CN106519150A - 一种荧光偏振荧光磁性分子印迹传感器的制备方法 - Google Patents
一种荧光偏振荧光磁性分子印迹传感器的制备方法 Download PDFInfo
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Abstract
本发明涉及传感器敏感元件及其制备方法,具体涉及一种荧光偏振荧光磁性分子印迹传感器的制备方法,该方法具体包括以下步骤:步骤一、Fe3O4纳米颗粒的制备;步骤二、Fe3O4@SiO2的制备;步骤三、荧光Fe3O4@SiO2的制备;步骤四、荧光MIP‑ Fe3O4@SiO2的制备;步骤五、非印迹荧光磁性聚合物(NIP‑ Fe3O4@SiO2)的制备。本发明方法制备了一种同时具有荧光和磁性的分子印迹聚合物,并采用荧光偏振技术对该聚合物和被测物质进行检测,得到荧光偏振荧光磁性分子印迹传感器。该方法克服传统荧光分子印迹传感器检测存在的只能检测具有荧光性质的被测物的问题;同时,该方法简化制备工艺流程,增加了检测灵敏性,将检测限可降低至ng/L。
Description
技术领域
本发明涉及传感器敏感元件及其制备方法,具体涉及一种荧光偏振荧光磁性分子印迹传感器的制备方法。
背景技术
生物传感器由于其高灵敏度和特异性已成为分析化学和生物化学领域中一个非常重要的课题。但由于生物分子固有的缺陷(使用环境要求较高,难以长期保存,且生物分子来源于生物活体,制备和纯化繁琐、昂贵)限制了生物传感器发展。获得廉价、稳定的识别元件,是生物传感器进一步发展的关键之一。最近二十多年来,一种全新的合成“人工抗体”的方法,即分子印迹技术得到研究。特别是表面分子印迹技术的研究,解决了传统分子印迹技术中存在的问题,如聚合物的高交联网状结构使模板分子不易洗脱和再结合,结合效率低下等问题。表面分子印迹技术是在载体表面进行分子印迹聚合物,形成二维网状结构,使模板分子易于吸附和洗脱,提高聚合物的选择性和吸附性。同时,将磁性纳米材料与表面分子印迹技术像结合,制备出磁性表面分子印迹聚合物,期可在外加电场下快速分离,具有主动识别和快速分离的优点。而将荧光材料标记在磁性表面分子印迹聚合物上,得到的荧光磁性表面分子印迹聚合物使制备的印迹聚合物同时具有了荧光和磁性性质,无论模板分子是否具有荧光性质,均可采用荧光法检测。该技术在简化操作步骤的同时,扩大检测范围,就有很强的应用价值。同时,在荧光检测方法中,荧光偏振是荧光检测的一个新的热点,其以物理学显现为基础,用来研究生命中分子之间的相互作用。该方法可最大程度模拟真实生命环境,实时跟踪监控分子之间的变化。并且具有检测灵敏的优点。目前有研究报道的关于荧光偏振技术的检测限如测定血清中环孢霉素,最低检测限可达5μg/L,测定范围是15-1000µg/L[199]。Maragos[200]建立的荧光偏振检测方法中对马梭菌毒素的检出限可低至0.5ng,线性范围是0.5-20mg/L。中国专利申请201410539526.7公开了一种磁性分子印迹纳米颗粒及其制备方法和应用。方法步骤如下:1) 在磁性四氧化三铁纳米颗粒或磁性γ- 三氧化二铁纳米颗粒表面包覆一层二氧化硅,并使二氧化硅表面带有氨基。2)在步骤1)得到的磁纳米颗粒表面偶联偶氮类引发剂; 3)以步骤2)负载有引发剂的磁纳米颗粒为引发剂,在有亲水性链转移剂存在的条件下,加入蛋白模板分子、功能单体和水溶性交联剂,在室温紫外光照射引发反应,在磁纳米颗粒表面原位合成磁性分子印迹聚合物。4)功能单体中加入摩尔(物质的量)百分比为1-5%的荧光功能单体进行荧光标记。5)检测时采用荧光显微镜进行检测。可看到发明人虽然也制备了荧光磁性分子印迹聚合物,但制备过程中采用的是荧光单体。荧光单体一般难以获得,且成本很高,因此产物的制备成本高。且在检测过程中,该发明采用的检测方法为荧光显微镜,其可以检测大分子物质,但对于小分子物质检测不够灵敏。
