CN115608339B - 一种用于九种真菌毒素同时富集净化的磁固相萃取剂 - Google Patents
一种用于九种真菌毒素同时富集净化的磁固相萃取剂 Download PDFInfo
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Abstract
本发明提供一种用于九种真菌毒素同时富集净化的磁性分散固相萃取剂,该固相萃取剂为磁性三嗪基共价有机骨架材料Fe3O4@COF(TAPT‑DHTA)。本发明首次使用Fe3O4@COF(TAPT‑DHTA)纳米材料为磁性吸附剂,磁固相萃取水果产品中九种常见的真菌毒素,建立一种高效、高回收率且价格低廉的纳米前处理方法,克服传统方法中基质效应高、前处理耗时、净化效果差的问题。
Description
技术领域
本发明涉及真菌毒素检测领域,具体的说涉及一种用于九种真菌毒素同时富集净化的磁固相萃取剂。
背景技术
水果及其制品为人体提供多种必需的维生素、矿物质和膳食纤维等营养物质。水果水分含量高、营养丰富,在贮藏、运输和加工过程中容易受到病原真菌感染而腐烂变质,水果产品的质量和安全引起广泛关注。真菌毒素是由产毒真菌在适宜的环境条件下产生的有毒次级代谢产物,在水果及其制品中最常见真菌毒素包括细交链格孢酮酸(TeA)、交链孢酚(AOH)、交链孢酚单甲醚(AME)、腾毒素(TEN)、交链孢霉烯(ALT)、细格菌素(ALS)、赭曲霉毒素A(OTA),黄曲霉毒素B1(AFB1),玉米赤霉烯酮(ZEN)等。这些真菌毒素具有致癌、致畸和致突变作用,对人类健康构成潜在风险。其中,欧洲食品安全局(EFSA)已将AOH和AME的毒理学关注阈值(TTC)确定为每天2.5μg/kg body weight/day,而TeA为1.5μg/kg bodyweight/day。国际癌症研究机构(IARC)也将AFB1和OTA分别列为I级和2B类致癌物质。这些毒素容易共存,一种水果往往会被多种真菌毒素共同污染,给食品安全带来较大的隐患。因此,建立水果中多种真菌毒素同时检测技术十分关键。
多种真菌毒素的同时富集净化前处理技术是建立灵敏检测方法的关键,有效富集目标物减少样品的基质干扰能够显著提高检测的准确性和灵敏度。目前,对真菌毒素的富集净化方法主要为QuEChERS方法和固相萃取法(SPE)等,但是应用于果蔬中链格孢毒素等毒素净化时存在回收率较低等缺点。
因此,亟需开发新的毒素富集净化技术用于水果中多种真菌毒素的同时富集净化。
发明内容
本发明的目的首先在于提供一种用于九种真菌毒素同时富集净化的磁固相萃取剂,该磁固相萃取剂为磁性三嗪基共价有机骨架材料Fe3O4@COF(TAPT-DHTA);
其中Fe3O4@COF(TAPT-DHTA)通过如下方法制备得到:
将TAPT、DHTA和Fe3O4纳米颗粒按照质量比例为1:0.7~1.2:0.5~2.5,m/m/m分散在二元溶剂1,4-二恶烷/丁醇(1:1,V:V)中;室温下60Hz超声处理20分钟后,加入乙酸作为催化剂,并在室温下搅拌2~3小时;然后,加入乙酸/去离子水(2:1,V:V),混合物在氮气气氛除氧30min后转移至70℃水浴锅中搅拌反应36~72小时,反应结束后使用乙醇清洗,离心收集最终产物,去离子水洗3-5次至母液无色,在60℃下烘干24h,得到褐色粉末即为Fe3O4@COF(TAPT-DHTA);
其中Fe3O4纳米颗粒是通过如下步骤制备的:准确称取2.6g FeCl3和1.59gFeCl2·4H2O,溶于12.5mL超纯水和0.43mL 12M HCl的混合溶液中,然后在剧烈搅拌条件下滴加至125mL 1.5M NaOH水溶液中;反应生成的黑色沉淀通过8000rpm转速下离心5min收集获得,收集的黑色沉淀用纯水清洗后于60℃烘箱中烘干得到Fe3O4纳米颗粒;
