CN115093525A - 一种多功能单体共价有机骨架分子印迹聚合物及其制备方法和应用 - Google Patents
一种多功能单体共价有机骨架分子印迹聚合物及其制备方法和应用 Download PDFInfo
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- CN115093525A CN115093525A CN202210662791.9A CN202210662791A CN115093525A CN 115093525 A CN115093525 A CN 115093525A CN 202210662791 A CN202210662791 A CN 202210662791A CN 115093525 A CN115093525 A CN 115093525A
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Abstract
一种多功能单体共价有机骨架分子印迹聚合物及其制备方法和应用。本发明属于分子印迹聚合物领域。本发明为解决现有分离花色苷的分子印迹聚合物亲和力和特异性较差以及对花色苷分离效率和产率较低，且分离周期长的技术问题。本发明的聚合物以C3G为模板分子，以磺酸功能化合物、DAAQ和金属盐为功能单体，以Tp为交联剂，在室温下，通过席夫碱反应制备而成。本发明的一种多功能单体共价有机骨架分子印迹聚合物用于分离花色苷。本发明通过多种功能单体与模板分子C3G的不同部位形成静电相互作用、π‑π作用、氢键和螯合作用，多种类型作用协同增强模板分子和功能单体间作用力，从而提高仿生受体的选择性和亲和性。
Description
技术领域
本发明属于分子印迹聚合物领域，具体涉及一种多功能单体共价有机骨架分子印迹聚合物及其制备方法和应用。
背景技术
花色苷(AOC)是一类具有清除自由基、抗肿瘤、抗炎、保护肝脏和骨骼等生理功能的水溶性色素，其结构组成为C6-C3-C6类黄酮骨架和糖类，目前发现的花色苷多达500多种。因其资源丰富和良好的生物活性，在食品、保健品和医药等行业显示出良好的应用潜力。花色苷的结构多样性与低稳定性为其分离纯化带来了困难。目前传统分离花色苷的方法(高效液相色谱、膜分离等)由于选择性差、分离效率低使得快速制备高纯度花色苷一直是个难题，成为制约花色苷深入研究与开发的瓶颈问题。构建具有快速分离、高效吸附和特异性识别花色苷的新型纳米分离材料，提高分离效率和产率，为推动花色苷构效关系的深入研究和产业化发展具有重要的理论意义及应用价值。
分子印迹技术作为一种典型的仿生技术，其目的是合成具有识别模板分子能力的分子印迹聚合物(MIPs)。MIPs具有选择性高、成本低、制备简单和物理化学稳定性好等优点，因此被应用于天然产物的分离纯化中以提高分离效率。但是MIPs的亲和力和特异性仍然与生物系统中的天然受体存在一定差距，这些缺陷是由分子识别过程中相互作用的差异引起的。再者因为AOC在水中是强溶剂化的，MIPs对它们的分子识别需要付出相当大的溶剂化代价，体现为相对较低的亲和力。花色苷分子印迹聚合物的开发还需要更多地探索和研究。
共价有机骨架(COFs)，是一类具有晶体结构的二维多孔材料，由碳、硼、氧、氢和氮等轻元素组成。大比表面积、可控的孔径大小、高孔隙度和化学稳定性保证了其广泛的应用，尤其是在吸附客体分子方面展现其高吸附量的特性，越来越多地被用作高效吸附剂。但是值得注意的是COFs还存在一些固有的局限性。(1)芳香骨架构成的COFs具有高疏水性，不利于吸附亲水性客体分子；(2)基于尺寸排阻实现选择性的COFs不适用于分离尺寸大小相似的客体分子。
发明内容
本发明为解决现有分离花色苷的分子印迹聚合物亲和力和特异性较差以及对花色苷分离效率和产率较低，且分离周期长的技术问题，而提供了一种多功能单体共价有机骨架分子印迹聚合物及其制备方法和应用。
