CN113138245B - 肉苁蓉中农药残留检测样品前处理方法及使用的吸附材料 - Google Patents
肉苁蓉中农药残留检测样品前处理方法及使用的吸附材料 Download PDFInfo
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Abstract
本发明提供了一种肉苁蓉中农药残留检测样品前处理方法及使用的吸附材料。前处理：肉苁蓉样品中加入乙酸乙腈溶液，加氯化钠，振荡，离心，提取液中加氯化钠、硫酸镁和吸附材料，涡旋，分离，上清液过有机膜，得待测样品。吸附材料的制备：混合二价铁盐和三价铁盐的饱和溶液，加氨水；剧烈搅拌，水浴恒温，分离洗涤烘干，得磁性四氧化三铁纳米粒子；碳纳米管粗品纯化后，加乙醇，加十八烷胺，搅拌，分离洗涤，真空干燥，得功能化碳纳米管；混合磁性四氧化三铁纳米粒子悬浮液和功能化碳纳米管悬浮液，搅拌，油浴，收集洗涤产物，真空烘干，得吸附材料。该吸附材料应用于肉苁蓉中16种农药残留的检测，可满足国家标准中农药最大残留限量标准要求。
Description
技术领域
本发明属于中药材农药残留检测技术领域，涉及一种肉苁蓉中农药残留检测样品前处理方法，该前处理方法将一种磁性碳纳米多孔复合材料与QuEChERS技术相结合，快速前处理检测样品；本发明还涉及一种该前处理方法中使用的吸附材料，该吸附材料为磁性四氧化三铁纳米粒子负载十八烷胺功能化碳纳米管多孔复合材料。
背景技术
肉苁蓉是中医药中的补益类药物,具有补肾阳、益精血、润肠通便的作用。肉苁蓉与同属植物管花肉苁蓉的干燥带鳞叶肉质茎为药典中药材肉苁蓉的基源植物。由于中草药种植期一般较长，尤其是像肉苁蓉这种根类药材，更易受到多种农药残留的污染，应当进行农药残留检测。但是，中药材样品分析过程中，前处理是必不可少的环节，现有技术中的前处理过程较为复杂繁琐。近年来，磁性碳纳米复合材料作为一种吸附剂在农兽药残留分析中有一定的应用价值．但作为分散固相萃取（dSPE）材料在中药材中农药残留分析，特别是肉苁蓉中农药残留分析中尚未报道。所以建立一种肉苁蓉中农药多残留快速检测技术显得非常必要。
发明内容
本发明的目的是提供一种肉苁蓉中农药残留检测样品前处理方法，能对检测样品进行快速简便的前处理。
本发明的另一个目的是提供一种上述前处理方法中使用的吸附材料。
为实现上述目的，本发明所采用的技术方案是：一种肉苁蓉中农药残留检测样品前处理方法，具体为：称取均质肉苁蓉样品10.00g于50mL离心管中，加入25mL乙酸乙腈溶液，震荡30min，加入2.5g氯化钠，振荡1min，离心，取提取液5mL于10mL离心管中，再加入1g氯化钠、2g硫酸镁和40mg吸附材料，涡旋60s，外加磁场分离，收集上清液，上清液过0.22 μm有机膜，得到待测样品。
制得的待测样品可进行GC-MS/MS分析。
乙酸乙腈溶液按体积比1︰99，由乙酸溶液和乙腈溶液混合而成。
本发明所采用的另一个技术方案是：一种上述前处理方法中使用的吸附材料，这样制得：
步骤1：制备磁性Fe3O4纳米粒子
将5.388g二价铁盐（FeCl2·4H2O）完全溶于水中，得第一饱和溶液，将1.286g三价铁盐（FeCl3·6H2O）完全溶于水中，得第二饱和溶液，混合第一饱和溶液和第二饱和溶液，加入20mL 质量分数为25%的NH3·H2O；剧烈搅拌，得混合液，在50～55℃温度下水浴恒温，混合液由橙红色逐渐变成黑色后，再继续搅拌55min后，停止反应，离心分离，用蒸馏水反复洗涤直至洗涤后溶 液的pH为中性，移去上层清液，将产物在70℃温度下真空干燥18 h，研磨，制得磁性四氧化三铁纳米粒子（标记为MNPs）；
