CN114790585B - 一种静电纺丝原位制备MOFs纳米酶的方法及其葡萄糖比色传感器 - Google Patents
一种静电纺丝原位制备MOFs纳米酶的方法及其葡萄糖比色传感器 Download PDFInfo
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Abstract
本发明涉及纳米酶材料领域内一种静电纺丝原位制备MOFs纳米酶的方法及其葡萄糖比色传感器，首先通过静电纺丝构筑材料的方法，以金属离子为金属盐，有机化合物为有机配体，高分子聚合物作为助纺材料同时也作为MOFs材料生长的位点，调节金属盐和配体以及助纺材料的比例，控制调节静电纺丝参数，以调控MOFs材料在一维纳米线上的有序排布，实现MOFs材料的定向生长和形貌控制，制备得到MOFs纳米酶。并进一步将MOFs纳米酶制备得到葡萄糖比色传感器。进行葡萄糖检测时，利用纳米酶的高催化活性，以催化TMB或邻苯二胺发生显色反应，实现对葡萄糖的快速检测，并且检测限范围更低。
Description
技术领域
本发明涉及纳米酶材料领域，特别是涉及一种静电纺丝原位制备MOFs纳米酶的方法及其葡萄糖比色传感器。
背景技术
人体血液中葡萄糖含量是糖尿病以及其他一些疾病的重要检测指标，如何简单、快速、高灵敏的检测葡萄糖是对糖尿病以及其他疾病进行的诊断和治疗重要检测环节之一。比色传感基于其颜色变化的不同，在一定的波长下显示出特定的吸收峰和差异，可以对小分子物质进行检测。因此，其携带性强，并可以在很短的时间内能够快速的检测物质，适合于一些物质的现场快速检测。而且在比色传感设备的搭建过程中，不需要耗费大型的仪器设备，对操作人员的专业要求相对较低。由于生物酶固有的缺陷限制了比色传感器的应用和发展，为了克服上述的生物酶的缺陷，纳米酶的快速发展促进了比色传感的发展。
酶是由活细胞产生的一类蛋白质或者核糖核酸分子。与常规的催化剂比较，酶具有催化效率高、底物特异性强以及选择性强等特点。正是由于酶这种天生的自然属性，使得其在医药、食品安全、环境监测以及化学品生产中起着非常重要的作用。但是，众所周知，大多数酶的本质是蛋白质，少部分的RNA，在使用的过程中，其稳定性差、对环境的适应能力较弱以及在其使用的过程中面临相对复杂的纯化过程和纯化设备造价高等缺陷，限制了其进一步应用。随着对纳米技术研究的不断深入，纳米材料模拟酶（纳米酶）已成为天然酶的替代品。与天然酶相比，纳米酶不仅具有相对较高以及稳定的催化活性，而且还具有成本低、合成可控、催化活性可调节和高稳定性等优点。
金属-有机框架（MOFs）材料是有机配体和金属离子通道经过自组装形成的一种具有周期性的网格晶体材料，其具有结构与功能多样化，比表面积大以及孔径可调等特点，在气体存储和分离，液相分离和萃取，催化和传感器等领域发挥了重要的作用。MOFs材料在构筑高性能纳米酶材料有着非常重要的意义，但是到目前为止，MOFs材料的制备方法还是基于传统的水热或者其他溶剂的方法，在后期的处理过程，较为繁琐。
静电纺丝技术因具有操作简单、成本低廉和环境友好等诸多优点，从而被视为最具有工业化应用前景的规模化制备纳米纤维材料的技术之一。通过该技术手段得到的纤维直径分布广泛(从几纳米到微米级)，得到的一维纳米纤维杂化材料具有诸多特性：比表面积大、孔隙率高、孔径小和连续性好等。基于材料的特性探索材料的理想组成，构筑新型材料结构，从而达到更加优异的性能，基于静电纺丝技术制备功能性纳米纤维杂化材料是目前研究最重要的方向之一。
发明内容
本发明针对现有技术MOFs和纳米酶自组装制备方法存在的不足，提供一种静电纺丝原位制备MOFs纳米酶的方法，采用静电纺丝构筑材料的方法，以金属离子为金属盐，咪唑类的化合物或者其他类型的有机化合物为有机配体，高分子量的聚合物作为助纺材料同时也作为MOFs材料生长的位点，调控MOFs材料在一维纳米线上的有序排布，实现MOFs材料的定向生长和形貌控制。
