Synthesis and evaluation of aryl oxalates as peroxyoxalate chemiluminescence reagents

Abstract

Eight aryl oxalates having an alkyoxy moiety were synthesised to improve the solubility in acetonitrile for the peroxyoxa I ate chem i I u m i nescence reaction system. Of these, bis [ 2-(3,6-d ioxa heptyloxyca rbo nyl)-4-fluorophenyl] oxalate showed the highest solubility (1685 mM). To evaluate these esters together with some known aryl oxalates as chemiluminescence reagents, a simple and rapid method using a flow injection system was developed. The chemiluminescence reaction system consisted of an oxalate, hydrogen peroxide, triethylamine and 9,lO-diphenylanthracene in acetonitrile. Of the oxalates synthesised, bis[2-(3,6-dioxaheptyloxycarbonyl)-4-bromophenyl] oxalate gave the highest intensity, which was about 100 times lower than that of bis(2,4-dinitrophenyI) oxalate. However, the chemiluminescence intensities of the oxalates synthesised continued for a far longer period of time than those of commercially available oxalates. Keywords : A r yl oxa la te; pe rox yoxa la te ch em ilu m in escen ce reaction; flow injection; b is[2-(3,6-d ioxa h ep t yloxycarbon yl)-4-fluorophen yl] oxalate Paper 9102035G

Flow‐chemiluminescence: a growing modality of pharmaceutical analysis

“…Tests have shown that alternative oxalates may be more suitable in special cases. [55][56][57] The chemiluminescent reaction of peroxyoxalate with TCPO has been studied in the presence of various catalysts, consisting of substituted imidazoles. 15 Some metal cations [particularly Cu(II)], enhance the chemiluminescence intensity produced by peroxyoxalates.…”

A Comprehensive Outlook of Synthetic Strategies and Applications of Redox‐Responsive Nanogels in Drug Delivery

“…ROS is an important indicator and a major characteristic of several pathological conditions, including cancer, where elevated intracellular levels have been reported in disease conditions . ROS‐responsive drug delivery carriers currently being developed mostly involve organochalcogens (selenium, tellurium, diselenium, and ditellurium), organoboron compounds (aryl boronic ester), sulfur containing compounds (thioether, thioketal, vinyl dithioether), aryl oxalates, and ferrocenes, either as cross‐linkers or as important constituents of polymeric backbone. Although very few studies have been reported for ROS‐responsive nanogels, it would be worthwhile to review some of the important reported results, due to the potential applicability of the ROS‐responsive units in the development of advanced redox‐responsive nanogel‐based systems in the near future.…”

Rational design and preliminary analytical evaluation of two novel oxamide reagents for aqueous peroxyoxalate chemiluminescence

“…On the basis of earlier work, there would appear to be at least two characteristics that are of significance in the design of useful reagent molecules for peroxyoxalate chemiluminescence. [4][5][6][7][9][10][11] The first criterion is that the substituents surrounding the central oxalate moiety must exhibit a significant degree of electron-withdrawing character. This results in an acyl carbon that is sufficiently activated towards nucleophilic attack by the hydroperoxide anion, which in the presence of further base leads to the generation of reactive intermediates which transfer the excitation energy to a fluorophore compound [12][13][14] (see Scheme 1).…”