多孔硅胶表面分子印迹青蒿素吸附剂的制备及其在超临界流体下的吸附分离行为
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摘要
青蒿素是从黄花蒿中分离出的一种具有高效抗疟疗效的植物活性成分,是世界卫生组织推荐治疗疟疾的首选药物。
分子印迹聚合物吸附剂能够专一性识别和吸附目标分子,选择性能力突出。而表面印迹技术将分子识别位点设计在印迹材料的表面上,减小了识别位点与目标分子之间的位阻效应。在传统有机溶剂中,印迹聚合物虽然能实现较好的分离效果,但吸附平衡时间却较长,吸附容量亦有限,且环境不友好。超临界CO2流体对青蒿素具有良好的溶解性能,渗透扩散能力又强,但超临界流体对于结构相近的类似物的选择性分离能力并不突出。若以超临界CO2作为溶剂介质替代有机溶剂,将印迹聚合物吸附剂应用其中,两种技术优势互补,能改善吸附过程的传质效果,提高吸附容量,缩短吸附平衡时间,而且环境友好,具有可持续发展前景。
本论文中介绍了硅胶表面青蒿素分子印迹聚合物的制备过程,在多孔硅胶(40-60目)上嫁接上乙烯基三乙氧基硅烷(VTES),然后以青蒿素为模板分子,丙烯酰胺(AM)和甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,成功制备出一种基于多孔硅胶表面的青蒿素分子印迹聚合物吸附剂。并利用元素分析、扫描电子显微镜、傅里叶红外光谱等分析检测手段对其进行表征,表征结果显示硅胶上聚合上了印迹层,BET吸附结果显示,印迹硅胶的比表面积为325.042m2/g,孔径为83.013A。
测定并分析了常温常压条件下,印迹聚合物在甲苯溶剂中对青蒿素的吸附分离行为。结果显示在青蒿素初始浓度为2.00mg/mL时,印迹聚合物对青蒿素的吸附量是随着吸附时间的增加而逐渐增加的,整个吸附过程呈现两个不同的阶段,前2h是一个快速吸附的阶段,大约10h左右,吸附趋于平衡。选用了Pseudo-first-order、Pseudo-second-order以及Elovich三个吸附动力学模型关联动力学实验数据,以Pseudo-second-order模型的关联效果最佳,相关系数R2为0.9730。青蒿素初始浓度在0.20～2.00mg/mL范围内,印迹聚合物和非印迹聚合物对青蒿素的吸附量都随着青蒿素初始浓度的增加而增加,但印迹聚合物的吸附量远高于非印迹聚合物。在青蒿素初始浓度为2.00mg/mL时,印迹聚合物对青蒿素的吸附量为32.44mg/g。选用了Langmuir、Freundlich以及Langmuir-Freundlich三个吸附等温线模型来关联等温线实验数据,以Langmuir-Freundlich模型的关联效果最好,相关系数R2为0.9953。在初始浓度为2.00mg/mL的青蒿素/蒿甲醚混合溶液中,印迹聚合物对青蒿素的选择性系数α为2.29,相对选择性系数β为2.03。在初始浓度为2.00mg/mL的青蒿素/蒿甲醚/蒿乙醚混合溶液中,印迹聚合物吸附青蒿素的选择性系数α分别为2.88和3.38,前者是相较于蒿甲醚,后者是相较于蒿乙醚,相对选择性系数β分别为2.74和3.10。
利用带有视频监测窗口的超临界相平衡监测仪观察并测定了固体青蒿素在超临界CO2中的溶解相平衡过程。在313K(11～31MPa)、323K(14～31MPa)、333K(16～31MPa)的温度压力条件范围内,青蒿素固体在超临界CO2中溶解度值的分布范围为0.498×10-3mol/mol～2.915×10-3mol/mol。温度一定的条件下,青蒿素在超临界CO2中的溶解度随压力的升高而变大。压力一定的条件下,在小于转折压力区(20～23MPa)时,青蒿素在超临界CO2中的溶解度随温度的升高而下降,在大于转折压力时,变化结果正好相反。选用Chrastil经验模型和Mendez-Santiago and Teja模型对实验数据进行关联,平均相对误差分别为8.32%和8.27%,表明模型计算值与实验值之间吻合度较好,离临界区越远,压力越大,相对误差越小。
考察了313K,20MPa时,印迹聚合物在超临界CO2中对青蒿素的吸附分离行为。在相同的初始浓度时,印迹聚合物对青蒿素的吸附量在大致趋势上是随着时间的增加而增加,整个吸附过程呈现两个不同的阶段,前0.5～1h是一个快速吸附的阶段,大约3h左右,吸附趋于平衡。选用了Pseudo-first-order和Pseudo-second-order吸附动力学方程拟合实验数据,在青蒿素初始浓度为1.74mg/mL时,Pseudo-second-order方程的拟合效果最佳,相关系数R2为0.9936。在相同的时间点,分子印迹聚合物对青蒿素的吸附量是随着青蒿素初始浓度的增加而增加。青蒿素初始浓度为1.74mg/mL时,印迹聚合物对青蒿素的吸附量可达123.89mg/g。在青蒿素/蒿甲醚的初始浓度为1.94mg/mL时,印迹聚合物对青蒿素的选择性系数α为3.29。
在本课题的实验条件范围内,印迹聚合物在超临界CO2中的吸附平衡时间不到甲苯中的1/3,吸附容量是是甲苯中的4倍左右,选择性系数较甲苯中有所提高。
Artemisinin is an effective antimalarial drug isolated from the herbal medicine Artemisia annua L. It is recommended to treat malaria by World Health Organization (WHO).
Molecularly imprinted polymer is a kind of adsorbent with the ability of specifically recognizing and binding the target molecules. The surface molecular imprinting technique can decrease the steric hindrance between recognition sites and target molecules by designing the molecular recognition sites on the surfaces of imprinted materials. In the conventional organic solvents, though good separation can be achieved by imprinted polymers, the time to reach adsorption equilibrium is long and the adsorption capacity