CN106622179B - 一种识别叶绿素的磁性分子印迹材料及其制备方法和应用 - Google Patents
一种识别叶绿素的磁性分子印迹材料及其制备方法和应用 Download PDFInfo
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- Investigating Or Analysing Biological Materials (AREA)
Abstract
本发明提供了一种识别叶绿素的磁性分子印迹材料及其制备方法和应用,该磁性分子印迹材料是通过如下方法制备得到的:(1)磁性纳米粒子Fe3O4的合成;(2)甲基丙烯酸(MAA)对磁性纳米粒子Fe3O4表面进行修饰;(3)磁性分子印迹材料Fe3O4@MIP的合成。本发明的识别叶绿素的磁性分子印迹材料可以用于选择性吸附叶绿素,吸附容量大,选择性好、磁性强、响应快、稳定性能好、重复利用率高,将其作为吸附剂应用于农药残留检测样品前处理中,可以去除农药残留分析中的常见干扰物叶绿素,成功建立了专门针对高色素农产品样品如韭菜、菠菜、茶叶中多种农药,尤其是平面结构农药残留的检测。
Description
技术领域
本发明涉及材料、分析化学技术领域,具体的说涉及一种识别叶绿素的磁性分子印迹材料及其制备方法和应用,。
背景技术
农药在作物和环境中的蓄积和残留一直是威胁人类食品安全和健康的重要来源之一。为了增加世界粮食的生产量,现代农业广泛使用化肥和农药。其中农药的使用种类繁多,包括有机磷(OOPs),有机氯(OCPs)和拟除虫菊酯类杀虫剂等。大量使用这些农药的后果便是这些化学物及其代谢产物在水和土壤等环境中残留和富集,并通过食物链最终进入人体。许多研究已经证明,部分农药具有致癌性,细胞毒性,遗传毒性,致突变性,致畸性和免疫损伤等,而高毒和剧毒的农药即使含量极低也会对非靶标生物和人类的健康存在危害。因此作物和环境中的农药残留监测也就成为了保障人类健康的必要手段。有鉴于此,农药残留检测已经成为食品安全例行监测中重要的一环。
准确测定农药残留量,监控其在规定的残留限量范围内,是当前保障食品安全和避免贸易纠纷的有效手段。2014年8月1日,食品中农药最大残留限量新国标GB2763-2014实施,较此前标准分别增加了65种农药、43种食品及1357项限量指标,约91%的限量等同或严于国际食品法典标准。因此建立农产品中痕量农药残留的准确、灵敏的检测技术,进而对农产品质量安全风险评估提供大数据支持,以及保障国民健康均具有重要意义。
农药残留分析的常用方法有很多种:如气相色谱法(GC)、高效液相色谱法(HPLC)、色谱-质谱联用(GC-MS/MS,UPLC-MS/MS)、免疫分析法、毛细管电泳分析等。大部分的方法在检测过程中还需要进行前处理,目前报道的前处理技术有液液萃取、基质固相分散、单液滴微萃取、固相萃取和分散固相萃取等。尤其值得一提的是2003年美国农业部开发的一种突破性的样品制备方法,简化了农药分析中样品制备步骤,即QuEChERS方法。目前,此方法在欧盟和美国被广泛使用。不过研究者发现其局限性是:QuEChERS方法中使用的石墨化炭黑(GCB)不仅对平面结构的分子如叶绿素有很强的吸附作用,可以去除基质中的色素杂质,而且对同样具有平面结构的农药分子也有很强的吸附能力,从而降低其回收率。而平面结构的农药并不少,常见的有多菌灵,百菌清,部分三嗪类除草剂和氨基甲酸酯类杀虫剂等。二者之间存在矛盾,若增加GCB的用量则除尽叶绿素的同时会显著降低平面结构农药的回收率,若减少GCB的用量兼顾平面结构农药的回收率则叶绿素去除不完全而出现高色素农产品样品中最常见的严重的基质干扰问题,两种情况都会影响农药残留量的准确定量。因此,需要开发一种可选择性吸附叶绿素,而对平面结构农药无吸附的新吸附材料,以弥补石墨化炭黑的不足。