本发明的一种多功能单体共价有机骨架分子印迹聚合物以矢车菊素-3-O-葡萄糖苷(C3G)为模板分子，以磺酸功能化合物、2,6-二氨基蒽醌(DAAQ)和金属盐为功能单体，以1,3,5-三醛基间苯三酚(Tp)为交联剂，在室温下，通过席夫碱反应制备而成。
进一步限定，磺酸功能化合物为对氨基苯磺酸(ASA)、5-氨基-1-萘磺酸(ANSA)、苯胺-2,4-二磺酸(PABDSA)、牛磺酸(APSA)或氨基甲烷磺酸(AESA)。
进一步限定，金属盐为CrCl2、CaCl2、AlCl3或CoCl2。
进一步限定，C3G、磺酸功能化合物、DAAQ、金属盐、交联剂的摩尔比为(0.01-0.04)：(0.2-0.6)：(0.2-0.4)：(0.06-0.10)：(0.2-0.4)。
本发明的一种多功能单体共价有机骨架分子印迹聚合物的制备方法按以下步骤进行：
步骤1：将十六烷基磺酸钠(SDS)、磺酸功能化合物、对甲基苯磺酸(PTSA)和DAAQ溶于四氢呋喃(THF)，超声10-20min，得到混合液；
步骤2：将C3G和金属盐溶于水，然后加入步骤1的混合液，磁力搅拌10-30min，再加入Tp的THF溶液，室温下反应6-12h，离心得到聚合物；
步骤3：依次用DMF和双蒸水洗涤，再用HCl/甲醇溶液洗脱模板分子，得到多功能单体共价有机骨架分子印迹聚合物。
进一步限定，步骤1中磺酸功能化合物的物质的量与THF的体积的比为0.4mmol：(1-4)mL，PTSA与磺酸功能化合物的物质的量的比为0.65：(0.2-0.6)，SDS的质量与磺酸功能化合物的物质的量的比为(20-90)mg：0.4mmol。
进一步限定，步骤2中金属盐的物质的量与水的体积的比为0.08mmol：(3-5)mL。
进一步限定，步骤2中Tp的THF溶液中Tp的浓度为0.05-0.2mol/L。
进一步限定，步骤2中离心的参数为：转速为9000-11000rpm，时间为10-20min。
进一步限定，步骤3中HCl/甲醇溶液中HCl的体积分数为0.4％-0.6％。
本发明的一种多功能单体共价有机骨架分子印迹聚合物用于分离花色苷(AOC)。
本发明与现有技术相比具有的显著效果，具体如下：
1)本发明以矢车菊素-3-O-葡萄糖苷为模板分子，以磺酸功能化合物、2,6-二氨基蒽醌和金属离子作为功能单体，通过多种功能单体与模板分子C3G的不同部位形成静电相互作用、π-π作用、氢键和螯合作用，多种类型作用协同增强模板分子和功能单体间作用力，从而提高仿生受体的选择性和亲和性。
2)本发明通过一锅法制备亲水性多功能单体共价有机骨架分子印迹聚合物(HMCMIPs)，实验方法简单，易于实现。室温下合成尽可能保持模板分子AOC原有的结构，保证了形成的印迹孔穴的准确性，实现精准识别。
3)本发明制得的亲水性多功能单体共价有机骨架分子印迹聚合物对C3G的结合常数高达3.33×106M-1，与文献报道的MIPs的结合常数(4.71×102M-1)相比提高了四个数量级，甚至高于天然识别受体凝集素的结合常数(103～104M-1)两到三个数量级。选择性比共价有机骨架分子印迹(MCMIPs)提高了大约6倍(对槲皮素的选择因子36.67)，亲水性多功能单体共价有机骨架分子印迹聚合物的吸附量高达1566mg/g，经过HMCMIPs分离可获得纯度为93.72％的C3G，回收率为97.09％，HMCMIPs的高选择性有效地提高分离效率，缩短分离周期，避免因多次分离造成的固定相不可逆吸附导致的损失，提高回收率。
附图说明
图1为实施例1的HMCMIPs(ASA-Ca2+)的红外图谱；
图2为实施例1的HMCMIPs(ASA-Ca2+)的XPS图谱；
