CN110951105B - 烟酰胺虚拟模板表面分子印迹材料及其制备方法和应用 - Google Patents

烟酰胺虚拟模板表面分子印迹材料及其制备方法和应用 Download PDF

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CN110951105B
CN110951105B CN201911188009.9A CN201911188009A CN110951105B CN 110951105 B CN110951105 B CN 110951105B CN 201911188009 A CN201911188009 A CN 201911188009A CN 110951105 B CN110951105 B CN 110951105B
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acetamiprid
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陈静钰
王洪新
吴世嘉
魏新林
黄鑫
王力
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Abstract

本发明公开了烟酰胺虚拟模板表面分子印迹材料及其制备方法和应用，所述制备方法包括制备改性硅胶载体、制备虚拟模板表面分子印迹材料等步骤。本发明新颖地采用吡虫啉和啶虫脒的结构类似物烟酰胺作为虚拟模板，制备硅胶表面分子印迹材料，不仅能够避免模板泄露造成的污染，而且能够特异性地脱除水溶性茶提取物中的吡虫啉和啶虫脒，对吡虫啉和啶虫脒的脱除率分别大于96％和93％，对提取物中茶多酚的损失小于10％。此外，本发明所制备的分子印迹吸附柱可以通过乙醇溶液进行洗脱，洗脱之后的吸附柱可以重新利用，因此能够很好地应用于茶提取物的制备工艺中，具有很好的应用前景。

Description

烟酰胺虚拟模板表面分子印迹材料及其制备方法和应用
技术领域
本发明属于化学材料技术领域，涉及一种虚拟模板表面分子印迹材料，具体为烟酰胺虚拟模板表面分子印迹材料及其制备方法和应用。
背景技术
水溶性茶提取物，尤其是茶多酚，是一种多羟基酚类化合物。它作为茶叶中具有保健功能的主要化学成分，是茶叶深加工的主要产物。在加工茶多酚的过程中面临主要问题之一是农药残留。茶多酚中的农药残留不仅会影响茶叶质量、损害消费者健康，而且会损害厂家的品牌声誉。吡虫啉和啶虫脒是茶叶种植过程中常用的高效氯烟碱类杀虫剂，在水和有机溶剂中具有良好的溶解性，因此在茶多酚的加工过程中非常容易残留。目前，农药残留的去除方法主要有物理法、化学法(KUSVURAN E,YILDIRIM D,MAVRUK F,et al.Removal ofchloropyrifos ethyl,tetradifon and chlorothalonil pesticide residues fromcitrus by using ozone[J].Journal of Hazardous Materials,2012,241(4):287-300.AFFAM AC,CHAUDHURI M.Degradation of pesticides chlorpyrifos,cypermethrinand chlorothalonil in aqueous solution by TiO 2 photocatalysis[J].2013,130(1):160-165.)和生物法(FERRARIO C,PITTINO F,TAGLIAFERRI I,et al.Bacteriacontribute to pesticide degradation in cryoconite holes in an Alpine glacier[J].Environmental Pollution,2017,230:919-926.)。其中，化学法和生物法由于安全性的问题，并不适用于茶多酚中农药的去除。在物理吸附法中，活性炭(MARCZEWSKI A W,SECZKOWSKA M,