NH3·H2O溶液为沉淀剂，
步骤2：制备纯化碳纳米管粉末
取1.00g经过预处理的碳纳米管粗品放入100mL的烧瓶中，依次加入15mL浓硝酸和45mL 浓硫酸，装好回流冷凝和吸收装置，加热回流1.5 h。冷却至室温，过滤多余的酸，所剩的粉末状物质即为纯净的碳纳米管，去离子水洗涤该纯净的碳纳米管至洗涤后溶液的pH值为7，放入烘箱中，在70℃温度下干燥8h，得纯化碳纳米管粉末；
步骤3：合成十八烷胺功能化碳纳米管
称取100mg纯化碳纳米管粉末于250mL圆底烧瓶中，加入100mL乙醇，超声30min使纯化碳纳米管粉末完全溶解，再加入400mg十八烷胺，室温下搅拌2h，离心分离，用二次水洗涤两次，真空干燥，制得十八烷胺功能化碳纳米管（标记为ODA/CNTs）；
步骤4：合成吸附材料
将10mL质量体积浓度为10mg/mL的磁性四氧化三铁纳米粒子悬浮液缓慢地加入10mL质量体积浓度为20mg/mL的十八烷胺功能化碳纳米管悬浮液中，不断搅拌，接着在110℃油浴中搅拌8h，之后，将磁铁放到烧瓶旁边收集黑色产物，用二次水洗涤黑色产物三次后，在80℃温度下真空烘干4h，制得吸附材料（磁性四氧化三铁纳米粒子负载十八烷胺功能化碳纳米管多孔复合材料（标记为：MNPs-ODA/CNTs））。
本发明首次合成磁性四氧化三铁纳米粒子负载十八烷胺功能化碳纳米管复合材料，并将其作为吸附材料与QuEChERS技术结合起来，建立了一种简单快速、灵敏度高、重复性好、准确高效的肉苁蓉中46种多农残（23种有机磷农药、15种有机氯农药、8种氨基甲酸酯类农药）检测分析样品的前处理方法，省去了过滤和离心等复杂的操作步骤，避免了目标物损失，提高检测精度，同时简化操作过程，提高净化效率，缩短前处理时间。该吸附材料作为吸附剂相当于传统的PSA、C18和GCB组成的混合吸附剂的净化体系，加快了样品处理速度，提高净化效率，方法选择性好、灵敏度和分辨率高，可满足国家标准中农药最大残留限量标准要求。
本发明吸附材料在有机溶剂中具有很好的溶解性和分散性，而且有效地增大了复合材料的比表面积，能够很好的消除基质干扰。
附图说明
图1是磁性四氧化三铁纳米粒子修饰功能化多壁碳纳米管纳米复合材料的合成机理图。
图2是实施例1合成的磁性四氧化三铁纳米粒子的透射电子显微镜图。
图3是实施例1制备的十八烷胺功能化碳纳米管的扫描电子显微镜图。
图4是实施例1合成的吸附材料的透射电子显微镜图。
图5是实施例1合成吸附材料的X-射线衍射谱图。
图6是实施例1合成吸附材料的氮气吸附-脱附图。
图7是实施例1合成吸附材料在肉苁蓉农药检测过程净化效果与其它三种吸附剂净化效果对比图。
图8是本发明合成吸附材料在肉苁蓉农药检测过程净化时用量研究图。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
实施例1
将5.388g二价铁盐（FeCl2·4H2O）完全溶于水中，得第一饱和溶液，将1.286g三价铁盐（FeCl3·6H2O）完全溶于水中，得第二饱和溶液，混合第一饱和溶液和第二饱和溶液，加入20mL质量分数25%的NH3·H2O；剧烈搅拌，得混合液；50℃温度下水浴恒温，混合液由橙红色逐渐变成黑色后，再继续搅拌55min后，停止反应，离心分离，用蒸馏水反复洗涤直至洗涤后溶 液的pH为中性，移去上层清液，将产物在70℃真空干燥18 h，研磨，制得磁性四氧化三铁纳米粒子（标记为MNPs）。
将1.00g经过预处理的碳纳米管粗品放入100mL的烧瓶中，依次加入15mL浓硝酸和45mL 浓硫酸，装好回流冷凝和吸收装置，加热回流1.5h。冷却至室温，过滤多余的酸，所剩的粉末状物质即为纯净的碳纳米管。将该纯净的碳纳米管用去离子水洗涤至洗涤后溶液的pH值为7，放入烘箱中在70℃干燥8h，得纯化碳纳米管粉末。
