Lee Chin-Yun, Hu Shu-Man, Xiao Jia-Qi, Chang Yu-Ming, Kusanagi Tatsuya, Wu Ting-Ying, Chiu Ya-Ru, Yang Yen-Ching, Huang Chao-Wei, Chen Hsien-Yeh
Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan.
Department of Tropical Agriculture and International Cooperation, National Pingtung University of Science and Technology, Pingtung 91201, Taiwan.
Polymers (Basel). 2021 Mar 4;13(5):786. doi: 10.3390/polym13050786.
Conventional porous materials are mostly synthesized in solution-based methods involving solvents and initiators, and the functionalization of these porous materials usually requires additional and complex steps. In the current study, a methyl propiolate-functionalized porous poly--xylylene material was fabricated based on a unique vapor sublimation and deposition process. The process used a water solution and ice as the template with a customizable shape and dimensions, and the conventional chemical vapor deposition (CVD) polymerization of poly--xylylene on such an ice template formed a three-dimensional, porous poly--xylylene material with interconnected porous structures. More importantly, the functionality of methyl propiolate was well preserved by using methyl propiolate-substituted [2,2]-paracyclophane during the vapor deposition polymerization process and was installed in one step on the final porous poly--xylylene products. This functionality exhibited an intact structure and reactivity during the proposed vapor sublimation and deposition process and was proven to have no decomposition or side products after further characterization and conjugation experiments. The electron-withdrawing methyl propiolate group readily provided efficient alkynes as click azide-terminated molecules under copper-free and mild conditions at room temperature and in environmentally friendly solvents, such as water. The resulting methyl propiolate-functionalized porous poly--xylylene exhibited interface properties with clickable specific covalent attachment toward azide-terminated target molecules, which are widely available for drugs and biomolecules. The fabricated functional porous materials represent an advanced material featuring porous structures, a straightforward synthetic approach, and precise and controlled interface click chemistry, rendering long-term stability and efficacy to conjugate target functionalities that are expected to attract a variety of new applications.
传统的多孔材料大多通过基于溶液的方法合成，涉及溶剂和引发剂，而这些多孔材料的功能化通常需要额外且复杂的步骤。在本研究中，基于独特的气相升华和沉积工艺制备了一种甲基丙炔酸酯功能化的多孔聚对二甲苯材料。该工艺使用水溶液和冰作为具有可定制形状和尺寸的模板，聚对二甲苯在这种冰模板上进行传统的化学气相沉积（CVD）聚合，形成了具有相互连接的多孔结构的三维多孔聚对二甲苯材料。更重要的是，在气相沉积聚合过程中使用甲基丙炔酸酯取代的[2,2]-对环芳烷，甲基丙炔酸酯的官能团得到了很好的保留，并一步安装在最终的多孔聚对二甲苯产物上。该官能团在提出的气相升华和沉积过程中表现出完整的结构和反应活性，经过进一步表征和共轭实验证明没有分解或副产物。吸电子的甲基丙炔酸酯基团在无铜且温和的条件下，于室温及水等环境友好型溶剂中， readily 提供高效的炔烃作为点击叠氮化物封端的分子。所得的甲基丙炔酸酯功能化的多孔聚对二甲苯表现出与叠氮化物封端的靶分子的可点击的特异性共价连接的界面性质，这些靶分子广泛应用于药物和生物分子。所制备的功能化多孔材料代表了一种先进材料，具有多孔结构、直接的合成方法以及精确可控的界面点击化学，为共轭靶功能提供长期稳定性和功效，有望吸引各种新应用。
