Investigation of the tris(2,2'-bipyridine)ruthenium(III) chemiluminescence reaction for the determination of aromatic amines and aldehydes by flow injection or liquid chromatography .

摘要

Studies have shown that compounds containing amine functional groups can be oxidized by tris(2,2′-bipyridine)ruthenium(III), [Ru(bpy)₃]3+, to produce light, The efficiency of light production is related to the degree of substitution of the amine, with primary amines giving the weakest signal. Amines containing aromatic rings have been particularly difficult to detect, The primary objective of this dissertation is to expand the classes of compounds that can be determined by [Ru(bpy)₃]3+ chemiluminescence (CL) by flow injection (FI) or HPLC. This study is presented in five parts.; Chapter one discusses photolysis of primary amines with aromatic substituents, with phenethylamine as the base structure, to enhance CL detectibility of these compounds. CL signal enhancement for these amines after photolysis ranged from 5–15 times, Photochemical products of benzylamine and phenethylamine believed to be responsible for CL enhancement were identified as imines.; Chapter two examines Schiff base reactions between aldehydes and primary amines to form imines for enhanced CL detection. The CL signal enhancement of primary amines, such as phenylalanine, upon reaction with benzaldehyde will be discussed under various solvent conditions and with photolysis. The CL determination of aldehydes such as benzaldehyde and glucose by reaction with propylamine will also be discussed.; Chapter three investigates the reaction between phenylisothiocyanate and aliphatic primary and secondary amines, including amino acids, and its quenching effect on [Ru(bpy)₃]3+ CL detection. FI determination of tertiary amines, such as triethanolamine, in the presence of primary and secondary amines will be examined.; Chapter four examines the stability of the electrochemically oxidized [Ru(bpy)₃]3+ in the batch mode. Non-continuous oxidation of [Ru(bpy)₃]2+ produces a [Ru(bpy)₃]3+ solution useful as a CL reagent for several hours. Stabilization of the [Ru(bpy) ₃]3+ reagent bound to polystyrene sulfonate or polyglutarnic acid is possible for several days although the CL signal was reduced,; Chapter five investigates the use of photolysis to enhance UV detection of primary amines with aromatic substituents. The degree of UV absorbance increase will be examined for on-line and off-line photolysis. The photolysis of these amines utilizing a new silicone capillary photoreactor will be compared to the standard Teflon tubing reactor.