称取100mg纯化碳纳米管粉末于250mL圆底烧瓶中，加入100mL乙醇超声30min，使纯化碳纳米管粉末完全溶解，再加入400mg十八烷胺，室温下搅拌2h，离心分离，二次水洗涤两次，真空干燥，得到十八烷胺功能化碳纳米管（标记为ODA/CNTs）。
将10mL质量体积浓度为10mg/mL的磁性四氧化三铁纳米粒子悬浮液缓慢地加入10mL质量体积浓度为20mg/mL的十八烷胺功能化碳纳米管悬浮液中，并不断搅拌，接着在110℃油浴中搅拌8h，将磁铁放到烧瓶旁边收集黑色产物，用二次水洗涤黑色产物三次，在80℃温度下真空烘干4h，制得吸附材料，该吸附材料为磁性四氧化三铁纳米粒子负载十八烷胺的功能化碳纳米管多孔复合材料（标记为：MNPs-ODA/CNTs）。
称取均质肉苁蓉样品10.00g于50mL离心管中，加入25mL乙酸乙腈溶液（乙酸溶液︰乙腈溶液=1︰99（体积比）），震荡30min，加入2.5g氯化钠，振荡1min，离心，取提取液5mL于10mL离心管中，加入1g氯化钠、2g硫酸镁和40mg吸附材料，涡旋60s，外加磁场分离，收集上清液，上清液过孔径0.22μm的有机膜，得到待测样品。
本发明通过简单的水热法成功地合成了磁性四氧化三铁纳米粒子负载十八烷胺功能化碳纳米管多孔复合材料，其合成机理如图1所示。该碳纳米管多孔复合材料在乙腈溶液中具有很好的溶解性和分散性，四氧化三铁纳米粒子均匀地分散在碳纳米管表面未出现团聚现象，而且有效地增大了复合材料的比表面积，因此，该碳纳米管多孔复合材料能够用于改善传统吸附剂自身的缺陷而能够成为一种改进的 QuEChERS技术应用于各种食品、药品及保健品中农药残留检测样品前处理中。
图2为合成的四氧化三铁纳米粒子的透射电镜及衍射图（TEM），从图2中可以看到本发明成功制备了超顺磁性纳米粒子。图3为合成的十八烷胺功能化多壁碳纳米管的扫描电镜图（SEM），图3显示，十八烷胺功能化多壁碳纳米管有效地增大了复合材料的比表面积，因此，最终合成的吸附材料有望用于改善传统吸附剂自身的缺陷而能够成为一种改进的QuEChERS技术应用于农药残留检测样品前处理中。
图4是实施例1合成的吸附材料的透射电镜及衍射图（TEM），图5为实施例1合成的吸附材料的X-射线衍射图，图6为实施例1合成的吸附材料的氮气吸附脱附图。从图4可以看出磁性纳米粒子均匀地分散在碳纳米管表面；从图5可以看到四氧化三铁纳米粒子四个衍射峰和碳纳米管一个衍射峰；从图6可以看出该吸附材料是一种典型І吸附行为。这些都进一步说明了本发明通过简单的水热法成功地合成了一种磁性碳纳米复合材料。
中药材在生长种植过程中不可避免的要使用农药，药农不合理的喷洒农药必然会导致中药材农药残留超标。这些残留的农药通过食物链的积累会对人体健康造成极大危害，还会对肉苁蓉药效的发挥产生不利影响。随着生活水平的提高，同时具有治疗与预防作用的“药食两用”药材受到人们的广泛关注。研究表明，许多中药材常常作为保健食品的原料。近几年来，肉苁蓉在国内外市场上受到了广泛的应用，但伴随着农药残留问题越来越突出。已经成为影响肉苁蓉用药安全的最重要的因素之一，由于市场上应用的大多数农药的脂溶性比较大，化学性质相对稳定，所以更易于沉积而不易降解，且残留时间长，严重威胁到了人民群众的身体健康。随着人民生活水平的不断提高，人们除了关注肉苁蓉的药用价值外，肉苁蓉用药的安全性方面也越来越受到广泛关注。
