CN109675531B - 一种磁性金属离子表面分子印迹材料的制备方法 - Google Patents
一种磁性金属离子表面分子印迹材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种磁性金属离子表面分子印迹材料的制备方法。首先制备出Fe3O4磁性材料;然后将四甲氧基硅烷与壳聚糖在醋酸溶液中水解得到凝胶材料,并将凝胶材料包裹在Fe3O4磁性材料上得到Fe3O4@SiO2材料;将制备的Fe3O4@SiO2材料接枝上亚氨基二乙酸与锌离子的配合物,在模板分子、交联剂、引发剂的作用下,通过聚合反应形成了具有核壳结构的聚合物,该聚合物洗脱模板分子后得到磁性Fe3O4@SiO2‑IDA‑Zn2+表面分子印迹材料。本发明模板分子与印迹材料之间有分子间作用力和金属离子配位作用,作用力强,可用于对实际样品中莱克多巴胺有效富集和检测中。
Description
技术领域
本发明属于固相萃取材料开发技术领域,具体涉及一种磁性金属离子表面分子印迹材料(Fe3O4@SiO2-IDA-Zn2+)的制备方法。该方法制备的表面分子印迹材料可用于对实际样品中莱克多巴胺有效富集和检测中。
背景技术
Fe3O4磁性纳米粒子因具有独特的磁学性质,在外加磁场的作用下被磁化而发生定向移动,并且在特定的位置可以从介质中分离出来作为磁固相萃取介质,在分离科学领域具有广阔的应用前景。
金属螯合层析是利用金属离子配位能力的吸附介质,利用过渡金属空轨道与有机分子官能团中N、O等孤对电子形成配位键,但是这种吸附介质并不具有针对某一种特定结构的分子进行特异性吸附的性能。分子印迹技术是一种分子识别技术,目的是为了制备对印迹分子有选择性结合位点的聚合物,即分子印迹聚合物,利用印迹聚合物与印迹分子的特异性识别作用可以用于分析对象的高选择性富集。
孙治安等公开了三聚氰胺磁性表面分子印迹聚合物的制备及其在牛奶样品中的应用,其分子印迹聚合物与模板分子之间的作用力是分子间作用力,其用作吸附剂时具有吸附时间长、分子间作用力较弱等缺点。
莱克多巴胺是人工合成的β-肾上腺受体激动剂,属于“瘦肉精”的一种,是一种激素类添加剂,用于动物后,具有激素残留的问题,对动物机体产生副作用,同时也会影响消费者的健康。本发明旨在提供一种分子印迹材料,可用于对莱克多巴胺的有效富集和检测中。
发明内容
本发明的目的在于提供一种磁性金属离子表面分子印迹材料(Fe3O4@SiO2-IDA-Zn2+)的制备方法,该方法中所得表面分子印迹材料与模板分子之间作用力强,稳定性好;模板分子洗脱效率高、用作吸附剂时吸附效率高;表面分子印迹材料富集样品后易于分离,可用于对模板分子的有效富集和检测中。
本发明解决技术问题是采用以下技术方案来实现的:
一种磁性金属离子表面分子印迹材料的制备方法,所述磁性金属离子表面分子印迹材料的组成式为Fe3O4@SiO2-IDA-Zn2+,其制备方法包括以下步骤:
(1)共沉淀法制备Fe3O4磁性材料:将氯化铁和氯化亚铁溶解于去离子水后,在搅拌状态下升温至40℃,加入浓氨水至体系溶液变黑,然后升温至60℃,持续搅拌1h得到Fe3O4磁性材料,然后清洗至中性,密封备用;
(2)制备Fe3O4@SiO2材料:将壳聚糖、冰醋酸加入到三颈烧瓶中,室温下搅拌2h;然后在三颈烧瓶中再加入四甲氧基硅烷,继续于室温搅拌2h,制得凝胶材料;将该凝胶材料与步骤(1)中得到的Fe3O4磁性材料混合,于40℃恒温水浴中搅拌4h,制备出包裹凝胶的Fe3O4磁性材料,即Fe3O4@SiO2材料;
(3)制备Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料:在步骤(2)所得Fe3O4@SiO2材料中加入亚氨基二乙酸,40℃水浴加热条件下搅拌20h;然后再加入硫酸锌,在40℃水浴加热条件下搅拌12h,随后升温至60℃继续搅拌12h;之后加入交联剂二甲基丙烯酸乙二醇酯、引发剂偶氮二异丁腈和模板分子莱克多巴胺溶液,在65℃水浴加热条件下搅拌24h,制备出Fe3O4@SiO2-IDA-Zn2+聚合物;最后用甲醇和乙酸的混合液进行索氏抽提洗脱模板分子,混合液中甲醇和乙酸的体积比为9:1,最后于60℃烘干制得Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料。
