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Theoretical study of lanthanide‐based in vivo luminescent probes for detecting hydrogen peroxide
Author(s) -
Hatanaka Miho,
Wakabayashi Tomonari
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25737
Subject(s) - lanthanide , intersystem crossing , excited state , chemistry , intramolecular force , ground state , quenching (fluorescence) , photochemistry , density functional theory , hydrogen bond , luminescence , hydrogen peroxide , fluorescence , ligand (biochemistry) , molecule , atomic physics , computational chemistry , materials science , singlet state , stereochemistry , ion , physics , optoelectronics , biochemistry , organic chemistry , receptor , quantum mechanics
The 4f‐4f emissions from lanthanide trication (Ln 3+ ) complexes are widely used in bioimaging probes. The emission intensity from Ln 3+ depends on the surroundings, and thus, the design of appropriate photo‐antenna ligands is indispensable. In this study, we focus on two probes for detecting hydrogen peroxide, for which emission intensities from Tb 3+ are enhanced chemo‐selectively by the H 2 O 2 ‐mediated oxidation of ligands. To understand the mechanism, the Gibbs free energy profiles of the ground and excited states related to emission and quenching are computed by combining our approximation—called the energy shift method—and density functional theory. The different emission intensities are mainly attributed to different activation barriers for excitation energy transfer from the ligand‐centered triplet (T1) to the Tb 3+ ‐centered excited state. Additionally, quenching from T1 to the ground state via intersystem crossing was inhibited by intramolecular hydrogen bonds only in the highly emissive Tb 3+ complexes. © 2018 Wiley Periodicals, Inc.