CN107118354B - 一种赭曲霉毒素金属有机骨架-分子印迹复合的分离介质的制备方法及应用 - Google Patents
一种赭曲霉毒素金属有机骨架-分子印迹复合的分离介质的制备方法及应用 Download PDFInfo
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Abstract
本发明属于分离介质制备技术领域，特别涉及一种赭曲霉毒素金属有机骨架‑分子印迹复合的分离介质的制备方法及应用，并以此作为固相萃取柱的填料应用于复杂基质中赭曲霉毒素选择性的富集、分离。所述印迹聚合物以赭曲霉毒素的结构类似物作为替代模板，将金属有机骨架与印迹聚合物相结合，制得赭曲霉毒素的金属有机骨架‑分子印迹复合的分离介质。本发明所制备的分离介质兼具金属有机骨架的多孔性特点和分子印迹聚合物对目标分子的分子识别能力，能够对赭曲霉毒素选择性的富集和分离，将其应用于复杂基质的样品前处理中，达到较好的净化、富集效果，有广阔的应用前景。
Description
技术领域
本发明属于食品安全分析检测技术领域，特别涉及一种适用于复杂基质中对赭曲霉毒素具有特异性分子识别能力的金属有机骨架-印迹聚合物的制备方法及其应用。
背景技术
赭曲霉毒素主要由曲霉属和青霉属菌株产生，具有致畸性，胚胎毒性，遗传毒性，神经毒性，免疫抑制性，致癌性，以及肾毒性，更为严重的是，它可以在离开宿主真菌的条件下继续存在，并且在人体内有长达35天的较长半衰期。因此，赭曲霉毒素已在世界范围内引起了广泛的关注，国际癌症研究机构已将赭曲霉毒素列为可能的致癌物质(2B类)。
2011年最新国标规定谷物及其制品中赭曲霉毒素A的最高限量值为5μg kg-1。由此可见，食品中OTA检测水平的灵敏性和特异性显得至关重要。
现在常用的真菌毒素检测方法有薄层色谱法(TLC)、免疫亲和柱-高效液相色谱法、紫外、荧光、质谱检测器以及酶联免疫吸附试验(ELISA)。但在化学分析中,实际样品的成分复杂，干扰物质较多,如果所分析的样品没有得到有效的处理，会导致其最终的检测数据有极大的误差，并且对精密的实验仪器造成不可估量的损害。实际样品的预处理非常耗时，且影响其检测效果，因此新型样品预处理方法的研究意义重大。
目前赭曲霉毒素的前处理除了液液萃取、固相萃取等传统方法外，免疫亲合柱是常用的样品前处理方法，但免疫亲合柱的净化效果容易受样品基质、pH、溶剂、盐浓度等的影响，同时其价格昂贵，难于重复使用，不适宜大面积推广使用，很大程度上限制了赭曲霉毒素检测的普及。
新近发展起来的分子印迹聚合物作为固相萃取柱的填料，以其高选择性和特异性的吸附能力、重复性高、检测线低、又不易受样品基体的干扰的特点，正被逐渐应用到食品中对痕量有毒有害物质的前处理过程中，弥补了传统固相萃取和免疫亲和柱的不足。
由于赭曲霉毒素有较强毒性和广泛传播性对试验操作人员有很强的毒性作用，毒素获取困难，价格昂贵。用毒素本身作模板分子会增加实验的成本和操作的危险性，所以研究用赭曲霉毒素的结构类似物作为替代模板合成印迹聚合物，避免了其中的模板因未洗脱完全，对目标分析物的检测造成干扰，降低对实验人员的伤害，毒素的特异性吸附不会造成太大影响且符合环境友好的要求。本发明中采用赭曲霉毒素的结构类似物作为替代模板合成印迹聚合物。
分子印迹技术虽然有制备方法简单，特异选择性好等特点，但合成的的聚合物的表面积较小，与毒素接触不充分，导致吸附速率较慢等缺点，不能使复杂基质中痕量的毒素充分富集，为进一步增加吸附量，本发明尝试将具有多空结构的金属有机骨架材料作为载体来合成新型的金属有机骨架-分子印迹复合物。这种复合物将两种材料的优点结合起来，不仅特异选择性好，而且接触面积大，吸附速率和吸附量也有很大程度提高，随着研究的进一步深入，这种新型复合物将具有极为广阔的应用前景，目前尚未见报道。
发明内容
