Coumarin-Based Thiol Chemosensor: Synthesis, Turn-On Mechanism, and Its Biological Application

Abstract

A new chemodosimetric probe (1) is reported that selectively detects thiols over other relevant biological species by the turning on of its fluorescence through a Michael type reaction. The fluorogenic process upon its reaction was revealed to be mediated by intramolecular charge transfer, as confirmed by time-dependent density functional theory calculations. The application of probe 1 to cells is also examined by confocal microscopy, and its cysteine preference was observed by an ex vivo LC-MS analysis of the cellular metabolite.

Fluorescent Dyes Used in Polymer Carriers as Imaging Agents in Anticancer Therapy

“…The sensitive fluorogenic probe which works preferentially with the cysteine (Cys) was obtained by condensation of coumarinaldehyde and diethyl malonate [126]. The coumarin-based chemodosimeter selectively recognizes thiols through the 1,4-addition reaction (Michael type) to the α,β-unsaturated carbonyl group in the conjugate of the coumarin analogues and formed thioeters.…”

Coumarin-Derived Fluorescent Chemosensors

“…Structure 92 has been judiciously designed and synthesized as a new type of selective benzenethiol fluorescent probe based on the thiolysis of dinitrophenyl ether (Lin et al, 2010a). Coumarin-based chemodosimeter 93 effectively and selectively recognizes thiols based on a Michael type reaction, showing a preference for Cys over other biological materials including Hcy and GSH (Jung et al, 2011a). Iminocoumarin-Cu(II) ensemble-based chemodosimeter 94 sensitively senses thiols followed by hydrolysis to give a marked fluorescence enhancement over other amino acids based on demetalization from Cu-complex (Jung et al, 2011b).…”

A new ensemble approach based chemosensor for the reversible detection of bio-thiols and its application in live cell imaging

“…In the last two decades, enormous efforts have been devoted to the development of fluorescent chemosensors for the detection of thiols based on various chemical mechanisms, such as Michael addition [16][17][18], cyclization with aldehyde [19][20][21], disulfide bond cleavage reaction [22,23], binding with nanoparticles [24,25], cleavage of sulfonamide and sulfonate ester [26][27][28][29][30]. Recently, chemosensing ensemble-based displacement approach has been reported as one of new mechanisms for the thiols detection [31][32][33][34][35][36][37][38][39][40].…”