本发明解决其技术问题还可采用以下技术措施进一步实现:
前述的磁性金属离子表面分子印迹材料的制备方法,其中,步骤(1)中氯化铁和氯化亚铁的摩尔比为1:(0.9~2)。
前述的磁性金属离子表面分子印迹材料的制备方法,其中,步骤(1)中氯化铁、氯化亚铁的质量分别是5.0g、3.5g,所用浓氨水的浓度为6mol/L。
前述的磁性金属离子表面分子印迹材料的制备方法,其中,步骤(2)中壳聚糖的用量是0.15~0.3g,冰醋酸体积为25ml,浓度为0.0521mol/L,四甲氧基硅烷的加入体积为0.8~1.2ml。
前述的磁性金属离子表面分子印迹材料的制备方法,其中,步骤(2)中壳聚糖的用量是0.2g,四甲氧基硅烷的加入体积为1ml。
前述的磁性金属离子表面分子印迹材料的制备方法,其中,步骤(3)中亚氨基二乙酸的加入量为0.001~0.003g,硫酸锌的加入量为0.0016~0.0096g;莱克多巴胺、二甲基丙烯酸乙二醇酯、偶氮二异丁腈的摩尔比为1:20:2。
前述的磁性金属离子表面分子印迹材料的制备方法,其中,步骤(3)中亚氨基二乙酸的加入量为0.0015g,硫酸锌的加入量为0.0064g,二甲基丙烯酸乙二醇酯、偶氮二异丁腈、莱克多巴胺溶液的用量分别为:0.2ml、0.02g、20ml,莱克多巴胺溶液浓度为20μg/ml;索氏抽提时间为144h。
前述的磁性金属离子表面分子印迹材料的制备方法,其中,制备的Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料用于莱克多巴胺的富集和检测中。
与现有技术相比,本发明具有以下优点:
(1)本发明利用金属离子配位作用制备的表面分子印迹聚合物,模板分子与印迹材料之间除了分子间作用力,还有金属离子配位作用,作用力较单独的分子力强。
(2)由于模板分子的结合位点处于聚合物的表面,当重新结合时,模板分子不需要进入聚合物的内部结构中,对于吸附动力学非常有利,在吸附过程中缩短了平衡时间,可以有效地提高洗脱效率和吸附容量。
(3)本发明采用共沉淀的方法将氯化铁、氯化亚铁、浓氨水在水浴条件下混合搅拌制备出Fe3O4磁性材料,以莱克多巴胺为模板分子,二甲基丙烯酸乙二醇酯为交联剂,Fe3O4@SiO2-IDA-Zn2+核壳材料为载体,成功制备了Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料。所制备的Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料由于Fe3O4具有超顺磁性,富集样品后易于分离、化学稳定性好,可用于对实际样品中莱克多巴胺的有效富集并用于对其进行分析检测。
(4)本发明将磁性材料易于分离、二氧化硅材料易功能化、过渡金属离子较好的配位能力和分子印迹材料专一识别特性相结合,具有制备简单、易于分离、化学稳定性好等优点,所制备的Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料对莱克多巴胺溶液具有特异性吸附性能,Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料对莱克多巴胺溶液的吸附在2.5min吸附率最高达到82.7%。
附图说明
图1为Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料的红外光谱测试结果:
图2为Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料吸附莱克多巴胺前后高效液相色谱的检测结果。
具体实施方式
为进一步阐述本发明采取的技术手段和技术效果,以下结合实施例,对本发明进行详细说明。
实施例1:
(1)Fe3O4磁性材料的制备
将5.0g氯化铁和3.5g氯化亚铁(摩尔比1:0.9)溶解于40mL去离子水后,在搅拌状态下升温至40℃,加入过量浓度为6mol/L的浓氨水至体系溶液变黑,然后升温至60℃,持续搅拌1h得到Fe3O4磁性材料,然后用去离子水清洗至中性,密封备用。
(2)Fe3O4@SiO2材料的制备
