Đorđević Luka, Jaynes Tyler J, Sai Hiroaki, Barbieri Marianna, Kupferberg Jacob E, Sather Nicholas A, Weigand Steven, Stupp Samuel I
Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova, 35131, Italy.
Center for Bio-inspired Energy Science, Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208, USA.
Adv Mater. 2025 Apr;37(16):e2418137. doi: 10.1002/adma.202418137. Epub 2025 Mar 12.
Mechanical expansion and contraction of pores within photosynthetic organisms regulate a series of processes that are necessary to manage light absorption, control gas exchange, and regulate water loss. These pores, known as stoma, allow the plant to maximize photosynthetic output depending on environmental conditions such as light intensity, humidity, and temperature by actively changing the size of the stomal opening. Despite advances in artificial photosynthetic systems, little is known about the effect of such mechanical actuation in synthetic materials where chemical reactions occur. It is reported here on a hybrid hydrogel that combines light-activated supramolecular polymers for superoxide production with thermal mechanical actuation of a covalent polymer. Superoxide production is important in organic synthesis and environmental remediation, and is a potential precursor to hydrogen peroxide liquid fuel. It is shown that the closing of pores in the hybrid hydrogel results in a substantial decrease in photocatalysis, but cycles of swollen and contracted states enhance photocatalysis. The observations motivate the development of biomimetic photosynthetic materials that integrate large scale motion and chemical reactions.
光合生物体内气孔的机械扩张和收缩调节着一系列过程,这些过程对于控制光吸收、气体交换和调节水分流失至关重要。这些被称为气孔的孔隙,使植物能够根据光照强度、湿度和温度等环境条件,通过主动改变气孔开口大小来最大化光合产量。尽管人工光合系统取得了进展,但对于这种机械驱动在发生化学反应的合成材料中的作用却知之甚少。本文报道了一种混合水凝胶,它将用于产生超氧化物的光活化超分子聚合物与共价聚合物的热机械驱动相结合。超氧化物的产生在有机合成和环境修复中很重要,并且是过氧化氢液体燃料的潜在前体。结果表明,混合水凝胶中孔隙的闭合会导致光催化作用大幅下降,但膨胀和收缩状态的循环会增强光催化作用。这些观察结果推动了集成大规模运动和化学反应的仿生光合材料的发展。