CN113004473B - 一种pH/温度双响应的MXene基分子印迹水凝胶及其制备方法 - Google Patents
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Abstract
本发明公开了一种具有pH/温度双响应的MXene基分子印迹水凝胶及其制备方法，其特征在于，采用N‑异丙基丙烯酰胺作为温度响应的功能单体，4‑乙烯基苯硼酸作为特异性识别人参皂苷Rb1的功能单体，功能化修饰的f‑MXene作为支撑材料，通过自由基聚合反应制备pH/温度双响应MXene基分子印迹水凝胶，实现了对人参皂苷Rb1的可控捕获与释放，为分子印迹水凝胶的应用提供了新的可能。
Description
技术领域
本发明涉及一种pH/温度双响应的MXene基分子印迹水凝胶及其制备方法，属于智能响应材料和生物医药技术领域。
背景技术
智能水凝胶作为一种智能响应材料，在生物医药领域具有重要的研究意义。其在外界环境刺激下(包括温度、pH值、离子强度、光、电场、磁场等)，自身的微观分子结构及分子构象发生可逆转变，从而导致材料自身的某些性质如空间结构、形状、表面特性等发生相应的变化，可实现目标分子的可控捕获与释放。这一特点使其在药物输送、分离材料、色谱分析、传感器加工、吸附分离、色谱分析等领域得到了广泛的应用。
分子印迹技术是一种高选择性的分离技术，其能够制备对模板分子(目标分子)具有专一识别性的分子印迹聚合物(Molecularly Imprinted Polymers,通常简写为MIPs)。由于MIPs与目标分子具有“锁-钥”关系，具有高选择性和高强度的优点，在药物输送水凝胶的制备研究中表现出优势。而硼酸化亲和材料作为一种独特的吸附材料，已成为选择性吸附和富集顺式二醇类物质(糖类物质、糖蛋白、糖苷类活性物质)的重要方法。硼酸官能团赋予其可逆共价键、pH响应捕获/释放、高选择性等优势。当pH值较高时(pH>7)，硼酸基质能与顺式二醇类化合物形成稳定的环状硼酸酯(共价键)；而当pH值较低时，硼酸酯键断裂，顺式二醇类物质实现可逆释放。
MXene是一类新型二维过渡金属碳(氮或碳氮)化物，其化学通式为Mn+1XnTx，其中，M代表前过渡金属元素(Early transition metals，如Sc，Ti，Zr等)，X代表C或CN元素，Tx代表表面官能团，n＝1，2或3。MXene具有高的比表面积、优异的导电性、优秀的机械性能和良好的亲水性等优点，已在储能、气体吸附、传感器、催化、纳米医药、诊断成像等领域展现出巨大的潜力，成为继石墨烯之后新的研究热点。
基于上述研究背景，本发明以N-异丙基丙烯酰胺作为温度响应的功能单体，4-乙烯基苯硼酸作为可逆结合人参皂苷Rb1的功能单体，人参皂苷Rb1作为模板分子，N,N-亚甲基双丙烯酰胺作为交联剂，功能化修饰的f-MXene作为支撑材料，通过自由基聚合反应制备pH/温度双响应MXene基分子印迹水凝胶。该方法合成的水凝胶实现了可控捕获与释放，具有高的选择性，为分子印迹水凝胶提供了新的方向。
发明内容
本发明的目的在于提供一种pH/温度双响应的MXene基分子印迹水凝胶及其制备方法：首先利用γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH570)对MXene进行功能化修饰，制备具有双键的f-MXene，然后在pH8.5的条件下，将N-异丙基丙烯酰胺(NIPAAm)、丙烯酰胺(AAm)、4-乙烯基苯硼酸(VPBA)、人参皂苷Rb1、f-MXene、N,N-亚甲基双丙烯酰胺(MBA)充分混合，VPBA与Rb1可形成可逆断裂的硼酸酯，而后引发自由基聚合反应，最后通过pH3-4的酸水洗脱模板分子Rb1，得到双响应MXene基分子印迹水凝胶。
