Sarkar Aritra, Dúzs Brigitta, Walther Andreas
Life-Like Materials and Systems, Department of Chemistry, University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
J Am Chem Soc. 2024 Apr 17;146(15):10281-10285. doi: 10.1021/jacs.4c02680. Epub 2024 Apr 3.
Fuel-driven dissipative formation of disulfide bonds using competing oxidative activation and reductive deactivation presents a possibly very versatile avenue for autonomous materials design. However, this is challenging to realize because of the direct annihilation of oxidizing fuel and a deactivating reducing agent. We overcome this challenge by introducing a redox-based enzymatic reaction network (ERN), enabling the dissipative disulfide formation for molecularly dissolved thiols in a fully autonomous manner. Moreover, the ERN allows for programming hydrogel lifetimes by utilizing thiol-terminated star polymers (sPEG-SH). The ERN can be customized to operate with aliphatic and aromatic thiols and should thus be broadly applicable to functional thiols.
利用竞争性氧化活化和还原失活，通过燃料驱动形成二硫键，为自主材料设计提供了一条可能非常通用的途径。然而，由于氧化燃料和失活还原剂的直接湮灭，这很难实现。我们通过引入基于氧化还原的酶促反应网络（ERN）克服了这一挑战，从而能够以完全自主的方式实现分子溶解硫醇的耗散性二硫键形成。此外，ERN通过使用硫醇封端的星形聚合物（sPEG-SH）实现水凝胶寿命的编程。ERN可以定制为与脂肪族和芳香族硫醇一起运行，因此应广泛适用于功能性硫醇。