针对复杂基质中存在的痕量赭曲霉毒素，样品前处理采用传统的液液溶剂萃取效率低，使用商品化的免疫亲和柱净化效果容易受样品基质、pH、溶剂、盐浓度等的影响，同时其价格昂贵，难于重复使用等问题，本发明以金属有机骨架为载体，采用沉淀聚合的方法合成金属有机骨架-分子印迹复合物，拟解决的技术问题是提供一种适用于复杂基质中对赭曲霉毒素具有特异性分子识别能力的金属有机骨架-分子印迹复合物的制备方法。
本发明实现上述目的的技术解决方案如下：
首先采用水热反应的方法以三水硝酸铜和均苯三甲酸为原料合成金属有机骨架材料，然后再加入模板分子、功能单体、交联剂、引发剂，在分子印迹合成的条件下，以金属有机骨架为载体合成金属有机骨架-分子印迹复合物。所述的溶剂为氯仿、乙醇、丙酮等；所述的模板分子为醌茜兰、氯霉素等赭曲霉毒素的结构类似物；所述的功能单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸、甲基丙烯酸、丙烯酰胺、氯甲基苯乙烯；所述的交联剂为乙二醇二甲醇丙烯酸酯、二乙烯基苯；所述的引发剂为偶氮二异丁腈、过氧化苯酰。
所述离介质通过如下步骤制得：
(1)金属有机骨架的制备：将三水硝酸铜溶于水，均苯三甲酸溶于无水乙醇，将两种溶液混合，采用水热反应的方法在反应釜中120℃反应12h，得到晶体，所得产物用乙醇和蒸馏水反复重洗后，在150℃真空条件下干燥8h进行活化，得到脱水的金属有机骨架材料；
(2)金属有机骨架-分子印迹复合物的制备：在溶剂中加入模板分子、功能单体、交联剂、引发剂，搅拌混匀后加入(1)制得的金属有机骨架，反应得到金属有机骨架-分子印迹复合物；所述的溶剂为氯仿、乙醇、丙酮等；所述的模板分子为醌茜兰、氯霉素、溶剂紫等赭曲霉毒素的结构类似物；所述的功能单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸、甲基丙烯酸、丙烯酰胺、氯甲基苯乙烯；所述的交联剂为乙二醇二甲醇丙烯酸酯、二乙烯基苯；所述的引发剂为偶氮二异丁腈、过氧化苯酰；
(3)模板分子的洗脱：把(2)制得的聚合物在索氏提取器用有机溶剂-酸的混合物抽提，洗去模板分子，直到不能检测出模板分子为止，再用有机溶剂洗去残留的酸，真空干燥至恒重，得到可以在复杂基质体系中对赭曲霉毒素有选择性吸附的金属有机骨架-分子印迹复合物。
同时用同样比例和方法制取非印迹聚合物(不加模板分子)。
步骤(2)中所述的模板分子、功能单体、交联剂的摩尔比例为1:3～8:10～30。
步骤(2)中所述的金属有机骨架的加入比例为1:1～10。
步骤(2)中所述的引发剂的比例为0.5％～4％，反应温度为50℃～100℃，反应时间为4小时～36小时。
步骤(3)中，所述的有机溶剂为甲醇、乙醇、乙腈，所述的酸为乙酸，金属有机骨架-分子印迹复合物用有机溶剂和酸混合液去除模板分子，处理后得到对赭曲霉毒素有选择性吸附的金属有机骨架-分子印迹复合物。
附图说明
图1为金属有机骨架-分子印迹复合物的扫描电镜图；
图2为分子印迹聚合物(a)和金属有机骨架-分子印迹复合物(b)的粒径分布图；
图3为金属有机骨架-分子印迹复合物对赭曲霉毒素的吸附曲线。
具体实施方式
实施例1
将1.0mmol 1-羟基-4-对甲苯氨基蒽醌加入含有1.5g经活化金属有机骨架，150mL的无水乙醇三口瓶中，然后加入5.0mmol甲基丙烯酸丁酯，30mmol乙二醇二甲基丙烯酸酯和2.5％的引发剂偶氮二异丁腈，超声5min，待溶液混合均匀，机械搅拌(转速200r min-1)，置于75℃恒温油浴中，反应5h，升高至90℃熟化1h，之后抽滤晾干后得到含有替代模板的有机骨架-分子印迹复合物。将复合物用甲醇/乙酸(4∶1，体积/体积)与甲醇清洗反应产物，直到无模板分子洗出为止。晾干后于40℃下真空干燥48h，得到有机骨架-分子印迹复合物。
实施例2
