Klein David M, Li Xinmeng, Boyle Aimee L, van der Pol Rianne, Tsina Vasiliki E, Sevink G J Agur, Brouwer Albert M, Bonnet Sylvestre
Leiden Institute of Chemistry, Leiden University, Leiden 2333 CC, The Netherlands.
Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam 1090 GD, The Netherlands.
Artif Photosynth. 2025 May 28;1(4):188-203. doi: 10.1021/aps.5c00010. eCollection 2025 Jul 24.
The ability to drive unidirectional photoinduced electron transfer through an insulating lipid membrane is one of the most striking features of the thylakoid membrane, and recreating this property artificially is considered as one of the holy grails of artificial photosynthesis. Here, we report two artificial metallopeptides, and , that were embedded in the membrane of dissymmetric liposomes containing an electron donor in the inner compartment and an electron acceptor in the bulk aqueous phase. Upon light irradiation under air, unidirectional electron transfer was observed from one side of the membrane to the other one with both metallopeptides. However, the mechanism of photoinduced electron transfer strongly depended on the metal center: the neutral peptide achieved genuine electron transfer through the membrane, but with the tetracationic peptide the transmembrane electron transfer appeared to be the result of light-induced leakage of the electron donor molecules through the lipid bilayer, followed by electron transfer on the same side of the membrane by peptides assembled parallel to the membrane. These results highlight both the unique potential of the neutral metallopeptide to drive transmembrane photoinduced electron transfer in artificial photosynthetic systems, as well as the importance of membrane-leakage studies to validate the working mechanism of such supramolecular systems.
驱动单向光致电子转移穿过绝缘脂质膜的能力是类囊体膜最显著的特征之一，而人工重现这一特性被视为人工光合作用的圣杯之一。在此，我们报道了两种人工金属肽， 和 ，它们被嵌入不对称脂质体膜中，脂质体的内室含有电子供体，本体水相中含有电子受体。在空气中光照时，两种金属肽均观察到从膜的一侧到另一侧的单向电子转移。然而，光致电子转移的机制强烈依赖于金属中心：中性的 肽通过膜实现了真正的电子转移，但对于四价阳离子的 肽，跨膜电子转移似乎是电子供体分子通过脂质双层光诱导泄漏的结果，随后由与膜平行组装的肽在膜的同一侧进行电子转移。这些结果既突出了中性金属肽 在人工光合系统中驱动跨膜光致电子转移的独特潜力，也强调了膜泄漏研究对于验证此类超分子系统工作机制的重要性。
