title: A fluorogenic reagent, 4-mercapto-7-methylthio-2,1,3-benzoxadiazole for carboxylic acids, designed by prediction of the fluorescence intensity.
abstract: During the course of our studies of the development of fluorogenic reagents having a 4,7-disubstituted benzofurazan structure, we previously proposed 7-acetylamino-4-mercapto-2,1,3-benzoxadiazole (AABD-SH) as a fluorogenic reagent for carboxylic acids. Since then, progress has made it possible to estimate the fluorescence quantum yields of the 4,7-disubstituted benzofurazan compounds on the basis of the PM3 calculation of their S1-T2 energies. Subsequently, a new fluorogenic reagent, 4-mercapto-7-methylthio-2,1,3-benzoxadiazole (MTBDSH) was designed and synthesized. In the presence of condensation reagents, triphenylphosphine (TPP) and 2,2'-dipyridyl disulfide (DPDS), MTBD-SH readily reacted with n-caprylic acid within 1 min at room temperature. The derivatives of five carboxylic acids (n-caprylic acid, n-capric acid, lauric acid, myristic acid, and palmitic acid) were well-separated on a reversed-phase column and were fluorimetrically detected at 519 nm with excitation at 391 nm. The detection limits (S/N = 3) were 2.4-5.0 fmol. Thus, MTBD-SH had properties that were considered to be superior. For carboxylic acids, itwas superior not only to AABD-SH, but also to many other conventional reagents. The superiority was examined in terms of its reactivity and sensitivity and the avoidance of interfering peaks that were derived from the reagent itself or degradation products in the chromatogram.
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, Japan.
authors.forename: S
authors.initials: S
authors.lastname: Uchiyama
authors.forename: T
authors.initials: T
authors.lastname: Santa
authors.forename: K
authors.initials: K
authors.lastname: Imai
mesh_terms: D002264:Carboxylic Acids / Q000032:analysis*; D002851:Chromatography, High Pressure Liquid; D005453:Fluorescence; D005456:Fluorescent Dyes / Q000737:chemistry*; D010069:Oxadiazoles / Q000737:chemistry*
chemical_list: C430325:4-mercapto-7-methythio-2,1,3-benzoxadiazole; D002264:Carboxylic Acids; D005456:Fluorescent Dyes; D010069:Oxadiazoles