In Situ Synthesis of Phenoxazine Dyes in Water: Application for “Turn-On” Fluorogenic and Chromogenic Detection of Nitric Oxide**

Sébastien Jenni; Kévin Renault; Garance Dejouy; Sylvain Debieu; Myriam Laly; Anthony Romieu

doi:10.1002/cptc.202100268

In Situ Synthesis of Phenoxazine Dyes in Water: Application for “Turn-On” Fluorogenic and Chromogenic Detection of Nitric Oxide**

Sébastien Jenni, Kévin Renault, Garance Dejouy, Sylvain Debieu, Myriam Laly, Anthony Romieu

Research output: Contribution to journal › Article › peer-review

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Abstract

The synthesis of phenoxazine dyes was revisited in order to access these fluorescent N,O-heterocycles under mild conditions. The combined sequential use of nitrosonium tetrafluoroborate (NOBF₄) and triphenylphosphine enables the facile conversion of bis(3-dimethylaminophenyl) ether into the methyl analogue of popular laser dye oxazine 1. The ability of nitrosonium cation (NO⁺) to initiate the domino reaction resulting in π-conjugated phenoxazine molecules under neutral conditions, then led us to explore the feasibility of expanding it in aqueous media. Thus, we explored the use of reactive signaling molecule nitric oxide (NO) as a biological trigger of phenoxazine synthesis in water. The implementation of a robust analytical methodology based on fluorescence assays and HPLC-fluorescence/-MS analyses, have enabled us to demonstrate the viability of this novel fluorogenic reaction-based process to selectively yield an intense “OFF-ON” response in the near-infrared (NIR-I) spectral region. This study is an important step towards the popularization of the concept of “covalent assembly” in the fields of optical sensing, bioimaging and molecular theranostics.

Original language	English
Article number	e202100268
Journal	ChemPhotoChem
Volume	6
Issue number	5
DOIs	https://doi.org/10.1002/cptc.202100268
Publication status	Published - May 2022

Funding

This work is part of the project \u201CMULTIMOD\u201D, supported by the Conseil R\u00E9gional de Bourgogne Franche-Comt\u00E9 and the European Union through the PO FEDER-FSE Bourgogne 2014/2020 programs. Financial supports from the French \u201CInvestissements d\u2032Avenir\u201D program, project ISITE BFC (contract ANR-15-IDEX-0003), especially for the post-doc fellowship of Dr. S\u00E9bastien Jenni, and Agence Nationale de la Recherche (ANR, AAPG 2018, PRCI, LuminoManufacOligo, ANR-18-CE07-0045), especially for the post-doc fellowship of Dr. K\u00E9vin Renault are also greatly acknowledged. GDR CNRS \u201CAgents d\u2032Imagerie Mol\u00E9culaire\u201D (AIM) 2037 is also thanked for its interest in this research topic. The authors thank the \u201CPlateforme d\u2032Analyse Chimique et de Synth\u00E8se Mol\u00E9culaire de l\u2032Universit\u00E9 de Bourgogne\u201D (PACSMUB, http://www.wpcm.fr) for access to analytical and molecular spectroscopy instruments. COBRA lab (UMR CNRS 6014) and Iris Biotech company are warmly thanked for the generous gift of some chemical reagents used in this work. The authors also thank Dr. Jacques Pliquett (Ph. D. student, 2015\u20132018, UBFC, ICMUB, P2DA & OCS teams) for the synthesis of aza-BODIPY dye used as a standard for determination of fluorescence quantum yields, and Prof. Ewen Bodio (University of Burgundy, ICMUB, UMR CNRS 6302, OCS team) for access to SAFAS Flx-Xenius XC spectrofluorimeter. This work is part of the project \u201CMULTIMOD\u201D, supported by the Conseil R\u00E9gional de Bourgogne Franche\u2010Comt\u00E9 and the European Union through the PO FEDER\u2010FSE Bourgogne 2014/2020 programs. Financial supports from the French \u201CInvestissements d\u2032Avenir\u201D program, project ISITE BFC (contract ANR\u201015\u2010IDEX\u20100003), especially for the post\u2010doc fellowship of Dr.\u2005S\u00E9bastien Jenni, and Agence Nationale de la Recherche (ANR, AAPG 2018, PRCI, LuminoManufacOligo, ANR\u201018\u2010CE07\u20100045), especially for the post\u2010doc fellowship of Dr.\u2005K\u00E9vin Renault are also greatly acknowledged. GDR CNRS \u201CAgents d\u2032Imagerie Mol\u00E9culaire\u201D (AIM) 2037 is also thanked for its interest in this research topic. The authors thank the \u201CPlateforme d\u2032Analyse Chimique et de Synth\u00E8se Mol\u00E9culaire de l\u2032Universit\u00E9 de Bourgogne\u201D (PACSMUB, http://www.wpcm.fr ) for access to analytical and molecular spectroscopy instruments. COBRA lab (UMR CNRS 6014) and Iris Biotech company are warmly thanked for the generous gift of some chemical reagents used in this work. The authors also thank Dr.\u2005Jacques Pliquett (Ph.\u2005D. student, 2015\u20132018, UBFC, ICMUB, P2DA & OCS teams) for the synthesis of aza\u2010BODIPY dye used as a standard for determination of fluorescence quantum yields, and Prof. Ewen Bodio (University of Burgundy, ICMUB, UMR CNRS 6302, OCS team) for access to SAFAS Flx\u2010Xenius XC spectrofluorimeter.

