CN105754036B - 一种检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法 - Google Patents
一种检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法 Download PDFInfo
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Abstract
一种检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,属于分子印迹光子晶体和分析检测技术领域。其通过油酸修饰的四氧化三铁磁性纳米粒子的制备、三聚氰胺磁性分子印迹纳米粒子的制备和磁性分子印迹光子晶体传感器的制备得到产品。所述三聚氰胺磁性分子印迹纳米粒子在外加磁场的作用下自组装成光子晶体结构,得到液态分子印迹光子晶体传感器。宏观上表现为随着三聚氰胺浓度的增加,该传感器的衍射色发生从弱紫色到绿色、黄色、最终橙红色的变化。本发明的制备方法中光子晶体的组装具有快速、简便的优势。本发明提供的分子印迹光子晶体传感器将三聚氰胺浓度变化的化学信号直接通过衍射色的变化这一光学信号传达,达到了裸眼检测的目的。
Description
技术领域
本发明涉及一种检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,属于分子印迹光子晶体和分析检测技术领域。
背景技术
三聚氰胺 (melamine) 是一种重要的三嗪类含氮杂环有机化合物,广泛用于木材加工、塑料、涂料和皮革等行业。由于三聚氰胺含氮量高(66.7%),价格便宜,被一些不法分子添加到饲料、牛奶、奶粉等食品中造成蛋白含量较高的假象。虽然三聚氰胺本身毒性很低,但是三聚氰胺进入人体后水解会产生三聚氰酸,并且三聚氰胺能与三聚氰酸形成不溶性的结晶复合物。人体摄入三聚氰胺后,会导致膀胱炎、慢性肾炎、肾衰竭,甚至是尿石症和膀胱癌。因此,研究制备一种对三聚氰胺具有高选择性的、灵敏的、准确的、便捷的检测方法具有重要意义。
分子印迹(molecular imprinting)是一种用于制备具有特殊识别功能的分子印迹聚合物方法。分子印迹聚合物是一类具有固定大小和形状的空穴并具有确定排列功能基团的交联高聚物,对模板分子具有高度的选择识别性能。光子晶体是由不同折射率的介质周期性排列而成的人工微结构,在物理、化学、电子和光学等领域得到了广泛的关注。作为一种新兴的光学材料,光子晶体具有光学可调控性能。根据布拉格衍射定律,光子晶体在外界的刺激下,晶体结构发生变化,会引起衍射波长的变化,即结构的微变化能够引起衍射波长的显著变化。将光子晶体所具有的独特光学特性与分子印迹聚合物所具有的出色的选择性和灵敏性相结合,制备得到分子印迹光子晶体传感器。分子印迹担任对目标化合物进行特异性地识别的功能,而光子晶体则将这一识别过程通过反射特定波长的光学信号表达出来,达到“裸眼检测”的效果。分子印迹光子晶体传感器具有高度的专一性、敏感性、快速响应和高度普适的优点,并且无需标记,具有自表达能力,操作简便,为有害物质的检测提供了一种新的思路。
国内外公开的关于分子印迹光子晶体传感器技术的报道都是采用传统的垂直沉积、蒸发诱导、电沉积等组装方法,存在模板组装时间长,蚀刻过程会破坏分子印迹位点等缺点。德国应用化学杂志(Angew. Chem. Int. Ed., 2006年,45卷,8145-8148页)报道了一种利用垂直沉积组装法制备得到二氧化硅微球光子晶体模板,然后在光子晶体模板空隙中填充分子印迹预聚液,紫外光照进行聚合,最后蚀刻掉二氧化硅模板得到具有手性识别功能的分子印迹光子晶体膜。荷兰的塔兰塔杂志(Talanta,2015年,14卷,157-162页)报道了一种利用垂直对流自组装方法将雌激素分子印迹的聚甲基丙烯酸甲酯微球组装成光子晶体结构,然后通过聚丙烯酰胺凝胶固定光子晶体结构,最后得到检测雌激素的分子印迹反蛋白结构光子晶体。
发明内容
