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Activity‐Based Sensing of Ascorbate by Using Copper‐Mediated Oxidative Bond Cleavage
Author(s) -
Yu Zuo Hang,
Reinhardt Christopher J.,
Wong Thomas HinFung,
Tong Ka Yan,
Chan Jefferson,
AuYeung Ho Yu
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000780
Subject(s) - chemistry , copper , bond cleavage , fluorescein , amine gas treating , reducing agent , fluorescence , selectivity , cleavage (geology) , photochemistry , ether , combinatorial chemistry , biochemistry , organic chemistry , fracture (geology) , catalysis , physics , geotechnical engineering , quantum mechanics , engineering
Ascorbate is an important biological reductant and enzyme cofactor. Although direct detection through ascorbate‐mediated reduction is possible, this approach suffers from poor selectivity due to the wide range of cellular reducing agents. To overcome this limitation, we leverage reduction potential of ascorbate to mediate a copper‐mediated oxidative bond cleavage of ether‐caged fluorophores. The copper(II) complexes supported by a {bis(2‐pyridylmethyl)}benzylamine or a {bis(2‐pyridylmethyl)}(2‐methoxybenzyl)amine ligand were identified as an ascorbate responsive unit and their reaction with ascorbate yields a copper‐based oxidant that enables rapid benzylic oxidation and the release of an ether‐caged dye (coumarin or fluorescein). The copper‐mediated bond cleavage is specific to ascorbate and the trigger can be readily derivatized for tuning photophysical properties of the probes. The probes were successfully applied for the fluorometric detection of ascorbate in commercial food samples, human plasma, and serum, and within live cells by using confocal microscopy and flow cytometry.