所述的f-MXene的结构如式I所示：
所述的人参皂苷Rb1的结构如式Ⅱ所示：
所述的可逆断裂的硼酸酯的结构如式Ⅲ所示：
本发明的技术方案如下：
(1)f-MXene的合成：
(2)分子印迹水凝胶的制备
通过自由基聚合反应制备分子印迹水凝胶。具体方法为：分别将N-异丙基丙烯酰胺(NIPAAm)、丙烯酰胺(AAm)、4-乙烯基苯硼酸(VPBA)、人参皂苷Rb1、f-MXene、N,N-亚甲基双丙烯酰胺(MBA)溶解在pH8.5的PBS中，充分溶解混合后，通N2除去体系中的O2，然后加入引发剂过硫酸铵(APS)、促进剂四甲基乙二胺(TEMED)，N2条件下密封反应24h，最后通过pH3-4的酸水洗脱模板分子Rb1，冷冻干燥得到双响应MXene基分子印迹水凝胶。
本发明采用N-异丙基丙烯酰胺作为温度响应的功能单体、4-乙烯基苯硼酸作为选择识别的功能单体、f-MXene作为支撑材料，制备得到了具有pH/温度双响应分子印迹水凝胶，实现了对人参皂苷Rb1的可控捕获与释放，为分子印迹水凝胶的应用提供了新的可能。
附图说明
图1为分子印迹水凝胶的吸附/脱附示意图；
图2为功能化的MXene(f-MXene)的红外谱图；
图3为功能化的MXene(f-MXene)的能谱分析结果；
图4为分子印迹水凝胶内部的透射电镜图；
图5为pH8.5的条件下不同添加量的非分子印迹和分子印迹水凝胶的溶胀率；
图6为不同pH条件下不同添加量的非分子印迹和分子印迹水凝胶对Rb1的吸附容量。
具体实施方式
下面给出的实例对本发明进行具体描述，但不限制本发明，本发明的范围由权利要求限定。
实施例1：
MXene的功能化修饰：取100mg MXene，溶于25mL水后，加入75mL乙醇，混合均匀后，逐滴加入KH570 200mg，加入冰醋酸调节pH至4，充N2，室温下搅拌48h。反应结束后，用乙醇/水＝1：1的溶液多次洗涤，除去未反应的冷冻干燥得到f-MXene。
分子印迹水凝胶的合成：取0.1584g N-异丙基丙烯酰胺(NIPAAm，1.4mmol)、0.0426g丙烯酰胺(AAm，0.6mmol)、0.0148g 4-乙烯基苯硼酸(VPBA，0.1mmol)、0.0366g人参皂苷Rb1(VPBA物质的量的1/3，0.033mmol)、0.01g f-MXene、0.0093g N,N-亚甲基双丙烯酰胺(MBA，0.06mmol)溶于4mL PBS(0.01M，pH8.5)中，充分溶解混合后，通N2鼓泡，除去氧气。而后在冰水浴的情况下加入0.01g APS、10μL TEMED，N2密封后常温反应24h。
模板分子的洗脱：将得到的水凝胶用磷酸水溶液(pH3-4)、去离子水依次洗脱，充分除去模板分子Rb1，直到液相检测中203nm处没有吸收峰。
实施例2：
MXene的功能化修饰：取100mg MXene，溶于25mL水后，加入75mL乙醇，混合均匀后，逐滴加入KH570 200mg，加入冰醋酸调节pH至4，充N2，室温下搅拌48h。反应结束后，用乙醇/水＝1：1的溶液多次洗涤，除去未反应的冷冻干燥得到f-MXene。
