【作者】 王敏；

【导师】 贾丽艳； 荆旭；

【作者基本信息】 山西农业大学 ， 食品科学与工程， 2024， 硕士

【摘要】 [目的]为了替代传统样品前处理技术中有毒萃取剂、有毒分散剂、复杂的分散设备和耗时的离心设备的使用,达到快速、安全、绿色的检测杀菌剂残留的目的,本论文建立了三种基于新型磁性低共熔溶剂-分散液液微萃取结合高效液相色谱法检测杀菌剂残留的方法。具体内容包括以下三部分:[方法](1)建立基于涡旋辅助磁性低共熔溶剂-分散液液微萃取-高效液相色谱法(VA-MDES-DLLME-HPLC)检测水、果汁和醋中的甲氧基丙烯酸酯类杀菌剂的方法。使用甲基三辛基氯化铵、三氯化铁和庚酸合成的绿色的疏水磁性低共熔溶剂作为萃取剂替代了有毒萃取剂的使用;通过涡旋辅助分散替代有毒分散剂的使用;通过外部磁场辅助进行相分离,缩短了分离时间。本试验对磁性低共熔溶剂的种类、磁性低共熔溶剂的摩尔比、磁性低共熔溶剂的体积、涡旋时间、羰基铁粉的加入量等影响因素进行了优化。(2)建立基于壳聚糖辅助磁性低共熔溶剂-分散液液微萃取-高效液相色谱法(CA-MDES-DLLME-HPLC)检测水中的甲氧基丙烯酸酯类杀菌剂的方法。使用四正辛基溴化铵、氯化铁和油酸合成的绿色的磁性低共熔溶剂替代了有毒萃取剂的使用;以壳聚糖辅助分散替代了有毒分散剂和其他辅助分散仪器的使用;通过外部磁场辅助进行相分离,缩短了分离时间。本试验对磁性低共熔溶剂的种类、磁性低共熔溶剂的比例、磁性低共熔溶剂的体积、壳聚糖的种类、壳聚糖溶液的质量浓度、壳聚糖溶液的体积、羰基铁粉的加入量、NaCl的加入量以及pH等影响因素进行了优化。(3)建立基于自分散磁性低共熔溶剂-分散液液微萃取-高效液相色谱法(SD-MDES-DLLME-HPLC)检测水、果汁、酒和醋中的琥珀酸脱氢酶抑制剂的方法。使用己基三苯基溴化鏻、氯化铁和己酸合成了一种新型的绿色的磁性低共熔溶剂,利用这个特殊的可以自分散的磁性低共熔溶剂,不需要任何辅助就可以快速萃取,避免了有毒萃取剂和分散剂和其他辅助分散仪器的使用,通过外部磁场辅助进行相分离,缩短了分离时间。本试验对磁性低共熔溶剂的种类、磁性低共熔溶剂的摩尔比、磁性低共熔溶剂的体积、NaCl的加入量、pH、样品溶液的体积等影响因素进行了优化。[结果](1)基于VA-MDES-DLLME-HPLC检测食品样品中的SF。萃取回收率为81.9%～108.9%。检出限在0.0010～0.0020 mg/L的范围内。该方法成功的应用于水、果汁和醋中的SF的检测。(2)基于CA-MDES-DLLME-HPLC检测水样品中的SF。萃取回收率为83.3%～107.4%。检出限在0.0010～0.0027 mg/L的范围内。该方法成功的应用于水中的SF的检测。(3)建立基于SD-MDES-DLLME-HPLC检测食品样品中的琥珀酸脱氢酶抑制剂。萃取回收率为78.5%～97.8%。检出限在0.0011～0.0029 mg/L的范围内。该方法成功的应用于水、果汁、酒和醋中的琥珀酸脱氢酶抑制剂的检测。[结论]本研究基于MDES-DLLME-HPLC建立了三种检测水性样品中的杀菌剂残留的检测方法。在本论文中采用绿色的疏水的磁性低共熔溶剂作为萃取剂,避免了有毒萃取剂的使用;采用涡旋辅助、壳聚糖辅助、磁性低共熔溶剂自分散辅助萃取剂分散,逐步避免了有毒分散剂以及复杂的分散仪器的使用;采用更加简便快速的磁分离进行相分离,避免了耗时的离心,实现了绿色、快速的萃取过程。采用傅里叶变换红外光谱、核磁共振波谱和振动样品磁强计测量技术证明了磁性低共熔溶剂的制备,采用分析生态模型和绿色分析程序指数工具验证了方法的绿色性。所建立的三种方法绿色、快速、高效,适用于水性样品中的杀菌剂残留检测。更多还原

