Prasoon Anupam, Ghouse Shaik, Nguyen Nguyen Ngan, Yang Hyejung, Müller Alina, Naisa Chandrasekhar, Paasch Silvia, Herbawe Abdallh, Aiti Muhannad Al, Cuniberti Gianaurelio, Brunner Eike, Feng Xinliang
Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany.
Max Planck Institute for Microstructure Physics, Halle (Saale), D-06120, Germany.
Nat Commun. 2024 Dec 3;15(1):10495. doi: 10.1038/s41467-024-54962-z.
The chemistry of the on-water surface, characterized by enhanced reactivity, distinct selectivity, and confined reaction geometry, offers significant potential for chemical and materials syntheses. However, the utilization of on-water surface synthesis is currently limited by the requirement for a stable air-water interface, which restricts its broader synthetic applications. In this work, we present a approach that mimics on-water surface chemistry using micelles. This method involves the self-assembly of charged surfactant molecules beyond their critical micelle concentration (CMC), forming micellar structures that simulate the air-water interface. This creates an environment conducive to chemical reactions, featuring a hydrophobic core and surrounding water layer. Utilizing such mimicking on-water surface with the assembly of porphyrin-based monomers featuring distinct confined geometry and preferential orientations, we achieve reactivity and selectivity (≥99%) in fourteen different reversible and irreversible chemical reactions. Extending the versatility of this approach, we further demonstrate its applicability to two-dimensional (2D) polymerization on micellar interfaces, successfully achieving the aqueous synthesis of crystalline 2D polymer thin layers. This strategy significantly broadens the accessibility of on-water surface chemistry for a wide range of chemical syntheses.
水上表面的化学性质具有反应活性增强、选择性独特和反应几何形状受限等特点，为化学和材料合成提供了巨大潜力。然而，目前水上表面合成的应用受到稳定气-水界面要求的限制，这限制了其更广泛的合成应用。在这项工作中，我们提出了一种使用胶束模拟水上表面化学的方法。该方法涉及带电表面活性剂分子在超过其临界胶束浓度（CMC）时的自组装，形成模拟气-水界面的胶束结构。这创造了一个有利于化学反应的环境，其特征是具有疏水核心和周围的水层。利用这种模拟水上表面与具有独特受限几何形状和优先取向的卟啉基单体组装，我们在十四种不同的可逆和不可逆化学反应中实现了反应活性和选择性（≥99%）。为扩展这种方法的通用性，我们进一步证明了其在胶束界面上二维（2D）聚合的适用性，成功实现了结晶二维聚合物薄层的水相合成。该策略显著拓宽了水上表面化学在广泛化学合成中的可及性。
