Near-Infrared Coumarin-Hemicyanine Hybrid Dyes Bearing an Intramolecular Nucleophile for Activatable Fluorescence and Raman Imaging
Coumarin-hemicyanine (CHC) hybrid fluorophores bearing an intramolecular nucleophile have been reported as ratiometric fluorescent probes based on the equilibrium between the π-conjugated open and cyclic closed forms. Here, we report red-shifted CHC derivatives that can serve as scaffold dyes of activated fluorescent probes and activated Raman probes. We prepared a series of cyano-substituted CHC derivatives and found that substitution at C-4 of the coumarin moiety is effective in extending the absorption wavelength. The near-infrared (NIR) emission of these 4CN-CHC derivatives exhibits high tissue penetration. Dual-color imaging with 4CN-CHC enabled ratiometric monitoring of the lysosomal pH changes. Furthermore, the coherent anti-Stokes Raman scattering (CARS) signals of 4CN-CHC derivatives could be regulated by modifying the open/closed equilibrium, and the different patterns of CARS spectra enabled us to perform multicomponent imaging. Thus, these 4CN-CHC derivatives expand the repertoire of functional probes for NIR and multiplexed vibrational imaging.
Authors
- Hiroyoshi Fujioka (ORCID: https://orcid.org/0000-0003-1904-0566)
- Satoshi Matsumoto (ORCID: https://orcid.org/0000-0003-4836-7170)
- Hideaki Kano (ORCID: https://orcid.org/0000-0003-3682-7627)
- Yasuteru Urano (ORCID: https://orcid.org/0000-0002-1220-6327)
- Minoru Kawatani (ORCID: https://orcid.org/0000-0002-0192-4366)
- K. Hiramatsu (ORCID: https://orcid.org/0000-0003-0767-019X)
- Minori Masaki (ORCID: https://orcid.org/0000-0002-0804-7220)
- Ryosuke Kojima (ORCID: https://orcid.org/0000-0002-3792-9222)
- Mako Kamiya (ORCID: https://orcid.org/0000-0002-5592-1849)
- Yoshio Murakami
- Ryo Sakamoto (ORCID: https://orcid.org/0000-0003-1382-8803)
Institutions
- Tokyo Institute of Technology (JP)
- Kyushu University (JP)
- University of Tsukuba (JP)
- Keio University (JP)
- Kirinyaga University (KE)
- Shanghai Institute for Science of Science (CN)
- Integrated Oncology (United States) (US)
- National Institute of Integrative Medicine (AU)
- Life Science Institute (JP)
- Institute of Science Tokyo (JP)
- The University of Tokyo (JP)
- Graduate School USA (US)
- Kumamoto University (JP)
- Tsukuba International University (JP)
Publication Details
- Journal
- Analytical Chemistry
- Published
- 2025-08-11
- DOI
- https://doi.org/10.1021/acs.analchem.5c02714
- Citations
- 1
- Primary Topic
- Spectroscopy Techniques in Biomedical and Chemical Research
- Type
- article
- Field-Weighted Citation Impact
- 1.63
Funders
- Konica Minolta Imaging Science Foundation
- Keio University
- Secom Science and Technology Foundation
- Mochida Memorial Foundation for Medical and Pharmaceutical Research
- Daiichi Sankyo Foundation of Life Science
- Astellas Foundation for Research on Metabolic Disorders
- Research Foundation for Opto-Science and Technology
- Japan Society for the Promotion of Science
- Core Research for Evolutional Science and Technology
- JST-Mirai Program
- ACT-X
- Moonshot Research and Development Program
- Fusion Oriented REsearch for disruptive Science and Technology