其中所述的九种真菌毒素为:TeA、AOH、AME、TEN、ALT、ALS、OTA、AFB1和ZEN。
本发明的目的还在于提供了一种用上述磁固相萃取剂Fe3O4@COF(TAPT-DHTA)对九种真菌毒素同时富集净化的方法,该方法包括如下步骤:
在1-5g待测样品中加入5~30mL乙腈-甲酸(乙腈与甲酸的体积比为99:1,V:V)溶液,涡旋后,室温下60Hz超声30~60min,提取待测样品中的目标真菌毒素;离心,取上清液2~10mL,氮气吹干,得到待富集净化样本;
接着将2~10mL的1%乙腈水溶液(pH3.0~6.0)(重量百分比)作为上样溶液加入待富集净化样本,并加入10~30mg Fe3O4@COF(TAPT-DHTA)进行磁固相搅拌吸附5~20min;然后采用磁性分离,弃掉上清液;接着加入2~10mL甲醇作为洗脱液,超声2~10min洗脱目标真菌毒素;
移取2~8mL上述含有真菌毒素的洗脱液在50℃的氮气流下吹干,重新溶解在0.5~3mL乙腈-5mmol L-1乙酸铵水溶液(乙腈与5mmol L-1乙酸铵水溶液的体积比为20:80,V:V)混合溶液中,通过0.22μm滤膜,上机进行UPLC-MS/MS分析;
其中UPLC-MS/MS分析的色谱条件和质谱条件分别如下:
色谱条件:色谱柱:Waters AcquityBEH C18色谱柱,100mm×2.1mm,1.7mm;流动相:流动相A为甲醇,流动相B为5mmol L-1乙酸铵水溶液;梯度洗脱程序:0-5min,30% A-90% A;5-7min,90% A;7-7.5min,90% A-30%A;7.5-8.5min,30% A;流速为0.4mL min-1;进样量3μL;柱温40℃;
质谱条件:分离出的化合物采用Waters XEVO TQ-S质谱仪,其电喷雾电离源可在正(ESI+)和负(ESI-)模式下工作;参数设定如下:源温度150℃;脱气温度500℃;锥体和脱溶气体流量分别为150L h-1和1000L h-1。
本发明建立了多反应监测MRM模式对目标物进行定量,并对各种真菌毒素监测条件进行优化,采用MassLynx v4.1和Targetlynx数据分析软件进行数据处理。
本发明的创新点:
1、本发明首次将磁性三嗪基共价有机骨架材料Fe3O4@COF(TAPT-DHTA)作为吸附剂,磁固相萃取净化水果中9种常见真菌毒素,净化效果好、重现性高;
2、本发明首次将三嗪基共价有机骨架材料COF(TAPT-DHTA)与磁性四氧化三铁Fe3O4纳米颗粒结合,反应形成Fe3O4@COF(TAPT-DHTA)。该复合纳米材料具有大的比表面积,高的热稳定性和化学稳定性。此外,TAPT-DHTA单体能够提供丰富的氮原子,羟基和芳环等,与富电子官能团有效结合,有效对复杂农产品中痕量真菌毒素进行富集净化。
3、本发明提供的对水果中九种真菌毒素同时富集净化的方法,技术操作简单,对操作人员要求低,且减少了甲醇、乙腈等有机溶剂的使用,极大的降低了成本,节省了时间。
4、本发明提供的对水果中九种真菌毒素同时富集净化的方法,采用UHPLC-MS/MS技术,能够有效去除基质效应,实现了对番茄,草莓,西瓜,甜瓜和山楂等水果中9种真菌毒素的准确定量分析。
附图说明
图1 Fe3O4纳米颗粒(A)和Fe3O4@COF(TAPT-DHTA)(B)的扫描电子显微镜图谱
图2番茄,草莓,西瓜,甜瓜,山楂样品采用磁固相萃取剂净化前和净化后的比较
图3标准溶液中9种真菌毒素(50μg kg-1)的MRM图谱
图4空白番茄基质液中9种真菌毒素(50μg kg-1)的MRM图谱