中国专利申请 201410214026.6 公开了一种分离、净化莱克多巴胺磁性分子印迹聚合物的制备方法,该方法制备磁性四氧化三铁纳米微球,并用ATPS 修 饰四氧化三铁材料 (ATPS-Fe3O4)。同时制备磁性Fe3O4功能单体,得到Fe3O4@MIPs。该材料只具有磁性,而不具有荧光性质。检测被测物质采用的是高效液相色谱测定方法,且检测最低浓度为20mg/L。该发明只是简化了分子印迹聚合物制备的方法,并没有改善对被测物质检测的灵敏性。
发明内容
本发明的目的是制备了一种同时具有荧光和磁性的分子印迹聚合物,并采用荧光偏振技术对该聚合物和被测物质进行检测,得到荧光偏振荧光磁性分子印迹传感器。该方法克服传统荧光分子印迹传感器检测存在的只能检测具有荧光性质的被测物的问题。同时,该方法简化制备工艺流程,增加了检测灵敏性,将检测限可降低至ng/L。
本发明的目的是通过以下技术方案来解决的:一种荧光偏振荧光磁性分子印迹传感器的制备方法,包括下述步骤:
步骤一、Fe3O4纳米颗粒的制备
1.72gFeCl2•4H2O和 4.72gFeCl3•6H2O和80mL的去离子水加入烧瓶中,连续通入氮气并置于DF-101S集热式恒温加热磁力搅拌器并进行剧烈搅拌使其溶解;当温度升高至80℃,将10毫升的氨水溶液慢慢滴入烧瓶中,反应30min;在外加磁场作用下将产物分离;用去离子水洗涤6次,以除去未反应的物质,干燥、保存;
步骤二、Fe3O4@SiO2的制备
300mg的磁纳米颗粒、50mL的异丙醇和4mL超纯水一起超声处理15-20mim,后依次加入5mL氨水和2mL 正硅酸四乙酯;室温下连续搅拌反应12h。在外加磁场下收集产物,并用超纯水彻底的洗六次,干燥;
步骤三、荧光Fe3O4@SiO2的制备
将20g Fe3O4@SiO2在甲烷磺酸溶液(质量分数为50%)中活化。将活化的Fe3O4@SiO2和30mL乙烯基三乙氧基烷(Triethoxyvinylsilane,TTS)加入400mL(乙醇:水=1:1)混合溶液中, 50℃反应24-30h,用乙醇和蒸馏水冲洗,干燥,得TTS-Fe3O4@SiO2;取3gTTS- Fe3O4@SiO2和10g甲基丙烯酸,1g丙烯酰胺以及200mL蒸馏水,0.018g过硫酸胺于200ml圆底烧瓶内,70℃反应7h,在外加电场下收集产物,并用乙醇和蒸馏水多次冲洗,并干燥;取得到的产物1g与15mg异硫氰酸荧光素,5mL乙醇,100mL蒸馏水混合,振荡5-6h;在外加磁场下收集产物,水洗,烘干;
步骤四、荧光MIP- Fe3O4@SiO2的制备
将合成荧光Fe3O4@SiO2和4mmol/L模板分子,溶入100mL氯仿溶液中,反应前通入氮气5min,振荡5-6h,之后加入交联剂乙二醇二甲基丙烯酸酯,在50℃水浴锅内搅拌加热8h。在外加磁场下收集产物,并洗脱、烘干;
步骤五、非印迹荧光磁性聚合物(NIP- Fe3O4@SiO2)的制备
重复制备过程除不加入模板分子外,其余步骤与步骤四相同。
与现有技术相比,本发明的优点是:
1、 采用普通荧光试剂对分子印迹聚合物进行标记,而不是采用荧光单体。这样降低制备成本,简化操作步骤;
