Nam Jung Seung, Hong Youngjoo, Lee Chae Gyu, Kim Tae In, Lee Chaiheon, Roh Deok-Ho, Lee In Seong, Kweon Songa, Ahn Gyunhyeok, Min Seung Kyu, Kim Byeong-Su, Kwon Tae-Hyuk
Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea.
Center for Wave Energy Materials, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea.
JACS Au. 2022 Mar 29;2(4):933-942. doi: 10.1021/jacsau.2c00050. eCollection 2022 Apr 25.
Reactive oxygen species have drawn attention owing to their strong oxidation ability. In particular, the singlet oxygen (O) produced by energy transfer is the predominant species for controlling oxidation reactions efficiently. However, conventional O generators, which rely on enhanced energy transfer, frequently suffer from poor solubility, low stability, and low biocompatibility. Herein, we introduce a hyperbranched aliphatic polyaminoglycerol (hPAG) as a O generator, which relies on spin-flip-based electron transfer. The coexistence of a lone pair electron on the nitrogen atom and a hydrogen-bonding donor (the protonated form of nitrogen and hydroxyl group) affords proximity between hPAG and O. Subsequent direct electron transfer after photo-irradiation induces hPAG-O formation, and the following spin-flip process generates O. The spin-flip-based electron transfer pathway is analyzed by a series of photophysical, electrochemical, and computational studies. The O generator, hPAG, is successfully employed in photodynamic therapy and as an antimicrobial reagent.
活性氧因其强大的氧化能力而备受关注。特别是通过能量转移产生的单线态氧（O）是有效控制氧化反应的主要物种。然而，传统的O发生器依赖于增强的能量转移，经常存在溶解性差、稳定性低和生物相容性低的问题。在此，我们引入一种超支化脂肪族聚氨基甘油（hPAG）作为O发生器，其依赖于基于自旋翻转的电子转移。氮原子上孤对电子与氢键供体（氮的质子化形式和羟基）的共存使得hPAG与O之间距离接近。光照射后的后续直接电子转移诱导hPAG-O形成，随后的自旋翻转过程产生O。通过一系列光物理、电化学和计算研究分析了基于自旋翻转的电子转移途径。O发生器hPAG已成功应用于光动力疗法并用作抗菌试剂。
