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General Design Strategy to Precisely Control the Emission of Fluorophores via a Twisted Intramolecular Charge Transfer (TICT) Process

  • Kenjiro Hanaoka*
    Kenjiro Hanaoka
    Graduate School of Pharmaceutical Sciences, Keio University, 1-5-30 Shibakoen, Minoto-ku, Tokyo105-8512, Japan
    *Email: [email protected]. Tel: +81-3-5400-2684.
    More by Kenjiro Hanaoka
    Orcidhttps://orcid.org/0000-0003-0797-4038
  • , 
  • Shimpei Iwaki
    Shimpei Iwaki
    Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo113-0033, Japan
    More by Shimpei Iwaki
  • , 
  • Kiyoshi Yagi
    Kiyoshi Yagi
    Theoretical Molecular Science Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama351-0198, Japan
    More by Kiyoshi Yagi
    Orcidhttps://orcid.org/0000-0003-1120-9355
  • , 
  • Takuya Myochin
    Takuya Myochin
    Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo113-0033, Japan
    More by Takuya Myochin
  • , 
  • Takayuki Ikeno
    Takayuki Ikeno
    Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo113-0033, Japan
    More by Takayuki Ikeno
  • , 
  • Hisashi Ohno
    Hisashi Ohno
    Graduate School of Pharmaceutical Sciences, Keio University, 1-5-30 Shibakoen, Minoto-ku, Tokyo105-8512, Japan
    More by Hisashi Ohno
  • , 
  • Eita Sasaki
    Eita Sasaki
    Graduate School of Pharmaceutical Sciences, Keio University, 1-5-30 Shibakoen, Minoto-ku, Tokyo105-8512, Japan
    More by Eita Sasaki
  • , 
  • Toru Komatsu
    Toru Komatsu
    Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo113-0033, Japan
    More by Toru Komatsu
    Orcidhttps://orcid.org/0000-0002-9268-6964
  • , 
  • Tasuku Ueno
    Tasuku Ueno
    Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo113-0033, Japan
    More by Tasuku Ueno
    Orcidhttps://orcid.org/0000-0001-6657-8209
  • , 
  • Motokazu Uchigashima
    Motokazu Uchigashima
    Department of Cellular Neuropathology, Brain Research Institute, Niigata University, Niigata951-8585, Japan
    More by Motokazu Uchigashima
  • , 
  • Takayasu Mikuni
    Takayasu Mikuni
    Department of Cellular Neuropathology, Brain Research Institute, Niigata University, Niigata951-8585, Japan
    More by Takayasu Mikuni
  • , 
  • Kazuki Tainaka
    Kazuki Tainaka
    Department of System Pathology for Neurological Disorders, Brain Research Institute, Niigata University, Niigata951-8585, Japan
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  • , 
  • Shinya Tahara
    Shinya Tahara
    Molecular Spectroscopy Laboratory, RIKEN  and  Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1 Hirosawa, Wako-shi, Saitama351-0198, Japan
    More by Shinya Tahara
    Orcidhttps://orcid.org/0000-0003-3979-3135
  • , 
  • Satoshi Takeuchi
    Satoshi Takeuchi
    Molecular Spectroscopy Laboratory, RIKEN  and  Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1 Hirosawa, Wako-shi, Saitama351-0198, Japan
    More by Satoshi Takeuchi
    Orcidhttps://orcid.org/0000-0003-2256-8628
  • , 
  • Tahei Tahara
    Tahei Tahara
    Molecular Spectroscopy Laboratory, RIKEN  and  Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1 Hirosawa, Wako-shi, Saitama351-0198, Japan
    More by Tahei Tahara
    Orcidhttps://orcid.org/0000-0002-6340-8535
  • , 
  • Masanobu Uchiyama
    Masanobu Uchiyama
    Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo113-0033, Japan
    More by Masanobu Uchiyama
    Orcidhttps://orcid.org/0000-0001-6385-5944
  • , 
  • Tetsuo Nagano
    Tetsuo Nagano
    Drug Discovery Initiative, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo113-0033, Japan
    More by Tetsuo Nagano
  • , and 
  • Yasuteru Urano*
    Yasuteru Urano
    Graduate School of Pharmaceutical Sciences  and  Graduate School of Medicine, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo113-0033, Japan
    *Email: [email protected]. Tel: +81-3-5841-4850.
    More by Yasuteru Urano
    Orcidhttps://orcid.org/0000-0002-1220-6327
Cite this: J. Am. Chem. Soc. 2022, 144, 43, 19778–19790
Publication Date (Web):October 3, 2022
https://doi.org/10.1021/jacs.2c06397
Copyright © 2022 American Chemical Society
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    Abstract

    Abstract Image

    Fluorogenic probes for bioimaging have become essential tools for life science and medicine, and the key to their development is a precise understanding of the mechanisms available for fluorescence off/on control, such as photoinduced electron transfer (PeT) and Förster resonance energy transfer (FRET). Here we establish a new molecular design strategy to rationally develop activatable fluorescent probes, which exhibit a fluorescence off/on change in response to target biomolecules, by controlling the twisted intramolecular charge transfer (TICT) process. This approach was developed on the basis of a thorough investigation of the fluorescence quenching mechanism of N-phenyl rhodamine dyes (commercially available as the QSY series) by means of time-dependent density functional theory (TD-DFT) calculations and photophysical evaluation of their derivatives. To illustrate and validate this TICT-based design strategy, we employed it to develop practical fluorogenic probes for HaloTag and SNAP-tag. We further show that the TICT-controlled fluorescence off/on mechanism is generalizable by synthesizing a Si–rhodamine-based fluorogenic probe for HaloTag, thus providing a palette of chemical dyes that spans the visible and near-infrared range.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c06397.

    • Additional experimental details, materials, methods, and synthetic methods of compounds including NMR spectra for compounds (PDF)

    • Text files of the DFT-calculated Cartesian coordinates (ZIP)

    • Molecular orbital corresponding to the HOMO gradually became localized to the aniline-like structure (Only the chemical structure is shown) (MP4)

    • Molecular orbital corresponding to the HOMO gradually became localized to the aniline-like structure (MP4)

    • Rotation of dihedral angle φ was suppressed around 140° in HaloTag protein (MP4)

    • Dihedral angle φ rapidly relaxed within 1 ps after photo excitation in water (MP4)

    • Fluorescence confocal imaging of HaloTag-expressing cells utilizing Halo rhodamine-4 (AVI)

    • Fluorescence confocal imaging of SNAP-tag-expressing cells utilizing SNAP rhodamine-3 (AVI)

    • Magnified views of the 3D fluorescence image of the whole brain (MP4)

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    This article is cited by 17 publications.

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