用实施例1合成的吸附材料作为吸附剂对肉苁蓉中16种农药残留进行检测，按实施例1的方法制得待测样品。同时，用现有技术中肉苁蓉待测样品的制备方法制得第一样品（PSA净化）、第二样品（C18净化）和第三样品（GCB净化），得到的样品的直观图，如图7所示。从图7可以看到，与现有技术中的吸附剂相比较，本发明合成的吸附材料对肉苁蓉中农药残留检测具有很好的净化效果，待测样品澄清透明，而用现有技术中的吸附剂净化后的待测样品呈现黄色，说明本发明吸附材料能够消除基质干扰，缩短样品处理时间，提高检测灵敏度。选取四种不同品种的肉苁蓉样品作为研究对象，用毒死蜱加标计算其回收率来探讨吸附剂在肉苁蓉农药残留检测样品前处理过程中的用量，本发明合成的吸附材料在肉苁蓉农药检测过程净化时用量研究图，如图8。从图8中可以看到当吸附材料用量为20mg时回收率达到最大值，且该吸附材料用丙酮洗涤三次烘干后可以反复利用，节约成本，经济环保。
选用16种代表性农药残留（9种有机磷农药、4种有机氯农药、3种氨基甲酸酯类农药）作为研究对象，以阴性样品菠菜作为基质进行加标试验，本发明吸附材料对肉苁蓉中16农药残留回收率研究结果表，如表1所示。
表1 本发明吸附材料对肉苁蓉中16农药残留回收率研究结果表
从表1可以看出，本发明吸附材料对肉苁蓉中农药残留检测具有很好的响应，回收率在75.5%～102.7%，相对标准偏差＜10，可应用于其它中药材农药残留检测样品前处理中。
Claims (2)
1.一种肉苁蓉中农药残留检测样品前处理方法，其特征在于，该前处理方法具体为：称取均质肉苁蓉样品10.00g，加入25mL乙酸乙腈溶液，震荡30min，加入2.5g氯化钠，振荡1min，离心，取提取液5mL，再加入1g氯化钠、2g硫酸镁和40mg吸附材料，涡旋60s，外加磁场分离，收集上清液，过0.22 μm有机膜，得到待测样品；
所述吸附材料的制备：
步骤1：将5.388g二价铁盐完全溶于水中，得第一饱和溶液，将1.286g三价铁盐完全溶于水中，得第二饱和溶液，混合第一饱和溶液和第二饱和溶液，加入20mL 质量分数为25%的NH3·H2O；剧烈搅拌，得混合液，在50～55℃温度下水浴恒温，混合液由橙红色逐渐变成黑色后，再继续搅拌55min后，停止反应，离心分离，用蒸馏水反复洗涤直至洗涤后溶液的pH为中性，移去上层清液，将产物在70℃温度下真空干燥18 h，研磨，制得磁性四氧化三铁纳米粒子；
步骤2：取1.00g碳纳米管粗品，依次加入15mL浓硝酸和45mL 浓硫酸，装好回流冷凝和吸收装置，加热回流1.5 h；冷却至室温，过滤多余的酸，得纯净的碳纳米管，洗涤该纯净的碳纳米管至洗涤后溶液的pH值为7，在70℃温度下干燥8h，得纯化碳纳米管粉末；
步骤3：称取100mg纯化碳纳米管粉末，加入100mL乙醇，超声30min使纯化碳纳米管粉末完全溶解，再加入400mg十八烷胺，室温下搅拌2h，离心分离，用二次水洗涤，真空干燥，制得十八烷胺功能化碳纳米管；
步骤4：将10mL质量体积浓度为10mg/mL的磁性四氧化三铁纳米粒子悬浮液缓慢地加入10mL质量体积浓度为20mg/mL的十八烷胺功能化碳纳米管悬浮液中，不断搅拌，接着在110℃油浴中搅拌8h，之后，用磁铁收集黑色产物，用二次水洗涤黑色产物，真空烘干，制得吸附材料；
肉苁蓉中残留农药为：马拉硫磷、乙酰甲胺磷、对硫磷、三唑磷、乐果、丙溴磷、毒死蜱、敌敌畏、氧乐果、五氯硝基苯、硫丹、艾氏剂、六氯苯、速灭威、呋喃丹和西维因。
2.如权利要求1所述的肉苁蓉中农药残留检测样品前处理方法，其特征在于，所述的乙酸乙腈溶液按体积比1︰99，由乙酸溶液和乙腈溶液混合而成。
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