近些年,分子印迹材料(MIPs,molecularly imprinted polymers)在固相萃取和传感器制备等方面发挥了重大作用,引起了人们的广泛重视。一般而言,分子印迹技术是指以某一特定的目标分子为模板,制备对该分子有特异选择性识别的聚合物的技术。该技术已经广泛运用在众多领域,然而目前报道的适用于农药检测的分子印迹材料通常均为专一性检测某种农药分子(即模板分子)或结构相近的化合物,运用在农产品安全检测中时无法实现多种类的农药多残留检测。
发明内容
本发明首先提供了一种识别叶绿素的磁性分子印迹材料的制备方法,该方法包括如下步骤:
(1)磁性纳米粒子Fe3O4的合成:
将六水合物氯化铁(FeCl3·6H2O)和四水合物氯化亚铁(FeCl2·4H2O)分别溶于水中,然后两者混合并通入氮气保护;
取水和氨水倒入烧瓶中,置于30-40℃水浴锅中,搅拌并通氮除氧,然后加入上述FeCl3·6H2O和FeCl2·4H2O的混合水溶液,搅拌1-2h,反应完成后将得到的黑色物质用磁铁分离,用水洗涤、,干燥,得到磁性纳米粒子Fe3O4;
(2)基丙烯酸(MAA)对磁性纳米粒子Fe3O4表面进行修饰:
将上述磁性纳米粒子Fe3O4分散于第一有机溶剂中,加入MAA,搅拌反应20-30h;
反应完成后,将得到的修饰好的Fe3O4用磁铁分离,用水和乙醇分别洗涤、干燥,得到MAA表面修饰的磁性纳米Fe3O4颗粒;
(3)磁性分子印迹材料Fe3O4@MIP的合成:
将上述MAA表面修饰的磁性纳米Fe3O4颗粒分散于第二有机溶剂中,称取含卟啉环类化合物模板分子和功能单体也溶于第二有机溶剂中,超声20-50min后两者混合,再超声20-50min;
向混合液中加入交联剂和引发剂,通入氮气2-7min后,密封容器;
在40-70℃下水浴摇床,自由基聚合反应16-30h;
反应完成后,将得到的分子印迹聚合物用磁铁分离,分别用水和第三有机溶剂洗涤,最后至PH值6-7,干燥,得到Fe3O4@MIP。
其中优选的方案为:
步骤(1)中FeCl3·6H2O和FeCl2·4H2O的摩尔比是1:(1.5-2.5);所述氨水浓度为25%-28%(质量比),水和氨水的添加比例为(10-25):1(体积比);
其中步骤(2)中所述的第一有机溶剂为甲醇、乙醇或甲苯中的一种;所述Fe3O4磁性纳米粒子在第一有机溶剂中的浓度为10-30mg/mL;所述MAA和第一有机溶剂的体积之比为(2-5):10;
其中步骤(3)中所述的第二有机溶剂为乙腈、乙醇或甲苯中的一种;所述的含卟啉环类化合物模板分子为叶绿素、血晶素或四苯基卟啉;所述的功能单体为甲基丙烯酸、甲基丙烯酰胺、对乙烯基苯甲酸、2-(三氟甲基)丙烯酸中的一种或多种;所述的交联剂为二甲基丙烯酸乙二醇酯或甲基丙烯酸缩水甘油酯;所述的引发剂为偶氮二异丁腈;所述MAA修饰的Fe3O4磁性纳米粒子在第二有机溶剂中的浓度为5-7mg/mL;所述卟啉环类化合物在第二有机溶剂中的浓度为3-10μmol/mL,所述功能单体在第二有机溶剂中的浓度为12-40μmol/mL,所述交联剂在第二有机溶剂中的浓度为60-200μmol/mL,所述引发剂在第二有机溶剂中的浓度为3-10μmol/mL;所述的第三有机溶剂为乙腈、甲醇或甲醇乙酸混合液中的一种;
