Chemoselective Alteration of Fluorophore Scaffolds as a Strategy for the Development of Ratiometric Chemodosimeters. Issue 15 (20th March 2017)

• Record Type: Journal Article
• Authors: Zhou, Xinqi; Lesiak, Lauren; Lai, Rui; Beck, Jon R.; Zhao, Jia; Elowsky, Christian G.; Li, Hui; Stains, Cliff I.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 15(2017)
• Page Start: 4197
• Page End: 4200
• Publication Date: 2017-03-20
• Subjects: bioorthogonal reaction -- fluorescent probes -- reactive oxygen species -- sensors -- signal transduction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201612628
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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 H2 O2 sensors. Both these fluorophores display far‐red to near‐infrared excitation and emission prior to reaction. Upon oxidation by H2 O2 both 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. Abstract : Ratiometric sensors : A novel method for designing ratiometric sensors termed chemoselective alteration of fluorophore scaffolds (CAFS) is disclosed. Two proof‐of‐concept hydrogen peroxide sensors with large excitation and emission shifts (≥66 nm) were obtained by using this approach.