is also limited. In addition, the organic solvents are not good for environment. Supercritical CO2 has good solubility for artemisinin and high diffusion ability, but it has not excellent selectivity for analogues. If imprinted polymers are employed in supercritical CO2 instead of organic solvents, the mass transfer rate and adsorption capcity should be impoved. Combination of molecular imprinting technique and supercritical technology is a promising and environment-friendly method with prospects of sustainable development.
In this paper, the preparation process of molecularly imprinted polymers (MIPs) for artemisinin was introduced. Silica gel (40-60mesh) were used as supporting matrix, and vinyltriethoxysilane (VTES) was grafted onto its surfaces. The preparation of MIPs for artemisinin was performed on the surfaces of the modified silica gel using artemisinin as the template, acrylamide (AM) and methacrylic acid (MAA) as the functional monomers and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. Elementary analysis, scanning electron microscopy, Fourier transform infrared spectroscopy and pore size analysis were used to characterize the prepared MIPs. The results showed that the imprinted film was coated onto the surfaces of silica gel. The surface area of MIPs was 325.042m2/g and pore size was 83.013?.
Under the normal temperature and pressure condition, the adsorption and separation behaviour was measured in toluene solvent. The adsorption reached equilibrium at about 10h, while fast adsorption took place during the first 2h. Pseudo-first-order, Pseudo-second-order and Elovich adsorption kinetic equations were used to correlate the experimental data of the adsorption kinetics, and pseudo-second-order equation had the best correlation (R2=0.9730). At varied initial concentrations of artemisinin (range from 0.20mg/mL to 2.00mg/mL), adsorption capcity of MIPs and NIPs (non-imprinted polymers) both increased with the initial concentration of artemisinin, but MIPs had much higher adsorption capcity than that of NIPs. The adsorption capcity was 32.44mg/g at an initial artemisinin concentration of 2.00mg/mL. Langmuir, Freundlich and Langmuir-Freundlich isotherms were used to correlate the experimental data of the adsorption isotherm, and Langmuir-Freundlich isotherm had the best correlation (R2=0.9953). The selectivity coefficient of MIPs for artemisinin was 2.29 in artemisinin/artemether mixed solution with the initial concentration of 2mg/mL of each substance, and the relative selectivity coefficient was 2.03. The selectivity coefficients of MIPs for artemisinin with respect to artemether and arteether were 2.88 and 3.38 in artemisinin/artemether/arteether mixed solution with the initial concentration of 2mg/mL of each substance, and the relative selectivity coefficients were 2.74 and 3.10, respectively.