另外优选的方案中,在步骤(1)中所述FeCl3·6H2O和FeCl2·4H2O的混合水溶液在加入水和氨水的混合液中时,是边搅拌边逐滴加入的,其中搅拌的速率为400-800rpm/min;这样可以得到分散性良好、粒径均匀适中的磁性纳米粒子Fe3O4;
步骤(2)中,为了得到均匀分散并均匀地将磁性纳米粒子Fe3O4表面修饰MAA,搅拌第一有机溶剂、磁性纳米粒子Fe3O4和MAA混合物时要均匀,搅拌的速率为500-1000rpm/min。
本发明还提供了一种由上述方法制备得到的识别叶绿素的磁性分子印迹材料Fe3O4@MIP。
本发明的识别叶绿素的磁性分子印迹材料用于农产品农药残留检测时的用途,其用于吸附叶绿素,去除干扰。
本发明所提供的分子印迹材料为磁性纳米仿生识别材料,有特异性强的识别位点和较好的吸附性能,吸附速率快、吸附容量大、稳定性能较好,可实现对高色素农产品样品中叶绿素干扰物的高效选择性识别和吸附,而对目标平面结构农药无吸附,一举解决了目前主流的叶绿素吸附剂GCB对二者无选择性吸附的难题。
针对高叶绿素含量的农产品样品,将本发明所提供的识别叶绿素的磁性分子印迹材料和QuEChERS方法相结合,可以建立一种高回收率、降低基质效应、快速、可靠的前处理方法,实现了农药多残留检测,极具实际应用价值。
通过红外光谱仪对所制备的磁性分子印迹纳米材料Fe3O4@MIP等进行表征,通过透射电镜(TEM)观察纳米颗粒表面形貌。通过静态和动态吸附性实验,以紫外-可见光谱仪测定并比较优化的磁性分子印迹纳米材料Fe3O4@MIP和非分子印迹材料Fe3O4@NIP对叶绿素的吸附容量和速率。并以QuEChERS前处理方法结合色谱质谱联用仪(GC-MS/MS和UPLC-MS/MS)分析比较使用磁性分子印迹纳米材料Fe3O4@MIP和石墨化炭黑(GCB)在吸附高色素农产品样品如韭菜、菠菜、茶叶中的叶绿素干扰物的效果,以及同等效果条件下评价所分析的68种目标平面结构农药的添加回收率和重复性试验的相对标准偏差。
本发明的识别叶绿素的磁性分子印迹材料改变了以往的一种分子印迹材料只能检测一种农药分子或相近结构农药的局限,将目的由目标农药分子捕捉变为干扰物去除,拓宽了分子印迹技术的运用思路。开发了一种可选择性吸附叶绿素,吸附容量大,而对平面结构农药无吸附的新型分子印迹材料Fe3O4@MIP,弥补了石墨化炭黑(GCB)的不足。针对高叶绿素含量农产品样品,将分子印迹技术和QuEChERS方法相结合,建立一种高回收率、降低基质效应、快速、可靠的前处理方法,实现了农药多残留检测,极具实际应用价值。
与现有技术相比,本发明的有益效果为:
(1)本发明以磁性四氧化三铁为载体制备磁性分子印迹材料,既保证了材料良好的磁学性质、分散性和稳定性,还便于根据实验目的对载体进行化学修饰。
(2)本发明在磁性四氧化三铁载体表面修饰MAA,采用表面分子印迹技术将聚合物接枝到载体表面,得到了表面覆盖有纳米级别尺寸的识别叶绿素分子的印迹薄层磁性功能化纳米材料。反应条件简便,材料形貌可控,选择性吸附性能、分散性和稳定性良好。
(3)本发明通过尝试几种含卟啉环类结构化合物模板分子,优化筛选功能单体、交联剂和引发剂种类,成功制备了能够识别叶绿素的磁性分子印迹纳米材料Fe3O4@MIP,可应用于高色素农产品样品中农药多残留检测的去除干扰物的前处理。
(4)本发明所提供的磁性分子印迹材料具有选择性识别叶绿素的吸附性能,而对目标平面结构农药无吸附。将该材料和QuEChERS方法相结合,建立了一种针对高叶绿素含量的农产品样品中农药多残留检测的高回收率、基质效应低、快速、可靠的前处理方法。弥补了目前农产品的农药残留前处理中重要干扰物叶绿素的特异性高效吸附的技术空白。
