分子印迹聚合物微球的制备及壳聚糖在毛细管电泳手性拆分中的应用研究
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摘要
分子印迹聚合物是一种具有特异性分子识别能力的新型功能材料,被广泛应用于色谱分离、固相萃取、生物模拟传感器、膜分离等众多领域。
以4-氨基安替比林为模板分子,十二醇/甲苯为溶剂,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法合成了一系列分子印迹聚合物,通过在水相中的结合实验研究了溶剂的种类和用量、聚合反应液中各组分的浓度对分子印迹聚合物识别能力的影响。在溶剂用量15mL,甲苯体积含量10%,模板分子浓度0.02mol/L,功能单体浓度0.1mol/L,交联剂浓度0.4mol/L,引发剂浓度0.002mol/L的条件下,制备出的分子印迹聚合物微球特异性识别能力最佳,对4-氨基安替比林及其结构类似物安替比林的分离因子为3.72。Scatchard分析表明,4-氨基安替比林与印迹聚合物之间存在2类不同的结合位点:高亲和力结合位点的平衡离解常数K_d=3.89μg/mL,最大表观结合常数Q_(max)=49.99μg/mg;低亲和力结合位点的离解常数K_d=84.03μg/mL,最大表观结合常数Q_(max)=11.69μg/mg。
以壳聚糖为手性添加剂,利用毛细管电泳对色氨酸对映体进行拆分,考察了缓冲液的盐浓度、壳聚糖质量浓度、Cu~(2+)浓度和缓冲液的pH值对分离过程的影响。实验结果表明,在盐浓度为5mmol/L,壳聚糖质量浓度为0.02%,Cu~(2+)浓度为1.5mmol/L,缓冲液的pH为3.5的条件下,色氨酸对映体分离效果良好,分离因子为1.87,分离度为1.02,分离重复性良好。
Molecular imprinting is a versatile and facile method for preparing synthetic polymers with predetermined molecular recognition properties.It can be employed in a variety of applications,such as chromatography separations,solid extractions, sensors,membrane separation and so on.
In the first part of this study,molecular imprinting polymer microspheres with 4-aminoantipyrine(4-AP) as template were prepared by precipitation polymerization. The mixtures of dodecanol and toluene,methacrylic acid,ethylene glycol dimethacrylate were used as solvent,functional monomer,cross linker,respectively. The ability of the polymers to rebind 4-AP specifically in aqueous solutions was assessed.A best adsorption behavior and molecular selectivity occurred when 15mL solvent with 10%toluene was used and the concentrations of template,functional monomer,cross linker as well as initiator were 0.02mol/L,0.1mol/L,0.4mol/L, 0.002mol/L,respectively.The separation factor was up to 3.72 when antipyrine was used as the competing molecule.Scatchard analysis showed that the MIPs recognized 4-AP with two classes of binding sites.The dissociation constants and the maximum apparent binding capacities were K_d=3.89μg/mL,Q_(max)=49.99μg/mg for high affinity binding site and K_d=84.03μg/mL,Q_(max)=11.69μg/mg for low affinity binding site.
In the second part of this study,chitosan,a cationic natural polymer,was employed as a chiral additive selector for enantioseparation of DL-tryptophan in capillary electrophoresis.The effects of several parameters on the ability of separation were studied.A best separation of tryptophan enantiomers was achieved by using 5mmol/L NaAc,0.02%(w/v) chitosan and 1.5mmol/L Cu~(2+) while the pH of the buffer was 3.5.The separation factor was 1.87 and the resolution was 1.02.The performance reproducibility was good.
以4-氨基安替比林为模板分子,十二醇/甲苯为溶剂,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法合成了一系列分子印迹聚合物,通过在水相中的结合实验研究了溶剂的种类和用量、聚合反应液中各组分的浓度对分子印迹聚合物识别能力的影响。在溶剂用量15mL,甲苯体积含量10%,模板分子浓度0.02mol/L,功能单体浓度0.1mol/L,交联剂浓度0.4mol/L,引发剂浓度0.002mol/L的条件下,制备出的分子印迹聚合物微球特异性识别能力最佳,对4-氨基安替比林及其结构类似物安替比林的分离因子为3.72。Scatchard分析表明,4-氨基安替比林与印迹聚合物之间存在2类不同的结合位点:高亲和力结合位点的平衡离解常数K_d=3.89μg/mL,最大表观结合常数Q_(max)=49.99μg/mg;低亲和力结合位点的离解常数K_d=84.03μg/mL,最大表观结合常数Q_(max)=11.69μg/mg。
以壳聚糖为手性添加剂,利用毛细管电泳对色氨酸对映体进行拆分,考察了缓冲液的盐浓度、壳聚糖质量浓度、Cu~(2+)浓度和缓冲液的pH值对分离过程的影响。实验结果表明,在盐浓度为5mmol/L,壳聚糖质量浓度为0.02%,Cu~(2+)浓度为1.5mmol/L,缓冲液的pH为3.5的条件下,色氨酸对映体分离效果良好,分离因子为1.87,分离度为1.02,分离重复性良好。
Molecular imprinting is a versatile and facile method for preparing synthetic polymers with predetermined molecular recognition properties.It can be employed in a variety of applications,such as chromatography separations,solid extractions, sensors,membrane separation and so on.
In the first part of this study,molecular imprinting polymer microspheres with 4-aminoantipyrine(4-AP) as template were prepared by precipitation polymerization. The mixtures of dodecanol and toluene,methacrylic acid,ethylene glycol dimethacrylate were used as solvent,functional monomer,cross linker,respectively. The ability of the polymers to rebind 4-AP specifically in aqueous solutions was assessed.A best adsorption behavior and molecular selectivity occurred when 15mL solvent with 10%toluene was used and the concentrations of template,functional monomer,cross linker as well as initiator were 0.02mol/L,0.1mol/L,0.4mol/L, 0.002mol/L,respectively.The separation factor was up to 3.72 when antipyrine was used as the competing molecule.Scatchard analysis showed that the MIPs recognized 4-AP with two classes of binding sites.The dissociation constants and the maximum apparent binding capacities were K_d=3.89μg/mL,Q_(max)=49.99μg/mg for high affinity binding site and K_d=84.03μg/mL,Q_(max)=11.69μg/mg for low affinity binding site.
In the second part of this study,chitosan,a cationic natural polymer,was employed as a chiral additive selector for enantioseparation of DL-tryptophan in capillary electrophoresis.The effects of several parameters on the ability of separation were studied.A best separation of tryptophan enantiomers was achieved by using 5mmol/L NaAc,0.02%(w/v) chitosan and 1.5mmol/L Cu~(2+) while the pH of the buffer was 3.5.The separation factor was 1.87 and the resolution was 1.02.The performance reproducibility was good.
引文
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