2、 经过本发明方法制备得到的产物,极大地提高了检测的灵敏性,其检测灵敏性高,使检测限达到ng级,最低检测限可达5ng/L。在对产物检测中,采用的是荧光偏振技术,可实现即时检测;
3、 经过本发明方法制备得到的产物,识别分辨率高、特异性强、稳定性好。传感器采用荧光标记的分子印迹聚合物对目标物质的特异性识别前后,偏振光的改变来进行物质的检测。制备不同浓度的模板分子溶液,得到最低检测限和响应时间;
4、 适用范围广:该分子印迹感器结合磁微球技术、光学技术、微电子技术及微机械加工技术等技术实现对生物传感器的开发,研制的生物传感器可实现物质分子水平的快速、准确和微量检测,可对被测物质进行准确、痕量、快速的探测。
附图说明
图1为荧光磁性纳米表面分子印迹聚合物的制备原理图;
图2为Fe304(a)、Fe3O4@SiO2(b)、荧光MIP- Fe3O4@SiO2(c)的磁性检测图;
图3为磁纳米颗粒Fe3O4(a)和Fe3O4 @SiO2(b)颗粒红外光谱图;
图4为荧光MIP- Fe3O4@SiO2(a)和Fe3O4@SiO2(b)的荧光显微镜的检测;
图5为Fe3O4、Fe3O4@SiO2与荧光MIP-Fe3O4@SiO2透射电镜检测结果;
图6为荧光MIP-Fe3O4@SiO2和NIP-Fe3O4@SiO2对棉酚的荧光偏振检测图。
具体实施方式:
参见图1,以下为本发明荧光磁性纳米分子印迹聚合物的设计原理图:
首先制备四氧化三铁磁性纳米颗粒,然后在磁性颗粒表面修饰一层二氧化硅,即Fe3O4@ SiO2微球。并以Fe3O4@ SiO2微球为载体,采用“接入法(grafting to)”技术。该技术是用偶联剂与Fe3O4@ SiO2表面的羟基相互作用,引入高活性基团,即以乙烯基三乙氧基硅烷(TTS)为偶联剂通过羟基偶联在硅胶表面。再加入功能单体,甲基丙烯酸和丙烯酰胺,形成多聚高分子链,并偶合在硅胶表面。加入荧光试剂,并将荧光试剂与丙烯酰胺的酰胺键结合。最后加入模板、交联剂,聚合生成分子印迹层。将模板分子洗脱后,得到荧光磁性纳米表面分子印迹聚合物。
在以上设计思路的基础上,一种荧光偏振荧光磁性分子印迹传感器的制备方法,具体步骤是:
步骤一、Fe3O4纳米颗粒的制备
1.72gFeCl2•4H2O和 4.72gFeCl3•6H2O和80mL的去离子水加入烧瓶中,连续通入氮气并置于DF-101S集热式恒温加热磁力搅拌器并进行剧烈搅拌使其溶解;当温度升高至80℃,将10毫升的氨水溶液慢慢滴入烧瓶中,反应30min;在外加磁场作用下将产物分离;用去离子水洗涤6次,以除去未反应的物质,干燥、保存;
步骤二、Fe3O4@SiO2的制备
300mg的磁纳米颗粒、50mL的异丙醇和4mL超纯水一起超声处理15-20mim,后依次加入5mL氨水和2mL 正硅酸四乙酯;室温下连续搅拌反应12h;在外加磁场下收集产物,并用超纯水彻底的洗六次,干燥;
步骤三、荧光Fe3O4@SiO2的制备
将20g Fe3O4@SiO2在甲烷磺酸溶液(质量分数为50%)中活化;将活化的Fe3O4@SiO2和30mL乙烯基三乙氧基烷(Triethoxyvinylsilane,TTS)加入400mL(乙醇:水=1:1)混合溶液中, 50℃反应24-30h,用乙醇和蒸馏水冲洗,干燥,得TTS-Fe3O4@SiO2;取3gTTS- Fe3O4@SiO2和10g甲基丙烯酸,1g丙烯酰胺以及200mL蒸馏水,0.018g过硫酸胺于200ml圆底烧瓶内,70℃反应7h,在外加电场下收集产物,并用乙醇和蒸馏水多次冲洗,并干燥;取得到的产物1g与15mg异硫氰酸荧光素,5mL乙醇,100mL蒸馏水混合,振荡5-6h;在外加磁场下收集产物,水洗,烘干;