本发明的目的是这样实现的，一种静电纺丝原位制备MOFs纳米酶的方法，其特征在于，
第1步，按如下质量比例准备静电纺丝液：助纺材料10-20份，有机溶剂70-80份，金属离子化合物0.1-1份，有机配体0.1-1份，表面活性剂0.01-0.05份；
第2步，按第1步的质量比例，将助纺材料与有机溶剂混合，常温下机械搅拌12-16h，搅拌速度为400 r/min~500 r/min，至完全溶解形成均相溶液；
第3步，均相溶液中加入金属离子化合物、有机配体和表面活性剂，机械搅拌至混合均匀，得到均相的静电纺丝前驱液；
第4 步，将第3步的静电纺丝前驱液置于静电纺丝装置，以工作电压为15-20 kV，纺丝液的推进速度为0.5-0.8 mL.h-1、接收器与针头的间距为10-12 cm的条件下进行纺丝，得到静电纺丝原位制备的连续纤维型MOFs纳米酶。
本发明是一种静电纺丝原位制备MOFs连续纤维纳米酶，采用静电纺丝构筑材料的方法，以金属离子为金属盐，咪唑类的化合物或者其他类型的有机化合物为有机配体，聚合物作为助纺材料同时也作为MOFs材料生长的位点，调节金属盐和配体以及助纺材料的配比，通过对静电纺丝过程中电压、纺丝速度以及接收板的距离的优化改时，调控MOFs材料在一维纳米线上的有序排布，实现MOFs材料的定向生长和形貌控制。避免了传统MOFs材料在制备过程中，存在结构不稳定，不连续的特点，与静电纺丝相结合，有序的实现MOFs材料的一维纳米材料的排列，实现了模拟酶活性显著增强的效果。
进一步地，所述助纺材料为分子量为15000-30000的聚丙烯腈、聚偏氟乙烯、聚乳酸、聚乙烯醇和聚乙烯醇缩丁醛。
为便于与助纺材料溶解形成稳定的纺丝溶液，所述有机溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、碳酸乙烯酯或硫氰酸钠。
进一步地，所述金属离子化合物为Co、Zn、Ni、Fe、Cu、Zr的硝酸盐、醋酸盐或者硫酸盐的化合物。
更进一步地，所述金属离子化合物为硝酸钴、硝酸锌、硝酸镍、硝酸铁、醋酸钴、醋酸锌、醋酸镍、硫酸钴或硫酸锌。
为便于为金属有机框架聚合物提供有机框架，所述有机配体为 3,3',5,5'-联苯四甲酸、 双(3,5-二羧基苯基)偶氮、乙炔基联苯-3,3',5,5'-四羧酸、四[4-(4'-羧基苯基)苯基]乙烯、9.10-二(3',5'-二羧基苯 基)蒽、1,1,2,2-四(4-羧基苯)乙烯、1,3,6,8-四(4-羧基苯)芘、[1,1’:4’,1″]三联苯-3,3″,5,5″-四甲酸、1,2,4,5-四(4-羧基苯基)苯、四(4-羧基苯基)硅烷、四(3-羧基苯基)硅或1,3,5,7-金刚烷四羧酸、2-甲基咪唑类。
为有改善金属离子化合物和有机配体在纺丝体系中的分散效果，并有效控制原位纺丝过程MOFs在纤维中的有序分布，所述表面活性剂为聚乙烯吡咯烷酮（PVP）、烷基酚聚氧乙烯醚、高碳脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯、脂肪酸聚氧乙烯酯、脂肪酸甲酯乙氧基化物、失水山梨醇酯或烷基醇酰胺。
为便于实现葡萄糖的快速转化，本发明还提供一种采用上述MOFs纳米酶制备的葡萄糖比色传感器，将MOFs纳米酶按1-5mg/mL的浓度配制成水溶液，与到PH为4～5的醋酸缓冲溶液按1：2000～5000的体积比混合，再加入指示剂混合均匀，得到葡萄糖比色传感器；所述指示剂为浓度为1-5mg/m的3,3',5,5'-四甲基联苯胺或邻苯二胺的二甲基砜溶液，加入的体积为10倍的纳米酶水溶液的体积，混合均匀后得到本实施例的葡萄糖比色传感器。
本发明的葡萄糖比色传感器，利用纳米酶的催化活性高，催化显色剂实现显色反应，其携带性强，可以实现对葡萄糖的快速检测。
附图说明
图1实施例1制备的MOFs纳米酶的电镜扫描图。
图2为实施例1制备的MOFs纳米酶的红外图谱。
图3为实施例1制备的基于MOFs纳米酶葡萄糖比色传感器的线性曲线。
具体实施方式