附图说明
图1包含图1(a)和图1(b),是实施例1制备的磁性纳米粒子Fe3O4的透射电镜图(图1(a))和磁性分子印迹材料Fe3O4@MIP的透射电镜图(图1(b))。
图2是实施例1制备的磁性纳米粒子Fe3O4,甲基丙烯酸(MAA)接枝改性磁性纳米粒子Fe3O4和磁性分子印迹材料Fe3O4@MIP的红外谱图。
图3是实施例1制备的磁性分子印迹材料Fe3O4@MIP和非分子印迹材料Fe3O4@NIP对叶绿素的吸附等温曲线。
图4是实施例1制备的磁性分子印迹材料Fe3O4@MIP和非分子印迹材料Fe3O4@NIP对叶绿素的动态吸附曲线。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
磁性分子印迹材料Fe3O4@MIP的制备。
具体包括如下步骤:
S11:磁性四氧化三铁(Fe3O4)纳米粒子的合成
称取6.763g六水合物氯化铁和1.99g四水合物氯化亚铁,然后分别溶于25mL和5mL超纯水后,两者混合并通入N2保护。取237mL超纯水和15mL氨水倒入500mL三口烧瓶中,置于35℃水浴锅中,在机械搅拌器作用下充分搅拌,并通入N2,除去溶液中的O2,然后将含有Fe3+和Fe2+的混合溶液逐滴加入,反应在35℃,N2保护和充分机械搅拌下进行1h,反应完成后将得到的黑色物质用超强磁铁分离,用超纯水洗涤,再用永久磁铁分离,重复用超纯水洗涤分离5次,置于60℃真空干燥,得到磁性Fe3O4纳米粒子。
S12:甲基丙烯酸(MAA)接枝改性磁性Fe3O4纳米粒子的制备
称取0.2g Fe3O4并加入10mL甲苯,超声分散30min后,加入2mL甲基丙烯酸(MAA),充分机械搅拌24h。反应完成后,将得到的修饰好的Fe3O4用超强磁铁分离,用水和乙醇洗涤,再用永久磁铁分离,重复用水和乙醇洗涤分离3次,置于60℃真空干燥,得到甲基丙烯酸表面修饰的磁性Fe3O4纳米粒子(Fe3O4-MAA)。
S13:识别叶绿素的磁性分子印迹材料Fe3O4@MIP的制备
称取0.2g Fe3O4-MAA溶于5mL乙腈中,超声30min,再称取0.0892g模板分子叶绿素和0.0334g MAA溶于25mL乙腈中,超声30min后,然后两者混合后倒入单口烧瓶中超声30min。向混合液中加入360μL二甲基丙烯酸乙二醇酯(EGDMA)和40mg偶氮二异丁腈(AIBN),通N2 5min后,用实心橡胶塞密封单口烧瓶,然后将单口烧瓶放入水浴摇床中,60℃,摇24h。反应完成后,将得到印迹聚合物用超强磁铁分离,用超纯水洗涤两次,超强磁铁分离,然后用甲醇/乙酸(v/v,9:1)洗涤四次,超强磁铁分离,60℃真空干燥,得到Fe3O4@MIP。
实施例2
磁性分子印迹材料Fe3O4@MIP的制备。
具体包括如下步骤:
S21:磁性四氧化三铁(Fe3O4)纳米粒子的合成
称取3.38g六水合物氯化铁和0.995g四水合物氯化亚铁,然后分别溶于15mL和3mL超纯水后,两者混合并通入N2保护。取118mL超纯水和8mL氨水倒入500mL三口烧瓶中,置于35℃水浴锅中,在机械搅拌器作用下充分搅拌,并通入N2,除去溶液中的O2,然后将含有Fe3+和Fe2+的混合溶液逐滴加入,反应在35℃,N2保护和充分机械搅拌下进行1h,反应完成后将得到的黑色物质用超强磁铁分离,用超纯水洗涤,再用永久磁铁分离,重复用超纯水洗涤分离5次,置于60℃真空干燥,得到磁性Fe3O4纳米粒子。
S22:甲基丙烯酸(MAA)接枝改性磁性Fe3O4纳米粒子的制备
