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光致断键:吸光度-碎片化悖论

Breaking Bonds by Light: The Absorbance-Fragmentation Paradox.

作者信息

Dunkel Petra, Tran Christine, Rigault Delphine, Kontra Bence, Deprez Eric, Tauc Patrick, Mucsi Zoltán, Dhimane Hamid, Dalko Peter I

机构信息

Pharmacological and Toxicological Chemistry and Biochemistry Laboratory, Université Paris Cité, 45 rue des Saints-Pères, Paris, 75270 cedex 05, France.

Department of Biological Chemistry, BrainVision Center Ltd, Liliom utca 43-45, 1094, Budapest, Hungary.

出版信息

Chemistry. 2025 Aug 18;31(46):e01839. doi: 10.1002/chem.202501839. Epub 2025 Jul 22.

DOI:10.1002/chem.202501839
PMID:40693306
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12363429/
Abstract

Multi-branched probes based on 2-hydroxymethylene 8-dimethylaminoquinoline (8-DMAQ) and triphenylamine (TPA) have been synthesized and compared under UV and femtosecond near-infrared two-photon (2P) activation conditions. While octupolar (3) and quadrupolar (2) DMAQ derivatives showed superior ε and 2P absorption cross-section (σ) values relative to the dipolar (1) probe, the fragmentation efficiency exhibited an inverse correlation with the enhanced absorption. Compound 1 emerged as the most effective probe reported to date for the release of organic substrates under both UV and 2P activation conditions at wavelengths accessible to commercially available lasers, achieving a quantum yield (Q) of 12% with σ = 86 GM and uncaging cross-section δ = 10.2 GM at 735 nm.

摘要

基于2-羟基亚甲基-8-二甲基氨基喹啉(8-DMAQ)和三苯胺(TPA)的多分支探针已被合成,并在紫外光和飞秒近红外双光子(2P)活化条件下进行了比较。虽然八极(3)和四极(2)DMAQ衍生物相对于偶极(1)探针显示出更高的ε和2P吸收截面(σ)值,但碎片化效率与增强的吸收呈负相关。化合物1是迄今为止报道的在商业可用激光器可及波长的紫外光和2P活化条件下用于释放有机底物的最有效探针,在735 nm处实现了12%的量子产率(Q),σ = 86 GM,解笼截面δ = 10.2 GM。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/19b009feaa50/CHEM-31-e01839-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/7f57af1da9bc/CHEM-31-e01839-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/47558555e80f/CHEM-31-e01839-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/ada3772425e4/CHEM-31-e01839-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/c4c290bf021c/CHEM-31-e01839-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/03648ba094da/CHEM-31-e01839-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/9f0c81a52f61/CHEM-31-e01839-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/46052729dba4/CHEM-31-e01839-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/19b009feaa50/CHEM-31-e01839-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/7f57af1da9bc/CHEM-31-e01839-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/47558555e80f/CHEM-31-e01839-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/ada3772425e4/CHEM-31-e01839-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/c4c290bf021c/CHEM-31-e01839-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/03648ba094da/CHEM-31-e01839-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/9f0c81a52f61/CHEM-31-e01839-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/46052729dba4/CHEM-31-e01839-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9cd3/12363429/19b009feaa50/CHEM-31-e01839-g002.jpg

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本文引用的文献

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Photocage-Selective Capture and Light-Controlled Release of Target Proteins.光笼选择性捕获与光控靶蛋白释放
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Visible-to-NIR-Light Activated Release: From Small Molecules to Nanomaterials.可见-近红外光激活释放:从小分子到纳米材料。
Chem Rev. 2020 Dec 23;120(24):13135-13272. doi: 10.1021/acs.chemrev.0c00663. Epub 2020 Oct 30.
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Conditionally Activatable Visible-Light Photocages.条件激活型可见光光笼
J Am Chem Soc. 2020 Sep 2;142(35):15164-15171. doi: 10.1021/jacs.0c07508. Epub 2020 Aug 18.
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Useful Caged Compounds for Cell Physiology.用于细胞生理学的有用笼状化合物。
Acc Chem Res. 2020 Aug 18;53(8):1593-1604. doi: 10.1021/acs.accounts.0c00292. Epub 2020 Jul 21.
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Two-Photon Excitable Photoremovable Protecting Groups Based on the Quinoline Scaffold for Use in Biology.基于喹啉支架的双光子激发光解保护基在生物学中的应用。
J Org Chem. 2020 Jan 17;85(2):726-744. doi: 10.1021/acs.joc.9b02780. Epub 2019 Dec 18.
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The Effect of Branching on the One- and Two-Photon Absorption, Cell Viability, and Localization of Cationic Triarylborane Chromophores with Dipolar versus Octupolar Charge Distributions for Cellular Imaging.支化对具有偶极子与八极子电荷分布的阳离子三芳基硼发色团的单光子和双光子吸收、细胞活力和细胞定位的影响,用于细胞成像。
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