Funders	Funder number
Université de Bourgogne
UBFC
Conseil régional de Bourgogne-Franche-Comté
European Commission
Agence Nationale de la Recherche	ANR‐18‐CE07‐0045, ANR-15-IDEX-0003
ICMUB	6302
Plateforme d′Analyse Chimique et de Synthèse Moléculaire de l′Université de Bourgogne	UMR CNRS 6014

Keywords

covalent assembly
domino reactions
fluorescent probes
nitric oxide
phenoxazine dyes

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10.1002/cptc.202100268

ChemPhotoChem - 2022 - Jenni - In Situ Synthesis of Phenoxazine Dyes in Water Application for Turn%E2%80%90On Fluorogenic andFinal published version, 4.36 MBLicence: CC BY-NC

Cite this

@article{2c4dff58d98f42139d96d58e4c3bbccd,

title = "In Situ Synthesis of Phenoxazine Dyes in Water: Application for “Turn-On” Fluorogenic and Chromogenic Detection of Nitric Oxide**",

abstract = "The synthesis of phenoxazine dyes was revisited in order to access these fluorescent N,O-heterocycles under mild conditions. The combined sequential use of nitrosonium tetrafluoroborate (NOBF4) and triphenylphosphine enables the facile conversion of bis(3-dimethylaminophenyl) ether into the methyl analogue of popular laser dye oxazine 1. The ability of nitrosonium cation (NO+) to initiate the domino reaction resulting in π-conjugated phenoxazine molecules under neutral conditions, then led us to explore the feasibility of expanding it in aqueous media. Thus, we explored the use of reactive signaling molecule nitric oxide (NO) as a biological trigger of phenoxazine synthesis in water. The implementation of a robust analytical methodology based on fluorescence assays and HPLC-fluorescence/-MS analyses, have enabled us to demonstrate the viability of this novel fluorogenic reaction-based process to selectively yield an intense “OFF-ON” response in the near-infrared (NIR-I) spectral region. This study is an important step towards the popularization of the concept of “covalent assembly” in the fields of optical sensing, bioimaging and molecular theranostics.",

keywords = "covalent assembly, domino reactions, fluorescent probes, nitric oxide, phenoxazine dyes",

author = "S{\'e}bastien Jenni and K{\'e}vin Renault and Garance Dejouy and Sylvain Debieu and Myriam Laly and Anthony Romieu",

