The distribution of copper between a buffered aqueous solution of the metal ion and a n organic solution of tobacco smoke condensate (TSC) in 4-methyl-2-pentanone (MIBK) has been studied. The analytical parameters, metal ion and hydrogen ion concentrations, were investigated. Metal ion concentrations were determihed by atomic absorption spectrophotometry. TSC was collected with use of a Mason Mark I11 Smoker and acetone traps maintained at 0°C. This material was transferred to MIBK by evaporation at reduced pressure. A 10-ml aliquot of an aqueous solution 0.1M in 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS) 0.01M in CuCl? and p H 5.6 t o 6.1 was equilibrated with a n equal volume of the MIBK solution of TSC, which contained the equivalent of five cigarettes. Analysis of a n aliquot from the organic phase after equilibration of the two phases yielded a maximum value of 300 pg of copper per cigarette when fresh, nonfractionated TSC was used. This simple, rapid extraction technique has been used to determine variations in the chemical activity of tobacco smoke condensate.his report presents initial results of our investigation on T the reaction between tobacco smoke condensate (TSC) and transition metals. Particular attention was directed toward the ligands present in the condensate, rather than metals or metallic constituents in native tobacco products or tobacco smoke. This study reports the reaction between tobacco tar and copper ions, which was demonstrated by changes in the distribution of copper between an aqueous phase and an immiscible solvent.The chemical nature of tobacco and tobacco smoke was reviewed recently by Stedman (1968), who noted, as have other investigators (Pillsbury et a/.. 1969; Swain et a/., Wartman et al., 1959), the variability of tobacco tar as a n analytical sample. Reactions using the alkylating activity (Stedman and Miller, 1967), reducing power (Hagopian, 1969), bacterial toxicity (Weiss and Weiss, 1967), and tumorigenicity (Bock et al., 1969) of tobacco tar have been reported. From a consideration of the reaction between TSC and copper ions, a procedure for assaying condensate was developed.
ExperimentalApparatus. A Beckman research model p H meter was used with a Sargent combination electrode. A Perkin-Elmer Model 303 atomic absorption spectrophotometer, with recorder readout, was used for the determination of copper. The copper hollow cathode lamp was operated at 15 mA in conjunction with acetylene and air-flow rates of 8 and 10 ft3/min, respectively, and wavelength setting of 324.7 A. Cigarettes were smoked on a Mark I11 Rotary Smoker (R. W. Mason, Clevedon, England). This unit smokes 24 cigarettes sequentially with a 2-sec puff per min per cigarette and a flow volume of 17.5 + 0.5 ccjsec. Both ends of the cigarettes are exposed to the atmosphere between puffs.Reagents. Stock solutions 0.2M in CuClz (Mallinckrodt, AR) and 1 .OM in 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS) (Fisher, Analyzed) were prepared with deionized water (Crystalab Deminizer). The 4-methyl-2-pent...