称取0.4g Fe3O4并加入20mL甲苯,超声分散30min后,加入4mL甲基丙烯酸(MAA),充分机械搅拌24h。反应完成后,将得到的修饰好的Fe3O4用超强磁铁分离,用水和乙醇洗涤,再用永久磁铁分离,重复用水和乙醇洗涤分离3次,置于60℃真空干燥,得到甲基丙烯酸表面修饰的磁性Fe3O4纳米粒子(Fe3O4-MAA)。
S23:识别叶绿素的磁性分子印迹材料Fe3O4@MIP的制备
称取0.4g Fe3O4-MAA溶于10mL乙腈中,超声30min,再称取0.1372g模板分子血晶素和0.0668g MAA溶于50mL乙腈中,超声30min后,然后两者混合后倒入单口烧瓶中超声30min。向混合液中加入760μL二甲基丙烯酸乙二醇酯(EGDMA)和80mg偶氮二异丁腈(AIBN),通N2 5min后,用实心橡胶塞密封单口烧瓶,然后将单口烧瓶放入水浴摇床中,60℃,摇24h。反应完成后,将得到印迹聚合物用超强磁铁分离,用超纯水洗涤两次,超强磁铁分离,然后用甲醇/乙酸(v/v,9:1)洗涤四次,超强磁铁分离,60℃真空干燥,得到Fe3O4@MIP。
实施例3
磁性分子印迹材料Fe3O4@MIP的制备。
具体包括如下步骤:
S31:磁性四氧化三铁(Fe3O4)纳米粒子的合成
称取5.07g六水合物氯化铁和1.49g四水合物氯化亚铁,然后分别溶于18mL和4mL超纯水后,两者混合并通入N2保护。取178mL超纯水和11mL氨水倒入500mL三口烧瓶中,置于35℃水浴锅中,在机械搅拌器作用下充分搅拌,并通入N2,除去溶液中的O2,然后将上述含有Fe3+和Fe2+的混合溶液逐滴加入,反应在35℃,N2保护和充分机械搅拌下进行1h,反应完成后将得到的黑色物质用超强磁铁分离,用超纯水洗涤,再用永久磁铁分离,重复用超纯水洗涤分离5次,置于60℃真空干燥,得到磁性Fe3O4纳米粒子。
S32:甲基丙烯酸(MAA)接枝改性磁性Fe3O4纳米粒子的制备
称取0.8g Fe3O4并加入40mL甲苯,超声分散30min后,加入8mL甲基丙烯酸(MAA),充分机械搅拌24h。反应完成后,将得到的修饰好的Fe3O4用超强磁铁分离,用水和乙醇洗涤,再用永久磁铁分离,重复用水和乙醇洗涤分离3次,置于60℃真空干燥,得到甲基丙烯酸表面修饰的磁性Fe3O4纳米粒子(Fe3O4-MAA)。
S33:识别叶绿素的磁性分子印迹材料Fe3O4@MIP的制备
称取0.1g Fe3O4-MAA溶于5mL乙腈中,超声30min,再称取0.0317g模板分子四苯基卟啉,0.0167g MAA溶于15mL乙腈中,超声30min后,然后两者混合后倒入单口烧瓶中超声30min。向混合液中加入180μL二甲基丙烯酸乙二醇酯(EGDMA)和20mg偶氮二异丁腈(AIBN),通N2 5min后,用实心橡胶塞密封单口烧瓶,然后将单口烧瓶放入水浴摇床中,60℃,摇24h。反应完成后,将得到印迹聚合物用超强磁铁分离,用超纯水洗涤两次,超强磁铁分离,然后用甲醇/乙酸(v/v,9:1)洗涤四次,超强磁铁分离,60℃真空干燥,得到Fe3O4@MIP。
对比例
对比例提供磁性非分子印迹材料Fe3O4@NIP的制备方法,参照实施例1,对比例中具体的制备过程除在步骤S13中不添加模板分子外,其余步骤均与实施例1相同。
实施例4
为了验证本发明的有益效果,采用本发明实施例1所制备的分子印迹材料进行性能测试,步骤如下:
(1)分别称取13份5mg实施例1制备的Fe3O4@MIP和对比例制备的Fe3O4@NIP分别加入到15mL的离心管中,再分别加入10mL初始浓度为0.03-0.72mg/mL的叶绿素乙醇溶液,在恒温水浴摇床中30℃振荡30min,通过超强磁铁分离上层液后,用紫外-可见光谱仪测定并计算各上层液中叶绿素浓度,波长扫描范围为400-750nm,叶绿素最大吸收波长在670nm。检测结果如图3所示。
由图3可以看出,随着叶绿素溶液浓度的增加,磁性分子印迹材料和非分子印迹材料对叶绿素的吸附能力都趋于增加,但磁性分子印迹材料对叶绿素的吸附能力显著高于非分子印迹材料,这说明所制备的磁性分子印迹材料Fe3O4@MIP对叶绿素的吸附是特异性的。经计算,Fe3O4@MIP和Fe3O4@NIP对叶绿素的饱和吸附容量分别为135.4mg/g、478.9mg/g。
(2)将20mg实施例1制备的Fe3O4@MIP和对比例制备的Fe3O4@NIP分别加入到40mL叶绿素浓度为0.36mg/mL的乙腈溶液中,在恒温水浴摇床中30℃振荡2h,期间定时通过超强磁铁分离,取同等体积的上层液出来,用紫外-可见光谱仪测定并计算各上层液中叶绿素浓度。检测结果如图4所示,可以看出,制备的磁性纳米材料50min内对叶绿素的吸附即可达到平衡。
(3)以QuEChERS前处理方法结合色谱质谱联用仪(GC-MS/MS和UPLC-MS/MS)分析比较使用磁性分子印迹纳米材料Fe3O4@MIP和石墨化炭黑(GCB)在吸附高色素农产品样品即韭菜、菠菜、茶叶中的叶绿素干扰物的效果,以及同等效果条件下评价所分析的68种目标平面结构农药的添加回收率和重复性试验的相对标准偏差。
称取10g匀浆粉碎后的样品(韭菜、菠菜)或2g粉碎后的茶叶(绿茶),加10mL水涡旋混匀水化,置于50mL离心管中,加入10mL预冷乙腈。加入2颗陶瓷均质子,手摇快速震荡约30s;然后加入提取盐包(含无水硫酸镁4g、氯化钠1g、柠檬酸钠1g及柠檬酸氢二钠0.5g),手摇快速震荡混匀约1min,防止盐类结块。于25℃,5000rpm/min离心10min。分别取1mL提取液分别放入含不同量的Fe3O4@MIP和GCB的2mL离心管内(按照各自的饱和吸附量通过预实验确定加入量,使得提取液中叶绿素被吸附的水平一致),充分涡旋震荡使充分吸附去除叶绿素杂质。含GCB吸附剂的样品于25℃,6000rpm/min离心10min,含Fe3O4@MIP吸附材料的样品在超强磁铁作用下分离得到上清液。过0.2μm的微孔滤膜,分别用GC-MS/MS和UPLC-MS/MS进样分析。
针对68种目标平面结构农药,3种基质样品每种测试了3组添加浓度水平,每组浓度6个平行样品(即n=6),计算平均添加回收率(AVE,%)和相对标准偏差(RSD,%),结果如表1-表3所示。
表1 Fe3O4@MIP和GCB作为净化叶绿素的吸附剂对68种平面结构农药添加回收率和相对标准偏差的结果比较(韭菜)
表2 Fe3O4@MIP和GCB作为净化叶绿素的吸附剂对68种平面结构农药添加回收率和相对标准偏差的结果比较(菠菜)
表3 Fe3O4@MIP和GCB作为净化叶绿素的吸附剂对68种平面结构农药添加回收率和相对标准偏差的结果比较(茶叶)