将0.2g壳聚糖、25ml浓度为0.0521mol/L冰醋酸加入到250ml三颈烧瓶中,室温下搅拌2h;在三颈烧瓶中加入1ml四甲氧基硅烷,继续于室温搅拌2h,制得凝胶材料;将该凝胶材料与实施例1中制备的Fe3O4磁性材料混合,于40℃恒温水浴中搅拌4h,制备出包裹凝胶的Fe3O4磁性材料,即Fe3O4@SiO2材料。
(3)Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料的制备
在步骤(2)所得Fe3O4@SiO2材料中加入0.0015g亚氨基二乙酸(IDA),于40℃水浴加热条件下搅拌20h;再加入0.0064g硫酸锌,在40℃水浴加热条件下搅拌12h,升温至60℃继续搅拌12h;然后加入0.2ml交联剂二甲基丙烯酸乙二醇酯、0.02g引发剂偶氮二异丁腈和20ml浓度为20μg/ml的模板分子莱克多巴胺溶液,在65℃水浴条件下搅拌24h,制备出Fe3O4@SiO2-IDA-Zn2+聚合物;该聚合物用甲醇和乙酸的混合液进行索氏抽提144h以洗脱模板分子,混合液中甲醇和乙酸的体积比为9:1,最后于60℃烘干制得Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料。
模板分子莱克多巴胺溶液、交联剂二甲基丙烯酸乙二醇酯、引发剂偶氮二异丁腈最佳摩尔比为1:20:2。
采用KBr压片法,对实施例1合成的Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料进行红外光谱表征,结果如图1所示。图1中,Fe3O4在581cm-1出有Fe-O-Fe键的伸缩振动峰,是Fe3O4的特征吸收峰;在3443cm-1的吸收峰为-OH的伸缩振动,对应的弯曲振动在1637cm-1出,Fe3O4经四甲氧基硅烷修饰后,出现1071cm-1处的Si-O键特征吸收峰,1637cm-1和3443cm-1处的加强峰推断为-NH2以及-OH吸收峰。这些吸收峰表明莱克多巴胺成功接枝在磁性颗粒Fe3O4表面。
图2是实施例1合成的Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料吸附莱克多巴胺前后高效液相色谱的检测结果,由图2可知,1ug/mL莱克多巴胺溶液出峰面积为2289,Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料吸附2.5min后面积为395,吸附率到达82.7%。
实施例2:
(1)Fe3O4磁性材料的制备
将5.0g氯化铁和5.9g氯化亚铁(摩尔比1:1.5)溶解于50mL去离子水后,在搅拌状态下升温至40℃,加入过量浓度为6mol/L的浓氨水至体系溶液变黑,然后升温至60℃,持续搅拌1h得到Fe3O4磁性材料,然后用去离子水清洗至中性,密封备用。
(2)Fe3O4@SiO2材料的制备
将0.15g壳聚糖、25ml浓度为0.0521mol/L冰醋酸加入到250ml三颈烧瓶中,室温下搅拌2h;在三颈烧瓶中加入0.8ml四甲氧基硅烷,继续于室温搅拌2h,制得凝胶材料;将该凝胶材料与实施例1中制备的Fe3O4磁性材料混合,于40℃恒温水浴中搅拌4h,制备出包裹凝胶的Fe3O4磁性材料,即Fe3O4@SiO2材料。
(3)Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料的制备
在步骤(2)所得Fe3O4@SiO2材料中加入0.001g亚氨基二乙酸(IDA),于40℃水浴加热条件下搅拌20h;再加入0.0046g硫酸锌,在40℃水浴加热条件下搅拌12h,升温至60℃继续搅拌12h;然后加入0.2ml交联剂二甲基丙烯酸乙二醇酯、0.02g引发剂偶氮二异丁腈和20ml浓度为20μg/ml的模板分子莱克多巴胺溶液,在65℃水浴条件下搅拌24h,制备出Fe3O4@SiO2-IDA-Zn2+聚合物;该聚合物用甲醇和乙酸的混合液进行索氏抽提144h以洗脱模板分子,混合液中甲醇和乙酸的体积比为9:1,最后于60℃烘干制得Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料。
实施例3:
(1)Fe3O4磁性材料的制备
将5.0g氯化铁和7.85g氯化亚铁(摩尔比1:2)溶解于50mL去离子水后,在搅拌状态下升温至40℃,加入过量浓度为6mol/L的浓氨水至体系溶液变黑,然后升温至60℃,持续搅拌1h得到Fe3O4磁性材料,然后用去离子水清洗至中性,密封备用。