Figure BDA0002292861800000011
A,et al.Adsorption equilibrium andkinetics of selected phenoxyacid pesticides on activated carbon:effect oftemperature[J].Adsorption-journal of the International Adsorption Society,2016,22(4-6):1-14.)、沸石(HUONG P.Nitrophenols removal from aqueous mediumusing Fe-nano mesoporous zeolite[J].Materials&Design,2016,101:210-217.)以及一些高分子材料(ZOLFAGHARI G.β-Cyclodextrin incorporated nanoporous carbon:Host–guest inclusion for removal of p-Nitrophenol and pesticides from aqueoussolutions[J].Chemical Engineering Journal,2016,283:1424-1434.)都被开发应用于农药残留的去除。然而，为了能够减少在农药脱出过程中茶多酚的损失，保证最终产品的质量和纯度，选择一种对吡虫啉和啶虫脒具有高选择性的材料十分必要。
分子印迹技术(MIT)是一种结合高分子化学、生物化学等学科发展起来的，具备特异性识别功能的新兴技术。通过MIT人工合成的、具有高稳定性、高选择性和易制备等特点的功能性识别材料被称为分子印迹聚合物(MIP)。迄今为止，MIP已在许多研究中被用于去除有害物质。例如，Sánchez-Polo(
Figure BDA0002292861800000021
M,VELO-GALA I,
Figure BDA0002292861800000022
JJ,et al.Molecular imprinted polymer to remove tetracycline from aqueoussolutions[J].Microporous and Mesoporous Materials,2015,203(203):32-40.)成功地合成了能够从水中脱除四环素(TC)的分子印迹聚合物。同样地，一种用于吸附Th(IV)的分子印迹固相萃取材料也被研究出来(JI X Z,LIU H J,WANG L L,et al.Study onadsorption of Th(IV)using surface modified dibenzoylmethane molecularimprinted polymer[J].Journal of Radioanalytical&Nuclear Chemistry,2013,295(1):265-70.)。然而，目前还没有用MIP同时吸附吡虫啉和啶虫脒的研究。虚拟模板分子印迹是一种能够有效避免模板泄漏的技术，在实际样品应用中，模板泄漏会在分离过程中造成严重的污染。烟酰胺是吡虫啉和乙脒的结构类似物，与吡虫啉和乙胺脒相比具有更低的毒性。烟酰胺具有抗炎作用，常作为食品添加剂、化妆品以及药物使用，被广泛认为是安全性较高的。选择烟酰胺作为虚拟模板，不仅可以同时对吡虫啉和啶虫脒进行脱除，避免模板泄漏造成的农药污染，还能够更为更多的消费者所接受。