图3为实施例1的HMCMIPs(ASA-Ca2+)与COFs的水分散性对比照片；
图4为实施例1的HMCMIPs(ASA-Ca2+)与COFs的接触角对比图；
图5为实施例1的HMCMIPs(ASA-Ca2+)与对比例2的HMCNIPs(ASA-Ca2+)的等温吸附曲线；
图6为实施例1的HMCMIPs(ASA-Ca2+)与对比例2的HMCNIPs(ASA-Ca2+)的吸附动力学曲线；
图7为实施例1的HMCMIPs(ASA-Ca2+)与对比例2的HMCNIPs(ASA-Ca2+)的特异性对比图；
图8为实施例1的HMCMIPs(ASA-Ca2+)的循环利用率柱形图；
图9为不同分离介质吸附黑果腺肋花楸粗提物前后样品色谱图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
下述实施例中所使用的实验方法如无特殊说明均为常规方法。所用材料、试剂、方法和仪器，未经特殊说明，均为本领域常规材料、试剂、方法和仪器，本领域技术人员均可通过商业渠道获得。
实施例1：本实施例的一种多功能单体共价有机骨架分子印迹聚合物以C3G为模板分子，以ASA、DAAQ和CaCl2为功能单体，以Tp为交联剂，在室温下，通过席夫碱反应制备而成，所述C3G、ASA、DAAQ、CaCl2、Tp的摩尔比为0.02：0.4：0.35：0.08：0.3。
制备上述多功能单体共价有机骨架分子印迹聚合物的方法按以下步骤进行：
步骤1：将55mg SDS、0.4mmol ASA、0.65mmol PTSA和0.35mmol DAAQ溶于2mL THF，超声15min，得到混合液；
步骤2：将0.02mmol C3G和0.08mmol CaCl2溶于4.5mL水，然后加入步骤1的混合液，磁力搅拌20min，再加入2.5mL Tp的THF溶液(Tp＝0.3mmol)，室温下反应6h，10000rpm下离心15min，得到聚合物；
步骤3：依次用DMF和双蒸水洗涤，再用HCl/甲醇溶液(HCl＝0.5vol％)洗脱模板分子，得到多功能单体共价有机骨架分子印迹聚合物HMCMIPs(ASA-Ca2+)。
对比例1：
步骤1：将55mg SDS、0.65mmol PTSA和0.35mmol DAAQ溶于2mLTHF，超声15min，得到混合液；
步骤2：向步骤1的混合液中加入4.5mL双蒸水，磁力搅拌20min，再加入2.5mLTp的THF溶液(Tp＝0.3mmol)，室温下反应6h，10000rpm下离心15min，得到聚合物；
步骤3：依次用DMF和双蒸水洗涤，得到共价有机骨架聚合物COFs。
对比例2：
步骤1：将55mg SDS、0.4mmol ASA、0.65mmol PTSA和0.35mmol DAAQ溶于2mL THF，超声15min，得到混合液；
步骤2：将0.08mmol Ca2+溶于4.5mL水，然后加入步骤1的混合液，磁力搅拌20min，再加入2.5mL Tp的THF溶液(Tp＝0.3mmol)，室温下反应6h，10000rpm下离心15min，得到聚合物；
步骤3：依次用DMF和双蒸水洗涤，再用HCl/甲醇溶液(HCl＝0.5wt％)洗脱模板分子，得到多功能单体共价有机骨架分子印迹聚合物HMCNIPs(ASA-Ca2+)。
检测试验
(1)红外检测：图1是HMCMIPs(ASA-Ca2+)的红外图谱。观察C＝O(1618cm-1)、C＝C(1572cm-1)、C＝C(苯环，1458cm-1)和C-N(1266cm-1)的伸缩振动吸收峰揭示了基于β-酮烯胺框架结构的形成。位于3424cm-1、1125cm-1、1036cm-1和1009cm-1的吸收峰则是磺酸基团的特征吸收峰。以上峰的出现说明HMCMIPs合成成功。
