TY - JOUR
T1 - Theoretical study of lanthanide-based in vivo luminescent probes for detecting hydrogen peroxide
AU - Hatanaka, Miho
AU - Wakabayashi, Tomonari
N1 - Funding Information:
The authors are grateful to Prof. Satoshi Maeda of Hokkaido University for the global reaction route mapping (GRRM) code. This work was in part supported by the JST through the PRESTO program (JPMJPR15NE) and by JSPS KAKENHI Grant Numbers JP17H06445 and JP18H03908. We also acknowledge computer resources provided by the Academic Center for Computing and Media Studies (ACCMS) at the Kyoto University and by the Research Center of Computer Science (RCCS) at the Institute for Molecular Science.
Funding Information:
[a] M. Hatanaka 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 E-mail: hatanaka@ms.naist.jp [b] M. Hatanaka PRESTO, Japan Science and Technology Agency (JST), Saitama 332-0012, Japan [c] T. Wakabayashi Graduate School of Science and Engineering, Kindai University, Osaka 577-8502, Japan Contract Grant sponsor: JSPS KAKENHI; Contract Grant numbers: JP18H03908, JP17H06445; Contract Grant sponsor: JST; Contract Grant number: JPMJPR15NE © 2018 Wiley Periodicals, Inc.
Publisher Copyright:
© 2018 Wiley Periodicals, Inc.
PY - 2019/1/15
Y1 - 2019/1/15
N2 - 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 H2O2-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.
AB - 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 H2O2-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.
KW - density functional theory
KW - excitation energy transfer
KW - intersystem crossing
KW - rare earth
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U2 - 10.1002/jcc.25737
DO - 10.1002/jcc.25737
M3 - Article
C2 - 30414197
AN - SCOPUS:85056298939
VL - 40
SP - 500
EP - 506
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 2
ER -