Yuan Jing, Gao Ying, Tian Xinzhuo, Su Wenhao, Su Yuxin, Niu Shengli, Meng Xiangying, Jia Tong, Yin Ronghuan, Hu Jianmin
Key Laboratory of Livestock Infectious Diseases, Ministry of Education, and Key Laboratory of Ruminant Infectious Disease Prevention and Control (East), Ministry of Agriculture and Rural Affairs, College of Animal Science and Veterinary Medicine, Shenyang Agricultural University, 120 Dongling Road, Shenyang 110866, China.
College of Sciences, Northeastern University, Shenyang 110819, China.
Molecules. 2024 Sep 6;29(17):4236. doi: 10.3390/molecules29174236.
In recent years, the advancement of computational chemistry has offered new insights into the rational design of molecularly imprinted polymers (MIPs). From this aspect, our study tried to give quantitative parameters for evaluating imprinting efficiency and exploring the formation mechanism of MIPs by combining simulation and experiments.
The pre-polymerization system of sulfadimethoxine (SDM) was investigated using a combination of quantum chemical (QC) calculations and molecular dynamics (MD) simulations. MIPs were prepared on the surface of silica gel by a surface-initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA ATRP).
The results of the QC calculations showed that carboxylic monomers exhibited higher bonding energies with template molecules than carboxylic ester monomers. MD simulations confirmed the hydrogen bonding sites predicted by QC calculations. Furthermore, it was observed that only two molecules of monomers could bind up to one molecule of SDM, even when the functional monomer ratio was up to 10. Two quantitative parameters, namely, the effective binding number (EBN) and the maximum hydrogen bond number (HBN), were defined. Higher values of EBN and HBN indicated a higher effective binding efficiency. Hydrogen bond occupancies and RDF analysis were performed to analyze the hydrogen bond formation between the template and the monomer from different perspectives. Furthermore, under the influence of the EBN and collision probability of the template and the monomers, the experimental results show that the optimal molar ratio of template to monomer is 1:3.
The method of monomer screening presented in this study can be extended to future investigations of pre-polymerization systems involving different templates and monomers.
近年来，计算化学的发展为分子印迹聚合物（MIPs）的合理设计提供了新的见解。从这方面来看，我们的研究试图通过结合模拟和实验给出用于评估印迹效率和探索MIPs形成机制的定量参数。
采用量子化学（QC）计算和分子动力学（MD）模拟相结合的方法研究了磺胺二甲氧嘧啶（SDM）的预聚合体系。通过表面引发的补充活化剂和还原剂原子转移自由基聚合（SI-SARA ATRP）在硅胶表面制备MIPs。
QC计算结果表明，羧酸单体与模板分子的结合能高于羧酸酯单体。MD模拟证实了QC计算预测的氢键位点。此外，观察到即使功能单体比例高达10，也只有两个单体分子能与一个SDM分子结合。定义了两个定量参数，即有效结合数（EBN）和最大氢键数（HBN）。EBN和HBN值越高表明有效结合效率越高。进行了氢键占有率和径向分布函数（RDF）分析，从不同角度分析模板与单体之间的氢键形成。此外，在EBN以及模板与单体的碰撞概率的影响下，实验结果表明模板与单体的最佳摩尔比为1:3。
本研究提出的单体筛选方法可扩展到未来涉及不同模板和单体的预聚合体系的研究中。
