色谱 ›› 2024, Vol. 42 ›› Issue (12): 1117-1125.DOI: 10.3724/SP.J.1123.2024.06008

• 研究论文 • 上一篇    下一篇

类红细胞状表面分子印迹聚合物的制备及其用于牛奶中四环素的选择性富集

商健1, 马林智2, 雷超1, 苏新科1, 刘宇1, 王悦2,3,*(), 高瑞霞2   

  1. 1.渭南市检验检测研究院, 陕西 渭南 714000
    2.西安交通大学化学学院, 陕西 西安 710049
    3.西安交通大学药学院, 陕西 西安 710061
  • 收稿日期:2024-06-26 出版日期:2024-12-08 发布日期:2024-12-09
  • 通讯作者: E-mail:yuewang0205@xjtu.edu.cn.
  • 作者简介:第一联系人:

    本文为“第24届全国色谱学术报告会优秀论文专辑”稿件.

  • 基金资助:
    陕西省市场监督管理局科技计划项目(2022KY21)

Preparation of a red-blood-cell-like surface molecularly imprinted polymer and its application to the selective enrichment of tetracycline in milk

SHANG Jian1, MA Linzhi2, LEI Chao1, SU Xinke1, LIU Yu1, WANG Yue2,3,*(), GAO Ruixia2   

  1. 1. Weinan Inspection and Research Institute, Weinan 714000, China
    2. School of Chemistry, Xi’an Jiaotong University, Xi’an 710049, China
    3. School of Pharmacy, Xi’an Jiaotong University, Xi’an 710061, China
  • Received:2024-06-26 Online:2024-12-08 Published:2024-12-09
  • Supported by:
    Science and Technology Planning Project of Shaanxi Administration for Market Regulation(2022KY21)

摘要:

分子印迹聚合物单位质量吸附容量是评价印迹材料吸附性能的重要指标之一,受红细胞双凹圆碟形貌比表面积大和优异稳定性的启发,合成了对四环素具有高选择性、大吸附容量、较快传质速率的类红细胞状表面分子印迹聚合物(RBC-SMIPs)。本工作首先以SiO2作为初始载体,广谱抗生素四环素作为模板分子,通过表面分子印迹技术将廉价易得的多巴胺功能单体包覆在SiO2载体表面,然后通过牺牲载体刻蚀技术将SiO2初始载体刻蚀去除,并调节多巴胺印迹层用量和包覆时间,调控所制备印迹材料的形貌,最终制备出大比表面积和优异选择性吸附性能的RBC-SMIPs。通过扫描电镜(SEM)、红外光谱(FT-IR)、N2吸附-解吸附等表征手段以及动力学、热力学、选择性、重复利用性等吸附实验证明该材料成功包覆聚多巴胺印迹层,所制备材料粒径均一、比表面积大、传质速率快(15 min)、重复利用性好、单位质量吸附容量和印迹因子分别高达76.16 mg/g和3.62。此外,将RBC-SMIPs作为固相萃取吸附剂与高效液相色谱结合,该方法在0.01~200 μg/mL范围内具有较高的线性相关系数(R2>0.9995),在3个加标水平下(0.01、0.05和0.10 μg/mL)平均回收率为92.1%~95.3%,实现了对牛奶样品中四环素的高效吸附、富集和检测。本工作所开发的类红细胞状表面分子印迹聚合物具有良好的实际应用能力。

关键词: 类红细胞状分子印迹聚合物, 表面印迹, 四环素, 选择性吸附

Abstract:

The adsorption capacity per unit mass of a molecularly imprinted polymer is an important indicator for evaluating the adsorption performance of an imprinted material. Inspired by the large specific surface areas and excellent stabilities of double concave circular red-blood-cell discs, we synthesized a highly selective red-blood-cell-like surface molecularly imprinted polymer (RBC-SMIP) with a large adsorption capacity and a fast mass-transfer rate for tetracycline. This work used SiO2 as the initial carrier and tetracycline, a broad-spectrum antibiotic, as the template molecule. Inexpensive and readily available dopamine functional monomers were subsequently coated on the surface of the SiO2 carrier using surface molecular imprinting technology, after which the initial SiO2 carrier was etched and removed using sacrificial-carrier-etching technology, with the dosage and coating time of the dopamine imprinting layer adjusted to regulate the morphology of the prepared imprinted material. An RBC-SMIP with a large specific surface area and excellent selective adsorption performance was finally prepared. Scanning electron microscopy (SEM) and infrared (FT-IR) spectroscopy, as well as N2-adsorption-desorption, kinetics, thermodynamics, selectivity, and reusability experiments confirmed that the material had successfully been coated the imprinted polydopamine layer, and that the prepared material contained particles of uniform size and exhibited a good specific surface area and pore volume, a rapid adsorption-equilibrium time (15 min), and excellent reusability. The RBC-SMIP exhibited a unit-mass adsorption capacity and imprinting factor of 76.16 mg/g and 3.62, respectively. The successful preparation of the RBC-SMIP provides a new approach for the selective adsorption and determination of trace tetracycline contents in environmental water. In addition, combining the RBC-SMIP (as a solid-phase extractor) with HPLC led to a method with a high linear correlation coefficient (R2>0.9995) in the 0.01-200 μg/mL linear range. Average recoveries of 92.1%-95.3% were determined at three spiked levels (0.01, 0.05, and 0.10 μg/mL), highlighting the ability of the method to efficiently adsorb, enrich, and detect tetracycline in milk samples. The red-blood-cell-like surface molecularly imprinted polymer developed in this work is expected to have significant practical applications.

Key words: red-blood-cell-like surface molecularly imprinted polymer (RBC-SMIPs), surface imprinting, tetracycline (TC), selective adsorption

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