Volume 30, Issue 11 e202303883
Research Article

Electrochemical Diselenation of BODIPY Fluorophores for Bioimaging Applications and Sensitization of 1O2

Ícaro A. O. Bozzi

Ícaro A. O. Bozzi

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais, Belo Horizonte, MG, 31270-901 Brazil

These authors contributed equally to this work.

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Dr. Luana A. Machado

Dr. Luana A. Machado

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais, Belo Horizonte, MG, 31270-901 Brazil

Institute for Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany

These authors contributed equally to this work.

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Emilay B. T. Diogo

Emilay B. T. Diogo

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais, Belo Horizonte, MG, 31270-901 Brazil

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Dr. Fábio G. Delolo

Dr. Fábio G. Delolo

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais, Belo Horizonte, MG, 31270-901 Brazil

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Luiza O. F. Barros

Luiza O. F. Barros

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais, Belo Horizonte, MG, 31270-901 Brazil

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Gabriela A. P. Graça

Gabriela A. P. Graça

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais, Belo Horizonte, MG, 31270-901 Brazil

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Prof. Dr. Maria H. Araujo

Prof. Dr. Maria H. Araujo

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais, Belo Horizonte, MG, 31270-901 Brazil

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Prof. Dr. Felipe T. Martins

Prof. Dr. Felipe T. Martins

Instituto de Química, Universidade Federal de Goiás, Goiânia, 74690-900 Brazil

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Prof. Dr. Leandro F. Pedrosa

Prof. Dr. Leandro F. Pedrosa

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal Fluminense, Volta Redonda, RJ, 27213-145 Brazil

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Lilian C. da Luz

Lilian C. da Luz

Instituto de Química, Universidade Federal do Rio Grande do Sul, Porto Alegre, 91501-970 RS, Brazil

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Emmanuel S. Moraes

Emmanuel S. Moraes

Universidade Estadual de Campinas (Unicamp), Cidade Universitária, 13083970 – Campinas, SP, Brazil

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Prof. Dr. Fabiano S. Rodembusch

Prof. Dr. Fabiano S. Rodembusch

Instituto de Química, Universidade Federal do Rio Grande do Sul, Porto Alegre, 91501-970 RS, Brazil

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Dr. João S. F. Guimarães

Dr. João S. F. Guimarães

Departamento de Fisiologia e Biofísica, Instituto de Ciências Biológicas, Universidade Federal de Minas Gerais, Belo Horizonte, Brazil

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Prof. Dr. André G. Oliveira

Prof. Dr. André G. Oliveira

Departamento de Fisiologia e Biofísica, Instituto de Ciências Biológicas, Universidade Federal de Minas Gerais, Belo Horizonte, Brazil

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Sebastian H. Röttger

Sebastian H. Röttger

DFG Cluster of Excellence livMatS @FIT and Albert-Ludwigs-Universität Freiburg, Institute of Organic Chemistry, Albertstraße 21, 79104 Freiburg (Breisgau), Germany

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Prof. Dr. Daniel B. Werz

Prof. Dr. Daniel B. Werz

DFG Cluster of Excellence livMatS @FIT and Albert-Ludwigs-Universität Freiburg, Institute of Organic Chemistry, Albertstraße 21, 79104 Freiburg (Breisgau), Germany

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Cauê P. Souza

Cauê P. Souza

School of Chemistry and Forensic Science, University of Kent, Park Wood Rd, Canterbury, CT2 7NH United Kingdom

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Dr. Felipe Fantuzzi

Dr. Felipe Fantuzzi

School of Chemistry and Forensic Science, University of Kent, Park Wood Rd, Canterbury, CT2 7NH United Kingdom

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Dr. Jianhua Han

Dr. Jianhua Han

Institute for Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany

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Prof. Dr. Todd B. Marder

Prof. Dr. Todd B. Marder

Institute for Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany

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Prof. Dr. Holger Braunschweig

Corresponding Author

Prof. Dr. Holger Braunschweig

Institute for Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany

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Prof. Dr. Eufrânio N. da Silva Júnior

Corresponding Author

Prof. Dr. Eufrânio N. da Silva Júnior

Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais, Belo Horizonte, MG, 31270-901 Brazil

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First published: 12 December 2023

Graphical Abstract

The synthesis of red-emitting BODIPY derivatives through a mild electrochemical diselenation process is reported. The study encompasses substrate scope exploration, photophysical characterization, computational analysis, and the demonstration of their potential as emission-tunable fluorescent probes with large Stokes shift for lipid droplet visualization, offering broad-ranging applications in bioimaging and related fields.

Abstract

We report a rapid, efficient, and scope-extensive approach for the late-stage electrochemical diselenation of BODIPYs. Photophysical analyses reveal red-shifted absorption – corroborated by TD-DFT and DLPNO-STEOM-CCSD computations – and color-tunable emission with large Stokes shifts in the selenium-containing derivatives compared to their precursors. In addition, due to the presence of the heavy Se atoms, competitive ISC generates triplet states which sensitize 1O2 and display phosphorescence in PMMA films at RT and in a frozen glass matrix at 77 K. Importantly, the selenium-containing BODIPYs demonstrate the ability to selectively stain lipid droplets, exhibiting distinct fluorescence in both green and red channels. This work highlights the potential of electrochemistry as an efficient method for synthesizing unique emission-tunable fluorophores with broad-ranging applications in bioimaging and related fields.

Conflict of interest

I.A.O.B., F.G.D., F.S.R., A.G.O., and E.N.S.J. are inventors on a pending patent related to the technology described in this work.

Data Availability Statement

The data that support the findings of this study are available in the supplementary material of this article.