发明内容
解决的技术问题：为了解决茶提取物水溶液中农药残留的问题，本发明采用吡虫啉和啶虫脒的结构类似物烟酰胺作为虚拟模板分子，不仅可以制备出能够同时脱除吡虫啉和啶虫脒的表面分子印迹材料，而且可以有效避免模板分子泄露导致的污染问题，提高了材料的安全性。以该材料作为柱填料制备固相萃取吸附柱，可以有效地脱除茶提取物水溶液中的吡虫啉和啶虫脒，而对茶多酚的损耗较小，在水溶性茶提取物的绿色加工中具有广泛的应用前景。鉴于此，本发明提供了烟酰胺虚拟模板表面分子印迹材料及其制备方法和应用。
技术方案：烟酰胺虚拟模板表面分子印迹材料的制备方法，所述方法包括以下步骤：
第1步、制备改性硅胶载体
将颗粒状硅胶浸入盐酸中处理，过滤、洗涤至中性并干燥，将干燥后的硅胶与甲苯按m/v(g/mL)＝1:40-1:8混合，逐滴加入3-氨丙基三乙氧基硅烷(APTS)和吡啶，氮气保护氛围中反应温度为363-383K，回流20-30h，经甲苯、丙酮、乙醚和甲醇对所得混合物洗涤后，真空干燥制备得到氨基改性硅胶；
将氨基改性硅胶与甲苯按m/v(g/mL)＝1:40-1:8混合，氮气保护氛围中加入丙烯酰氯，磁力搅拌后逐滴加入三乙胺，室温搅拌反应20-30h，经甲苯、丙酮、乙醚和甲醇对所得混合物洗涤后，真空干燥制备得到酰基改性硅胶；
第2步、制备虚拟模板表面分子印迹材料
将烟酰胺按m/v(mg/mL)＝1:1-3:1溶于甲醇的水溶液中，加入酰基改性硅胶和甲基丙烯酸(MAA)超声分散后避光反应2-6h，其中烟酰胺和酰基改性硅胶的质量比为5:6-5:3；反应结束后，在氮气氛围中加入二甲基丙烯酸乙二醇酯(EGDMA)和偶氮二异丁腈(AIBN)，323-343K水浴条件下密封反应20-28h，采用索氏提取法除去模板，洗涤、干燥制得虚拟模板表面分子印迹材料。
优选的，第1步中APTS的加入体积为甲苯的1/20-1/2，吡啶的加入体积为甲苯的1/80-1/8。
根据权利要求1所述的烟酰胺虚拟模板表面分子印迹材料的制备方法，其特征在于，第1步中丙烯酰氯的加入体积为甲苯的1/16-1/2。
以上任一所述方法制备获得的烟酰胺虚拟模板表面分子印迹材料。
所述烟酰胺虚拟模板表面分子印迹材料在脱除茶提取物水溶液中吡虫啉和啶虫脒中的应用。
优选的，所述烟酰胺虚拟模板表面分子印迹材料脱除茶提取物水溶液中吡虫啉和啶虫脒的步骤如下：
S1、制备分子印迹固相吸附柱
将烟酰胺虚拟模板表面分子印迹(DMIP)通过湿法装柱填充到装填有下筛板的SPE小柱中，压入上筛板，获得分子印迹固相吸附柱，加入甲醇对柱子进行活化备用；
S2、脱除应用
在浓度为10-60wt％的茶提取物水溶液中添加吡虫啉和啶虫脒，使其浓度分别为1-20μg·mL-1，将该水溶液作为上样液，通过S1制备的固相吸附柱进行吸附，控制样液流速，用2-8倍柱体积的去离子水洗去弱保留化合物，合并洗脱液与过柱液并检测；
S3、循环使用
用甲醇-乙酸体积比为9:1的混合溶剂对第S2吸附有吡虫啉和啶虫脒的吸附柱进行洗脱，调节并控制流速为0.5-2mL·min-1，使得吸附柱循环使用。
优选的，S2中水溶性茶提取物的损失小于10％，对吡虫啉和啶虫脒的脱除率分别大于96％和93％。
优选的，S3中吸附柱内96％以上的吡虫啉和98％以上的啶虫脒被洗脱。
优选的，所述茶提取物为茶多酚或茶氨酸。
优选的，水溶性茶提取物的重量百分含量为20-50wt％。
有益效果：本发明所述方法新颖地将烟酰胺作为虚拟模板分子，制备了硅胶表面分子印迹材料，该材料可以特异性地吸附茶提取物中的吡虫啉和啶虫脒，且对茶提取物中的茶多酚具有较小的损耗，对吡虫啉和啶虫脒的脱除率分别大于96％和93％，对提取物中茶多酚的损失小于10％。此外，本发明所制备的吸附柱在使用甲醇/乙酸溶液进行洗脱之后可以重新利用，因此能够很好地应用于茶提取物的加工工艺中，具有很好的应用前景。
