摘要
采用DFT/B3LYP-D3(BJ)/6-31G(d,p)计算模拟方法分析探讨了双(对硝基苯基)磷酸酯(BNPP)替代对氧磷(PO)用作有机磷神经毒剂分子印迹聚合物(MIPs)模板分子模拟物的可行性.通过对比BNPP和PO两种模板分子分别与各种功能单体形成的复合物的构型稳定性和结合能大小,确认了以4-甲基丙烯酰胺基安替比林(MAAP)为第一功能单体、甲基丙烯酸(MAA)为第二功能单体组成的双功能单体体系是最佳功能单体体系.以BNPP为模板分子、MAAP-MAA为单体体系、乙二醇二甲基丙烯酸酯(EGDMA)为交联剂、纳米二氧化硅为载体,采用表面印迹技术制备了SiO2@BNPP分子印迹聚合物,并对聚合物的表面形貌和吸附性能进行了分析.实验结果表明,当n(BNPP)/n(MAAP)/n(MAA)/n(EGDMA)为1∶1∶4∶20时, MIPs的吸附容量最大可达19.03 mg/g,对4-硝基苯酚(4-NP)的分离因子为17.50;MIPs能够快速吸附模板分子, 5 min即可达到吸附平衡量的92%,动态吸附平衡时间仅为15 min,重复使用5次后仍能保持良好的吸附能力;吸附过程符合准二级动力学模型和Langmuir等温吸附模型, Scatchard方程分析表明MIPs中存在两类吸附作用位点.实验结果与计算模拟结果的一致性表明,计算模拟对有机磷神经毒剂MIPs的设计和研究具有一定的指导意义.
We herein firstly present paraoxon(PO)can be alternative to bis(4-nitrophenyl)phosphate(BNPP)as template simulants of organophosphorus nerve agents molecularly imprinted polymers(MIPs).Geometric optimization and frequency computational calculation of template-monomer complexes were carried out by B3LYP-D3(BJ)/6-31G(d,p)level of DFT theory.The configuration stability and binding energy of the complexes formed by both BNPP and PO with various functional monomers were compared and discussed in detail.And it was confirmed that the bifunc⁃tional monomer system composed of 4-methylacrylamide antipyrine(MAAP)and methacrylic acid(MAA)were the optimum monomers in this study. Then the core-shell MIPs of SiO_(2)@BNPP were prepared by the surface molecular im⁃ printing technology with BNPP as template molecule,MAAP-MAA as monomers,ethylene glycol dimethacrylate (EGDMA)as crosslinker,and silica nanoparticles as supports. The surface morphology of MIPs was analyzed with SEM and TEM,and then the adsorption properties of the MIPs were measured. The results showed that the maximum absorption capacity of the derived MIPs to BNPP template was 19.03 mg/g when n(BNPP)/n(MAAP)/n(MAA)/ n(EGDMA)was 1∶1∶4∶20. The separation coefficient of MIPs to 4-nitrophenol(4-NP)was 17.50. Furthermore, MIPs had rapid adsorption ability to the BNPP templates,which could reach 92% of the adsorption equilibrium in 5 min,and the adsorption equilibrium time was only 15 min. The MIPs still maintained good reusability after 5 times of reuse. The adsorption process of MIPs to the template was appropriately described by pseudo second-order kinetic model and Langmuir isothermal adsorption equation. Scatchard equation analysis showed that MIPs had two classes of adsorption sites. The consistency between the experimental results and the computational simulation shows that the computational calculation simulation is helpful for the design of organophosphorus nerve agent MIPs.
作者
翁美琪
商桂铭
王家泰
李盛华
樊志
林松
郭敏杰
WENG Meiqi;SHANG Guiming;WANG Jiatai;LI Shenghua;FAN Zhi;LIN Song;GUO Minjie(College of Chemical Engineering and Materials,Tianjin University of Science and Technology,Tianjin 300457,China;Institute of Medical Support Technology,Academy of Military Sciences,Tianjin 300161,China)
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2022年第8期91-102,共12页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:21804099)
天津市科技重大专项-科技军民融合项目(批准号:18ZXJMTG00070)
中央引导地方科技发展专项(批准号:21ZYQCSY00050)资助。
关键词
计算模拟
有机磷神经毒剂
表面分子印迹聚合物
双(对硝基苯基)磷酸酯
对氧磷
Computational simulation
Organophosphorus nerve agent
Surface molecularly imprinted polymer
Bis(p-nitrophenyl)phosphate
Paraoxon