A supercritical apparatus with a video detection window was applied in the observation of the process of artemisinin dissolved in supercritical CO2 and the determination of artemisinin solubility in supercritical CO2 at 313K (11～31MPa),323K (14～31MPa),333K (16～31MPa) by static method. The range of experimental solubility data was from 0.498×10-3 to 2.915×10-3mol/mol. At a fixed temperature, the solubility of artemisinin in supercritical CO2 increases with the pressure. At a fixed pressure, the effect of temperature on the solubility shifts from negative at the pressures below the crossover region to positive at the pressures above the crossover region. Chrastil and Mendez-Santiago-Teja models were selected to correlate the experimental solubility data. The average absolute relative deviation of the two correlations was 8.32% and 8.33%, respectively, which showed the good agreement between calculated values and experimental values. The relative deviation will be smaller when the experimental conditions are far away from the critical point.
Under the 313K,20MPa condition, the adsorption and separation behaviour was measured in supercritical CO2. The adsorption reached equilibrium at about 3h, while fast adsorption took place during the first 0.5～1h. Pseudo-first-order and Pseudo-second-order adsorption kinetic equations were used to fit the experimental data, and pseudo-second-order equation had the better correlation (R2=0.9936). Adsorption capcity of MIPs for artemisinin increased with the initial concentration of artemisinin, and the adsorption capcity was 123.89mg/g at an initial artemisinin concentration of 1.74mg/mL. The selectivity coefficient of MIPs for artemisinin was 3.29 in artemisinin/artemether mixed solution with the initial concentration of 1.94mg/mL of each substance.
Under the experimental conditions, adsorption equilibrium time in supercritical CO2 was less than 1/3 of that in toluene, adsorption capcity of MIPs in supercritical CO2 was as 4 times as that in toluene, and the selectivity coefficient of MIPs in supercritical CO2 increased when compared with that in toluene.
分子印迹聚合物吸附剂能够专一性识别和吸附目标分子,选择性能力突出。而表面印迹技术将分子识别位点设计在印迹材料的表面上,减小了识别位点与目标分子之间的位阻效应。在传统有机溶剂中,印迹聚合物虽然能实现较好的分离效果,但吸附平衡时间却较长,吸附容量亦有限,且环境不友好。超临界CO2流体对青蒿素具有良好的溶解性能,渗透扩散能力又强,但超临界流体对于结构相近的类似物的选择性分离能力并不突出。若以超临界CO2作为溶剂介质替代有机溶剂,将印迹聚合物吸附剂应用其中,两种技术优势互补,能改善吸附过程的传质效果,提高吸附容量,缩短吸附平衡时间,而且环境友好,具有可持续发展前景。
本论文中介绍了硅胶表面青蒿素分子印迹聚合物的制备过程,在多孔硅胶(40-60目)上嫁接上乙烯基三乙氧基硅烷(VTES),然后以青蒿素为模板分子,丙烯酰胺(AM)和甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,成功制备出一种基于多孔硅胶表面的青蒿素分子印迹聚合物吸附剂。并利用元素分析、扫描电子显微镜、傅里叶红外光谱等分析检测手段对其进行表征,表征结果显示硅胶上聚合上了印迹层,BET吸附结果显示,印迹硅胶的比表面积为325.042m2/g,孔径为83.013A。