note = "Funding Information: This work is part of the project “MULTIMOD”, supported by the Conseil R{\'e}gional de Bourgogne Franche‐Comt{\'e} and the European Union through the PO FEDER‐FSE Bourgogne 2014/2020 programs. Financial supports from the French “Investissements d′Avenir” program, project ISITE BFC (contract ANR‐15‐IDEX‐0003), especially for the post‐doc fellowship of Dr. S{\'e}bastien Jenni, and Agence Nationale de la Recherche (ANR, AAPG 2018, PRCI, LuminoManufacOligo, ANR‐18‐CE07‐0045), especially for the post‐doc fellowship of Dr. K{\'e}vin Renault are also greatly acknowledged. GDR CNRS “Agents d′Imagerie Mol{\'e}culaire” (AIM) 2037 is also thanked for its interest in this research topic. The authors thank the “Plateforme d′Analyse Chimique et de Synth{\`e}se Mol{\'e}culaire de l′Universit{\'e} de Bourgogne” (PACSMUB, http://www.wpcm.fr ) for access to analytical and molecular spectroscopy instruments. COBRA lab (UMR CNRS 6014) and Iris Biotech company are warmly thanked for the generous gift of some chemical reagents used in this work. The authors also thank Dr. Jacques Pliquett (Ph. D. student, 2015–2018, UBFC, ICMUB, P2DA \& OCS teams) for the synthesis of aza‐BODIPY dye used as a standard for determination of fluorescence quantum yields, and Prof. Ewen Bodio (University of Burgundy, ICMUB, UMR CNRS 6302, OCS team) for access to SAFAS Flx‐Xenius XC spectrofluorimeter. Funding Information: This work is part of the project “MULTIMOD”, supported by the Conseil R{\'e}gional de Bourgogne Franche-Comt{\'e} and the European Union through the PO FEDER-FSE Bourgogne 2014/2020 programs. Financial supports from the French “Investissements d′Avenir” program, project ISITE BFC (contract ANR-15-IDEX-0003), especially for the post-doc fellowship of Dr. S{\'e}bastien Jenni, and Agence Nationale de la Recherche (ANR, AAPG 2018, PRCI, LuminoManufacOligo, ANR-18-CE07-0045), especially for the post-doc fellowship of Dr. K{\'e}vin Renault are also greatly acknowledged. GDR CNRS “Agents d′Imagerie Mol{\'e}culaire” (AIM) 2037 is also thanked for its interest in this research topic. The authors thank the “Plateforme d′Analyse Chimique et de Synth{\`e}se Mol{\'e}culaire de l′Universit{\'e} de Bourgogne” (PACSMUB, http://www.wpcm.fr) for access to analytical and molecular spectroscopy instruments. COBRA lab (UMR CNRS 6014) and Iris Biotech company are warmly thanked for the generous gift of some chemical reagents used in this work. The authors also thank Dr. Jacques Pliquett (Ph. D. student, 2015–2018, UBFC, ICMUB, P2DA \& OCS teams) for the synthesis of aza-BODIPY dye used as a standard for determination of fluorescence quantum yields, and Prof. Ewen Bodio (University of Burgundy, ICMUB, UMR CNRS 6302, OCS team) for access to SAFAS Flx-Xenius XC spectrofluorimeter. Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

month = may,

doi = "10.1002/cptc.202100268",

language = "English",

volume = "6",

journal = "ChemPhotoChem",

issn = "2367-0932",

publisher = "Wiley-VCH",

number = "5",

}

TY - JOUR

T1 - In Situ Synthesis of Phenoxazine Dyes in Water

T2 - Application for “Turn-On” Fluorogenic and Chromogenic Detection of Nitric Oxide**

