Formation of Dihydroxybenzenes in Cigarette Smoke. Part 1. Contribution from Chlorogenic Acid and Rutin

Abstract

Catechol and alkylcatechols are known co-carcinogens present in cigarette smoke. Hydroquinone, although nongenotoxic, can form a metabolite with nephrotoxic properties and is a potential human carcinogen. The formation of dihydroxybenzenes during smoking originates with the pyrolysis of several precursors from tobacco. These include cellulose, chlorogenic acid, rutin, etc. The present study attempts to quantitate the contribution of chlorogenic acid and rutin to the formation of dihydroxybenzenes and of some alkyldihydroxybenzenes. Also it estimates the contribution to the formation of dihydroxybenzenes from other potential precursors including glucose, fructose, sucrose, cellulose, pectin, starch, and lignin. The study was done in three parts: 1. pyrolytic evaluation of the amount of dihydroxybenzenes in smoke generated from isolated potential precursors; 2. analysis of smoke from cigarettes made from a variety of tobaccos (14 single grades) and two blended cigarettes, followed by correlations of dihydroxybenzenes yield with the tobacco content of various suspected precursors; 3. addition of chlorogenic acid or rutin to several tobaccos followed by the smoking of the spiked cigarettes and measurement of dihydroxybenzenes yield increase. The study shows that for a variety of singlegrade cigarettes and for two blended cigarettes (one being the 2R4F Kentucky reference), the contribution of chlorogenic acid and of rutin to the formation of catechol and hydroquinone in smoke depends on the blend. For the 2R4F cigarette, the contribution from chlorogenic acid is 8.7% for catechol, and 7.7% for hydroquinone (for ISO smoking protocol). For the same cigarette, the contribution from rutin is 3.7% for catechol and 5.1% for hydroquinone. The results of the study are in agreement with a previously reported finding indicating that chlorogenic acid contributes about 13% to the catechol formation in smoke for the 1R1 Kentucky reference cigarette. The study results suggest that other components in tobacco, besides chlorogenic acid, rutin, glucose, fructose, sucrose, cellulose, pectin, starch, and lignin are major contributors to the formation of catechol and hydroquinone in cigarette smoke.

Formation of Dihydroxybenzenes in Cigarette Smoke. Part 2. Contribution from Quinic Acid and Myo-Inositol

“…This present study describes the contribution of tobacco quinic acid (or (1S,3R,4S,5R)-1,3,4,5-tetrahydroxycyclohexanecarboxylic acid) and myo-inositol (or (1R,2R,3S,4S,5R,6S)-cyclohexane-1,2,3,4,5,6-hexol) to the formation of dihydroxybenzenes in cigarette smoke. The study is a continuation of a previous one showing the contribution of chlorogenic acid and rutin as precursors for these compounds (6). The yields of dihydroxybenzenes formed by pyrolysis of quinic acid and myo-inositol are relatively high and both quinic acid and myo-inositol can be present in some tobacco types at levels as high as 1% by weight.…”

“…The experiments performed in this study are similar to those previously reported for the evaluation of the contribution of tobacco chlorogenic acid and rutin to smoke dihydroxybenzenes formation (6). It consisted of three different types of experiments.…”

“…One type was the pyrolysis of pure compounds suspected to be precursors for catechol and other dihydroxybenzenes. The second type was the analysis of quinic acid and myo-inositol in tobaccos, and the third was the analysis of catechol and hydroquinone in smoke from cigarettes made with tobaccos previously analyzed for polyphenols (6). Two of the cigarettes used in this study were commercially available, other cigarettes were made in a pilot plant at R. J. Reynolds Tobacco Co., and other cigarettes were handmade.…”

“…La présenté étude décrit la contribution de l'acide quinique présent dans le tabac (ou acide (1S,3R,4S,5R)-1,3,4,5-tétrahydroxycyclohexanecarboxylique) et du myo-inositol (ou (1R,2R,3S,4S,5R,6S)-cyclohexane-1,2,3,4,5,6-hexol) dans la formation de dihydroxybenzènes dans la fumée de cigarette. Cette étude fait suite à une première étude qui a démontré la contribution de l'acide chlorogénique et de la rutine en tant que précurseurs de ces composés (6). Les rendements de dihydroxybenzènes formés par pyrolyse de l'acide quinique et du myo-inositol sont relativement élevés et l'acide quinique de même que le myo-inositol peuvent être présents dans certains types de tabac à des niveaux de concentration pouvant atteindre jusqu'à 1 % en masse.…”

“…In der vorliegenden Studie wird der Beitrag von Chinasäure im Tabak (1S,3R,4S,5R)-1,3,4,5-Tetrahydroxycyclohexancarbonsäure und myo-Inosit (1R,2R,3S,4S,5R,6S)-Cyclohexan-1,2,3,4,5,6-hexol zur Entstehung von Dihydroxybenzolen im Zigarettenrauch beschrieben. Die Studie ist eine Fortführung einer vorangegangenen Studie, in der der Beitrag von Chlorogensäure und Rutin als Vorläufer dieser Substanzen gezeigt wurde (6). Die Ausbeuten an Dihydroxybenzolen, die DOI: 10.2478/cttr-2013-0929 durch Pyrolyse von Chinasäure und myo-Inosit entstehen, sind relativ hoch, und sowohl Chinasäure als auch myo-Inosit kann in bestimmten Tabakarten mit bis zu 1% vorkommen.…”