Wang Shaoyu, Zhang Jing, Chu Lichao, Xiao Hongquan, Miao Changqing, Pan Zhengxuan, Qiao Yanan, Wang Zengyao, Zhou Baolong
School of Pharmacy, Shandong Second Medical University, Weifang, Shandong 261053, PR China.
The First Affiliated Hospital of Shandong Second Medical University (Weifang People's Hospital), Shandong Second Medical University, Weifang, 261044, Shandong, PR China.
Biomater Adv. 2024 May;159:213814. doi: 10.1016/j.bioadv.2024.213814. Epub 2024 Feb 26.
Controllable preparation of materials with new structure has always been the top priority of polymer materials science research. Here, the supramolecular binding strategy is adopted to develop covalent organic frameworks (COFs) with novel structures and functions. Based on this, a two-dimensional crown-ether ring threaded covalent organic framework (COF), denoted as Crown-COPF with intrinsic photothermal (PTT) and photodynamic (PDT) therapeutic capacity, was facilely developed using crown-ether threaded rotaxane and porphyrin as building blocks. Crown-COPF with discrete mechanically interlocked blocks in the open pore could be used as a molecular machine, in which crown-ether served as the wheel sliding along the axle under the laser stimulation. As a result, Crown-COPF combining with the bactericidal power of crown ether displayed a significant photothermal and photodynamic antibacterial activity towards both the Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus), far exceeding the traditional Crown-free COF. Noteworthily, the bactericidal performance could be further enhanced via impregnation of Zn ions (Crown-COPF-Zn) flexible coordinated with the multiple coordination sites (crown-ether, bipyridine, and porphyrin), which not only endow the positive charge with the skeleton, enhancing its ability to bind to the bacterial membrane, but also introduce the bactericidal ability of zinc ions. Notably, in vivo experiments on mice with back infections indicates Crown-COPF-Zn with self-adaptive multinuclear zinc center, could effectively promote the repairing of wounds. This study paves a new avenue for the effectively preparation of porous polymers with brand new structure, which provides opportunities for COF and mechanically interlocked polymers (MIPs) research and applications.
可控制备具有新结构的材料一直是高分子材料科学研究的重中之重。在此,采用超分子结合策略来开发具有新颖结构和功能的共价有机框架(COF)。基于此,以冠醚穿线轮烷和卟啉为构建单元,简便地开发了一种具有固有光热(PTT)和光动力(PDT)治疗能力的二维冠醚环穿线共价有机框架(COF),记为Crown-COPF。具有离散机械互锁块的开孔Crown-COPF可作为分子机器,其中冠醚在激光刺激下作为轮子沿轴滑动。结果,结合了冠醚杀菌能力的Crown-COPF对革兰氏阴性菌(大肠杆菌)和革兰氏阳性菌(金黄色葡萄球菌)均表现出显著的光热和光动力抗菌活性,远远超过传统的无冠COF。值得注意的是,通过与多个配位位点(冠醚、联吡啶和卟啉)柔性配位的锌离子(Crown-COPF-Zn)浸渍可进一步增强杀菌性能,这不仅赋予骨架正电荷,增强其与细菌膜结合的能力,还引入了锌离子的杀菌能力。值得注意的是,对背部感染小鼠的体内实验表明,具有自适应多核锌中心的Crown-COPF-Zn能够有效促进伤口修复。该研究为有效制备具有全新结构的多孔聚合物开辟了一条新途径,为COF和机械互锁聚合物(MIP)的研究与应用提供了机遇。