Department of Chemistry and Applied Bioscience, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland.
Department of Chemistry, Materials and Chemical Engineering "Giulio Natta" Politecnico di Milano, Via Mancinelli 7, Milano, 20131, Italy.
Small. 2020 Oct;16(40):e2001207. doi: 10.1002/smll.202001207. Epub 2020 Sep 6.
The confinement of organic synthesis within waterborne nanoreactors is regarded with increasing attention to improve its yield and reduce the environmental impact. However, many catalysts, such as graphene, are barely dispersible in aqueous media and many chemical reactions cannot be performed in the presence of water due to thermodynamic limitations. Therefore, there is an urgent need to develop novel strategies to carry out these processes in more sustainable conditions. To pursue this goal, in this work, a waterborne supramolecular nanoreactor is developed. The system comprises a polymeric micelle obtained from the self-assembly of pyrrole-based amphiphilic block copolymers. The active catalytic component is represented by few graphene layers, functionalized with pyrrole to enhance their interaction with the micelle core and hence their nanoencapsulation. Using this nanoreactor, it is possible to synthesize imines starting from primary amines and aldehydes or ketones with high yield and in short time (Y = 90% after 5 min) at room temperature. Moreover, an efficient strategy to recycle the reactor is proposed, thus increasing the potential of this technology.
将有机合成限制在水基纳米反应器中受到越来越多的关注，以提高其产率并减少对环境的影响。然而，许多催化剂，如石墨烯，在水介质中几乎不可分散，并且由于热力学限制，许多化学反应不能在存在水的情况下进行。因此，迫切需要开发新的策略，以在更可持续的条件下进行这些过程。为了实现这一目标，本工作开发了一种水基超分子纳米反应器。该系统由基于吡咯的两亲嵌段共聚物自组装而成的聚合物胶束组成。活性催化组分由几层功能化的石墨烯组成，通过吡咯官能化来增强与胶束核的相互作用，从而实现其纳米封装。使用这种纳米反应器，可以从伯胺和醛或酮在室温下以高产率和短时间（5 分钟后 Y = 90%）合成亚胺。此外，还提出了一种有效的回收反应器的策略，从而提高了这项技术的潜力。
