Pickering高内相乳液模板构建双重识别自支撑多孔印迹膜选择性分离纯化木犀草素的研究

The component of extracts from peanut shell is complex, which requires further separation and purification to remove impurities in order to promote luteolin's application in health-care products, anticancer, antibacterial, and other clinical treatment. This project intends to utilize molecularly imprinted polymers modified graphene oxide (GO) as stabilizer for the construction of Pickering high internal phase emulsions (HIPE), and substituted boronic acid monomer and non-covalent imprinted monomer will be introduced into their continuous phase. Then free-standing molecularly imprinted porous membrane with double recognition abilities, fabricated via thermal initiated imprinting polymerization of Pickering HIPE template in an optimized mold, will be adopted for the selective separation and purification of luteolin from extracts. This research is aimed at selective separation and purification of luteolin by free-standing molecularly imprinted porous membrane with double recognition abilities, and the membrane preparation method and performance optimization are recognized as critical control point. Through adjusting membrane thickness, controlling over the pore structure, and optimizing recognition ability of imprinted binding sites, the purity and yield of luteolin will be effectively elevated. On this basis, the adjustments and controls law of preparation of free-standing molecularly imprinted porous membrane with double recognition abilities will be elucidated. The mechanism and synergetic effect of imprinted binding sites with double recognition abilities for the enhancement of selectivity will also be investigated. Moreover, the structure-activity relationship of the free-standing molecularly imprinted porous membrane with double recognition abilities will be revealed, and the possible recognition and mass transfer mechanism will be described. Finally, a new strategy for the selective separation and purification of luteolin from peanut shell extracts will be established.

花生壳中木犀草素提取液成分复杂，需进一步分离纯化才能应用于保健品和抗癌、抑菌等临床治疗环节。本项目拟以印迹聚合物修饰的氧化石墨烯(GO)为稳定粒子构建Pickering高内相乳液(HIPE)模板，连续相中同时引入取代硼酸单体和非共价印迹单体，转入优化的模具中热引发印迹聚合制备双重识别自支撑多孔印迹膜，并用于选择性分离纯化花生壳提取液中的木犀草素。研究中以自支撑多孔印迹膜选择性分离纯化木犀草素为主线，以膜的制备方法和性能优化为关键控制点，通过膜厚度可控调节、孔结构有效控制和印迹位点识别程度增强提高木犀草素的纯度和得率。在此基础上，阐明Pickering HIPE模板构建双重识别自支撑多孔印迹膜及其微结构调控的规律，探究双重识别印迹位点协同增强膜识别能力的机理；揭示双重识别自支撑多孔印迹膜的构效关系，解释可能的识别与传质机制，建立选择性分离纯化花生壳提取液中木犀草素的新方法。

木犀草素（LTL）是一种典型的黄酮类化合物，结构中含有邻二羟基的官能团，具有极高的生物医药功能。花生壳废渣是LTL含量最高的原料之一，其提取液成分复杂，需进一步分离纯化才能应用于抗癌和抑菌等临床治疗环节。本项目集中分子印迹技术、硼亲和、光引发策略、离子亲和和乳液模板法的优点，基于多种液滴反应器，构建了多级孔型、界面修饰型、膜块型、核/壳型、多重识别型等多种吸附材料，并用于选择性分离纯化木犀草素，并考察了纯化的木犀产品的纯度、得率、抗菌效果。研究中以选择性分离纯化过程为主线，利用静/动态吸附实验，系统讨论了分子印迹吸附剂对木犀草素的吸附分离与富集的平衡、动力学和选择性识别行为，并建立了相应的模型，以吸附分离材料的制备方法和吸附性能优化为关键控制点，得到了高纯的木犀草素，最高纯度达到99.8%。。负责人及项目组成员严格遵守《国家自然科学基金条例》规定，紧密围绕项目研究内容开展了一系列富有成效的研究工作，已累计在Journal of Materials Chemistry A、Small、ACS Applied Materials Interfaces和Chemical Engineering Journal等国际知名期刊上发表SCI论文26篇（其中标注基金号26篇），其中一区论文24篇，影响因子大于8的24篇；申请国家发明专利17件，已授权11件；项目研究中共独立培养了博士生1名、硕士生3名；联合培养了博士生2名、硕士生1名；另有2名博士生和4名硕士研究生在读。