Department of Chemistry, University of Torino, Via Giuria 7, 10125 - Torino, Italy.
J Mater Chem B. 2022 Sep 15;10(35):6724-6731. doi: 10.1039/d2tb00245k.
Solid phase synthesis (SPS) of molecularly imprinted nanopolymers (nanoMIPs) represents an innovative method to prepare nanomaterials with tailor-made molecular recognition properties towards peptides and proteins. The synthesis of nanoMIPs by SPS usually involves a pre-polymerization formulation, where the cross-linker is invariably ,'-methylen-bis-acrylamide (BIS). To date, the effect of cross-linkers on the binding properties of nanoMIPs prepared using cross-linkers other than BIS has never been reported. In this work, in order to investigate the effect of different cross-linkers in protein-imprinted nanoMIPs prepared by SPS, alongside BIS we considered other similar cross-linkers: ,'-ethylene dimethacrylamide (EDAM), ,-bis-methacryloylethanolamine (NOBE), ethylene glycol dimethacrilate (EDMA) and glycerol dimethacrylate (GDMA), replacing BIS with them in pre-polymerization mixtures. The synthetized nanoMIPs were homogeneous, with a polydispersity index of 0.24-0.30 and a mean diameter of 129-169 nm in water. The binding properties of the nanoMIPs were measured equilibrium partition experiments with the template, rabbit IgG (RIgG), and the selectivity was evaluated with respect to bovine IgG (BIgG), bovine serum albumin (BSA) and hen egg lysozyme (LZM). The experimental results show that all the cross-linkers, with the exception of EDMA, endowed nanoMIPs with high binding affinities for the template (BIS: 16.0 × 10 mol L, EDAM: 8.8 × 10 mol L, NOBE: 15.8 × 10 mol L, and GDMA: 12.8 × 10 mol L), medium to high imprinting factors (BIS: 12.3, EDAM: 5.5, NOBE: 7.2, and GDMA: 11.6) and good selectivity towards other proteins but markedly dependent on the structure of the cross-linker, confirming the importance of the latter in the SPS of imprinted nanopolymers.
固相合成（SPS）分子印迹纳米聚合物（nanoMIPs）是一种制备对肽和蛋白质具有定制分子识别性能的纳米材料的创新方法。通过 SPS 合成 nanoMIPs 通常涉及预聚合配方，其中交联剂始终是亚甲基双丙烯酰胺（BIS）。迄今为止，从未有报道过使用 BIS 以外的交联剂制备 nanoMIPs 时交联剂对其结合性能的影响。在这项工作中，为了研究不同交联剂对通过 SPS 制备的蛋白质印迹 nanoMIPs 的影响，除了 BIS 之外，我们还考虑了其他类似的交联剂：亚乙基二甲基丙烯酰胺（EDAM）、双（甲基丙烯酰基）乙醇胺（NOBE）、乙二醇二甲基丙烯酸酯（EDMA）和甘油二甲基丙烯酸酯（GDMA），并用它们替代预聚合混合物中的 BIS。合成的 nanoMIPs 是均匀的，水相中多分散指数为 0.24-0.30，平均直径为 129-169nm。通过平衡分配实验测量 nanoMIPs 与模板兔免疫球蛋白 G（RIgG）的结合性能，并评估其相对于牛免疫球蛋白 G（BIgG）、牛血清白蛋白（BSA）和鸡卵溶菌酶（LZM）的选择性。实验结果表明，除 EDMA 外，所有交联剂都赋予 nanoMIPs 对模板（BIS：16.0×10 mol L，EDAM：8.8×10 mol L，NOBE：15.8×10 mol L，GDMA：12.8×10 mol L）的高结合亲和力、中等至高的印迹因子（BIS：12.3、EDAM：5.5、NOBE：7.2、GDMA：11.6）和对其他蛋白质的良好选择性，但明显依赖于交联剂的结构，证实了后者在印迹纳米聚合物的 SPS 中的重要性。
