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通过电子给体-受体连接的分子传感器的激发态工程实现单线态氧的笼蔽和光触发释放。

Caging and photo-triggered uncaging of singlet oxygen by excited state engineering of electron donor-acceptor-linked molecular sensors.

机构信息

Graduate School of Environmental Science, Hokkaido University, N10, W5, Sapporo, 060-0810, Japan.

Research Institute for Electronic Science, Hokkaido University, N20, W10, Sapporo, 001-0020, Japan.

出版信息

Sci Rep. 2022 Jul 5;12(1):11371. doi: 10.1038/s41598-022-15054-4.

DOI:10.1038/s41598-022-15054-4
PMID:35790770
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9256616/
Abstract

Singlet oxygen (O), one of the most sought-after species in oxidative chemical reactions and photodynamic cancer therapy, is activated and neutralized in the atmosphere and living cells. It is essential to see "when" and "where" O is produced and delivered to understand and utilize it. There is an increasing demand for molecular sensor tools to capture, store, and supply O, controlled by light and engineered singlet and triplet states, indicating the O-capturing-releasing state. Here, we demonstrate the outstanding potential of an aminocoumarin-methylanthracene-based electron donor-acceptor molecule (1). Spectroscopic measurements confirm the formation of an endoperoxide (1-O) which is not strongly fluorescent and remarkably different from previously reported O sensor molecules. Moreover, the photoexcitation on the dye in 1-O triggers fluorescence enhancement by the oxidative rearrangement and a competing O release. The unique ability of 1 will pave the way for the spatially and temporally controlled utilization of O in various areas such as chemical reactions and phototherapies.

摘要

单线态氧 (O) 是氧化化学反应和光动力癌症治疗中最受追捧的物种之一,它在大气和活细胞中被激活和中和。了解和利用 O,关键是要看到“何时”和“何地”产生和输送 O。因此,人们对分子传感器工具的需求越来越大,这些工具可以通过光和工程的单线态和三线态来捕获、存储和供应 O,并指示 O 的捕获-释放状态。在这里,我们展示了一种基于氨基香豆素-蒽的电子给体-受体分子 (1) 的卓越潜力。光谱测量证实了内过氧化物 (1-O) 的形成,1-O 不具有强烈的荧光性,与以前报道的 O 传感器分子显著不同。此外,在 1-O 中的染料的光激发通过氧化重排和竞争的 O 释放触发荧光增强。1 的独特能力将为化学反应和光疗等各个领域中 O 的时空控制利用铺平道路。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/25d82a1fa0f7/41598_2022_15054_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/fdd58ef85a8e/41598_2022_15054_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/db3f239584f7/41598_2022_15054_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/89ec3dbd3290/41598_2022_15054_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/25d82a1fa0f7/41598_2022_15054_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/fdd58ef85a8e/41598_2022_15054_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/db3f239584f7/41598_2022_15054_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/89ec3dbd3290/41598_2022_15054_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/21b8/9256616/25d82a1fa0f7/41598_2022_15054_Fig4_HTML.jpg

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