附图说明
图1是本发明所述方法的技术流程图。
具体实施方式
以下实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
实施例1 茶多酚水溶液中吡虫啉和啶虫脒的脱除
本实施例提供了一种烟酰胺虚拟模板表面分子印迹脱除茶多酚水溶液中吡虫啉和啶虫脒的应用，该方法总共分为4步，分别为虚拟模板分子印迹固相萃取柱的制备、茶多酚水溶液的制备及预处理、过柱吸附和吸附柱再利用。具体操作方法如下：
1)分子印迹柱的制备具体是将1000mg DMIP粉末与5mL去超纯水混匀后，通过湿法装柱填充到装填有下筛板的SPE小柱中，压入上筛板，获得分子印迹固相萃取柱。
2)茶多酚水溶液的制备及预处理是称取2.0g茶多酚固体与100mL超纯水溶液中，制备成20g·L-1的茶多酚溶液，添加吡虫啉和啶虫脒使其浓度分别为10μg·mL-1，通过0.25μm滤膜过滤后备用。
3)然后将10mL上述步骤2)中的茶多酚水溶液通过上述1)中制备的DMIP固相萃取柱中，调节流速1.5mL/min，待茶多酚溶液完全通过后，用20mL超纯水洗脱弱保留化合物，合并吸附液并测量吸附前后吡虫啉，啶虫脒以及茶多酚的浓度。检测结果显示，该吸附柱对吡虫啉的吸附率为98.6％，对啶虫脒的吸附率为95.3％，对茶多酚的吸附率仅为7.2％。
4)采用40mL甲醇-乙酸(v/v,9:1)混合溶剂对上述3)中吸附柱上的吡虫啉和啶虫脒进行洗脱，调节并控制流速为1.5mL·min-1，合并洗脱液后进行检测，检测结果显示吸附在吸附柱中97.8％的吡虫啉和98.2％的啶虫脒被洗脱液洗脱。
5)循环吸附上述2)中的茶多酚水溶液10次后，其对吡虫啉和啶虫脒的吸附率仍然达到88.9％和87.6％。
实施例2 大容量茶多酚水溶液中吡虫啉和啶虫脒的脱除
根据实施例1中的方法，增加茶多酚水溶液的处理量，具体操作方法如下：
1)分子印迹柱的制备具体是将1000mg DMIP粉末与5mL去超纯水混匀后，通过湿法装柱填充到装填有下筛板的SPE小柱中，压入上筛板，获得分子印迹固相萃取柱。
2)茶多酚水溶液的制备及预处理是称取2.0g茶多酚固体与100mL超纯水溶液中，制备成20g·L-1的茶多酚溶液，添加吡虫啉和啶虫脒使其浓度分别为10μg·mL-1，通过0.25μm滤膜过滤后备用。
3)然后将50mL上述步骤2)中的茶多酚水溶液通过上述1)中制备的DMIP固相萃取柱中，调节流速1.5mL/min，待茶多酚溶液完全通过后，用20mL超纯水洗脱弱保留化合物，合并吸附液并测量吸附前后吡虫啉，啶虫脒以及茶多酚的浓度。检测结果显示，该吸附柱对吡虫啉的吸附率为97.2％，对啶虫脒的吸附率为94.8％，对茶多酚的吸附率仅为5.8％。
4)采用80mL甲醇-乙酸(v/v,9:1)混合溶剂对上述3)中吸附柱上的吡虫啉和啶虫脒进行洗脱，调节并控制流速为1.5mL·min-1，合并洗脱液后进行检测，检测结果显示吸附在吸附柱中96.5％的吡虫啉和96.9％的啶虫脒被洗脱液洗脱。
5)循环吸附上述2)中的茶多酚水溶液10次后，其对吡虫啉和啶虫脒的吸附率仍然达到87.6％和85.2％。
实施例3 茶氨酸水溶液中吡虫啉和啶虫脒的脱除
根据实施例1中的方法，将茶多酚水溶液改换为茶氨酸水溶液，具体操作方法如下：
1)分子印迹柱的制备具体是将1000mg DMIP粉末与5mL去超纯水混匀后，通过湿法装柱填充到装填有下筛板的SPE小柱中，压入上筛板，获得分子印迹固相萃取柱。
2)茶氨酸水溶液的制备及预处理是称取2.0g茶氨酸固体与100mL超纯水溶液中，制备成20g·L-1的茶氨酸溶液，添加吡虫啉和啶虫脒使其浓度分别为10μg·mL-1，通过0.25μm滤膜过滤后备用。