测定并分析了常温常压条件下,印迹聚合物在甲苯溶剂中对青蒿素的吸附分离行为。结果显示在青蒿素初始浓度为2.00mg/mL时,印迹聚合物对青蒿素的吸附量是随着吸附时间的增加而逐渐增加的,整个吸附过程呈现两个不同的阶段,前2h是一个快速吸附的阶段,大约10h左右,吸附趋于平衡。选用了Pseudo-first-order、Pseudo-second-order以及Elovich三个吸附动力学模型关联动力学实验数据,以Pseudo-second-order模型的关联效果最佳,相关系数R2为0.9730。青蒿素初始浓度在0.20～2.00mg/mL范围内,印迹聚合物和非印迹聚合物对青蒿素的吸附量都随着青蒿素初始浓度的增加而增加,但印迹聚合物的吸附量远高于非印迹聚合物。在青蒿素初始浓度为2.00mg/mL时,印迹聚合物对青蒿素的吸附量为32.44mg/g。选用了Langmuir、Freundlich以及Langmuir-Freundlich三个吸附等温线模型来关联等温线实验数据,以Langmuir-Freundlich模型的关联效果最好,相关系数R2为0.9953。在初始浓度为2.00mg/mL的青蒿素/蒿甲醚混合溶液中,印迹聚合物对青蒿素的选择性系数α为2.29,相对选择性系数β为2.03。在初始浓度为2.00mg/mL的青蒿素/蒿甲醚/蒿乙醚混合溶液中,印迹聚合物吸附青蒿素的选择性系数α分别为2.88和3.38,前者是相较于蒿甲醚,后者是相较于蒿乙醚,相对选择性系数β分别为2.74和3.10。
利用带有视频监测窗口的超临界相平衡监测仪观察并测定了固体青蒿素在超临界CO2中的溶解相平衡过程。在313K(11～31MPa)、323K(14～31MPa)、333K(16～31MPa)的温度压力条件范围内,青蒿素固体在超临界CO2中溶解度值的分布范围为0.498×10-3mol/mol～2.915×10-3mol/mol。温度一定的条件下,青蒿素在超临界CO2中的溶解度随压力的升高而变大。压力一定的条件下,在小于转折压力区(20～23MPa)时,青蒿素在超临界CO2中的溶解度随温度的升高而下降,在大于转折压力时,变化结果正好相反。选用Chrastil经验模型和Mendez-Santiago and Teja模型对实验数据进行关联,平均相对误差分别为8.32%和8.27%,表明模型计算值与实验值之间吻合度较好,离临界区越远,压力越大,相对误差越小。
考察了313K,20MPa时,印迹聚合物在超临界CO2中对青蒿素的吸附分离行为。在相同的初始浓度时,印迹聚合物对青蒿素的吸附量在大致趋势上是随着时间的增加而增加,整个吸附过程呈现两个不同的阶段,前0.5～1h是一个快速吸附的阶段,大约3h左右,吸附趋于平衡。选用了Pseudo-first-order和Pseudo-second-order吸附动力学方程拟合实验数据,在青蒿素初始浓度为1.74mg/mL时,Pseudo-second-order方程的拟合效果最佳,相关系数R2为0.9936。在相同的时间点,分子印迹聚合物对青蒿素的吸附量是随着青蒿素初始浓度的增加而增加。青蒿素初始浓度为1.74mg/mL时,印迹聚合物对青蒿素的吸附量可达123.89mg/g。在青蒿素/蒿甲醚的初始浓度为1.94mg/mL时,印迹聚合物对青蒿素的选择性系数α为3.29。
在本课题的实验条件范围内,印迹聚合物在超临界CO2中的吸附平衡时间不到甲苯中的1/3,吸附容量是是甲苯中的4倍左右,选择性系数较甲苯中有所提高。
Artemisinin is an effective antimalarial drug isolated from the herbal medicine Artemisia annua L. It is recommended to treat malaria by World Health Organization (WHO).
Molecularly imprinted polymer is a kind of adsorbent with the ability of specifically recognizing and binding the target molecules. The surface molecular imprinting technique can decrease the steric hindrance between recognition sites and target molecules by designing the molecular recognition sites on the surfaces of imprinted materials. In the conventional organic solvents, though good separation can be achieved by imprinted polymers, the time to reach adsorption equilibrium is long and the adsorption capacity is also limited. In addition, the organic solvents are not good for environment. Supercritical CO2 has good solubility for artemisinin and high diffusion ability, but it has not excellent selectivity for analogues. If imprinted polymers are employed in supercritical CO2 instead of organic solvents, the mass transfer rate and adsorption capcity should be impoved. Combination of molecular imprinting technique and supercritical technology is a promising and environment-friendly method with prospects of sustainable development.
