Chemoselective Alteration of Fluorophore Scaffolds as a Strategy for the Development of Ratiometric Chemodosimeters.
Ratiometric sensors generally couple binding events or chemical reactions at a distal site to changes in the fluorescence of a core fluorophore scaffold. However, such approaches are often hindered by spectral overlap of the product and reactant species. We provide a strategy to design ratiometric sensors that display dramatic spectral shifts by leveraging the chemoselective reactivity of novel functional groups inserted within fluorophore scaffolds. As a proof-of-principle, fluorophores containing a borinate (RF620) or silanediol (SiOH2R) functionality at the bridging position of the xanthene ring system are developed as endogenous H2O2sensors. Both these fluorophores display far-red to near-infrared excitation and emission prior to reaction. Upon oxidation by H2O2both sensors are chemically converted to tetramethylrhodamine, producing significant (≥66 nm) blue-shifts in excitation and emission maxima. This work provides a new concept for the development of ratiometric probes.
Department of Chemistry, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.
Xinqi
X
Zhou
Department of Chemistry, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.
Lauren
L
Lesiak
Department of Chemistry, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.|Nebraska Center for Materials and Nanoscience, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.
Rui
R
Lai
Department of Chemistry, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.
Jon R
JR
Beck
Department of Chemistry, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.
Jia
J
Zhao
Department of Agronomy and Horticulture, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.
Christian G
CG
Elowsky
Department of Chemistry, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.|Nebraska Center for Materials and Nanoscience, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.
Hui
H
Li
Department of Chemistry, University of Nebraska - Lincoln, Lincoln, NE, 68588, USA.
Cliff I
CI
Stains
D001889:Borinic Acids / Q000737:chemistry; D005456:Fluorescent Dyes / Q000138:chemical synthesis* / Q000737:chemistry; D006367:HeLa Cells; D006801:Humans; D018613:Microscopy, Confocal; D008856:Microscopy, Fluorescence; D015394:Molecular Structure; D012235:Rhodamines / Q000138:chemical synthesis* / Q000737:chemistry; D012821:Silanes / Q000737:chemistry; D014966:Xanthenes / Q000737:chemistry
D001889:Borinic Acids; D005456:Fluorescent Dyes; D012235:Rhodamines; D012821:Silanes; D014966:Xanthenes; C475536:silanediol; C005358:tetramethylrhodamine
bioorthogonal reaction; fluorescent probes; reactive oxygen species; sensors; signal transduction