步骤四、荧光MIP- Fe3O4@SiO2的制备
将合成荧光Fe3O4@SiO2和4mmol/L模板分子,溶入100mL氯仿溶液中,反应前通入氮气5min,振荡5-6h,之后加入交联剂乙二醇二甲基丙烯酸酯,在50℃水浴锅内搅拌加热8h;在外加磁场下收集产物,并洗脱、烘干;
步骤五、非印迹荧光磁性聚合物(NIP- Fe3O4@SiO2)的制备
重复制备过程除不加入模板分子外,其余步骤与步骤四相同。
下面通过实施例对本发明进行进一步的说明:
实施例1:
一种荧光偏振荧光磁性分子印迹传感器的制备方法,具体步骤是:
步骤一、Fe3O4纳米颗粒的制备
1.72gFeCl2•4H2O和 4.72gFeCl3•6H2O和80mL的去离子水加入烧瓶中,连续通入氮气并置于DF-101S集热式恒温加热磁力搅拌器并进行剧烈搅拌使其溶解;当温度升高至80℃,将10毫升的氨水溶液慢慢滴入烧瓶中,反应30min;在外加磁场作用下将产物分离;用去离子水洗涤6次,以除去未反应的物质,干燥、保存;
步骤二、Fe3O4@SiO2的制备
300mg的磁纳米颗粒、50mL的异丙醇和4mL超纯水一起超声处理20mim,后依次加入5mL氨水和2mL 正硅酸四乙酯;室温下连续搅拌反应12h;在外加磁场下收集产物,并用超纯水彻底的洗六次,干燥;
步骤三、荧光Fe3O4@SiO2的制备
将20g Fe3O4@SiO2在甲烷磺酸溶液(质量分数为50%)中活化;将活化的Fe3O4@SiO2和30mL乙烯基三乙氧基烷(Triethoxyvinylsilane,TTS)加入400mL(乙醇:水=1:1)混合溶液中, 50℃反应24h,用乙醇和蒸馏水冲洗,干燥,得TTS-Fe3O4@SiO2;取3gTTS- Fe3O4@SiO2和10g甲基丙烯酸,1g丙烯酰胺以及200mL蒸馏水,0.018g过硫酸胺于200ml圆底烧瓶内,70℃反应7h,在外加电场下收集产物,并用乙醇和蒸馏水多次冲洗,并干燥;取得到的产物1g与15mg异硫氰酸荧光素,5mL乙醇,100mL蒸馏水混合,振荡6h;在外加磁场下收集产物,水洗,烘干;
步骤四、荧光MIP- Fe3O4@SiO2的制备
将合成荧光Fe3O4@SiO2和4mmol/L模板分子,溶入100mL氯仿溶液中,反应前通入氮气5min,振荡6h,之后加入交联剂乙二醇二甲基丙烯酸酯,在50℃水浴锅内搅拌加热8h;在外加磁场下收集产物,并洗脱、烘干;
步骤五、非印迹荧光磁性聚合物(NIP- Fe3O4@SiO2)的制备
重复制备过程除不加入模板分子外,其余步骤与步骤四相同。
实施例2:
一种荧光偏振荧光磁性分子印迹传感器的制备方法,具体步骤是:
步骤一、Fe3O4纳米颗粒的制备
1.72gFeCl2•4H2O和 4.72gFeCl3•6H2O和80mL的去离子水加入烧瓶中,连续通入氮气并置于DF-101S集热式恒温加热磁力搅拌器并进行剧烈搅拌使其溶解;当温度升高至80℃,将10毫升的氨水溶液慢慢滴入烧瓶中,反应30min;在外加磁场作用下将产物分离;用去离子水洗涤6次,以除去未反应的物质,干燥、保存;
步骤二、Fe3O4@SiO2的制备
300mg的磁纳米颗粒、50mL的异丙醇和4mL超纯水一起超声处理15mim,后依次加入5mL氨水和2mL 正硅酸四乙酯;室温下连续搅拌反应12h;在外加磁场下收集产物,并用超纯水彻底的洗六次,干燥;
