Institut für Organische Chemie, Karlsruher Institut für Technologie, Fritz-Haber-Weg 6, 76131, Karlsruhe, Germany.
Institut für Technische Chemie und Polymerchemie, Karlsruher Institut für Technologie (KIT), Engesserstraße 18, 76128, Karlsruhe, Germany.
Chemistry. 2021 Jun 1;27(31):8094-8099. doi: 10.1002/chem.202005486. Epub 2021 May 1.
Molecular photoswitches triggered with red or NIR light are optimal for photomodulation of complex biological systems, including efficient penetration of the human body for therapeutic purposes ("therapeutic window"). Yet, they are rarely reported, and even more rarely functional under aqueous conditions. In this work, fluorinated azobenzenes are shown to exhibit efficient E→Z photoisomerization with red light (PSS >75 % Z) upon conjugation with unsaturated substituents. Initially demonstrated for aldehyde groups, this effect was also observed in a more complex structure by incorporating the chromophore into a cyclic dipeptide with propensity for self-assembly. Under physiological conditions, the latter molecule formed a supramolecular material that reversibly changed its viscosity upon irradiation with red light. Our observation can lead to design of new photopharmacology agents or phototriggered materials for in vivo use.
用红光或近红外光触发的分子光开关最适合于复杂生物系统的光调节,包括高效穿透人体以达到治疗目的(“治疗窗口”)。然而,它们很少被报道,在水相条件下更是如此。在这项工作中,氟代偶氮苯与不饱和取代基共轭后,用红光(PSS >75% Z)显示出高效的 E→Z 光致异构化。最初在醛基中证明了这一效应,通过将生色团引入具有自组装倾向的环状二肽中,也观察到了这种效应。在生理条件下,后者分子形成了超分子材料,用红光照射可使其粘度可逆变化。我们的观察结果可以为设计新的光药理学试剂或用于体内应用的光触发材料提供依据。