下面结合具体的实施例详细说明本发明静电纺丝原位制备MOFs纳米酶的方法及其葡萄糖比色传感器。
实施例1
本实施例的静电纺丝原位制备MOFs纳米酶的方法中，首先准备如下质量比例的静电纺丝液原料：
PAN（聚丙烯睛）10份，二甲基甲酰胺70份，硝酸钴，0.1份，2-甲基咪唑0.1份，PVP（聚乙烯吡咯烷酮）0.01份。
然后将助纺材料PAN与DMF混合，常温下机械搅拌12 h，搅拌速度为400 r/min，至完全溶解形成均相溶液；向前述均相溶液中加入硝酸钴、2-甲基咪唑和PVP机械搅拌至混合均匀，得到均相的静电纺丝前驱液；将前述静电纺丝前驱液置于静电纺丝装置，以工作电压为15 kV，纺丝液的推进速度为0.5 mL.h-1、接收器与针头的间距为10 cm的条件下进行纺丝，得到静电纺丝原位制备的连续纤维型ZIF-67@@PAN纳米酶。
对本实施例的MOFs纳米酶进行电镜扫描观察如图1所示，从图中，可以看出成功制备得到ZIF-67@@PAN纳米酶材料，在纤维内部排布较为有序，颗粒大小形态均。该MOFs纳米酶的红外光谱如图2所示，从图中可以在1578、1305、1105以及749cm-1均为ZIF-67典型的特征峰，成功制备得到原位纺丝的ZIF-67@PAN纳米酶材料，并具备优良的纳米酶性能。
以上述ZIF-67@ PAN纳米酶制备葡萄糖比色传感器，具体过程为将上述MOFs@PAN纳米酶配置成1mg/mL的水溶液，与PH=4的醋酸缓冲溶液按1：2000的体积比与混合，再加入体积为纳米酶水溶液的体积10倍指示剂TMB（3,3',5,5'-四甲基联苯胺）溶液，（本实施例中的TMB溶液为浓度为1mg/m的3,3',5,5'-四甲基联苯胺的二甲基砜溶液），混合均匀后得到本实施例的葡萄糖比色传感器。
实施例2
本实施例的静电纺丝原位制备MOFs纳米酶的方法中，首先准备如下质量比例的静电纺丝液原料：PVDF（聚偏氟乙烯） 720 15份；DMSo（二甲基亚砜）75份；醋酸锌0.5份；3,3',5,5'-联苯四甲酸 0.5份；高碳脂肪醇聚氧乙烯醚 0.05份。
然后将助纺材料PVDF 720与DMSo混合，常温下机械搅拌14 h，搅拌速度为500 r/min，至完全溶解形成均相溶液；向前述均相溶液中加入醋酸锌、3,3',5,5'-联苯四甲酸和高碳脂肪醇聚氧乙烯醚机械搅拌至混合均匀，得到均相的静电纺丝前驱液；将前述静电纺丝前驱液置于静电纺丝装置，以工作电压为18 kV，纺丝液的推进速度为0.6 mL.h-1、接收器与针头的间距为10 cm的条件下进行纺丝，得到静电纺丝原位制备的连续纤维型MOFs@PVDF纳米酶。
然后以上述MOFs @ PVDF纳米酶制备葡萄糖比色传感器，具体过程为将上述MOFs@ PVDF纳米酶配置成2 mg/mL的水溶液，与PH=4.5的醋酸缓冲溶液按1：3000的体积比与混合，再加入体积为纳米酶水溶液的体积12倍指示剂TMB（3,3',5,5'-四甲基联苯胺）溶液，（本实施例中的TMB溶液为浓度为2.5 mg/mL的3,3',5,5'-四甲基联苯胺的二甲基砜溶液），混合均匀后得到本实施例的葡萄糖比色传感器。
实施例3
本实施例的静电纺丝原位制备MOFs纳米酶的方法中，首先准备如下质量比例的静电纺丝液原料：PLA（聚乳酸） 4060D 20份；DMAc（二甲基乙酰胺）80份；硝酸铁1份；四[4-(4'-羧基苯基)苯基]乙烯 1份；脂肪酸聚氧乙烯醚0.03份。然后将助纺材料PLA 4060D与DMAc混合，常温下机械搅拌12 h，搅拌速度为400 r/min，至完全溶解形成均相溶液；向前述均相溶液中加入硝酸铁、四[4-(4'-羧基苯基)苯基]乙烯和脂肪酸聚氧乙烯醚机械搅拌至混合均匀，得到均相的静电纺丝前驱液；将前述静电纺丝前驱液置于静电纺丝装置，以工作电压为18 kV，纺丝液的推进速度为0.8 mL.h-1、接收器与针头的间距为12 cm的条件下进行纺丝，得到静电纺丝原位制备的连续纤维型MOFs@PLA纳米酶。