具体实施方式
试剂与材料:
甲醇和乙腈购于德国默克;
甲酸、醋酸铵、正丁醇(BuOH)、1,4-二恶烷均购于上海阿拉丁有限公司;
2,4,6-三(4-氨基苯基)-1,3,5-三嗪(TAPT),2,5-二羟基对苯二甲酸(DHTA)购于上海源叶生物科技有限公司;
氯化亚铁,氯化铁,盐酸,氢氧化钠等购于国药集团化学试剂有限公司。
实验用水均为超纯水;
TeA、AOH、AME、TEN、ALT、ALS、OTA、AFB1、ZEN毒素标准品均购于青岛普瑞邦生物工程有限公司,将其溶解在乙腈中配置成10μg mL-1的标准品储备液待用。标准品储备液存放在-20℃的冰箱中;
所有用于HPLC分析的有机溶剂、酸、碱、盐都是分析纯级别;
0.22μm的滤膜购买于领航实验室仪器有限公司;
Waters XEVO TQ-S质谱:Waters,Milford,MA,USA
Waters AcquityBEH C18色谱柱(100mm×2.1mm,1.7mm):沃特世科技(上海)有限公司
实施例1 Fe3O4@COF(TAPT-DHTA)的制备
(1)Fe3O4纳米颗粒的合成:准确称取2.6g FeCl3和1.59g FeCl2·4H2O,溶于12.5mL超纯水和0.43mL 12M HCl的混合溶液中,然后在剧烈搅拌条件下滴加至125mL 1.5M NaOH水溶液中。反应生成的黑色沉淀通过8000rpm转速下离心5min收集获得,收集的黑色沉淀物用纯水清洗3次后于60℃烘箱中烘干8小时。
(2)Fe3O4@COF(TAPT-DHTA)的合成:将86mg TAPT、106mg DHTA和200mg Fe3O4分散在40mL二元溶剂1,4-二恶烷/丁醇(1:1,V:V)中。超声处理20分钟后,加入0.5mL乙酸作为催化剂,并在室温(25℃)下搅拌2小时。然后,加入4.5mL乙酸/去离子水(2:1,V:V),混合物在氮气气氛除氧30min后转移至70℃水浴锅中搅拌反应48小时,反应结束后使用乙醇清洗三次,离心收集最终产物,去离子水洗3-5次至母液无色,在60℃下烘干24h,得到褐色粉末即为Fe3O4@COF(TAPT-DHTA)。
从扫描电子显微镜图谱(图1)可以看出,Fe3O4纳米颗粒与Fe3O4@COF(TAPT-DHTA)均为分散性较好的球形结构,直径分别约为200nm和850nm。
实施例2待测样品的采集及真菌毒素的富集净化
(1)待测样品采集:番茄,草莓,西瓜,甜瓜,山楂均为普通市售产品,用搅拌机粉碎或匀浆于﹣4℃下保存。
准确称取已经粉碎或匀浆的番茄,草莓,西瓜,甜瓜,山楂样品2.0g于50mL离心管中,加入10mL提取液(乙腈/甲酸;99/1,V/V),涡旋1min使其混合均匀,然后超声处理(80Hz,30±2℃)60min,震荡提取20min。将混合物以8000rpm离心5min,准确移取3mL上清液并在45℃下氮吹浓缩干燥。
使用3mL上样液1%乙腈水溶液(pH4.0))将氮吹干的固体重新溶解,并加入20mgFe3O4@COF(TAPT-DHTA),使悬浮液搅拌8min以使真菌毒素在Fe3O4@COF(TAPT-DHTA)纳米复合材料上充分吸附,之后使用磁铁将混合物分离并收集。使用3mL甲醇洗脱靶向真菌毒素4min,洗脱液经45℃氮吹浓缩后重新溶解于1mL含有5mmol L-1乙酸铵的乙腈/水中(20/80,V/V),得到待测样品溶液。
在UHPLC-MS/MS分析之前,将获得的待测样品溶液通过0.22μm尼龙过滤器过滤。
空白基质溶液:不含有九种目标真菌毒素的番茄,草莓,山楂,西瓜,甜瓜样品参照上述步骤处理后得到的溶液。
(2)UHPLC-MS/MS检测分析
