Guo Jinshan, Poros-Tarcali Eszter, Pérez-Mercader Juan
Department of Earth and Planetary Science and Origins of Life Initiative, Harvard University, Cambridge, MA, United States.
Santa Fe Institute, Santa Fe, NM, United States.
Front Chem. 2021 Feb 22;9:576349. doi: 10.3389/fchem.2021.576349. eCollection 2021.
Using the radicals generated during pH oscillations, a semibatch pH oscillator is used as the chemical fuel and engine to drive polymerization induced self-assembly (PISA) for the one-pot autonomous synthesis of functional giant vesicles. Vesicles with diameters ranging from sub-micron to ∼5 µm are generated. Radical formation is found to be switched ON/OFF and be autonomously controlled by the pH oscillator itself, inducing a periodic polymerization process. The mechanism underlying these complex processes is studied and compared to conventional (non-oscillatory) initiation by the same redox pair. The pH oscillations along with the continuous increase in salt concentration in the semibatch reactor make the self-assembled objects undergo morphological evolution. This process provides a self-regulated means for the synthesis of soft giant polymersomes and opens the door for new applications of pH oscillators in a variety of contexts, from the exploration of new geochemical scenarios for the origin of life and the autonomous emergence of the necessary free-energy and proton gradients, to the creation of active functional microreactors and programmable release of cargo molecules for pH-responsive materials.
利用pH振荡过程中产生的自由基，半间歇式pH振荡器被用作化学燃料和引擎，以驱动聚合诱导自组装（PISA），实现一锅法自主合成功能性巨型囊泡。生成了直径范围从亚微米到约5微米的囊泡。发现自由基的形成可通过pH振荡器自身进行开启/关闭和自主控制，从而引发周期性聚合过程。研究了这些复杂过程的潜在机制，并与同一氧化还原对的传统（非振荡）引发方式进行了比较。半间歇式反应器中pH的振荡以及盐浓度的持续增加，使得自组装物体发生形态演变。这一过程为合成柔软的巨型聚合物囊泡提供了一种自我调节的方法，并为pH振荡器在各种场景中的新应用打开了大门，从探索生命起源的新地球化学场景以及必要的自由能和质子梯度的自主出现，到创建活性功能微反应器以及实现pH响应材料中货物分子的可编程释放。