然后以上述MOFs @ PLA纳米酶制备葡萄糖比色传感器，具体过程为将上述MOFs @PLA纳米酶配置成5 mg/mL的水溶液，与PH=5的醋酸缓冲溶液按1：5000的体积比与混合，再加入体积为纳米酶水溶液的体积15倍指示剂邻苯二胺溶液，（本实施例中的邻苯二胺溶液为浓度为5 mg/mL的邻苯二胺的二甲基砜溶液），混合均匀后得到本实施例的葡萄糖比色传感器。
实施例4
本实施例的静电纺丝原位制备MOFs纳米酶的方法中，首先准备如下质量比例的静电纺丝液原料：聚乙烯醇 20份；碳酸乙烯酯 75份；醋酸锌1份；1,2,4,5-四(4-羧基苯基)苯1份；脂肪酸聚氧乙烯酯 0.05份。
然后将助纺材料聚乙烯醇与碳酸乙烯酯混合，常温下机械搅拌16 h，搅拌速度为500 r/min，至完全溶解形成均相溶液；向前述均相溶液中加入醋酸锌、1,2,4,5-四(4-羧基苯基)苯和高碳脂肪醇聚氧乙烯醚机械搅拌至混合均匀，得到均相的静电纺丝前驱液；将前述静电纺丝前驱液置于静电纺丝装置，以工作电压为20 kV，纺丝液的推进速度为0.8mL.h-1、接收器与针头的间距为12 cm的条件下进行纺丝，得到静电纺丝原位制备的连续纤维型MOFs@聚乙烯醇纳米酶。
接着以上述MOFs @ 聚乙烯醇纳米酶制备葡萄糖比色传感器，具体过程为将上述MOFs @ 聚乙烯醇纳米酶配置成4 mg/mL的水溶液，与PH=4.5的醋酸缓冲溶液按1：3500的体积比与混合，再加入体积为纳米酶水溶液的体积13倍指示剂邻苯二胺溶液，（本实施例中的TMB溶液为浓度为1mg/m的邻苯二胺的二甲基砜溶液），混合均匀后得到本实施例的葡萄糖比色传感器。
实施例5（检测例）
采用实施例1的葡萄糖比色传感器按如下过程进行葡萄糖比色检测：首先配制葡萄糖的比色检测体系：40μL的实施例1的葡萄糖传感器以及20μL不同加标浓度的葡萄糖溶液混合，用 0.1 M HAc-NaAc 缓冲液（pH 4.0）将反应体系补足至 4 mL，15℃水浴30 min，于652 nm 波长进行紫外-可见吸光度测量如图3A所示。根据652 nm处的吸光度，取6个不同葡萄糖浓度下的吸光度，做线性曲线。得到图3B的线性曲线。
同时，按上述方法进行现有技术中相关无机氧化酶的葡萄糖比色检测，其检测限和线性范围如表1所述。通过对比，本发明制备得到的葡萄糖传感器的检测限和检测范围对比具有更小的检测限，和更低的检测范围。
表格1 该传感器与现有葡萄糖传感器检测限以及线性范围比较
。
Claims (4)
1.一种静电纺丝原位制备MOFs纳米酶的方法，其特征在于，
第1步，按如下质量比例准备静电纺丝液：助纺材料10～20份，有机溶剂70～80份，金属离子化合物0.1-1份，有机配体0.1～1份，表面活性剂0.01～0.05份；
第2步，按第1步的质量比例，将助纺材料与有机溶剂混合，常温下机械搅拌12～16h，搅拌速度为400 r/min～500 r/min，至完全溶解形成均相溶液；
第3步，均相溶液中加入金属离子化合物、有机配体和表面活性剂，机械搅拌至混合均匀，得到均相的静电纺丝前驱液；
第4 步，将第3步的静电纺丝前驱液置于静电纺丝装置，以工作电压为15～20 kV，纺丝液的推进速度为0.5～0.8 mL.h-1、接收器与针头的间距为10～12 cm的条件下进行纺丝，得到静电纺丝原位制备的连续纤维型MOFs纳米酶；
第一步中，所述助纺材料为分子量为15000～30000的聚丙烯腈、聚偏氟乙烯、聚乳酸、聚乙烯醇和聚乙烯醇缩丁醛；所述有机溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、碳酸乙烯酯或硫氰酸钠；所述金属离子化合物为Co、Zn、Ni、Fe、Cu、Zr的硝酸盐、醋酸盐或者硫酸盐的化合物；所述有机配体为 3,3',5,5'-联苯四甲酸、 双(3,5-二羧基苯基)偶氮、乙炔基联苯-3,3',5,5'-四羧酸、四[4-(4'-羧基苯基)苯基]乙烯、9.10-二(3',5'-二羧基苯基)蒽、1,1,2,2-四(4-羧基苯)乙烯、1,3,6,8-四(4-羧基苯)芘、[1,1’:4’,1″]三联苯-3,3″,5,5″-四甲酸、1,2,4,5-四(4-羧基苯基)苯、四(4-羧基苯基)硅烷、四(3-羧基苯基)硅或1,3,5,7-金刚烷四羧酸、2-甲基咪唑类；所述表面活性剂为聚乙烯吡咯烷酮（PVP）、烷基酚聚氧乙烯醚、高碳脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯、脂肪酸甲酯乙氧基化物、失水山梨醇酯或烷基醇酰胺。