【Abstract】 [Objective]In order to replace the use of toxic extractants,toxic dispersants,complex dispersion equipment,and time-consuming centrifugal equipment in the traditional pretreatment technology,three detection methods of fungicide residues based on magnetic deep eutectic solvent-dispersive liquid-liquid microextraction combined with high-performance liquid chromatography were established in this paper to achieve the purpose of rapid,safe,and green detection of fungicide residues.The specific content includes the following three parts:[Method](1)A detection method of strobilurin fungicides(SFs)in water,juice,and vinegar based on vortex-assisted magnetic deep eutectic solvent-dispersive liquid-liquid microextraction-high performance liquid chromatography(VA-MDES-DLLME-HPLC)was established.A green and hydrophobic MDES synthesized by methyltrioctylammonium chloride,ferric chloride,and heptanoic acid was used as the extractant to replace toxic extractants.The use of toxic dispersants was replaced by vortex-assisted dispersion,and the phase separation was assisted by an external magnetic field to shorten the separation time.In this experiment,the influencing factors such as the type of MDES,the molar ratio of MDES,the volume of the MDES,the vortex time,and the amount of carbonyl iron powder added were optimized.(2)A detection method of SFs in water based on chitosan-assisted magnetic deep eutectic solvent-dispersive liquid-liquid microextraction-high performance liquid chromatography(CA-MDES-DLLME-HPLC)was established.The green MDES synthesized with tetraoctylammonium bromide,ferric chloride,and oleic acid was used instead of toxic extractants.Chitosan-assisted dispersion replaced the use of toxic dispersants and other assisted dispersion instruments.At the same time,the phase separation was assisted by an external magnetic field,which shortened the separation time.In this experiment,the influencing factors such as the type of MDES,the molar ratio of MDES,the volume of MDES,the type of chitosan,the mass concentration of chitosan solution,the volume of chitosan solution,the amount of carbonyl iron powder added,the amount of NaCl added,and pH were optimized.(3)A detection method of succinate dehydrogenase inhibitors(SDHIs)in water,juice,wine,and vinegar was established based on self-dispersion magnetic deep eutectic solvent-dispersive liquid-liquid microextraction-high performance liquid chromatography(SD-MDES-DLLME-HPLC).A new and green MDES was synthesized using hexyltriphenylphosphonium bromide,ferric chloride,and hexanoic acid.This special MDES could be separated by self-dispersion.Fungicides can be extracted quickly without any assistance,avoiding the use of toxic extractants and dispersants and other auxiliary dispersion instruments,and shortening the separation time through the assistance of an external magnetic field for phase separation.In this experiment,the influencing factors such as the type of MDES,the molar ratio of MDES,the volume of MDES,the amount of NaCl added,pH,and the volume of sample solution were optimized.[Results](1)Determination of SFs in food samples was based on VA-MDES-DLLME-HPLC.The extraction recovery was 81.9–108.9%.The limit of detection(LOD)was in the range of 0.0010–0.0020 mg L-1.This technique has been used to the analysis of SFs in water,juice,and vinegar.(2)Detection of SFs in water samples was based on CA-MDES-DLLME-HPLC.The extraction recovery was 83.3–107.4%.The LOD was in the range of 0.0010–0.0027 mg L-1.This technique has been used to the analysis of SFs in water.(3)Detection of SDHIs in water,juice,wine,and vinegar was based on SD-MDES-DLLME-HPLC.The extraction recovery was 78.5–97.8%.The LOD was in the range of 0.0011–0.0029 mg L-1.This technique has been used to the analysis of succinate dehydrogenase inhibitors in water,juice,wine,and vinegar.[Conclusion]In this study,three detection methods of fungicide residues in aqueous samples were established based on MDES-DLLME-HPLC.The green and hydrophobic MDES was used as the extractant to avoid the use of toxic extractants.Vortex-assisted,chitosan-assisted,and self-dispersion MDESs were used to achieve dispersion,which gradually avoided the use of toxic dispersants and complex dispersion instruments.The simple and fast magnetic separation was used to achieve phase separation,which avoided time-consuming centrifugation and realized a green,and fast extraction process.Fourier-transform infrared spectroscopy,nuclear magnetic resonance spectroscopy,and vibrating sample magnetometer analysis were used to demonstrate the preparation of MDESs.The Analytical Eco-Scale and Green Analytical Procedure Index tools were used to verify the greenness of the method.The three established methods are green,fast,efficient,and suitable for the detection of fungicide residues in aqueous samples.更多还原