色谱条件:色谱柱:Waters AcquityBEH C18色谱柱(100mm×2.1mm,1.7mm);流动相:流动相A为甲醇,流动相B为5mmol L-1乙酸铵溶液;梯度洗脱程序:0-5min,30% A-90% A;5-7min,90% A;7-7.5min,90% A-30% A;7.5-8.5min,30% A;;流速为0.4mL min-1;进样量3μL;柱温40℃。
质谱条件:分离出的化合物采用Waters XEVO TQ-S质谱仪,其电喷雾电离源可在正(ESI+)和负(ESI-)模式下工作。参数设定如下:离子源温度150℃;脱气温度500℃。锥体和脱溶气体流量分别为150L h-1和1000L h-1。
建立了多反应监测MRM模式对目标物进行定量,并对各真菌毒素检测条件进行了优化。采用MassLynx v4.1和Targetlynx数据分析软件进行数据处理,优化后的参数(母离子、子离子和碰撞能量)如表1所示。
表1九种真菌毒素的质谱参数
(3)结果分析
九种真菌毒素的回收率范围在75%-110%之间。
分析5种样品(番茄、草莓、西瓜、甜瓜和山楂)各20份样品,研究发现,ALT,TeA和AOH三种毒素污染最为严重。其中ALT在5种水果基质中均有检出,在番茄、草莓、西瓜、甜瓜和山楂中的检出率及浓度范围分别为70%(8.6-278.8μg kg-1)、100%(45.9-199.5μg kg-1)、25%(29.5-56.3μg kg-1)、50%(43.4-123.7μg kg-1)和45%(38.8-190.4μg kg-1)。TeA在番茄和草莓中的检出率分别为50%和45%,浓度范围分别为3.8-6.5μg kg-1和1.9-5.6μgkg-1。AOH在番茄、草莓和山楂中的检出率分别为10%,15%和25%,浓度范围分别为3.5-4.0μg kg-1,4.9-20.0μg kg-1和3.7-14.2μg kg-1。
实施例3磁固相萃取技术基质效应评估
用乙腈-5mmol L-1乙酸铵水溶液(20:80,V:V)基质标准溶液和空白基质溶液分别稀释标准储备液(10μg mL-1),得到分析物浓度分别为(0.1、0.5、1、5、10、20、50、100、200ngmL-1)的系列标准品。
经过Fe3O4@COF(DAPT-DHTA)纳米材料的磁固相萃取富集净化后的样品液与未净化样品液相比,明显澄清透明(图2)。说明经过净化的样品液,可以有效除去色素、纤维等干扰杂质,达到净化的目的。
9种真菌毒素(20μg kg-1)在乙腈-5mmol L-1乙酸铵水溶液(20:80,V:V)混合溶液和空白小麦基质溶液中的MRM图谱如图3和图4所示,峰型良好,保留时间能够区分。基质效应见表2,范围为46.31-144.88%,说明为保证结果的准确性,需要采用基质匹配校准曲线来消除基质效应。
表2九种真菌毒素基质效应
实施例4所建立的磁固相萃取-UHPLC-MS/MS分析方法验证
通过线性曲线、检出限、定量限、回收率和精密度等指标对所建立的方法进行验证,以保证方法的灵敏度、准确度和重复性。
9种毒素的不同浓度的混标分别用乙腈-5mmol L-1乙酸铵水溶液(20:80,V:V)和空白基质溶液稀释制备,用于构建线性标准曲线。
采用基质校正标准曲线进行准确定量;定量限和检测限(信噪比S/N=3和10)用于评价灵敏度;回收率,日内和日间精密度在空白基质溶液中加标进行测试,番茄、草莓、西瓜、甜瓜和山楂空白样品分别用低、中、高三个浓度进行加标(2μg kg-1,50μg kg-1,100μgkg-1),每个浓度有3个平行,通过比较每个分析物的计算浓度和加标浓度来考察回收率,回收率在70%到120%之间是可以接受的。当日3个浓度水平的相对标准偏差(RSD)用于评价日内精密度,而连续5天的结果用于评价日间精密度。
