the abietic acid was the target for the quantitation of copper abietate. Another high-resolution mass spectrometer was used to qualitatively analyze the copper abietate derivative. Results showed that the correlation coefficient R2 was 0.999 6 for copper abietate, the recovery of copper abietate in the selected fruit and vegetable samples was in the range of 77%-108%, and the relative standard deviations of copper abietate in the three fruits and vegetables, pitaya, cowpea, and mango were less than 5%. These results indicated that the accuracy of the copper rosin acid analysis method in fruits and vegetables met the requirements of detection and analysis. The limit of detection (LOD) for copper abietate was 0.03 mg/kg and the limit of quantitation (LOQ) was 0.1 mg/kg. The method is simple, accurate, and fast for the determination of residue of copper abietate in fruits and vegetables, where the sensitivity and accuracy can meet the requirements of copper abietate residue detection in fruits and vegetables.
[1] 吴朝波, 任承才, 朱明军, 等.春雷霉素与松脂酸铜复配防治槟榔叶斑病的效果研究[J].中国农技推广, 2021, 37(6):91-96.
WU C B, REN C C, ZHU M J, et al.Study on the effect of the combination of chunleimycin and copper rosin acid on prevention and treatment of areca leaf spot [J].China Agricultural Technology Extension, 2021, 37(6):91-96.
[2] 叶火春, 冯岗, 杨佳何, 等.吡唑醚菌酯与嘧菌环胺、松脂酸铜复配对杧果蒂腐病菌的毒力增效[J].热带农业科学, 2016, 36(10):37-42.
YE H C, FENG G, YANG J H, et al.Synergistic interaction of the mixtures of pyraclostrobin with cyprodinil or copper abietate on mango stem end rot caused by Botryodiplodia theobroma pat[J].Chinese Journal of Tropical Agriculture, 2016, 36(10):37-42.
[3] 江一红, 全金成, 谭炳林.不同药剂组合防治沃柑溃疡病田间效果评价[J].南方园艺, 2019, 30(6):12-14.
JIANG Y H, QUAN J C, TAN B L.Evaluation of field effect of different combinations of reagents on the prevention and treatment of citrus ulcer disease [J].Southern Horticulture, 2019, 30(6):12-14.
[4] 孙萍. 浅谈松脂酸铜在蟹田防治水稻病毒病应用效果[J].现代农业, 2018(9):20-21.
SUN P.Brief discussion on the application effect of copper abietate in the prevention and treatment of rice virus disease in crab fields [J].Modern Agriculture, 2018(9):20-21.
[5] KADLIKOVA K, VACLAVIKOVA M, HALESOVA T, et al.The investigation of honey bee pesticide poisoning incidents in Czechia[J].Chemosphere, 2021, 263:128056.
[6] 杨德毅, 刘莉, 李依岚, 等.高效液相色谱测定柑橘中松脂酸铜残留量的不确定度评定[J].农产品质量与安全, 2018(5):74-79.
YANG D Y, LIU L, LI Y L, et al.Uncertainty evaluation of rosin acid copper residue in citrus by HPLC[J].Quality and Safety of Agro-Products, 2018(5):74-79.
[7] 钟世欢, 陈青俊, 王京, 等.QuEChERS-HPLC测定柚类果实中柠檬苦素类化合物[J].食品与发酵工业, 2022, 48(4):261-265.
ZHONG S H, CHEN Q J, WANG J, et al.Determination of limonins in pomelo fruits by QuEChERS-HPLC[J].Food and Fermentation Industries, 2022, 48(4):261-265.
[8] 钮怡清. 高效液相色谱法检测辣椒、花椒粉中五种合成色素[J].食品与发酵工业, 2021, 47(24):256-260.
NIU Y Q.Determination of five kinds of synthetic pigments in chili powder and paprika powder by HPLC[J].Food and Fermentation Industries, 2021, 47(24):256-260.