(2)X射线光电子能谱检测：通过XPS研究HMCMIPs(ASA-Ca2+)的元素组成和化学键，如图2所示。从XPS全谱中可以发现O1s(531.11eV)、N1s(398.86eV)、Ca2p(347.12eV)、C1s(284.17eV)和S2p(167.58eV)的峰，与HMCMIPs构成相符，为磺酸基团和Ca2+成功修饰提供了充分证据。
(3)水分散性和接触角检测：将实施例1的HMCMIPs(ASA-Ca2+)和对比例1的COFs加入到水中，观察其分散性，并对其接触角进行检测，结果如图3-4所示，可以看出，HMCMIPs(ASA-Ca2+)在水中呈现均匀分散状态，其水接触角为49°，由此可见，HMCMIP是亲水的，磺酸基团的引入提高了HMCMIPs的亲水性。
(4)吸附性能研究：
为研究HMCMIPs(ASA-Ca2+)的吸附性能，首先评估吸附初始时C3G不同的浓度对HMCMIPs吸附量的影响，对比例2的HMCNIPs的吸附性能同样被考察作为对照。结果如图5所示，可以看出，HMCMIPs和HMCNIPs的吸附量随C3G的初始浓度增加而增加。随后，因吸附位点全部与C3G结合后，吸附达到平衡，吸附量分别为1566和1039mg/g，由此可见，本发明的HMCMIPs中由于多功能单体的引入，大幅增加了与C3G结合的吸附位点，同时通过多功能基团与C3G不同片段之间形成的多类型作用(静电相互作用、π-π作用、氢键和螯合作用)显著提高了吸附量。
图6为实施例1的HMCMIPs(ASA-Ca2+)和对比例2的HMCMNIPs(ASA-Ca2+)的吸附动力学曲线，可以看出，实施例1的HMCMIPs(ASA-Ca2+)在40min时基本达到吸附平衡，吸附速率快。HMCMIPs吸附C3G的初始吸附速率常数为213.65mg/(g·min)，远超于文献报道的分子印迹聚合物(8.475mg/(g·min)、136.99mg/(g·min))。
(5)特异性检测：选择槲皮素(Qu)、柚皮苷(Nar)、芦丁(Ru)、新橙皮苷二氢查耳酮(NHDC)、水杨酸(SAA)、芥子酸(SIA)SIA、咖啡酸(CA)和对羟基苯乙酸(p-HPA)作为结构类似物评价实施例1的HMCMIPs(ASA-Ca2+)的选择性，结果见图7。可以看出，HMCMIPs对C3G的吸附能力远高于其它类似物，说明HMCMIPs对C3G的选择性较好，这种选择性是由HMCMIPs的形状记忆效应和化学基团选择性提供的。实施例1的HMCMIPs和对比例2的HMCNIPs的分配系数(Kd)、选择系数(ksel)和相对选择系数(krel)列于表1，市售聚酰胺树脂(PAM)的分配系数和选择系数列于表2。实施例1的HMCMIPs、对比例2的HMCNIPs和PAM对Qu的ksel分别为36.67、8.36、0.96。HMCMIPs表现出优异的选择性。
表1 HMCMIPs和HMCNIPs对不同物质的分配系数、选择系数和相对选择系数
表2 PAM对不同物质的分配系数和选择系数
(6)重复利用率检测：采用吸附-解吸循环实验评价实施例1的HMCMIPs的重复利用性，结果见图8。可以看出，经过10次使用后，HMCMIPs的吸附效率最终下降了17.64％，表明HMCMIPs具有良好的稳定性和重复利用性。
应用例1：将实施例1的HMCMIPs用于吸附黑果腺肋花楸粗提物，具体过程如下：
采用含0.1％盐酸的70％乙醇溶液提取得到了黑果腺肋花楸粗提物原液，然后利用实施例1的HMCMIPs对其进行吸附，以商品化分离介质大孔树脂AB-8、聚酰胺树脂、葡聚糖凝胶Sephadex G-200和阴离子交换树脂DEAE-52作为对照组，对黑果腺肋花楸粗提物原液和吸附后样品通过HPLC进行分析(色谱条件：流动相为0.4％甲酸/水(流动相A)和乙腈(流动相B)，流速1mL/min，柱温30℃。梯度洗脱程序为：0～20min，10％B；20～30min，10％～13％B；30～60min，13％～50％B；60～70min，50％～100％B；检测波长254nm，进样量5μL。)，结果见图9。