3)然后将10mL上述步骤2)中的茶氨酸水溶液通过上述1)中制备的DMIP固相萃取柱中，调节流速1.5mL/min，待茶多酚溶液完全通过后，用20mL超纯水洗脱弱保留化合物，合并吸附液并测量吸附前后吡虫啉，啶虫脒以及茶氨酸的浓度。检测结果显示，该吸附柱对吡虫啉的吸附率为98.5％，对啶虫脒的吸附率为96.3％，对茶氨酸的吸附率仅为6.4％。
4)采用40mL甲醇-乙酸(v/v,9:1)混合溶剂对上述3)中吸附柱上的吡虫啉和啶虫脒进行洗脱，调节并控制流速为1.5mL·min-1，合并洗脱液后进行检测，检测结果显示吸附在吸附柱中97.2％的吡虫啉和97.6％的啶虫脒被洗脱液洗脱。
5)循环吸附上述1)中的茶氨酸水溶液10次后，其对吡虫啉和啶虫脒的吸附率仍然达到89.2％和87.4％。

Claims (8)

1.烟酰胺虚拟模板表面分子印迹材料在脱除茶提取物水溶液中吡虫啉和啶虫脒中的应用，其特征在于，所述烟酰胺虚拟模板表面分子印迹材料由以下方法制得：
第1步、制备改性硅胶载体
将颗粒状硅胶浸入盐酸中处理，过滤、洗涤至中性并干燥，将干燥后的硅胶与甲苯按m/v（g/mL）=1:40-1:8混合，逐滴加入APTS和吡啶，氮气保护氛围中反应温度为363-383K，回流20-30h，经甲苯、丙酮、乙醚和甲醇对所得混合物洗涤后，真空干燥制备得到氨基改性硅胶；
将氨基改性硅胶与甲苯按m/v（g/mL）=1:40-1:8混合，氮气保护氛围中加入丙烯酰氯，磁力搅拌后逐滴加入三乙胺，室温搅拌反应20-30h，经甲苯、丙酮、乙醚和甲醇对所得混合物洗涤后，真空干燥制备得到酰基改性硅胶；
第2步、制备虚拟模板表面分子印迹材料
将烟酰胺按m/v（mg/mL）=1:1-3:1溶于甲醇的水溶液中，加入酰基改性硅胶和MAA超声分散后避光反应2-6h，其中烟酰胺和酰基改性硅胶的质量比为5:6-5:3；反应结束后，在氮气氛围中加入EGDMA和AIBN，323-343 K水浴条件下密封反应20-28h，采用索氏提取法除去模板，洗涤、干燥制得虚拟模板表面分子印迹材料。
2.根据权利要求1所述的应用，其特征在于，第1步中APTS的加入体积为甲苯的1/20-1/2，吡啶的加入体积为甲苯的1/80-1/8。
3.根据权利要求1所述的应用，其特征在于，第1步中丙烯酰氯的加入体积为甲苯的1/16-1/2。
4.根据权利要求1所述的应用，其特征在于，所述烟酰胺虚拟模板表面分子印迹材料脱除茶提取物水溶液中吡虫啉和啶虫脒的步骤如下：
S1、制备分子印迹固相吸附柱
将DMIP通过湿法装柱填充到装填有下筛板的SPE小柱中，压入上筛板，获得分子印迹固相吸附柱，加入甲醇对柱子进行活化备用；
S2、脱除应用
在浓度为10-60wt%的茶提取物水溶液中添加吡虫啉和啶虫脒，使其浓度分别为1-20 μg·mL-1，将该水溶液作为上样液，通过S1制备的固相吸附柱进行吸附，控制样液流速，用2-8倍柱体积的去离子水洗去弱保留化合物，合并洗脱液与过柱液并检测；
S3、循环使用
用甲醇-乙酸体积比为9:1的混合溶剂对第S2吸附有吡虫啉和啶虫脒的吸附柱进行洗脱，调节并控制流速为0.5-2 mL·min-1，使得吸附柱循环使用。
5.根据权利要求1所述的应用，其特征在于，S2中水溶性茶提取物的损失小于10%，对吡虫啉和啶虫脒的脱除率分别大于96%和93%。
6.根据权利要求1所述的应用，其特征在于，S3中吸附柱内96%以上的吡虫啉和98%以上的啶虫脒被洗脱。
7.根据权利要求1所述的应用，其特征在于，所述茶提取物为茶多酚或茶氨酸。
8.根据权利要求1所述的应用，其特征在于，水溶性茶提取物的重量百分含量为20-50wt%。
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