AU - Jenni, Sébastien

AU - Renault, Kévin

AU - Dejouy, Garance

AU - Debieu, Sylvain

AU - Laly, Myriam

AU - Romieu, Anthony

N1 - Funding Information: This work is part of the project “MULTIMOD”, supported by the Conseil Régional de Bourgogne Franche‐Comté and the European Union through the PO FEDER‐FSE Bourgogne 2014/2020 programs. Financial supports from the French “Investissements d′Avenir” program, project ISITE BFC (contract ANR‐15‐IDEX‐0003), especially for the post‐doc fellowship of Dr. Sébastien Jenni, and Agence Nationale de la Recherche (ANR, AAPG 2018, PRCI, LuminoManufacOligo, ANR‐18‐CE07‐0045), especially for the post‐doc fellowship of Dr. Kévin Renault are also greatly acknowledged. GDR CNRS “Agents d′Imagerie Moléculaire” (AIM) 2037 is also thanked for its interest in this research topic. The authors thank the “Plateforme d′Analyse Chimique et de Synthèse Moléculaire de l′Université de Bourgogne” (PACSMUB, http://www.wpcm.fr ) for access to analytical and molecular spectroscopy instruments. COBRA lab (UMR CNRS 6014) and Iris Biotech company are warmly thanked for the generous gift of some chemical reagents used in this work. The authors also thank Dr. Jacques Pliquett (Ph. D. student, 2015–2018, UBFC, ICMUB, P2DA & OCS teams) for the synthesis of aza‐BODIPY dye used as a standard for determination of fluorescence quantum yields, and Prof. Ewen Bodio (University of Burgundy, ICMUB, UMR CNRS 6302, OCS team) for access to SAFAS Flx‐Xenius XC spectrofluorimeter. Funding Information: This work is part of the project “MULTIMOD”, supported by the Conseil Régional de Bourgogne Franche-Comté and the European Union through the PO FEDER-FSE Bourgogne 2014/2020 programs. Financial supports from the French “Investissements d′Avenir” program, project ISITE BFC (contract ANR-15-IDEX-0003), especially for the post-doc fellowship of Dr. Sébastien Jenni, and Agence Nationale de la Recherche (ANR, AAPG 2018, PRCI, LuminoManufacOligo, ANR-18-CE07-0045), especially for the post-doc fellowship of Dr. Kévin Renault are also greatly acknowledged. GDR CNRS “Agents d′Imagerie Moléculaire” (AIM) 2037 is also thanked for its interest in this research topic. The authors thank the “Plateforme d′Analyse Chimique et de Synthèse Moléculaire de l′Université de Bourgogne” (PACSMUB, http://www.wpcm.fr) for access to analytical and molecular spectroscopy instruments. COBRA lab (UMR CNRS 6014) and Iris Biotech company are warmly thanked for the generous gift of some chemical reagents used in this work. The authors also thank Dr. Jacques Pliquett (Ph. D. student, 2015–2018, UBFC, ICMUB, P2DA & OCS teams) for the synthesis of aza-BODIPY dye used as a standard for determination of fluorescence quantum yields, and Prof. Ewen Bodio (University of Burgundy, ICMUB, UMR CNRS 6302, OCS team) for access to SAFAS Flx-Xenius XC spectrofluorimeter. Publisher Copyright: © 2022 Wiley-VCH GmbH.

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Y1 - 2022/5

N2 - The synthesis of phenoxazine dyes was revisited in order to access these fluorescent N,O-heterocycles under mild conditions. The combined sequential use of nitrosonium tetrafluoroborate (NOBF4) and triphenylphosphine enables the facile conversion of bis(3-dimethylaminophenyl) ether into the methyl analogue of popular laser dye oxazine 1. The ability of nitrosonium cation (NO+) to initiate the domino reaction resulting in π-conjugated phenoxazine molecules under neutral conditions, then led us to explore the feasibility of expanding it in aqueous media. Thus, we explored the use of reactive signaling molecule nitric oxide (NO) as a biological trigger of phenoxazine synthesis in water. The implementation of a robust analytical methodology based on fluorescence assays and HPLC-fluorescence/-MS analyses, have enabled us to demonstrate the viability of this novel fluorogenic reaction-based process to selectively yield an intense “OFF-ON” response in the near-infrared (NIR-I) spectral region. This study is an important step towards the popularization of the concept of “covalent assembly” in the fields of optical sensing, bioimaging and molecular theranostics.

AB - The synthesis of phenoxazine dyes was revisited in order to access these fluorescent N,O-heterocycles under mild conditions. The combined sequential use of nitrosonium tetrafluoroborate (NOBF4) and triphenylphosphine enables the facile conversion of bis(3-dimethylaminophenyl) ether into the methyl analogue of popular laser dye oxazine 1. The ability of nitrosonium cation (NO+) to initiate the domino reaction resulting in π-conjugated phenoxazine molecules under neutral conditions, then led us to explore the feasibility of expanding it in aqueous media. Thus, we explored the use of reactive signaling molecule nitric oxide (NO) as a biological trigger of phenoxazine synthesis in water. The implementation of a robust analytical methodology based on fluorescence assays and HPLC-fluorescence/-MS analyses, have enabled us to demonstrate the viability of this novel fluorogenic reaction-based process to selectively yield an intense “OFF-ON” response in the near-infrared (NIR-I) spectral region. This study is an important step towards the popularization of the concept of “covalent assembly” in the fields of optical sensing, bioimaging and molecular theranostics.

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KW - fluorescent probes

KW - nitric oxide

KW - phenoxazine dyes

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DO - 10.1002/cptc.202100268

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JO - ChemPhotoChem

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ER -

In Situ Synthesis of Phenoxazine Dyes in Water: Application for “Turn-On” Fluorogenic and Chromogenic Detection of Nitric Oxide**

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