Department of Coatings and Polymeric Materials, North Dakota State University, Fargo, North Dakota 58108, United States.
Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota 58108, United States.
J Phys Chem Lett. 2022 May 19;13(19):4374-4380. doi: 10.1021/acs.jpclett.2c00802. Epub 2022 May 11.
The development of reusable polymeric materials inspires an attempt to combine renewable biomass with upcycling to form a biorenewable closed system. It has been reported that 2,5-furandicarboxylic acid (FDCA) can be recovered for recycling when incorporated as monomers into photodegradable polymeric systems. Here, we conduct density functional theory (DFT) studies with periodic boundary conditions on microscopic structures involved in the photodegradation of polymeric chains incorporating FDCA and 2-nitro-1,3-benzenedimethanol. The photodegradation process of polymeric chains is studied using time-dependent excited-state molecular dynamics (TDESMD) in vacuum and aqueous environments. Changes in the photophysical properties for reaction intermediates are characterized by ground-state observables. The distribution of reaction intermediates and products is obtained from TDESMD trajectories using cheminformatics techniques. Results show that a higher degree of polymeric chain degradation is achieved in the vacuum environment. Additionally, one finds that the FDCA molecule is recoverable in the aqueous environment, in qualitative agreement with experimental findings.
可重复使用的聚合物材料的发展激发了人们尝试将可再生生物质与升级回收结合起来，形成一个生物可再生的封闭系统。据报道，当 2,5-呋喃二甲酸（FDCA）作为单体掺入光降解聚合物系统中时，可以回收再利用。在这里，我们使用含 FDCA 和 2-硝基-1,3-苯二甲醇的聚合物链光降解中涉及的微观结构的周期性边界条件进行密度泛函理论（DFT）研究。在真空和水相环境中使用含时激发态分子动力学（TDESMD）研究聚合物链的光降解过程。通过基态可观测量来表征反应中间体的光物理性质变化。使用化学信息学技术从 TDESMD 轨迹中获得反应中间体和产物的分布。结果表明，在真空环境中可以实现更高程度的聚合物链降解。此外，人们发现 FDCA 分子在水相环境中是可回收的，这与实验结果定性一致。
