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J Comput Chem. 2019 Jan 15;40(2):500-506. doi: 10.1002/jcc.25737. Epub 2018 Nov 10.

Theoretical study of lanthanide-based in vivo luminescent probes for detecting hydrogen peroxide.

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Institute for Research Initiatives, Division for Research Strategy, Graduate School of Science and Technology, Data Science Center, Nara Institute of Science and Technology, Nara, 630-0192, Japan.
PRESTO, Japan Science and Technology Agency (JST), Saitama, 332-0012, Japan.
Graduate School of Science and Engineering, Kindai University, Osaka, 577-8502, Japan.


The 4f-4f emissions from lanthanide trication (Ln3+ ) complexes are widely used in bioimaging probes. The emission intensity from Ln3+ 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 Tb3+ are enhanced chemo-selectively by the H2 O2 -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 Tb3+ -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 Tb3+ complexes.


density functional theory; excitation energy transfer; intersystem crossing; rare earth


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