A Phenylselenium-Substituted BODIPY Fluorescent Turn-off Probe for Fluorescence Imaging of Hydrogen Sulfide in Living Cells

Abstract

Herein a phenylselenium-substituted BODIPY (1) fluorescent turn-off sensor was developed for the purpose to achieve excellent selectivity and sensitivity for HS detection based on the substitution reaction of the phenylselenide group at the 3-position with HS. The excess addition of hydrogen sulfide promoted further substitution of the phenylselenide group at the 5-position of the probe and was accompanied by a further decrease in fluorescence emission intensity. Sensor 1 demonstrated remarkable performance with 49-fold red color fluorescence intensity decrease at longer excitation wavelength, a low detection limit (0.0025 μM), and specific fluorescent response toward HS over anions, biothiols, and other amino acids in neutral media. It showed no obvious cell toxicity and good membrane permeability, which was well exploited for intracellular HS detection and imaging through fluorescence microscopy imaging.

BODIPY‐Based Fluorescent Probes for Biothiols

“…In addition, Qin and Guo et al developed ap henylseleniumsubstituted BODIPY fluorescent turn-off probe 11 for H 2 Sd etection based on the thiolysis reactiono ft he phenylselenide with H 2 S( Scheme 1). [45] As two phenylselenoether moieties are present in the probe, thiolysis of one or two phenylselenide groups could be achieved depending on the amounto fH 2 S treated. The replacement of phenylselenoether with am ercap-to group resulted in ad eclinei nt he fluorescence emission.…”

A Benzooxazole‐Based Probe for the Sensitive Detection of Hydrogen Sulfide: Kinetic and Transition‐State Studies and In Vitro Application in HepG2 Cells

“…In our present work, we have designed an easily synthesizable benzooxazole conjugated fluorescent H 2 S probe ( Scheme ) where thiolysis of dinitrophenyl ether followed by inhibiting photo induced electron transfer (d‐PET) process leads to the enhancement of fluorescence intensity. Moreover, the pH dependent kinetic studies confirm the involvement of both H 2 S and its deprotonated form, HS – , during the reaction time as the weak acid H 2 S generally equilibrates with HS – in aqueous medium . The pKa 1 of H 2 S is nearly 7.04, while pKa 2 is likely to be∼ 19, which indicates the presence of H 2 S in the form of H 2 S and bisulfide (HS – ), with an insignificant amount of sulfide anion (S 2– ) under physiological conditions .…”

“…In recent times, numerous fluorescent probes have been developed for highly specific and sensitive in‐vivo imaging and in‐vitro detection of H 2 S in biological systems . These probes are normally designed on the basis of H 2 S‐persuaded highly specific reactions, like (i) reduction of azide and nitroso groups to amine,, (ii) thiolysis of dinitrophenyl ether or other leaving groups,, (iii) metal sulfide precipitation,, (iv) nucleophilic 1,4‐addition i. e., Michael‐type addition,, (v) a coordinative‐based approach, and (vi) cleavage of an S–O bond,, which are moderately slow and irreversible …”

Fluorescent probes based on nucleophilic aromatic substitution reactions for reactive sulfur and selenium species: Recent progress, applications, and design strategies

“…Most fluorescent probes based on S N Ar reactions for RSS and RSeS can achieve the “off–on” effect after reaction with the analyte [7] , [8] . Benzenesulfonate [80] , [81] , [82] , [83] , [84] , [85] , [86] , [87] , [88] , phenyl-O ether [89] , [90] , [91] , [92] , [93] , [94] , [95] , [96] , [97] , [98] , phenyl-S ether [99] , [100] , [101] , [102] , phenyl-Se ether [103] , [104] , 7-nitro-2,1,3-benzoxadiazole (NBD) [105] , [106] , [107] , [108] , [109] , [110] , [111] , benzoate, and selenium-nitrogen bonds are all good detection groups [21] , [22] (see Table1 ).…”