(2)Fe3O4@SiO2材料的制备
将0.3g壳聚糖、25ml浓度为0.0521mol/L冰醋酸加入到250ml三颈烧瓶中,室温下搅拌2h;在三颈烧瓶中加入1.2ml四甲氧基硅烷,继续于室温搅拌2h,制得凝胶材料;将该凝胶材料与实施例1中制备的Fe3O4磁性材料混合,于40℃恒温水浴中搅拌4h,制备出包裹凝胶的Fe3O4磁性材料,即Fe3O4@SiO2材料。
(3)Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料的制备
在步骤(2)所得Fe3O4@SiO2材料中加入0.003g亚氨基二乙酸(IDA),于40℃水浴加热条件下搅拌20h;再加入0.0096g硫酸锌,在40℃水浴加热条件下搅拌12h,升温至60℃继续搅拌12h;然后加入0.2ml交联剂二甲基丙烯酸乙二醇酯、0.02g引发剂偶氮二异丁腈和20ml浓度为20μg/ml的模板分子莱克多巴胺溶液,在65℃水浴条件下搅拌24h,制备出Fe3O4@SiO2-IDA-Zn2+聚合物;该聚合物用甲醇和乙酸的混合液进行索氏抽提144h以洗脱模板分子,混合液中甲醇和乙酸的体积比为9:1,最后于60℃烘干制得Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料。
本发明通过对反应条件的控制,采用共沉淀法制备Fe3O4磁性材料,然后将四甲氧基硅烷与壳聚糖在醋酸溶液中水解得到的凝胶包裹在Fe3O4上,进而接枝上亚氨基二乙酸与锌离子的配合物,以莱克多巴胺为模板分子、二甲基丙烯酸乙二醇酯为交联剂、偶氮二异丁腈为引发剂,通过自由基聚合反应制备了具有核壳结构的Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料。该表面分子印迹材料对莱克多巴胺溶液具有特异性吸附性能,可用于对实际样品中莱克多巴胺的有效富集并用于对其进行分析检测。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (1)
1.一种用于莱克多巴胺富集和检测的磁性金属离子表面分子印迹材料,其特征在于其组成式为Fe3O4@SiO2-IDA-Zn2+,该Fe3O4@SiO2-IDA-Zn2+磁性金属离子表面分子印迹材料对1ug/mL的莱克多巴胺溶液吸附2.5min后的吸附率达82.7%;
所述的Fe3O4@SiO2-IDA-Zn2+磁性金属离子表面分子印迹材料是按照以下方法制备所得:
(1)共沉淀法制备Fe3O4磁性材料:将5.0g氯化铁和3.5g氯化亚铁溶解于去离子水后,在搅拌状态下升温至40℃,加入过量浓度为6mol/L的浓氨水至体系溶液变黑,然后升温至60℃,持续搅拌1h得到Fe3O4磁性材料,然后用去离子水清洗至中性,密封备用;
(2)制备Fe3O4@SiO2材料:将0.2g壳聚糖、25ml浓度为0.0521mol/L的冰醋酸加入到三颈烧瓶中,室温下搅拌2h;然后在三颈烧瓶中再加入1ml四甲氧基硅烷,继续于室温搅拌2h,制得凝胶材料;将该凝胶材料与步骤(1)中得到的Fe3O4磁性材料混合,于40℃恒温水浴中搅拌4h,制备出包裹凝胶的Fe3O4磁性材料,即Fe3O4@SiO2材料;
(3)制备Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料:在步骤(2)所得Fe3O4@SiO2材料中加入0.0015g亚氨基二乙酸,40℃水浴加热条件下搅拌20h;然后再加入0.0064g硫酸锌,在40℃水浴加热条件下搅拌12h,随后升温至60℃继续搅拌12h;之后加入0.2ml交联剂二甲基丙烯酸乙二醇酯、0.02g引发剂偶氮二异丁腈和20ml浓度为20μg/ml的模板分子莱克多巴胺溶液,在65℃水浴加热条件下搅拌24h,制备出Fe3O4@SiO2-IDA-Zn2+聚合物;最后用体积比为9:1的甲醇和乙酸的混合液进行索氏抽提洗脱模板分子,最后于60℃烘干制得所述的Fe3O4@SiO2-IDA-Zn2+表面分子印迹材料。
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