分子印迹水凝胶的合成：取0.1584g N-异丙基丙烯酰胺(NIPAAm，1.4mmol)、0.0426g丙烯酰胺(AAm，0.6mmol)、0.0059g 4-乙烯基苯硼酸(VPBA，0.04mmol)、0.0144g人参皂苷Rb1(VPBA物质的量的1/3，0.013mmol)、0.01g f-MXene、0.0093g N,N-亚甲基双丙烯酰胺(MBA，0.06mmol)溶于4mL PBS(0.01M，pH8.5)中，充分溶解混合后，通N2鼓泡，除去氧气。而后在冰水浴的情况下加入0.01g APS、10μL TEMED，N2密封后常温反应24h。
模板分子的洗脱：将得到的水凝胶用磷酸水溶液(pH3-4)、去离子水依次洗脱，充分除去模板分子Rb1，直到液相检测中203nm处没有吸收峰。
实施例3：
非分子印迹水凝胶的合成
MXene的功能化修饰：取100mg MXene，溶于25mL水后，加入75mL乙醇，混合均匀后，逐滴加入KH570 200mg，加入冰醋酸调节pH至4，充N2，室温下搅拌48h。反应结束后，用乙醇/水＝1：1的溶液多次洗涤，除去未反应的冷冻干燥得到f-MXene。
非分子印迹水凝胶的合成：取0.1584g N-异丙基丙烯酰胺(NIPAAm，1.4mmol)、0.0426g丙烯酰胺(AAm，0.6mmol)、0.0148g 4-乙烯基苯硼酸(VPBA，0.1mmol)、0.01g f-MXene、0.0093g N,N-亚甲基双丙烯酰胺(MBA，0.06mmol)溶于4mL PBS(0.01M，pH8.5)中，充分溶解混合后，通N2鼓泡，除去氧气。而后在冰水浴的情况下加入0.01g APS、10μL TEMED，N2密封后常温反应24h。
实施例4：
pH8.5的条件下不同添加量的非分子印迹和分子印迹水凝胶的溶胀效果
MXene的功能化修饰：取100mg MXene，溶于25mL水后，加入75mL乙醇，混合均匀后，逐滴加入KH570 200mg，加入冰醋酸调节pH至4，充N2，室温下搅拌48h。反应结束后，用乙醇/水＝1：1的溶液多次洗涤，除去未反应的冷冻干燥得到f-MXene。
分子印迹水凝胶的合成：取0.1584g N-异丙基丙烯酰胺(NIPAAm，1.4mmol)、0.0426g丙烯酰胺(AAm，0.6mmol)、0.0148g 4-乙烯基苯硼酸(VPBA，0.1mmol)、0.0366g人参皂苷Rb1(VPBA物质的量的1/3，0.033mmol)、0.01g f-MXene、0.0093g N,N-亚甲基双丙烯酰胺(MBA，0.06mmol)溶于4mL PBS(0.01M，pH8.5)中，充分溶解混合后，通N2鼓泡，除去氧气。而后在冰水浴的情况下加入0.01g APS、10μL TEMED，N2密封后常温反应24h。
模板分子的洗脱：将得到的水凝胶用磷酸水溶液(pH3-4)、去离子水依次洗脱，充分除去模板分子Rb1，直到液相检测中203nm处没有吸收峰。最后冷冻干燥，以便溶胀性能检测。
溶胀性能检测：准确称取一定量(约0.02g)冷干后的水凝胶，在32℃下，将其放在5mL Rb1的碱性PBS溶液(浓度约为1.0mg/mL)中溶胀一定时间，达到平衡后，去掉表面的水分，再次称量。通过
计算，得到溶胀率。如图4所示。
实施例5：
不同pH条件下不同添加量的非分子印迹和分子印迹水凝胶对Rb1的吸附容量
MXene的功能化修饰：取100mg MXene，溶于25mL水后，加入75mL乙醇，混合均匀后，逐滴加入KH570 200mg，加入冰醋酸调节pH至4，充N2，室温下搅拌48h。反应结束后，用乙醇/水＝1：1的溶液多次洗涤，除去未反应的冷冻干燥得到f-MXene。