2.根据权利要求1所述的静电纺丝原位制备MOFs纳米酶的方法，其特征在于，所述金属离子化合物为硝酸钴、硝酸锌、硝酸镍、硝酸铁、醋酸钴、醋酸锌、醋酸镍、硫酸钴或硫酸锌。
3.根据权利要求1-2任一项所述的MOFs纳米酶制备的葡萄糖比色传感器，其特征在于，将MOFs纳米酶按1～5mg/mL的浓度配制成水溶液，与pH为4～5的醋酸缓冲溶液按1：2000～5000的体积比混合，再加入指示剂混合均匀，得到葡萄糖比色传感器。
4.根据权利要求3所述的所述的MOFs纳米酶制备的葡萄糖比色传感器，其特征在于，所述指示剂为浓度为1～5mg/mL的3,3',5,5'-四甲基联苯胺或邻苯二胺的二甲基砜溶液，加入体积量为混合液总量的0.2～0.5%，所述指示剂溶液的加入的体积量为MOFs纳米酶水溶液体积量10～15倍。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816064A (zh) * | 2018-06-26 | 2018-11-16 | 中国科学院青岛生物能源与过程研究所 | 一种原位生长金属有机框架材料的壳聚糖纳米纤维膜的制备方法 |
| CN109283164A (zh) * | 2018-09-30 | 2019-01-29 | 武汉大学 | 一种基于镧系mof掺杂的静电纺丝纤维膜作为选择性检测尿酸的荧光传感器及其制备方法 |
| CN111537589A (zh) * | 2020-05-13 | 2020-08-14 | 山东大学 | 一种基于钴基金属有机框架无酶葡萄糖传感器检测葡萄糖的方法 |
| CN113054207A (zh) * | 2021-03-02 | 2021-06-29 | 北京科技大学 | 金属盐辅助快速生长金属有机骨架衍生物的制备方法 |
| CN113398312A (zh) * | 2021-05-27 | 2021-09-17 | 华南理工大学 | 一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维及其制备方法与应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816064A (zh) * | 2018-06-26 | 2018-11-16 | 中国科学院青岛生物能源与过程研究所 | 一种原位生长金属有机框架材料的壳聚糖纳米纤维膜的制备方法 |
| CN109283164A (zh) * | 2018-09-30 | 2019-01-29 | 武汉大学 | 一种基于镧系mof掺杂的静电纺丝纤维膜作为选择性检测尿酸的荧光传感器及其制备方法 |
| CN111537589A (zh) * | 2020-05-13 | 2020-08-14 | 山东大学 | 一种基于钴基金属有机框架无酶葡萄糖传感器检测葡萄糖的方法 |
| CN113054207A (zh) * | 2021-03-02 | 2021-06-29 | 北京科技大学 | 金属盐辅助快速生长金属有机骨架衍生物的制备方法 |
| CN113398312A (zh) * | 2021-05-27 | 2021-09-17 | 华南理工大学 | 一种负载金属有机框架纳米酶与葡萄糖的抗菌纤维及其制备方法与应用 |
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