由图9可以看出，HMCMIPs的选择性取决于化学基团和分子形状，使其对C3G(保留时间为17.22min)具有更强的亲和能力，优先吸附C3G而不受其它组分的干扰。HMCMIPs洗脱液中C3G的纯度达到93.72％，纯度显著提高，C3G的回收率为97.09％。整个分离过程在2h内就可以完成，非常快速。
其它商品化分离介质，如大孔树脂AB-8、聚酰胺树脂、葡聚糖凝胶Sephadex G-200和阴离子交换树脂DEAE-52对C3G的识别能力较弱，对杂质也具有吸附作用。四种分离填料对C3G吸附量低，C3G回收率仅为8.34％～20.09％。相同条件下得到的洗脱液中C3G纯度小于46.28％。由此可见HMCMIPs的高选择性有效地提高了分离效率，缩短分离周期，避免多次分离造成的固定相不可逆吸附导致的损失，提高回收率。
以上所述仅为本发明的较佳实施例而已，鉴于本发明所属领域的技术人员可以对上述实施方式进行适当的变更和修改，因此，本发明并不局限于上面所述的具体实施方式，对本发明的一些修改和变更也应当落入本发明的权利要求的保护范围之内。
Claims (10)
1.一种多功能单体共价有机骨架分子印迹聚合物，其特征在于，该聚合物以C3G为模板分子，以磺酸功能化合物、DAAQ和金属盐为功能单体，以Tp为交联剂，在室温下，通过席夫碱反应制备而成。
2.根据权利要求1所述的一种多功能单体共价有机骨架分子印迹聚合物，其特征在于，磺酸功能化合物为ASA、ANSA、PABDSA、APSA或AESA。
3.根据权利要求1所述的一种多功能单体共价有机骨架分子印迹聚合物，其特征在于，金属盐为CrCl2、CaCl2、AlCl3或CoCl2。
4.根据权利要求1所述的一种多功能单体共价有机骨架分子印迹聚合物，其特征在于，C3G、磺酸功能化合物、DAAQ、金属盐、交联剂的摩尔比为(0.01-0.04)：(0.2-0.6)：(0.2-0.4)：(0.06-0.10)：(0.2-0.4)。
5.如权利要求1-4任意一项所述的一种多功能单体共价有机骨架分子印迹聚合物的制备方法，其特征在于，该方法按以下步骤进行：
步骤1：将SDS、磺酸功能化合物、PTSA和DAAQ溶于THF，超声10-20min，得到混合液；
步骤2：将C3G和金属盐溶于水，然后加入步骤1的混合液，磁力搅拌10-30min，再加入Tp的THF溶液，室温下反应6-12h，离心得到聚合物；
步骤3：依次用DMF和双蒸水洗涤，再用HCl/甲醇溶液洗脱模板分子，得到多功能单体共价有机骨架分子印迹聚合物。
6.根据权利要求5所述的制备方法，其特征在于，步骤1中磺酸功能化合物的物质的量与THF的体积的比为0.4mmol：(1-4)mL，PTSA与磺酸功能化合物的物质的量的比为0.65：(0.2-0.6)，SDS的质量与磺酸功能化合物的物质的量的比为(20-90)mg：0.4mmol。
7.根据权利要求5所述的制备方法，其特征在于，步骤2中金属盐的物质的量与水的体积的比为0.08mmol：(3-5)mL，Tp的THF溶液中Tp的浓度为0.05-0.2mol/L。
8.根据权利要求5所述的制备方法，其特征在于，步骤2中离心的参数为：转速为9000-11000rpm，时间为10-20min。
9.根据权利要求5所述的制备方法，其特征在于，步骤3中HCl/甲醇溶液中HCl的体积分数为0.4％-0.6％。
10.如权利要求1-4任意一项所述的一种多功能单体共价有机骨架分子印迹聚合物的应用，其特征在于，将其用于分离AOC。
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