将1.0mmol 1-羟基-4-对甲苯氨基蒽醌加入含有1.5g经活化的金属有机骨架的150mL的无水乙醇三口瓶中，然后加入7.0mmol甲基丙烯酸丁酯，30mmol乙二醇二甲基丙烯酸酯和2.5％的引发剂偶氮二异丁腈，超声5min，待溶液混合均匀，机械搅拌(转速200rmin-1)，置于75℃恒温油浴中，反应5h，升高至90℃熟化1h，之后抽滤晾干后得含有替代模板的有机骨架-分子印迹复合物。将复合物用甲醇/乙酸(4∶1，体积/体积)与甲醇清洗反应产物，直到无模板分子洗出为止。晾干后于40℃下真空干燥48h，得到有机骨架-分子印迹复合物。
实施例3
将1.0mmol 1-羟基-4-对甲苯氨基蒽醌加入含有1.5g经活化的金属有机骨架的150mL的无水乙醇三口瓶中，然后加入7.0mmol的甲基丙烯酸丁酯，15mmol的乙二醇二甲基丙烯酸酯和2.5％的引发剂偶氮二异丁腈，超声5min，待溶液混合均匀，机械搅拌(转速200rmin-1)，置于75℃恒温油浴中，反应5h，升高至90℃熟化1h，之后抽滤晾干后得含有替代模板的有机骨架-分子印迹复合物。将复合物用甲醇/乙酸(4∶1，体积/体积)与甲醇清洗反应产物，直到无模板分子洗出为止。晾干后于40℃下真空干燥48h，得到有机骨架-分子印迹复合物。
实施例4
研究分子印迹材料的吸附性能。将10mg的有机骨架-分子印迹复合物置于5ml离心管中，分别加入4ml不同浓度(0.1，0.2，0.5，1，2，5，10，15，20μg/mL)的赭曲霉毒素的甲醇/水(1:9，V/V)标准溶液，在室温下静置10h。准确移取1mL的上清液，高效液相-荧光检测器测定其吸附后游离赭曲霉毒素的浓度，根据标准曲线计算赭曲霉毒素的浓度，根据吸附前后毒素浓度的变化计算聚合物的吸附量Q。同时平行做分子印迹聚合物和非印迹聚合物对赭曲霉毒素的吸附实验，即将10mg的分子印迹聚合物和非印迹聚合物置于5ml离心管中，分别加入4ml赭曲霉毒素的甲醇/水标准溶液。随着赭曲霉毒素浓度的升高，吸附容量逐渐增大。
Claims (3)
1.复杂基质中对赭曲霉毒素具有特异性分子识别能力的金属有机骨架-分子印迹复合物的制备方法，其特征在于，包括如下步骤：
（1）金属有机骨架的制备：将三水硝酸铜溶于水，均苯三甲酸溶于无水乙醇，将两种溶液混合，采用水热反应的方法在反应釜中120℃反应12h，得到晶体，所得产物用乙醇和蒸馏水反复重洗后，在150℃真空条件下干燥8h进行活化，得到脱水的金属有机骨架材料；
（2）金属有机骨架-分子印迹复合物的制备：在溶剂中加入模板分子、功能单体、交联剂、引发剂，搅拌混匀后加入（1）制得的金属有机骨架，反应得到金属有机骨架-分子印迹复合物；所述的溶剂为氯仿、乙醇或丙酮；所述的模板分子为醌茜兰、氯霉素；所述的功能单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸、甲基丙烯酸、丙烯酰胺或氯甲基苯乙烯；所述的交联剂为乙二醇二甲醇丙烯酸酯或二乙烯基苯；所述的引发剂为偶氮二异丁腈或过氧化苯酰；
（3）模板分子的洗脱：把（2）制得的聚合物在索氏提取器中用有机溶剂-酸的混合物抽提，洗去模板分子，直到不能检测出模板分子为止，再用有机溶剂洗去残留的酸，真空干燥至恒重，得到可以在复杂基质体系中对赭曲霉毒素有选择性吸附的金属有机骨架-分子印迹复合物。
2.如权利要求1所述的金属有机骨架-分子印迹复合物的制备方法，其特征在于，步骤（2）中所述的模板分子、功能单体、交联剂的摩尔比例为1: 3～8: 10～30。
3.如权利要求1所述的金属有机骨架-分子印迹复合物的制备方法，其特征在于，步骤（3）中，所述的有机溶剂为甲醇、乙醇或乙腈，所述的酸为乙酸，金属有机骨架-分子印迹复合物用有机溶剂和酸混合液去除模板分子，处理后得到对赭曲霉毒素有选择性吸附的金属有机骨架-分子印迹复合物。
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Granted publication date: 20201106 |