实验结果表明,加标的番茄、草莓、西瓜、甜瓜和山楂基质溶液及溶剂(乙腈-5mmolL-1乙酸铵水溶液(20:80,V:V))中,9种真菌毒素在0.5-200μg kg-1范围内峰面积与浓度呈良好线性,线性相关系数(R2)均大于0.993;LOD和LOQ分别为0.01-0.5μg kg-1和0.05-1.0μgkg-1。
9种目标化合物在番茄,草莓,西甜瓜和山楂中的回收率的范围为75.2-116.9%,日内精密度为2.08-11.8%,日间精密度为2.8-12.6%。
上述结果表面本发明的方法具有准确性和可重复性,可同时用于番茄,草莓,西瓜,甜瓜和山楂等的9种真菌毒素的分析。
Claims (2)
1.一种用磁固相萃取剂Fe3O4@COF对九种真菌毒素同时富集净化的方法,其特征在于,该方法包括如下步骤:
在1-5g待测样品中加入5~30 mL乙腈-甲酸溶液,涡旋后,室温下60 Hz超声30~60 min,提取待测样品中的目标真菌毒素;离心,取上清液2~10 mL,氮气吹干,得到待富集净化样本;
接着将2~10 mL 的1%乙腈水溶液作为上样溶液加入待富集净化样本,并加入10~30 mgFe3O4@COF进行磁固相搅拌吸附5~20 min;然后采用磁性分离,弃掉上清液;接着加入2~10mL甲醇作为洗脱液,超声2~10 min洗脱目标真菌毒素;
移取2~8 mL上述含有真菌毒素的洗脱液在50℃的氮气流下吹干,重新溶解在0.5~3 mL乙腈-5 mmol L−1乙酸铵水溶液的混合溶液中,通过0.22 μm滤膜,上机进行UPLC-MS/MS分析;
其中Fe3O4@COF通过如下方法制备得到:
将2,4,6-三(4-氨基苯基)-1,3,5-三嗪TAPT、2,5-二羟基对苯二甲酸DHTA和Fe3O4纳米颗粒按照质量比例为1:0.7~1.2:0.5~2.5,分散在二元溶剂1,4-二恶烷/丁醇中;室温下60Hz超声处理 20 分钟后,加入乙酸作为催化剂,并在室温下搅拌2~3小时;然后,加入乙酸/去离子水, 混合物在氮气气氛除氧30 min后转移至70℃水浴锅中搅拌反应36~72小时,反应结束后使用乙醇清洗,离心收集最终产物,去离子水洗3-5次至母液无色,在60℃下烘干24 h,得到褐色粉末即为Fe3O4@COF;
其中所述的九种真菌毒素为:细交链格孢酮酸TeA、交链孢酚AOH、交链孢酚单甲醚AME、腾毒素TEN、交链孢霉烯ALT、细格菌素ALS、赭曲霉毒素A OTA、黄曲霉毒素B1 AFB1和玉米赤霉烯酮ZEN。
2.根据权利要求1所述的对九种真菌毒素同时富集净化的方法,其特征在于,其中UPLC-MS/MS分析的色谱条件和质谱条件分别如下:
色谱条件:色谱柱:Waters Acquity UPLC®BEH C18 色谱柱,100 mm×2.1 mm, 1.7mm; 流动相:流动相A为甲醇,流动相B为5 mmol L-1乙酸铵水溶液;梯度洗脱程序:0-5 min,30% A-90% A;5-7 min,90% A;7-7.5 min,90% A-30% A;7.5-8.5 min,30% A;流速为0.4mL min-1;进样量3 μL;柱温40℃;
质谱条件:分离出的化合物采用Waters XEVO TQ-S质谱仪,其电喷雾电离源在正ESI+和负ESI−模式下工作;参数设定如下:离子源温度150℃;脱气温度500℃;锥体和脱溶气体流量分别为150 L h−1和1000 L h−1。
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