Chalcogen-based ratiometric reversible BODIPY redox sensors for the determination of enantioselective methionine sulfoxide reductase activity

Abstract

A series of sulfur- and selenium-substituted BODIPY derivatives are introduced as reversible ratiometric turn-on/off redox sensors for ROS and enzymatic redox processes.

XPS and quantum chemical analysis of 4Me-BODIPY derivatives

“…2 Due to the ease of structural modification based on BODIPY derivatives, it is possible to obtain luminophores that absorb and emit in almost the entire spectral range. 3 Such a set of practically significant physicochemical properties allows the use of dyes in this class in various fields, including molecular sensorics, 4,5 medical diagnostics, [6][7][8] biochemistry, [9][10][11][12] etc.…”

On the mechanism of visible‐light sensitized photosulfoxidation of toluidine blue O

“…9 Figure 1C shows an example of a sulfur-substitued BODIPY derivative that cycles reversibly as a redox sensor between the sulfide and sulfoxide forms. 10 How TBO self-sensitized photooxidation leads to not only demethylation but also sulfoxidation paths, remains to be clarified. In the present work, we consider TBO in the self-sensitized photooxidative formation of TBO sulfoxide.…”

“…(C) Literature example of a BODIPY redox sensor that cycles between the corresponding sulfide with reactive oxygen species and the sulfoxide in a reversible enzymatic process (see ref. 10), bearing rough similarity to the formation of TBO sulfoxide.…”

“…For example, a dimeric BODIPY sulfoxide was reported to undergo an SO extrusion process 9 . Figure 1C shows an example of a sulfur‐substitued BODIPY derivative that cycles reversibly as a redox sensor between the sulfide and sulfoxide forms 10 …”

Sulfonothioated meso-Methyl BODIPY Shows Enhanced Uncaging Efficiency and Releases H2Sn

“…Compound 1 has absorption and emission maxima at 516 and 530 nm (with a Stokes shift Δ v ̃ of 512 cm –1 ), respectively, and a fluorescence quantum yield Φ f of 0.014. This unusually low fluorescence quantum yield is a consequence of (i) efficient photorelease and (ii) quenching of the excited BODIPY core by charge transfer from the electron-rich sulfur moiety . Irradiating 1 with green light (λ irr = 525 nm), both in solution and adsorbed on a silica plate soaked with its methanolic solution, yielded highly emissive photoproducts (Figure a,b).…”