Stable, Bright, and Long-Fluorescence-Lifetime Dyes for Deep-Near-Infrared Bioimaging.

Autor: Li J; State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; Shanghai Key Laboratory of Chemical Biology, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China., Dong Y; State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; Shanghai Key Laboratory of Chemical Biology, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China., Wei R; State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; Shanghai Key Laboratory of Chemical Biology, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China., Jiang G; State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China., Yao C; State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; Shanghai Key Laboratory of Chemical Biology, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China., Lv M; State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China., Wu Y; Molecular Imaging Center, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zuchongzhi Road, Shanghai, 201203, China., Gardner SH; Department of Chemistry and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, 600 S. Mathews Ave., Urbana, Illinois 61801, United States., Zhang F; Shanghai Frontiers Science Center for Chinese Medicine Chemical Biology, Institute of Interdisciplinary Integrative Medicine Research, Shanghai University of Traditional Chinese Medicine, 1200 Cailun Road, Shanghai, 201203, China., Lucero MY; Department of Chemistry and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, 600 S. Mathews Ave., Urbana, Illinois 61801, United States., Huang J; Pharmacology and Toxicology Division, Shanghai Institute of Food and Drug Control, 1111 Halei Road, Shanghai, 201203, China., Chen H; Molecular Imaging Center, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zuchongzhi Road, Shanghai, 201203, China., Ge G; Shanghai Frontiers Science Center for Chinese Medicine Chemical Biology, Institute of Interdisciplinary Integrative Medicine Research, Shanghai University of Traditional Chinese Medicine, 1200 Cailun Road, Shanghai, 201203, China., Chan J; Department of Chemistry and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, 600 S. Mathews Ave., Urbana, Illinois 61801, United States., Chen J; State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China., Sun H; State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China., Luo X; State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; Shanghai Key Laboratory of Chemical Biology, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, China., Qian X; State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; Shanghai Key Laboratory of Chemical Biology, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, China., Yang Y; State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.; Shanghai Key Laboratory of Chemical Biology, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2022 Aug 10; Vol. 144 (31), pp. 14351-14362. Date of Electronic Publication: 2022 Jul 29.
DOI: 10.1021/jacs.2c05826
Abstrakt: Near-infrared (NIR) fluorophores absorbing maximally in the region beyond 800 nm, i.e., deep-NIR spectral region, are actively sought for biomedical applications. Ideal dyes are bright, nontoxic, photostable, biocompatible, and easily derivatized to introduce functionalities (e.g., for bioconjugation or aqueous solubility). The rational design of such fluorophores remains a major challenge. Silicon-substituted rhodamines have been successful for bioimaging applications in the red spectral region. The longer-wavelength silicon-substituted congeners for the deep-NIR spectral region are unknown to date. We successfully prepared four silicon-substituted bis-benzannulated rhodamine dyes ( ESi5a-ESi5d ), with an efficient five-step cascade on a gram-scale. Because of the extensive overlapping of their HOMO-LUMO orbitals, ESi5a-ESi5d are highly absorbing (λ abs ≈ 865 nm and ε > 10 5 cm -1 M -1 ). By restraining both the rotational freedom via annulation and the vibrational freedom via silicon-imparted strain, the fluorochromic scaffold of ESi5 is highly rigid, resulting in an unusually long fluorescence lifetime (τ > 700 ps in CH 2 Cl 2 ) and a high fluorescence quantum yield (ϕ = 0.14 in CH 2 Cl 2 ). Their half-lives toward photobleaching are 2 orders of magnitude longer than the current standard (ICG in serum). They are stable in the presence of biorelevant concentration of nucleophiles or reactive oxygen species. They are minimally toxic and readily metabolized. Upon tail vein injection of ESi5a (as an example), the vasculature of a nude mouse was imaged with a high signal-to-background ratio. ESi5 dyes have broad potentials for bioimaging in the deep-NIR spectral region.
Databáze: MEDLINE
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