Screening of functional monomers and preparation of molecularly imprinted polymers (MIPs) in molecularly imprinted polymers of steranes
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摘要: 为了制备对甾烷类化合物具有特异性选择能力的分子印迹聚合物(MIPs)，利用紫外光谱法对预聚合体系进行筛选，确定功能单体的种类、配比及其作用方式。将3种模板分子(胆固醇、β-谷固醇、去氧胆酸)分别与4种功能单体，即丙烯酸(AA)、甲基丙烯酸(MAA)、甲基丙烯酸甲酯(MMA)、丙烯酰胺(AM))的相互作用强度进行对比。研究结果发现，功能单体AA均可与3种模板分子发生较强的相互作用并形成稳定的预聚合体系，从而优选出AA为MIPs的功能单体。另外，通过不同比例AA紫外光谱吸光度变化和差示紫外光谱分析，显示3种模板分子与功能单体AA的最佳浓度比均为1∶4，且形成的稳定配合物构型分别为胆固醇-1AA、β-谷固醇-1AA及去氧胆酸-3AA。同时，以EDGMA为交联剂、AIBN为引发剂，采用沉淀聚合法成功合成了MIPs，傅立叶变换红外光谱(FTIR)分析结果显示MIPs制备良好。因此，此方法可用于对甾烷类化合物具有特异性选择能力的MIPs功能单体的筛选及其制备，并为深层—超深层烃源岩油源对比研究提供技术支持。Abstract: To prepare molecularly imprinted polymers (MIPs) with specific selectivity for steranes, the prepolyme-rization system was screened by UV spectroscopy to determine the type, proportion and mode of action of functional monomers. In this study, the interaction intensities between three template molecules (cholesterol, β-sitosterol, deoxycholic acid) and four functional monomers (acrylic acid (AA), methacrylic acid (MAA), methyl methacrylate (MMA), and acrylamide (AM)) are compared respectively. The results show that the functional monomer AA can interact strongly with the three template molecules and form a stable prepolymerization system, so AA is selected as the functional monomer of MIPs. In addition, the UV spectral absorbance change and differential UV spectral analysis of different proportions of AA show that the optimal concentration ratios of the three template molecules to functional monomer AA are all 1:4, and the stable complex configurations formed are cholesterol-1AA, β-sitosterol-1AA and deoxycholic acid-3AA, respectively. The MIPs are successfully synthesized by precipitation polymerization using EDGMA as dispersant and AIBN as initiator, and the results of FTIR show that MIPs are well prepared. Therefore, this method can be used for the screening and preparation of MIPs functional monomers with specific selectivity for steranes, and provide technical support for the study of oil-source correlation between deep and ultra-deep source rocks.
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Key words:
- steranes /
- molecularly imprinted polymer /
- UV spectrum /
- template molecule /
- functional monomer
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图 1 模板与功能单体的化学结构
Figure 1. Chemical structure of template molecules and functional monomers
图 2 胆固醇、不同功能单体及其混合溶液的紫外吸收光谱
Figure 2. UV absorption spectra of cholesterol, different functional monomers and their mixed solutions
图 3 β-谷固醇、不同功能单体及其混合溶液的紫外吸收光谱
Figure 3. UV absorption spectra of β-sitosterol, different functional monomers and their mixed solutions
图 4 去氧胆酸、不同功能单体及其混合溶液的紫外吸收光谱
Figure 4. UV absorption spectra of deoxycholic acid, different functional monomers and their mixed solutions
图 5 胆固醇与不同比例丙烯酸混合溶液的紫外吸收光谱
a.浓度为1∶0~1∶8的紫外光谱图；b.浓度比为1∶0~1∶8混合溶液的最大吸收波长与相对应吸光值的变化曲线
