ABSTRACT
A simple controlled chemical reduction of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and related nitramine compounds with zinc amalgam generates species that elicit intense chemiluminescence with tris(2,2'-bipyridine)ruthenium(III), which extends this widely utilised chemiluminescence reagent to a new class of analyte and presents a sound chemical basis for a screening test for nitramine high explosives. Examination of the chemiluminescence profiles under stopped-flow conditions revealed contributions from multiple transient species formed in the initial reduction step.
Subject(s)
2,2'-Dipyridyl/analogs & derivatives , Aniline Compounds/analysis , Explosive Agents/analysis , Nitrobenzenes/analysis , Organometallic Compounds/chemistry , Triazines/analysis , 2,2'-Dipyridyl/chemistry , Flow Injection Analysis , Luminescent Measurements , Mercuric Chloride/chemistry , Zinc/chemistryABSTRACT
Two exceedingly stable [Ru(bipy)(3)](3+) reagents were prepared by dissolving either [Ru(bipy)(3)](ClO(4))(2) in acetonitrile (containing 0.05 M HClO(4)) or [Ru(bipy)(3)]Cl(2)·6H(2)O in 95:5 glacial acetic acid-acetic anhydride (containing 0.05 M H(2)SO(4)) followed by oxidation with PbO(2). These conveniently prepared solutions provide highly reproducible chemiluminescence detection over long periods of analysis, avoiding the need for recalibration or preparation of fresh reagent solutions and without the complications associated with online chemical or electrochemical oxidations. The reagent prepared in acetonitrile produced much greater signal intensities with a range of analytes and was deemed most suitable for high-performance liquid chromatography (HPLC) with postcolumn chemiluminescence detection.
