Photo-induced defluorination acyl fluoride exchange as a fluorogenic photo-click reaction for photo-affinity labeling

Photo-click chemistry has emerged as a powerful tool for revolutionizing bioconjugation technologies in pharmacological and various biomimetic applications. However, enriching the photo-click reactions to expand the bioconjugation toolkit remains challenging, especially when focusing on spatiotempor...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2023-03, Vol.14 (13), p.363-3641
Main Authors: Deng, Lijun, Zhang, Cefei, Li, Baolin, Fu, Jielin, Zhang, Zhong, Li, Sitong, Zhao, Xiaohu, Su, Zhishan, Hu, Changwei, Yu, Zhipeng
Format: Article
Language:English
Subjects:
Affinity
Amines
Aqueous environments
Atomic energy levels
Biomimetics
Carbonic anhydrase
Chemical reactions
Chemical synthesis
Chemistry
Defluorination
Fluorides
Thiols
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Summary:Photo-click chemistry has emerged as a powerful tool for revolutionizing bioconjugation technologies in pharmacological and various biomimetic applications. However, enriching the photo-click reactions to expand the bioconjugation toolkit remains challenging, especially when focusing on spatiotemporal control endowed by light activation. Herein, we describe a photo-induced defluorination acyl fluoride exchange (photo-DAFEx) as a novel type of photo-click reaction that is mediated through acyl fluorides produced by the photo-defluorination of m -trifluoromethylaniline to covalently conjugate with primary/secondary amines and thiols in an aqueous environment. (TD)-DFT calculations, together with experimental discovery, indicate that the m -NH 2 PhF 2 C(sp 3 )-F bond in the excited triplet state is cleaved by water molecules, which is key to inducing defluorination. Intriguingly, the benzoyl amide linkages built by this photo-click reaction exhibited a satisfactory fluorogenic performance, which allowed visualization of its formation in situ . Accordingly, this photo-controlled covalent strategy was exploited not only for the decoration of small molecules, peptide cyclization and functionalization of proteins in vitro , but also for designing photo-affinity probes targeting endogenous carbonic anhydrase II (hCA-II) in living cells. Photo-DAFEx as a novel photo-click reaction is mediating through photo-defluorination and conjugates to specific nucleophiles in aqueous. The Photo-DAFEx inspires the design of photo-affinity labeling probes toward lysine with fluorogenic feature.
ISSN:2041-6520
2041-6539
DOI:10.1039/d2sc04636a