Interaction of biogenic amines with components of cigarette smoke: Formation of cyanomethylamine derivatives

Abstract

A reaction of the biogenic amines 5-hydroxytryptamine, dopamine, histamine, p-tyramine, β-phenylethylamine and tryptamine with components of cigarette smoke was observed. The adducts formed from 5-hydroxytryptamine and β-phenylethylamine were purified by Chromatographie procedures and identified by high resolution mass spectrometry. The structures of some of these compounds were established as cyanomethylamine derivatives, i.e. RCH 2CH 2NHCH 2CN. In the case of 5-hydroxytryptamine, a cyanomethyl-β-1,2,3,4-tetrahydrocarboline product formed via a Pictet-Spengler condensation reaction was isolated. The mass spectra of such adducts and their fragment ions were observed to be identical to those of chemically synthesized cyanomethylamines. Both formaldehyde and cyanide, which are known to be present in cigarette smoke, were involved in the reaction with the primary amines. The reaction was time dependent and was enhanced by an increase in temperature or by incubation under alkaline conditions. Cyanomethyl adduct formation was increased when smoke from cigarettes with higher tar and nicotine content was used. When the amines were incubated with human saliva obtained after cigarette smoking, cyanomethylamine products were readily detected.