本发明的目的在于克服现有的三聚氰胺检测方法的不足之处,提供了一种组装快速、制备简单,并且选择性好、灵敏度高的检测三聚氰胺的光学传感器,达到了实时、快速的“裸眼检测”的效果。
本发明的技术方案,一种检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,步骤为:
(1)油酸修饰的四氧化三铁磁性纳米粒子的制备:将三价铁盐和二价铁盐混合,依次加入沉淀剂氨水和修饰剂油酸,在60-100℃、氮气保护下,通过化学共沉淀法制备得到油酸修饰的四氧化三铁磁性纳米粒子;
(2)三聚氰胺磁性分子印迹纳米粒子的制备:将步骤(1)制备得到的油酸修饰的四氧化三铁磁性纳米粒子分散于有机溶剂中得到磁流体,通过细乳液聚合法的预乳化、细乳化、聚合三个步骤制备得到三聚氰胺磁性分子印迹纳米粒子;进行三聚氰胺模板洗脱;
(3)磁性分子印迹光子晶体传感器的制备:将步骤(2)制备所得洗脱掉三聚氰胺模板的磁性分子印迹纳米粒子分散在水溶液中,在外加磁场作用下进行自组装,得到液态检测三聚氰胺的磁性分子印迹光子晶体传感器。
所述检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,具体步骤为:
(1)油酸修饰的四氧化三铁磁性纳米粒子的制备:在0.01mol三价铁盐和0.01mol二价铁盐中加入90-150mL经过通氮气除氧气处理的超纯水,50-60KHz频率下超声溶解,得到混合溶液;将混合溶液在60-100℃油浴加热,依次加入10-30mL氨水和0.1-1.0g油酸,反应全程通氮气除氧气,反应0.5-2 h;反应结束后用磁铁置于烧瓶底部吸附粒子;将收集到的粒子用去离子水洗到中性,最后放入真空干燥箱中40-50℃干燥,即得到油酸修饰的四氧化三铁磁性纳米粒子;
(2)三聚氰胺磁性分子印迹纳米粒子的制备:
a、细乳液A的制备:将步骤(1)制备得到的油酸修饰的四氧化三铁磁性纳米粒子0.1-1.0g分散于1-5mL有机溶剂中形成磁流体;然后将磁流体加入到40mL浓度为0.5-1.5mg/mL的乳化剂溶液中以300-500r/min的速度搅拌进行预乳化20-40min;将预乳化完全的乳状液进行超声波分散,得到细乳液A;
b、细乳液B的制备:将三聚氰胺模板、功能单体和交联剂按照mmol比为1-5:5-10:5-10,加入到40mL浓度为0.1-5mg/mL的乳化剂溶液中,混合后进行超声波分散,得到细乳液B;
c、聚合反应:将细乳液A、B 混合后再次超声波分散,在此混合液中加入10-20mg引发剂引发聚合反应,60-80℃反应16-20h,磁分离得到三聚氰胺磁性分子印迹纳米粒子;
d、模板分子的洗脱:将步骤c得到的三聚氰胺磁性分子印迹纳米粒子洗脱掉三聚氰胺模板,选择甲醇为洗脱液,洗脱液的量为10-50mL/次,洗脱时间为20-40min/次,洗脱次数为5-10次, 40-60℃烘干备用;
(3)磁性分子印迹光子晶体传感器的制备:将步骤(2)制备所得洗脱掉三聚氰胺模板的磁性分子印迹纳米粒子分散在水溶液中,浓度为5-10mg/mL,传感器溶液的总体积为2mL;然后在磁场强度为0.2-0.4T的外加磁场作用下进行自组装,得到产品液态检测三聚氰胺的磁性分子印迹光子晶体传感器。
步骤(2)a和(2)b中所述乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵或曲拉通X-100中的一种。
所述功能单体为甲基丙烯酸甲酯、甲基丙烯酸、丙烯酰胺或丙烯酸中的一种或两种;交联剂为乙二醇二甲基丙烯酸酯、二缩三丙二醇二丙烯酸酯或三羟甲基丙烷三甲基丙烯酸酯中的一种。
步骤(2)c中所述引发剂为过硫酸钾或过硫酸铵。
所述有机溶剂为环己烷、三氯甲烷、丙酮、正庚烷或二氯甲烷中的一种。
本发明提供了一种制备可以检测三聚氰胺的磁性分子印迹光子晶体传感器的方法,采用细乳液聚合法制备得到三聚氰胺磁性分子印迹纳米粒子,所述三聚氰胺磁性分子印迹纳米粒子在外加磁场的作用下自组装成光子晶体结构,得到液态分子印迹光子晶体传感器。在没有三聚氰胺目标分子存在时,分子印迹光子晶体传感器在磁场中呈现弱紫色的衍射色甚至无色。随着传感器溶液中三聚氰胺浓度的增加,粒子间静电斥力变大,光子晶体结构中粒子间隙变大,导致分子印迹光子晶体传感器衍射波长红移量变大。宏观上表现为随着三聚氰胺浓度的增加,该传感器的衍射色发生从弱紫色到绿色、黄色、最终橙红色的变化。