分子印迹水凝胶的合成：取0.1584g N-异丙基丙烯酰胺(NIPAAm，1.4mmol)、0.0426g丙烯酰胺(AAm，0.6mmol)、0.0148g 4-乙烯基苯硼酸(VPBA，0.1mmol)、0.0366g人参皂苷Rb1(VPBA物质的量的1/3，0.033mmol)、0.01g f-MXene、0.0093g N,N-亚甲基双丙烯酰胺(MBA，0.06mmol)溶于4mL PBS(0.01M，pH8.5)中，充分溶解混合后，通N2鼓泡，除去氧气。而后在冰水浴的情况下加入0.01g APS、10μL TEMED，N2密封后常温反应24h。
模板分子的洗脱：将得到的水凝胶用磷酸水溶液(pH3-4)、去离子水依次洗脱，充分除去模板分子Rb1，直到液相检测中203nm处没有吸收峰。最后冷冻干燥，以便溶胀性能检测。
吸附容量的检测：取约0.02g水凝胶分别分散在5mL Rb1的pH5.5、pH7.2、pH8.5的PBS溶液(Rb1浓度约为1.0mg/mL)中，在32℃下振荡24h。而后离心，取上清液通过高效液相色谱法检测Rb1的浓度。通过Q＝(C0-Ct)×V/W计算吸附容量，每组数据测三次。如图5所示。
Claims (5)
1.一种具有pH/温度双响应的MXene基分子印迹水凝胶，其特征在于，采用N-异丙基丙烯酰胺作为温度响应的功能单体，4-乙烯基苯硼酸作为可逆结合人参皂苷Rb1的功能单体，γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH570)修饰的f-MXene作为支撑材料，通过自由基聚合反应制备pH/温度双响应MXene基分子印迹水凝胶。
2.根据权利要求1所述的pH/温度双响应的MXene基分子印迹水凝胶，可用于对人参皂苷Rb1的可控捕获与释放。
3.根据权利要求1所述的具有pH/温度双响应的MXene基分子印迹水凝胶的制备方法，包括如下步骤：
(1)将MXene通过γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH570)进行功能化修饰，取一定量的MXene，分散于适量水中，加入乙醇，混合均匀后，逐滴加入KH570，而后调节pH至4，通入N2，室温下搅拌48h，反应结束后，用乙醇/水溶液多次洗涤，然后冷冻干燥得到功能化修饰的f-MXene；
(2)将步骤(1)中制得的f-MXene与功能单体混合均匀以制备分子印迹水凝胶，取一定量的N-异丙基丙烯酰胺(NIPAAm)、丙烯酰胺(AAm)、4-乙烯基苯硼酸(VPBA)、人参皂苷Rb1、f-MXene、N,N-亚甲基双丙烯酰胺(MBA)溶于适量pH8.5的PBS溶液中，充分混合后，通N2除去氧气，而后在冰水浴中加入一定量的过硫酸铵(APS)和四甲基乙二胺(TEMED)，N2密封后常温反应24h，得到水凝胶；
(3)将得到的水凝胶用pH 3-4的磷酸水溶液、去离子水依次洗脱，充分洗脱除去模板分子Rb1，直到采用高效液相色谱未检出Rb1，然后冷冻干燥得到MXene基分子印迹水凝胶产品。
4.根据权利要求3所述的一种具有pH/温度双响应的MXene基分子印迹水凝胶的制备方法，其特征在于，步骤(1)中水和乙醇的体积比为1:3，MXene和KH570的质量比为0.5:1。
5.根据权利要求3所述的一种具有pH/温度双响应的MXene基分子印迹水凝胶的制备方法，其特征在于，步骤(2)中N-异丙基丙烯酰胺、丙烯酰胺、N,N-亚甲基双丙烯酰胺的摩尔比为23:10:1，4-乙烯基苯硼酸和人参皂苷Rb1的摩尔比为3:1。
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