[9] 林琎, 周艳明, 范维娣, 等.高效液相色谱法分析23%松脂酸铜水乳剂[J].现代农药, 2016, 15(5):40-41;51.
LIN J, ZHOU Y M, FAN W D, et al.Analysis of songzhisuantong 23% EW by HPLC[J].Modern Agrochemicals, 2016, 15(5):40-41;51.
[10] MITANI K, FUJIOKA M, UCHIDA A, et al.Analysis of abietic acid and dehydroabietic acid in food samples by in-tube solid-phase microextraction coupled with liquid chromatography-mass spectrometry[J].Journal of Chromatography A, 2007, 1 146(1):61-66.
[11] 陈安珍, 沙启营, 单秀明, 等.跌打片中松香酸的HPLC和HPLC-MS/MS检测方法研究[J].中成药, 2013, 35(9):1 940-1 942.
CHEN A Z, SHA Q Y, SHAN X M, et al.Determination of abietic acid in Dieda tablets by HPLC and HPLC-MS/MS[J].Chinese Traditional Patent Medicine, 2013, 35(9):1 940-1 942.
[12] 王忠合, 李晓婷, 胡文梅, 等.超高效液相色谱-高分辨质谱法测定肉类特征肽[J].食品与发酵工业, 2021, 47(18):258-266.
WANG Z H, LI X T, HU W M, et al.Determination of peptide markers of meat species by ultra-high pressure liquid chromatography coupled with high resolution mass spectrometry[J].Food and Fermentation Industries, 2021, 47(18):258-266.
[13] YANG B, YING Y, ZOU J, et al.Comprehensive characterization and quantification of multiple components in Dan-Huang-Qu-Yu capsule using a multivariate data processing approach based on microwave-assisted extraction with UHPLC and Q Exactive quadrupole-orbitrap high-resolution mass spectrometry[J].Journal of Separation Science, 2019, 42(11):2 069-2 079.
[14] ZUO L H, ZHONG Q Y, WANG Z H, et al.Simultaneous determination and pharmacokinetic study of twelve bioactive compounds in rat plasma after intravenous administration of Xuebijing injection by UHPLC-Q-Orbitrap HRMS[J].Journal of Pharmaceutical and Biomedical Analysis, 2017, 146:347-353.
[15] 马慧颖, 王金兰, 王丹, 等.松脂酸铜的合成[J].齐齐哈尔大学学报(自然科学版), 2019, 35(3):68-70.
MA H Y, WANG J L, WANG D, et al.Study on derivation of pine resin from Pinus sylvestris var.mongolica[J].Journal of Qiqihar University (Natural Science Edition), 2019, 35(3):68-70.
[16] 王英锋, 魏小燕.HPLC测定枫香脂碱提物中脱氢松香酸和松香酸的含量[J].中国中药杂志, 2013, 38(1):57-59.
WANG Y F, WEI X Y.Determination of dehydroabietic acid and abietic acid in aqueous alkali extract of Liquidambaris resina by HPLC[J].China Journal of Chinese Materia Medica, 2013, 38(1):57-59.
[17] 李富贤, 米彩峰, 石会丽.RP-HPLC测定清毒素胶囊中松香酸的含量[J].中国中药杂志, 2008, 33(9):1 086-1 087.
LI F X, MI C F, SHI H L.Determination of rosmarinic acid in clear toxin capsules by RP-HPLC [J].China Journal of Chinese Materia Medica, 2008, 33(9):1 086-1 087.
[18] 南丹, 蒋丽丹, 蔡秋香, 等.30%松脂酸钠水乳剂农药的RP-HPLC分析[J].广州化工, 2012, 40(6):99-100;119.
NAN D, JIANG L D, CAI Q X, et al.Analysis of 30% sodium abietate aqueous emulsion biopesticide by RP-HPLC[J].Guangzhou Chemical Industry, 2012, 40(6):99-100;119.
