Synthesis and Properties of Arsenic(III)-Reactive Coumarin-Appended Benzothiazolines: A New Approach for Inorganic Arsenic Detection

• Published in: Inorganic chemistry 2013-03, Vol.52 (5), p.2323-2334
• Main Authors: Ezeh, Vivian C, Harrop, Todd C
• Format: Article
• Language: English
• Subjects: Arsenic - analysis; Benzothiazoles - chemical synthesis; Benzothiazoles - chemistry; Coumarins - chemistry; Molecular Structure
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic301730z

The EPA has established a maximum contaminant level (MCL) of 10 ppb for arsenic (As) in drinking water requiring sensitive and selective detection methodologies. To tackle this challenge, we have been active in constructing small molecules that react specifically with As3+ to furnish a new fluorescent species (termed a chemodosimeter). We report in this contribution, the synthesis and spectroscopy of two small-molecule fluorescent probes that we term ArsenoFluors (or AFs) as As-specific chemodosimeters. The AFs (AF1 and AF2) incorporate a coumarin fluorescent reporter coupled with an As-reactive benzothiazoline functional group. AFs react with As3+ to yield the highly fluorescent coumarin-6 dye (C6) resulting in a 20–25-fold fluorescence enhancement at λem ∼ 500 nm with detection limits of 0.14–0.23 ppb in tetrahydrofuran (THF) at 298 K. The AFs also react with common environmental As3+ sources such as sodium arsenite in a THF/CHES (N-cyclohexyl-2-aminoethanesulfonic acid) (1:1, pH 9, 298 K) mixture resulting in a modest fluorescence turn-ON (1.5- to 3-fold) due to the quenched nature of coumarin-6 derivatives in high polarity solvents. Bulk analysis of the reaction of the AFs with As3+ revealed that the C6 derivatives and the Schiff-base disulfide of the AFs (SB1 and SB2) are the ultimate end-products of this chemistry with the formation of C6 being the principle photoproduct responsible for the As3+-specific turn-ON. It appears that a likely species that is traversed in the reaction path is an As–hydride–ligand complex that is a putative intermediate in the proposed reaction path.