The Chemical Composition of Tobacco and Tobacco Smoke R
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THE CHEMICAL COMPOSITION OF TOBACCO AND TOBACCO SMOKE R. L. STEDMAN Eastern Utilization Research and Development Division, Agricultural Research Service, United States Department of Agriculture, Philadelphia, Pennsylvania 19118 Received October 18, 1967 CONTENTS I. Introduction ............................................ ................... 153 11. Tobacco Processing and Physicochemical Properties of Tobacco ke.. .............. 154 111. Chemical Composition of Tobacco Leaf and Smoke. ............................... -. 155 A. Alkanes ................................... ............................. 155 B. Alkenes and Alkynes. .................. .................... 156 1. Isoprenoid Hydrocarbons. ........... .................... 156 2. Other Alkenes and Alkynes. .............................................. 158 C. Aromatic Hydrocar .................... 158 D. Sterols and Oxygen nds.. ............................... 161 1. Sterols. ....... ................................................. 161 2. Oxygenated Isop onstituents .............................. E. Alcohols and Esters.. ................................ ._........................ F. Aldehydes, Ketones, and Quinones. ....................................... G. Nitriles, Cyclic Ethers, and Sulfur Compounds. ................................. 169 H. Acids.. .... .._..... -. .. ................................................ 169 I. Phenols and Phenolic Ethers.. ................................................ 171 1. Chlorogenic Acids. .. ................................................. 172 2. Other Polyphenols. , ......................... 173 3. Other Phenols and Pheno ................... J. Alkaloids and Other Bases.. ................. .......... .......... K. Brown Pigments. .......... ......................... 178 L. Carbohydrates. ............ ......................... 180 M. Amino Acids, Proteins, and Related Compounds.. .............................. 182 N. Miscellaneous Components, , ........................ .......................................... .................... 188 B. Sterols.. ................... ............. ......................... VI. Technology ..................................................................... 195 VII. Addendum ..................................................................... 197 VIII. References ...................................................................... 198 I. INTRODUCTION some information on chemical carcinogens, ciliostatic The last comprehensive review of the constituents of agents, and irritants (307). Two other books have tobacco and tobacco smoke appeared in 1959 (263). appeared on the biological effects of tobacco and smoke, Since then, numerous reports linking smoking and one having two short chapters on the chemistry of health (527) have contributed greatly to increased effort smoke (254) and the other including information on in this field, and several books and reviews have been alkaloids (595). A tabulation of known components of published dealing with selected chemical aspects of cigarette smoke has been published which is supple- smoking and health relationships. A comprehensive mented periodically (38) ; however, no critical evalua- review with more than 6000 literature citations is avail- tion of the cited reports is given therein. An extensive able dealing mostly with medical aspects but containing Russian work on the chemistry of tobacco has been 153 154 R. L. STEDMAN translated into English, but much of the data must be ing, all tobacco is subjected to a curing process which is regarded as historical (513). Two reviews dealing with basically a dehydration accompanied by certain chem- the general composition of tobacco and smoke have ical changes resulting in the development of desired been published, but coverage of the subject is not com- color and other properties. The major curing processes plete in both cases (437, 554). However, an exhaus- are flue-curing, in which heat is provided to effect the tive survey has appeared on the relationships between drying, and air-curing, in which ambient temperatures the chemical composition and experimental carcino- are employed. Following curing, tobacco is treated in a genic effects of tobacco (644); an expanded version of series of industrial processes, including moisture adjust- this work will be published as a book in late 1967 (648). ment, aging or fermentation, blending, and addition of Several surveys with varying degrees of age and humectants and flavors (117,164,165,213). The exact thoroughness are available covering selected groups of treatment will vary with the ultimate form of the leaf or smoke constituents : polynuclear aromatic smoking product and the particular manufacturer’s hydrocarbons (l52), terpenes (47), phenols (223, 628), practice. Fermentation is a vigorous process involving and alkaloids (399,492). storage at elevated temperatures with relatively high None of these works can be considered an adequate moisture levels in the tobacco and is employed with sequel to the comprehensive survey on composition cigar and snuff tobaccos. Aging is a relatively mild published in 1959. The present work is intended to fill prolonged (up to 3 years) storage at ambient tempera- this role. The procedure followed herein is to provide ture and relatively low moisture levels and is used for information which supplements the 1959 review or cigarette tobaccos. On the basis of sparse information, other surveys for which coverage is considered adequate. the chemical changes occurring during aging are more In listing the known constituents of tobacco leaf and subtle than those of fermentation (134, 165,166). smoke, literature citations are given for every compo- For research and development purposes, cigarettes, nent; for some compounds, the citations are to the 1959 cigars, and pipes are smoked mechanically in machines survey or to other reviews which, in turn, list the orig- which superficially simulate the act of smoking by inal references. However, original publications were humans. Most smoking machines operate on a con- consulted in making the lists. The inclusion of refer- stant-volume or constant-pressure principle, but other ences to components was deemed necessary to facilitate designs have been reported including a “pressure the location of original reports which was difficult in the procedure” which is claimed to reduce the aging effects 1959 review since compounds were listed merely as being of smoke (371). Many different machines have been absent or present. Except for certain trivial names proposed for research purposes (151,332,490,644), and which are widely used in the field, the nomenclature of fully automatic models are commercially available with Chemical Abstracts is employed herein. daily smoking capacities as high as 1000 cigarettes Many of the newly reported constituents of leaf and (151). Whole smoke is collected in a variety of ways smoke occur in trace amounts; in some instances, the depending on the end use, but, for large-scale composi- isolated quantities have been much less than 1 mg. tional work, condensation at low temperature is usually Application of classical methods to identify the isolates employed. Other methods include collection of partic- has not been possible in such cases, and identification ulate matter on Cambridge filters or condensation of has been based on chromatographic and spectrometric smoke by electrostatic precipitation, both of which give comparisons with authentic compounds. Under the essentially the same yields as low-temperature conden- conditions, these procedures appear to be adequate for sation (41) although significant compositional differ- identification provided the criteria are not limited ences may exist, e.g., free-radical contents (644). excessively. The present survey lists those compounds Artifacts may be introduced by many systems of collec- for which claims of identity appear to be reasonably tion and storage since smoke components in the trapped justified. material may react to form products not in the fresh smoke, e.g., nitrophenols (274) and cyanohydrins (361). 11. TOBACCOPROCESSING AND PHYSICOCHEMICALTo reduce the inherent variability in these systems, PROPERTIESOF TOBACCO SMOKE standard methods of collecting and handling smoke Most tobacco products use processed leaves of condensate have been developed for analytical (41) and Nicotiana tabacum as their major ingredient. In biological (1 18) use. Although such standardizations Eastern Europe, the Soviet Union, and perhaps India, are desirable, they provide little assistance in one of the Nicotiana rustica is used to some extent. Traditionally, current major problems involving smoke composition : tobacco is classified into types which differ in the con- the determination of the constituents actually present ditions of growth, processing, and eventual use; the in the particulate matter of fresh mainstream smoke major cigarette types used in the United States and emitting from a cigarette or other smoking product. Europe are flue-cured (“bright,” “Virginia”), burley, Little progress has been made in this area, mainly Maryland, and Turkish (“Oriental”). After harvest- because of the inadequacies of current methodological CHEMICALCOMPOSITION OF TOBACCOAND TOBACCOSMOKE 155 procedures. The solution of many pragmatic problems smoke (239). No significant differences have been ob- involving the organoleptic properties and biological served in the particle diameters and numbers of particles effects of tobacco smoke may lie in this