Figure 5. UV absorption spectra of mixed solutions of cholesterol and acrylic acid in different proportions
图 6 β-谷固醇与不同比例丙烯酸混合溶液的紫外吸收光谱
a.浓度比为1∶0~1∶8的紫外光谱检测；b.浓度比1∶0~1∶8混合溶液的最大吸收波长与相对应吸光值的变化曲线
Figure 6. UV absorption spectra of mixed solutions of β-sitosterol and acrylic acid in different proportions
图 7 去氧胆酸与不同比例丙烯酸混合溶液的紫外光谱图
a.浓度比为1∶1~1∶8的紫外光谱检测；b.浓度比1∶0~1∶8混合溶液的最大吸收波长与相对应吸光值的变化曲线
Figure 7. UV absorption spectra of mixed solutions of deoxycholic acid and acrylic acid in different proportions
图 8 胆固醇预组装差示紫外光谱图
a.浓度比为1∶1~1∶8的差示紫外光谱；b.浓度比为1∶2，1∶4，1∶6，1∶8时ΔΑ与ΔΑ/bmn的线性关系
Figure 8. Differential UV spectra of cholesterol preassembly
图 9 β-谷固醇预组装差示紫外光谱图
a.浓度比为1∶1~1∶8的差示紫外光谱图；b.浓度比为1∶2、1∶4、1∶6、1∶8时ΔΑ与ΔΑ/bmn的线性关系图
Figure 9. Differential UV spectra of β-sitosterol preassembly
图 10 去氧胆酸预组装差示紫外光谱图
a.浓度比为1∶1~1∶8的差示紫外光谱图；b.浓度比为1∶2、1∶4、1∶6、1∶8时ΔΑ与ΔΑ/bmn的线性关系图
Figure 10. Differential UV spectra of deoxycholic acid preassembly
图 11 模板分子与丙烯酸(AA)的结合示意
Figure 11. Schematic diagram of binding of template molecules to acrylic acid (AA)
图 12 MIPs、NIP、去氧胆酸和AA红外吸收光谱
Figure 12. Infrared absorption spectra of MIPs, NIP, deoxycholic acid and AA
图 14 去氧胆酸虚拟分子印迹聚合物的合成示意
Figure 14. Synthesis of virtual molecularly imprinted polymers of deoxycholic acid
图 15 不同温度聚合物微球的扫描电镜图
Figure 15. SEM images of polymer microspheres at different temperatures
表 1 制备分子印迹聚合物(MIPs)相关实验的主要试剂
Table 1. Main reagents used in related experiments for preparing MIPs
试剂名称 试剂级别 生产厂家 胆固醇 AR 天津市大茂化学试剂厂 β-谷固醇 AR 合肥巴斯夫生物科技有限公司 去氧胆酸 AR 麦克林生物科技有限公司 AA AR 天津市大茂化学试剂厂 MAA AR 天津市大茂化学试剂厂 MMA AR 天津市大茂化学试剂厂 AM AR 上海广诺化学科技有限公司 EDGMA AR 北京百灵威科技有限公司 AIBN AR 天津市大茂化学试剂厂 甲醇 HPLC 北京迈瑞达科技有限公司 乙腈 HPLC 北京迈瑞达科技有限公司 
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表 2 制备MIPs相关实验的主要仪器设备
Table 2. Main instruments and equipments used in related experiments for preparing MIPs
实验仪器 型号 生产厂家 紫外可见光度计 UV-2600 谱质分析检测技术(上海)有限公司 傅立叶红外光谱仪 Bruker Alpha 泰科施普(北京)技术有限公司 电子恒温不锈钢水浴锅 HHS-2S 上海虞龙仪器设备有限公司 场发射扫描电子显微镜 Merlin Compact 德国蔡司 气相色谱/质谱联用仪 6890N(GC)/5737N(MS) 美国安捷伦科技有限公司 回旋式振荡器 HY-5 江苏盛兰仪器制造有限公司
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表 3 制备MIP和NIP的组分材料及含量
Table 3. Components and contents for preparing MIP and NIP
聚合物 模板分子类型 模板分子/mmol 功能单体/mmol 交联剂(EDGMA)/mmol 引发剂(AIBN)/mg 致孔剂(乙腈)/mL 温度/℃ 吸附量/(mg·g-1) 印迹因子 分配常数/(g·mL-1) MIP1 胆固醇 0.5 2 10 160.5 60 60 0.670 2.778 0.183 MIP2 β-谷固醇 0.5 2 10 160.5 60 60 0.779 3.231 0.226 MIP3 去氧胆酸 0.5 2 10 160.5 60 60 0.877 3.638 0.270 MIP4 去氧胆酸 0.5 2 10 160.5 60 50 0.418 MIP5 去氧胆酸 0.5 2 10 160.5 60 70 0.695 NIP 2 10 160.5 60 60 0.241 0.053
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表 4 模板分子与功能单体的最大理论吸光度与实际吸光度差值
Table 4. Difference between the maximum theoretical absorbance and the actual absorbance of template molecules and functional monomers
模板分子 功能单体 AA MAA MMA AM 胆固醇 1.063 08 0.847 14 0.861 46 0.718 72 β-谷固醇 0.908 60 0.668 06 0.621 24 0.368 06 去氧胆酸 0.298 62 0.133 27 0.095 51 0.060 29
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