本发明的有益效果:本发明结合了分子印迹和光子晶体两项技术的优点,得到可以检测三聚氰胺的磁性分子印迹光子晶体传感器。本发明的制备方法中光子晶体的自组装具有快速、简便的优势。本发明提供的分子印迹光子晶体传感器将三聚氰胺浓度变化的化学信号直接通过衍射色的变化这一光学信号传达,达到了裸眼检测的目的。
附图说明
图1 为实施例1制备的三聚氰胺磁性分子印迹纳米粒子的TEM图。
图2 为实施例1制备的磁性分子印迹光子晶体在不同浓度三聚氰胺溶液中响应的光学照片(三聚氰胺浓度:A、0mg/mL,B、10-5 mg/mL,C、10-4 mg/mL,D、10-3 mg/mL,E、10-2 mg/mL)。
图3为实施例1制备的磁性分子印迹光子晶体在不同浓度三聚氰胺溶液中响应的衍射光谱图(三聚氰胺浓度:A、0mg/mL,B、10-5 mg/mL,C、10-4 mg/mL,D、10-3 mg/mL,E、10-2mg/mL)。
具体实施方式
实施例1
(1)油酸修饰的四氧化三铁磁性纳米粒子的制备:以共沉淀法制备油酸修饰的四氧化三铁磁性纳米粒子。将0.01mol氯化铁和0.01mol硫酸亚铁加入150mL经过通氮气除氧气处理的超纯水,50-60KHz超声溶解,得到混合溶液。将所得混合溶液转移至250mL三口烧瓶后,置于60℃油浴。依次加入20mL氨水和0.5g 油酸,反应全程通氮气除氧气,反应0.5h。反应结束后,磁铁置于烧瓶底部吸附粒子。收集到的粒子用去离子水洗到中性,真空干燥箱中40℃干燥,得到油酸修饰的四氧化三铁磁性纳米粒子。
(2)三聚氰胺磁性分子印迹纳米粒子的制备:
a、称取0.5g油酸修饰的四氧化三铁磁性纳米粒子分散于5mL环己烷形成磁流体,将磁流体加入到十二烷基苯磺酸钠水溶液(0.75mg/mL,40 mL)中搅拌进行预乳化。将预乳化完全的乳状液进行超声波分散,得到细乳液A;
b、称取1mmol三聚氰胺、1mmol功能单体甲基丙烯酸、6mmol功能单体丙烯酰胺、6mmol交联剂乙二醇二甲基丙烯酸酯形成油相,乳化剂十二烷基苯磺酸钠水溶液(0.75mg/mL,40 mL)形成水相,油水两相混合后进行超声波分散,得到细乳液B。
c、将细乳液A、B 混合后再次超声波分散,将此混合液转移到三口烧瓶中,加入10mg过硫酸钾引发剂引发聚合反应,70℃、反应18h,磁分离得到三聚氰胺磁性分子印迹纳米粒子。
d、选择甲醇为洗脱液,将步骤c得到的三聚氰胺磁性分子印迹纳米粒子洗脱掉三聚氰胺模板,洗脱液的量为10mL/次,洗脱时间为10min/次,洗脱次数为5次,40-60℃烘干备用。
(3)磁性分子印迹光子晶体传感器的制备:称取5mg 洗脱掉模板分子的磁性分子印迹纳米粒子,分别超声分散于2mL水及2mL不同浓度的三聚氰胺水溶液(10-5-10-2 mg/mL)中,施加外磁场进行自组装,得到可以检测三聚氰胺的磁性分子印迹光子晶体传感器。
对所述三聚氰胺磁性分子印迹纳米粒子进行透射电镜扫描,结果参见图1。由图1可知,三聚氰胺磁性分子印迹纳米粒子为具有核壳结构的规则球体,分子印迹聚合物形成壳层结构,油酸修饰的四氧化三铁磁性纳米粒子组成的团簇构成内核,粒径为100nm左右,单分散分布。
所述检测三聚氰胺的磁性分子印迹光子晶体传感器在水溶液及不同浓度的三聚氰胺溶液中的检测响应情况参见图2。图2为磁性分子印迹光子晶体在不同浓度三聚氰胺溶液中响应的光学照片(三聚氰胺浓度:A、0mg/mL,B、10-5 mg/mL,C、10-4 mg/mL,D、10-3 mg/mL,E、10-2 mg/mL)。由图2可知,磁场作用下,所述磁性分子印迹光子晶体传感器在不同浓度的三聚氰胺水溶液中衍射不同颜色的光,并且随着三聚氰胺溶液浓度的增加,衍射波长发生红移。结果表明本发明提供的检测三聚氰胺的磁性分子印迹光子晶体传感器具有组装快速、响应灵敏的特点,可实现对三聚氰胺的检测,并达到裸眼检测的效果。
