Wu Le, Liu Yumeng, Zhang Ziying, Pan Liang, Dong Xinzhu, Feng Shun, Zhang Chungu
School of Life Science and Engineering, Southwest Jiaotong University, Chengdu, China.
J Sep Sci. 2025 Aug;48(8):e70255. doi: 10.1002/jssc.70255.
Here, we present a copper-mediated magnetic molecularly imprinted polymer (Cu-mMIP) as dispersive solid-phase extracting material (dSPE) for fast, selective, and specific extraction of a metabolic biomarker vitamin B1 (VB1) in complex biological matrices. With emulsifier-free emulsion polymerization using styrene and itaconic acid as functional co-monomers, Cu as central atom, and FeO nanoparticles (NPs) as core, the resulted Cu-mMIP addresses VB1's structural challenges (conformational flexibility, hydrophilicity) while enabling rapid magnetic separation (< 10 s). The Cu-mMIP demonstrates exceptional specificity for VB1, achieving an imprinting factor of 5.63 and a maximum adsorption capacity of 48.75 mg/g, 2.36-fold higher than non-copper counterparts. Adsorption equilibrium is attained within 20 min, driven by chemisorption via pseudo-second-order kinetics. Competitive binding assays reveal twofold selectivity for VB1 over its structural analog thiamine pyrophosphate and negligible interference from other B vitamins (VB2, VB9, and VB12). When applied to simulated human plasma, the method achieved a detection limit of 9 ng/mL (S/N = 3) with recoveries of 84.3%-90.5% at three spiking levels (RSD < 5%, n = 3), effectively eliminating matrix interferences. This work establishes a scalable, high-efficiency platform for clinical nutrient analysis, combining molecular imprinting precision with metal coordination robustness, and advances separation science by addressing critical challenges in biomarker enrichment and high-throughput sample pretreatment.
在此，我们展示了一种铜介导的磁性分子印迹聚合物（Cu-mMIP）作为分散固相萃取材料（dSPE），用于在复杂生物基质中快速、选择性且特异性地萃取代谢生物标志物维生素B1（VB1）。以苯乙烯和衣康酸作为功能共聚单体，铜作为中心原子，氧化亚铁纳米颗粒（NPs）作为核心，通过无乳化剂乳液聚合，所得的Cu-mMIP解决了VB1的结构挑战（构象灵活性、亲水性），同时实现了快速磁分离（<10秒）。Cu-mMIP对VB1表现出卓越的特异性，印迹因子达到5.63，最大吸附容量为48.75 mg/g，比不含铜的对应物高2.36倍。吸附平衡在20分钟内达到，由通过伪二级动力学的化学吸附驱动。竞争性结合试验表明，VB1对其结构类似物硫胺素焦磷酸的选择性是其两倍，并且来自其他B族维生素（VB2、VB9和VB12）的干扰可忽略不计。当应用于模拟人体血浆时，该方法的检测限为9 ng/mL（S/N = 3），在三个加标水平下回收率为84.3%-90.5%（RSD < 5%，n = 3），有效消除了基质干扰。这项工作建立了一个可扩展的高效临床营养分析平台，将分子印迹的精度与金属配位的稳健性相结合，并通过解决生物标志物富集和高通量样品预处理中的关键挑战推动了分离科学的发展。