In this paper, the preparation process of molecularly imprinted polymers (MIPs) for artemisinin was introduced. Silica gel (40-60mesh) were used as supporting matrix, and vinyltriethoxysilane (VTES) was grafted onto its surfaces. The preparation of MIPs for artemisinin was performed on the surfaces of the modified silica gel using artemisinin as the template, acrylamide (AM) and methacrylic acid (MAA) as the functional monomers and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. Elementary analysis, scanning electron microscopy, Fourier transform infrared spectroscopy and pore size analysis were used to characterize the prepared MIPs. The results showed that the imprinted film was coated onto the surfaces of silica gel. The surface area of MIPs was 325.042m2/g and pore size was 83.013?.
Under the normal temperature and pressure condition, the adsorption and separation behaviour was measured in toluene solvent. The adsorption reached equilibrium at about 10h, while fast adsorption took place during the first 2h. Pseudo-first-order, Pseudo-second-order and Elovich adsorption kinetic equations were used to correlate the experimental data of the adsorption kinetics, and pseudo-second-order equation had the best correlation (R2=0.9730). At varied initial concentrations of artemisinin (range from 0.20mg/mL to 2.00mg/mL), adsorption capcity of MIPs and NIPs (non-imprinted polymers) both increased with the initial concentration of artemisinin, but MIPs had much higher adsorption capcity than that of NIPs. The adsorption capcity was 32.44mg/g at an initial artemisinin concentration of 2.00mg/mL. Langmuir, Freundlich and Langmuir-Freundlich isotherms were used to correlate the experimental data of the adsorption isotherm, and Langmuir-Freundlich isotherm had the best correlation (R2=0.9953). The selectivity coefficient of MIPs for artemisinin was 2.29 in artemisinin/artemether mixed solution with the initial concentration of 2mg/mL of each substance, and the relative selectivity coefficient was 2.03. The selectivity coefficients of MIPs for artemisinin with respect to artemether and arteether were 2.88 and 3.38 in artemisinin/artemether/arteether mixed solution with the initial concentration of 2mg/mL of each substance, and the relative selectivity coefficients were 2.74 and 3.10, respectively.
A supercritical apparatus with a video detection window was applied in the observation of the process of artemisinin dissolved in supercritical CO2 and the determination of artemisinin solubility in supercritical CO2 at 313K (11～31MPa),323K (14～31MPa),333K (16～31MPa) by static method. The range of experimental solubility data was from 0.498×10-3 to 2.915×10-3mol/mol. At a fixed temperature, the solubility of artemisinin in supercritical CO2 increases with the pressure. At a fixed pressure, the effect of temperature on the solubility shifts from negative at the pressures below the crossover region to positive at the pressures above the crossover region. Chrastil and Mendez-Santiago-Teja models were selected to correlate the experimental solubility data. The average absolute relative deviation of the two correlations was 8.32% and 8.33%, respectively, which showed the good agreement between calculated values and experimental values. The relative deviation will be smaller when the experimental conditions are far away from the critical point.
Under the 313K,20MPa condition, the adsorption and separation behaviour was measured in supercritical CO2. The adsorption reached equilibrium at about 3h, while fast adsorption took place during the first 0.5～1h. Pseudo-first-order and Pseudo-second-order adsorption kinetic equations were used to fit the experimental data, and pseudo-second-order equation had the better correlation (R2=0.9936). Adsorption capcity of MIPs for artemisinin increased with the initial concentration of artemisinin, and the adsorption capcity was 123.89mg/g at an initial artemisinin concentration of 1.74mg/mL. The selectivity coefficient of MIPs for artemisinin was 3.29 in artemisinin/artemether mixed solution with the initial concentration of 1.94mg/mL of each substance.
Under the experimental conditions, adsorption equilibrium time in supercritical CO2 was less than 1/3 of that in toluene, adsorption capcity of MIPs in supercritical CO2 was as 4 times as that in toluene, and the selectivity coefficient of MIPs in supercritical CO2 increased when compared with that in toluene.
引文
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