实施例2
(1)油酸修饰的四氧化三铁磁性纳米粒子的制备:以共沉淀法制备油酸修饰的四氧化三铁磁性纳米粒子。将0.01mol氯化铁和0.01mol氯化亚铁加入120mL经过通氮气除氧气处理的超纯水,50-60KHz超声溶解,得到混合溶液。将所得混合溶液转移至250mL三口烧瓶后,置于90℃油浴。依次加入30mL氨水和1g 油酸,反应全程通氮气除氧气,反应2h。反应结束后,磁铁置于烧瓶底部吸附粒子。收集到的粒子用去离子水洗到中性,真空干燥箱中50℃干燥,得到油酸修饰的四氧化三铁磁性纳米粒子。
(2)三聚氰胺磁性分子印迹纳米粒子的制备:
a、称取1g油酸修饰的四氧化三铁磁性纳米粒子分散于5mL丙酮形成磁流体,将磁流体加入到十二烷基硫酸钠水溶液(0.75mg/mL,40 mL)中搅拌进行预乳化。将预乳化完全的乳状液进行超声波分散,得到细乳液A;
b、称取1mmol三聚氰胺、1mmol功能单体甲基丙烯酸、6mmol功能单体丙烯酰胺、6mmol交联剂二缩三丙二醇二丙烯酸酯形成油相,乳化剂十二烷基硫酸钠水溶液(0.75mg/mL,40 mL)形成水相,油水两相混合后进行超声波分散,得到细乳液B。
c、将细乳液A、B 混合后再次超声波分散,将此混合液转移到三口烧瓶中,加入20mg过硫酸钾引发剂引发聚合反应,80℃、反应16h,磁分离得到三聚氰胺磁性分子印迹纳米粒子。
d、选择甲醇为洗脱液,将步骤c得到的三聚氰胺磁性分子印迹纳米粒子洗脱掉三聚氰胺模板,洗脱液的量为10mL/次,洗脱时间为10min/次,洗脱次数为5次,40-60℃烘干备用。
(3)磁性分子印迹光子晶体传感器的制备:称取5mg 洗脱掉模板分子的磁性分子印迹纳米粒子,分别超声分散于2mL水及2mL不同浓度的三聚氰胺水溶液(10-4-10-2 mg/mL)中,施加外磁场进行磁组装,得到可以检测三聚氰胺的磁性分子印迹光子晶体传感器。
实施例3
(1)油酸修饰的四氧化三铁磁性纳米粒子的制备:以共沉淀法制备油酸修饰的四氧化三铁磁性纳米粒子。将0.01mol氯化铁和0.01mol硫酸亚铁加入90mL经过通氮气除氧气处理的超纯水,50-60KHz超声溶解,得到混合溶液。将所得混合溶液转移至250mL三口烧瓶后,置于80℃油浴。依次加入10mL氨水和0.1g 油酸,反应全程通氮气除氧气,反应1h。反应结束后,磁铁置于烧瓶底部吸附粒子。收集到的粒子用去离子水洗到中性,真空干燥箱中45℃干燥,得到油酸修饰的四氧化三铁磁性纳米粒子。
(2)三聚氰胺磁性分子印迹纳米粒子的制备:
a、称取0.2g油酸修饰的四氧化三铁磁性纳米粒子分散于5mL三氯甲烷形成磁流体,将磁流体加入到十六烷基三甲基溴化铵水溶液(0.75mg/mL,40 mL)中搅拌进行预乳化。将预乳化完全的乳状液进行超声波分散,得到细乳液A;
b、称取1mmol三聚氰胺、1mmol功能单体甲基丙烯酸甲酯、6mmol功能单体丙烯酸、6mmol交联剂三羟甲基丙烷三甲基丙烯酸酯形成油相,乳化剂十六烷基三甲基溴化铵水溶液(0.75mg/mL,40 mL)形成水相,油水两相混合后进行超声波分散,得到细乳液B。
c、将细乳液A、B 混合后再次超声波分散,将此混合液转移到三口烧瓶中,加入10mg过硫酸钾引发剂引发聚合反应,60℃、反应20h,磁分离得到三聚氰胺磁性分子印迹纳米粒子。
d、选择甲醇为洗脱液,将步骤c得到的三聚氰胺磁性分子印迹纳米粒子洗脱掉三聚氰胺模板,洗脱液的量为10mL/次,洗脱时间为10min/次,洗脱次数为5次,40-60℃烘干备用。
(3)磁性分子印迹光子晶体传感器的制备:称取5mg 洗脱掉模板分子的磁性分子印迹纳米粒子,分别超声分散于2mL水及2mL不同浓度的三聚氰胺水溶液(10-4-10-2 mg/mL)中,施加外磁场进行磁组装,得到可以检测三聚氰胺的磁性分子印迹光子晶体传感器。
Claims (6)
1.一种检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,其特征在于步骤为:
(1)油酸修饰的四氧化三铁磁性纳米粒子的制备:将三价铁盐和二价铁盐混合,依次加入沉淀剂氨水和修饰剂油酸,在60-100℃、氮气保护下,通过化学共沉淀法制备得到油酸修饰的四氧化三铁磁性纳米粒子;
(2)三聚氰胺磁性分子印迹纳米粒子的制备:将步骤(1)制备得到的油酸修饰的四氧化三铁磁性纳米粒子分散于有机溶剂中得到磁流体,通过细乳液聚合法的预乳化、细乳化、聚合三个步骤制备得到三聚氰胺磁性分子印迹纳米粒子;进行三聚氰胺模板洗脱;
(3)磁性分子印迹光子晶体传感器的制备:将步骤(2)制备所得洗脱掉三聚氰胺模板的磁性分子印迹纳米粒子分散在水溶液中,在外加磁场作用下进行自组装,得到液态检测三聚氰胺的磁性分子印迹光子晶体传感器。
2.根据权利要求1所述检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,其特征在于具体步骤为:
(1)油酸修饰的四氧化三铁磁性纳米粒子的制备:在0.01mol三价铁盐和0.01mol二价铁盐中加入90-150mL经过通氮气除氧气处理的超纯水,50-60KHz频率下超声溶解,得到混合溶液;将混合溶液在60-100℃油浴加热,依次加入10-30mL氨水和0.1-1.0g油酸,反应全程通氮气除氧气,反应0.5-2 h;反应结束后用磁铁置于烧瓶底部吸附粒子;将收集到的粒子用去离子水洗到中性,最后放入真空干燥箱中40-50℃干燥,即得到油酸修饰的四氧化三铁磁性纳米粒子;
(2)三聚氰胺磁性分子印迹纳米粒子的制备:
a、细乳液A的制备:将步骤(1)制备得到的油酸修饰的四氧化三铁磁性纳米粒子0.1-1.0g分散于1-5mL有机溶剂中形成磁流体;然后将磁流体加入到40mL浓度为0.5-1.5mg/mL的乳化剂溶液中以300-500r/min的速度搅拌进行预乳化20-40min;将预乳化完全的乳状液进行超声波分散,得到细乳液A;
b、细乳液B的制备:将三聚氰胺模板、功能单体和交联剂按照mmol比为1-5:5-10:5-10,加入到40mL浓度为0.1-5mg/mL的乳化剂溶液中,混合后进行超声波分散,得到细乳液B;
c、聚合反应:将细乳液A、B混合后再次超声波分散,在此混合液中加入10-20mg引发剂引发聚合反应,60-80℃反应16-20h,磁分离得到三聚氰胺磁性分子印迹纳米粒子;
d、模板分子的洗脱:将步骤c得到的三聚氰胺磁性分子印迹纳米粒子洗脱掉三聚氰胺模板,选择甲醇为洗脱液,洗脱液的量为10-50mL/次,洗脱时间为20-40min/次,洗脱次数为5-10次,40-60℃烘干备用;
(3)磁性分子印迹光子晶体传感器的制备:将步骤(2)制备所得洗脱掉三聚氰胺模板的磁性分子印迹纳米粒子分散在水溶液中,浓度为5-10mg/mL,传感器溶液的总体积为2mL;然后在磁场强度为0.2-0.4T的外加磁场作用下进行自组装,得到产品液态检测三聚氰胺的磁性分子印迹光子晶体传感器。
3.根据权利要求2所述检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,其特征在于:步骤(2)a和(2)b中所述乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵或曲拉通X-100中的一种。
4.根据权利要求2所述检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,其特征在于:所述功能单体为甲基丙烯酸甲酯、甲基丙烯酸、丙烯酰胺或丙烯酸中的一种或两种;交联剂为乙二醇二甲基丙烯酸酯、二缩三丙二醇二丙烯酸酯或三羟甲基丙烷三甲基丙烯酸酯中的一种。
5.根据权利要求2所述检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,其特征在于:所述引发剂为过硫酸钾或过硫酸铵。
6.根据权利要求2所述检测三聚氰胺的磁性分子印迹光子晶体传感器的制备方法,其特征在于:所述有机溶剂为环己烷、三氯甲烷、丙酮、正庚烷或二氯甲烷中的一种。
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