步骤三、荧光Fe3O4@SiO2的制备
将20g Fe3O4@SiO2在甲烷磺酸溶液(质量分数为50%)中活化;将活化的Fe3O4@SiO2和30mL乙烯基三乙氧基烷(Triethoxyvinylsilane,TTS)加入400mL(乙醇:水=1:1)混合溶液中, 50℃反应30h,用乙醇和蒸馏水冲洗,干燥,得TTS-Fe3O4@SiO2;取3gTTS- Fe3O4@SiO2和10g甲基丙烯酸,1g丙烯酰胺以及200mL蒸馏水,0.018g过硫酸胺于200ml圆底烧瓶内,70℃反应7h,在外加电场下收集产物,并用乙醇和蒸馏水多次冲洗,并干燥;取得到的产物1g与15mg异硫氰酸荧光素,5mL乙醇,100mL蒸馏水混合,振荡5h;在外加磁场下收集产物,水洗,烘干;
步骤四、荧光MIP- Fe3O4@SiO2的制备
将合成荧光Fe3O4@SiO2和4mmol/L模板分子,溶入100mL氯仿溶液中,反应前通入氮气5min,振荡5h,之后加入交联剂乙二醇二甲基丙烯酸酯,在50℃水浴锅内搅拌加热8h;在外加磁场下收集产物,并洗脱、烘干;
步骤五、非印迹荧光磁性聚合物(NIP- Fe3O4@SiO2)的制备
重复制备过程除不加入模板分子外,其余步骤与步骤四相同。
通过上述实施例2制备得到的产物,其检测如下:
参见图2:可看到颗粒分散在水中,使水呈黑色浑浊状态。用磁铁对分散在水中的颗粒进行吸附,可以明显看出水中的颗粒全部被磁铁吸附至一侧,溶液液重新变澄清。由此可证明所制备的Fe304、Fe3O4@SiO2、荧光MIP- Fe3O4@SiO2是具有磁性的。
采用红外光谱、荧光显微镜和透射电镜对制备的荧光磁性纳米分子印迹聚合物的结构进行检测。
参见图3:可以看到两处有特征峰,其中561cm-1处的吸收峰是Fe-O的特征振动峰,而1400cm-1表示羟基的振动峰。可知Fe3O4磁性纳米颗粒的制备无误。图3(b)表示Fe3O4 @SiO2,图中可见1091 cm-1处有吸收峰,为Si-O的特征峰,证明SiO2成功包覆在Fe3O4微粒表面。
参见图4:图4(a)为柚皮苷荧光MIP-Fe3O4@SiO2,图4(b)为Fe3O4@SiO2。比较两者之间的差别,可以看到在图4(a)中,硅胶颗粒表面有非常明显的荧光光圈,而在图4(b)中根本看不到任何荧光光圈。前后两者的差别证明了荧光分子成功的修饰在荧光MIP-Fe3O4@SiO2上。
参见图5:图5(a)为Fe3O4,可以看到图中磁颗粒大小、形状、空间分布都较为均匀,且平均颗粒直径约为70nm。图5(b)为Fe3O4@SiO2,可看到规则的圆形颗粒,由于Fe3O4被SiO2包裹,直径增大为100nm左右。图5(c)为荧光MIP-Fe3O4@SiO2,很明显颗粒大小、形状和分布都不规则,且颗粒直径约在100-200nm之间。这是由于Fe3O4@SiO2外部包覆单体、荧光试剂(异硫氰酸荧光剂)、交联剂后使荧光MIP-Fe3O4@SiO2直径变大。
参见图6:
对荧光偏振法对结合能力进行检测时,取等量的荧光MIP-Fe3O4@SiO2 和NIP- Fe3O4@SiO2,分别加入到不同浓度的被测物质的标准溶液及去离子水的离心管中,静置使被测物分子与荧光MIP- Fe3O4@SiO2和NIP- Fe3O4@SiO2相互作用。用移液枪取少许混合溶液,在384孔板上进行点样,十二份样品加在384孔板上的位置分别记为A1,B1,C1,D1,E1,F1 和A2, B2,C2, D2, E2, F2。其中A~E表示的溶液浓度,F为去离子水,即0。A1-F1 表示荧光MIP-Fe3O4@SiO2对被测物质的结合能力,A2-F2表示NIP- Fe3O4@SiO2对被测物质的结合能力。将点样好的384孔板放入荧光偏振检测仪中,进行检测,可得出实验数据。