由结果可知,在3种高色素农产品的多残留分析检测中,用Fe3O4@MIP作为吸附剂去除叶绿素的同时,对选取的68种目标平面结构农药均无明显吸附,使得几乎所有目标平面结构农药在3种浓度测试水平的添加回收率都在70%~120%之间,RSD≤30%,符合国家标准对于农药多残留分析的检测要求。而相应地用GCB作为吸附剂,绝大多数平面结构农药在3种高色素农产品基质的3种浓度添加水平测试下,其平均回收率在70%以下,多数在40%~60%之间,甚至有一部分农药的添加回收率在20%~30%,有相当一部分的RSD波动范围也超过30%。因此可以得出结论,Fe3O4@MIP对叶绿素的吸附存在选择性,它通过分子印迹材料的识别位点对叶绿素进行特异性吸附,而不影响平面结构农药。GCB对目标平面结构农药存在不同程度的吸附,从而影响农药的添加回收率和相对标准偏差,使得农药残留测定的定量结果不准确,而Fe3O4@MIP对叶绿素的选择性吸附,其效果大大优于GCB通过物理方式对含有平面结构的物质均吸附的特性。
Claims (4)
1.一种识别叶绿素的磁性分子印迹材料的制备方法,该方法包括如下步骤:
(1)磁性纳米粒子Fe3O4的合成:
将FeCl3·6H2O和FeCl2·4H2O分别溶于水中,然后两者混合并通入氮气保护;
取水和氨水倒入烧瓶中,置于30-40℃水浴锅中,搅拌并通氮除氧,然后加入上述FeCl3·6H2O和FeCl2·4H2O的混合水溶液,搅拌1h,反应完成后将得到的黑色物质用磁铁分离,用水洗涤,干燥,得到磁性纳米粒子Fe3O4;
(2)甲基丙烯酸对磁性纳米粒子Fe3O4表面进行修饰:
将上述磁性纳米粒子Fe3O4分散于第一有机溶剂中,加入MAA,搅拌反应20-30h;
反应完成后,将得到的修饰好的Fe3O4用磁铁分离,用水和乙醇分别洗涤、干燥,得到MAA表面修饰的磁性纳米Fe3O4颗粒;
(3)磁性分子印迹材料Fe3O4@MIP的合成:
将上述MAA表面修饰的磁性纳米Fe3O4颗粒分散于第二有机溶剂中,称取含卟啉环类化合物模板分子和功能单体也溶于第二有机溶剂中,超声20-50min后两者混合,再超声20-50min;
向混合液中加入交联剂和引发剂,通入氮气2-7min后,密封容器;
在40-70℃下水浴摇床,自由基聚合反应16-30h;
反应完成后,将得到的分子印迹聚合物用磁铁分离,分别用水和第三有机溶剂洗涤,最后至pH值6-7,干燥,得到Fe3O4@MIP;
其中所述的第一有机溶剂为甲醇、乙醇或甲苯中的一种;所述的第二有机溶剂为乙腈、乙醇或甲苯中的一种;所述的含卟啉环类化合物模板分子为叶绿素、血晶素或四苯基卟啉;所述的功能单体为甲基丙烯酰胺、对乙烯基苯甲酸、2-(三氟甲基)丙烯酸中的一种或多种;所述的交联剂为二甲基丙烯酸乙二醇酯或甲基丙烯酸缩水甘油酯;所述的引发剂为偶氮二异丁腈;所述的第三有机溶剂为乙腈、甲醇或甲醇乙酸混合液中的一种。
2.根据权利要求1所述的识别叶绿素的磁性分子印迹材料的制备方法,其中
步骤(1)中FeCl3·6H2O和FeCl2·4H2O的摩尔比是1:1.5-2.5;所述氨水浓度为25%-28%,水和氨水的添加比例为10-25:1;
其中步骤(2)中所述Fe3O4磁性纳米粒子在第一有机溶剂中的浓度为10-30mg/mL;所述MAA和第一有机溶剂的体积之比为2-5:10;
其中步骤(3)中所述的MAA修饰的Fe3O4磁性纳米粒子在第二有机溶剂中的浓度为5-7mg/mL;所述卟啉环类化合物在第二有机溶剂中的浓度为3-10μmol/mL,所述功能单体在第二有机溶剂中的浓度为12-40μmol/mL,所述交联剂在第二有机溶剂中的浓度为60-200μmol/mL,所述引发剂在第二有机溶剂中的浓度为6-10μmol/mL。
3.一种由权利要求1或2任一项所述方法制备得到的识别叶绿素的磁性分子印迹材料Fe3O4@MIP。
4.权利要求3所述识别叶绿素的磁性分子印迹材料用于农产品农药残留检测时的用途,其用于吸附叶绿素,去除干扰。
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