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接枝聚N,N-二甲胺基丙基丙烯酰胺制备大孔聚合物阴离子交换层析介质及其吸附性能

徐千惠,徐振,马子奥,乔娟,李楠,马磊,靳海波,张荣月   

  1. 北京石油化工学院新材料与化工学院,燃料清洁化及高效催化减排技术北京市重点实验室
  • 收稿日期:2025-08-31 修回日期:2025-09-29 网络首发:2025-09-30 发布日期:2025-09-30
  • 通讯作者: 张荣月 E-mail:zhangrongyue@bipt.edu.cn
  • 基金资助:
    国家自然科学基金(项目编号:32372445)资助

Preparation of Macroporous Polymer Anion Exchange Chromatography Media by Grafting Poly( N,N-dimethylaminopropyl acrylamide) and Their Adsorption Properties

Xu Qianhui,Xu Zhen,Ma Ziao,Qiao Juan,Li Nan,Ma Lei,Jin Haibo,Zhang Rongyue   

  1. Beijing Key Laboratory of Clean Fuel and Efficient Catalytic Emission Reduction Technology, College of New Materials and Chemical Engineering, Beijing University of Petrochemical Technology
  • Received:2025-08-31 Revised:2025-09-29 Online First:2025-09-30 Published:2025-09-30
  • Contact: Zhang Rongyue E-mail:zhangrongyue@bipt.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China (No. 32372445)

摘要: 本研究针对传统大孔聚合物离子交换层析介质比表面积低而导致蛋白吸附容量低的问题,提出了一种基于“grafting to”法的新型制备方法来提高蛋白吸附容量。以过硫酸铵为引发剂,引发甲基丙烯酸2-氨基乙酯(2-AM)和N,N-二甲胺基丙基丙烯酰胺(DMAPAA)两种单体共聚,获得带有伯胺基团的预聚物,通过调节2-AM和DMAPAA二者摩尔比,控制所得预聚物pDMAPAA的平均聚合度范围为2~10。将该预聚物接枝到大孔聚丙烯酸酯类微球表面,制备弱阴离子交换层析介质。通过对偶联条件进行优化确定最佳制备条件,并以BSA为模型蛋白,探究了不同配基密度以及不同链长的接枝型介质对蛋白静态吸附容量(SBC)的影响规律、不同链长介质的吸附动力学及离子强度对不同配基密度的介质吸附行为的影响。结果表明,接枝链长增加(2~10单元),介质的离子交换容量(IC)和静态吸附容量(SBC)显著提升,平衡吸附容量qe从130.9±3 mg/mL增加至196.5±5 mg/mL,但准二级吸附速率常数k2减小;配基密度升高,使SBC从95.6±2 mg/mL增加至174.0±3 mg/mL;盐浓度升高(0~0.25 mg/mL),导致SBC下降,较高配基密度的介质表现出更强的盐耐受性。该研究对高性能弱阴离子交换层析介质的可控制备和应用具有较好的参考意义。

关键词: 大孔阴离子交换层析介质, Grafting to法, N,N-二甲胺基丙基丙烯酰胺, 配基密度, 蛋白质吸附

Abstract: The low protein adsorption capacity is caused by the low specific surface area of traditional macroporous polymer-based ion exchange chromatography media. A novel preparation method based on a "grafting to" strategy was proposed to enhance the protein adsorption capacity in this study. A pre-polymer containing primary amine groups was synthesized by copolymerizing two monomers, 2-aminoethyl methacrylate (2-AM) and N,N-dimethylaminopropylacrylamide (DMAPAA), using ammonium persulfate as the initiator. The average degree of polymerization of the resulting pre-polymer, pDMAPAA, was controlled between 2 and 10 by adjusting the molar ratio of 2-AM to DMAPAA.This pre-polymer was then grafted onto the surface of macroporous polyacrylate microspheres to fabricate a weak anion exchange chromatography medium.The optimal preparation conditions were determined by optimizing the coupling parameters. Using BSA as a model protein, the effects of ligand density and grafted chain length on the static binding capacity (SBC), the adsorption kinetics of media with different chain lengths, and the influence of ionic strength on adsorption behavior at different ligand densities were investigated. The results showed that increasing the grafted chain length (2~10 units) significantly enhanced the ion exchange capacity (IC) and SBC of the media. The equilibrium adsorption capacity (qe) increased from 130.9±3 mg/mL to 196.5±5 mg/mL, while the pseudo-second-order adsorption rate constant (k?) decreased. A higher ligand density increased the SBC from 95.6±2 mg/mL to 174.0±3 mg/mL. Increasing the salt concentration (0~0.25 mol/L) led to a decrease in SBC, with media of higher ligand density exhibiting stronger salt tolerance. This study provides a valuable reference for the controlled preparation and application of high-performance weak anion exchange chromatography media.

Key words: Macroporous anion exchange chromatography media, Grafting to, DMAPAA, Ligand density, Protein adsorption

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