从图中可以看到,随着被测物质溶液浓度增加,荧光偏振光值增大。这是由于荧光标记的小分子抗原在溶液中旋转速度快 ,荧光偏振光强度小,当荧光标记的小分子抗原与其相应抗体结合后 ,所形成的大分子在溶液中旋转速度变慢,荧光偏振光强度增大。荧光偏振程度的差异 ,与溶液中荧光MIP-Fe3O4@SiO2和被测物质的结合量有关。随着被测物质溶液浓度的增加,被测物分子与荧光MIP-Fe3O4@SiO2的结合量也在增加,故荧光偏振的值也逐渐增大。当结合到达到饱和时,荧光偏振值趋于稳定,即当浓度达到45ng/L时,荧光MIP-Fe3O4@SiO2与被测物的结合趋于饱和(如图6所示)。而NIP- Fe3O4@SiO2与被测物分子是通过静电吸附特相互作用的,无特异性,故荧光偏振值很小,且随溶液浓度的增大变化不明显。且可看到荧光偏振的最低检测限为5ng/L。因此说明荧光偏振方法检测分子印迹聚合物对被测物质的结合能力更为灵敏。
Claims (1)
1.一种荧光偏振荧光磁性分子印迹传感器的制备方法,其特征在于:
包括下述步骤:
步骤一、Fe3O4纳米颗粒的制备
1.72gFeCl2•4H2O和 4.72gFeCl3•6H2O和80mL的去离子水加入烧瓶中,连续通入氮气并置于DF-101S集热式恒温加热磁力搅拌器并进行剧烈搅拌使其溶解;当温度升高至80℃,将10毫升的氨水溶液慢慢滴入烧瓶中,反应30min;在外加磁场作用下将产物分离;用去离子水洗涤6次,以除去未反应的物质,干燥、保存;
步骤二、Fe3O4@SiO2的制备
300mg的磁纳米颗粒、50mL的异丙醇和4mL超纯水一起超声处理15-20mim,后依次加入5mL氨水和2mL 正硅酸四乙酯;室温下连续搅拌反应12h;在外加磁场下收集产物,并用超纯水彻底的洗六次,干燥;
步骤三、荧光Fe3O4@SiO2的制备
将20g Fe3O4@SiO2在甲烷磺酸溶液(质量分数为50%)中活化;将活化的Fe3O4@SiO2和30mL乙烯基三乙氧基烷(Triethoxyvinylsilane,TTS)加入400mL(乙醇:水=1:1)混合溶液中, 50℃反应24-30h,用乙醇和蒸馏水冲洗,干燥,得TTS-Fe3O4@SiO2;取3gTTS- Fe3O4@SiO2和10g甲基丙烯酸,1g丙烯酰胺以及200mL蒸馏水,0.018g过硫酸胺于200ml圆底烧瓶内,70℃反应7h,在外加电场下收集产物,并用乙醇和蒸馏水多次冲洗,并干燥;取得到的产物1g与15mg异硫氰酸荧光素,5mL乙醇,100mL蒸馏水混合,振荡5-6h;在外加磁场下收集产物,水洗,烘干;
步骤四、荧光MIP- Fe3O4@SiO2的制备
将合成荧光Fe3O4@SiO2和4mmol/L模板分子,溶入100mL氯仿溶液中,反应前通入氮气5min,振荡5-6h,之后加入交联剂乙二醇二甲基丙烯酸酯,在50℃水浴锅内搅拌加热8h;在外加磁场下收集产物,并洗脱、烘干;
步骤五、非印迹荧光磁性聚合物(NIP- Fe3O4@SiO2)的制备
重复制备过程除不加入模板分子外,其余步骤与步骤四相同。
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