First Fluorescent Photoinduced Electron Transfer (PET) Reagent for Hydroperoxides

Abstract

A novel fluorescent reagent for hydroperoxides, 4-(2-diphenylphosphinoethylamino)-7-nitro-2,1,3-benzoxadiazole (1), was developed on the basis of the method for designing photoinduced electron transfer (PET) reagents having a benzofurazan skeleton. Compound 1 was quantitatively reacted with hydroperoxides to give its fluorescent derivative, 2. In acetonitrile, the Phi value (0.44) of 2 was 31 times greater than that of 1. The long excitation (458 nm) and emission (520 nm) wavelengths of 2 are suitable for the determination of hydroperoxides, especially in biosamples. [structure: see text]

Recent progress in the development of derivatization reagents having a benzofurazan structure

“…After the reaction of the quenching group with target compounds such as peracid or hydroperoxide, intra-molecular dynamic quenching of these compounds did not occur, and the fluorescence was recovered. We synthesized NBDBz-p-NMe 2 (Uchiyama et al, 2000b) and EPB (Onoda et al, 2002b) for peracid, and NBD-DPP (Onoda et al, 2003) for hydroperoxide ( Table 2). We also synthesized compounds 1-3 in Table 2 (Onoda et al, 2005) for hydroperoxide.…”

Phosphines and Related Tervalent Phosphorus Systems

“…358 The reaction of 2-aminoethyldiphenylphosphine with a fluoronitrobenzoxadiazole yields phosphine (152), of interest as a new reagent for the detection of hydroperoxides, the resulting phosphine oxide fluorescing strongly. 359 N-acylation of phosphinoalkylamines, derived from valinol and proline, with picolinic and quinaldic acids has given a new series of N,P-ligands. 360 N-acylation and -alkylation of 2-(diphenylphosphino)methylpyrroline has been used to provide a series of unsymmetrical terdentate PNN ligands, e.g., (153).…”

Simple and Rapid Determination of Hydrogen Peroxide Using Phosphine-based Fluorescent Reagents with Sodium Tungstate Dihydrate

“…Phosphine-based fluorescent reagents have been reported to react with hydroperoxides at 50 -60˚C, 21,23,24 and the selectivity for hydrogen peroxide over hydroperoxides was low in the absence of sodium tungstate dihydrate. To investigate the selectivity of our method, the reaction was tested using hydroperoxides in place of hydrogen peroxide.…”

“…5 Furthermore, hydrogen peroxide is a major reactive oxygen species in living systems, and is related to many diseases. [6][7][8] Therefore, much effort has been expended to its detection, and several methods have so far been reported, including permanganate titration, spectrophotometry, 9,10 fluorometry, [11][12][13][14][15][16][17][18][19][20][21][22][23][24] and chemiluminescence; 25,26 the appropriate method is chosen depending on the particular situation.…”

“…Therefore, it would be interesting to develop a chemical approach: the use of stable artificial mimetic peroxidase as an alternative to HRP, [15][16][17] or the use of fluorescent reagents, which form fluorescent derivatives from non-fluorescent reagents after the reaction with hydrogen peroxide under non-enzymatic condition. [18][19][20][21][22] Among them, phosphine-based fluorescent reagents [21][22][23][24] that contain a phosphine moiety and whose fluorescence is enhanced after the oxidation could be one of the great tools. According to our previous study, the non-enzymatic detection of hydrogen peroxide has been achieved with such reagents, although there have been some problems: e.g., the reaction conditions necessary for derivatization are not suitable for routine measurements (at 50 -60˚C for >1 h), and the selectivity for hydrogen peroxide over hydroperoxides is low (data not reported).…”