Enabling In Vivo Photocatalytic Activation of Rapid Bioorthogonal Chemistry by Repurposing Silicon-Rhodamine Fluorophores as Cytocompatible Far-Red Photocatalysts.

Autor:	Wang C; Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States., Zhang H; Department of Materials Science and Engineering, University of Delaware, Newark, Delaware 19716, United States., Zhang T; Department of Radiology and Biomedical Research Imaging Center, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Zou X; Department of Materials Science and Engineering, University of Delaware, Newark, Delaware 19716, United States., Wang H; Department of Radiology and Biomedical Research Imaging Center, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Rosenberger JE; Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States., Vannam R; Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States., Trout WS; Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States., Grimm JB; Janelia Research Campus, Howard Hughes Medical Institute, Ashburn, Virginia 20147, United States., Lavis LD; Janelia Research Campus, Howard Hughes Medical Institute, Ashburn, Virginia 20147, United States., Thorpe C; Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States., Jia X; Department of Materials Science and Engineering, University of Delaware, Newark, Delaware 19716, United States.; Delaware Biotechnology Institute, Newark, Delaware 19711, United States., Li Z; Department of Radiology and Biomedical Research Imaging Center, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States., Fox JM; Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.; Department of Materials Science and Engineering, University of Delaware, Newark, Delaware 19716, United States.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2021 Jul 21; Vol. 143 (28), pp. 10793-10803. Date of Electronic Publication: 2021 Jul 12.
DOI:	10.1021/jacs.1c05547
Abstrakt:	Chromophores that absorb in the tissue-penetrant far-red/near-infrared window have long served as photocatalysts to generate singlet oxygen for photodynamic therapy. However, the cytotoxicity and side reactions associated with singlet oxygen sensitization have posed a problem for using long-wavelength photocatalysis to initiate other types of chemical reactions in biological environments. Herein, silicon-Rhodamine compounds (SiRs) are described as photocatalysts for inducing rapid bioorthogonal chemistry using 660 nm light through the oxidation of a dihydrotetrazine to a tetrazine in the presence of trans- cyclooctene dienophiles. SiRs have been commonly used as fluorophores for bioimaging but have not been applied to catalyze chemical reactions. A series of SiR derivatives were evaluated, and the Janelia Fluor-SiR dyes were found to be especially effective in catalyzing photooxidation (typically 3%). A dihydrotetrazine/tetrazine pair is described that displays high stability in both oxidation states. A protein that was site-selectively modified by trans- cyclooctene was quantitatively conjugated upon exposure to 660 nm light and a dihydrotetrazine. By contrast, a previously described methylene blue catalyst was found to rapidly degrade the protein. SiR-red light photocatalysis was used to cross-link hyaluronic acid derivatives functionalized by dihydrotetrazine and trans- cyclooctenes, enabling 3D culture of human prostate cancer cells. Photoinducible hydrogel formation could also be carried out in live mice through subcutaneous injection of a Cy7-labeled hydrogel precursor solution, followed by brief irradiation to produce a stable hydrogel. This cytocompatible method for using red light photocatalysis to activate bioorthogonal chemistry is anticipated to find broad applications where spatiotemporal control is needed in biological environments.
Databáze:	MEDLINE
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