Orestes T. Chortyk

Pyrolytic evaluation of low chlorogenic acid tobaccos in the formation of the tobacco smoke co-carcinogen catechol

Abstract The major polyphenolic acid of tobacco is 3-O-caffeoylquinic acid, also called chlorogenic acid. Pyrolysis and smoking studies were conducted on a series of tobaccos to define the relationship between levels of leaf caffeoylquinic acids (CQA) and catechol, the co-carcinogenic smoke compound derived from the CQA. A large number of flue cured tobaccos with varying levels of CQA (0.0004 to 2.5% dry weight) were pyrolyzed and pyrolyzate catechol yields were determined. It was found that decreasing CQA levels in leaf produced decreased catechol yields in the pyrolyzates. Statistical analysis of the data showed that a linear relationship existed between smoke catechol and leaf chlorogenic acids, down to the 0.2% leaf CQA level. A 50% reduction in pyrolyzate catechol yields was noted for the 0.2% CQA tobacco vs the 2.5% CQA tobacco. Beyond the 0.2% level, further reductions in CQA contents had no effect on catechol yields. It is well known that pyrolyzate and cigarette smoke compounds are closely related. Consequently, a reduction of CQA in commercial flue-cured tobaccos from the present 1.5–2.5% to approximately 0.2% would reduce cigarette smoke catechol levels by approximately 50%. Data are presented to indicate that high molecular weight brown pigments may be the additional source of catechols in smoke. The above conclusion on the relationship of CQA levels to smoke catechols was confirmed by analyses of smoke condensates from cigarettes of the corresponding tobaccos. Thus, low CQA tobaccos could be used in formulating smoking products that would produce significantly reduced levels of catechol in tobacco smoke.

Preparation of fused-silica polar stationary phase wallcoated open tubular columns

Abstract Recent methodology, developed in our laboratory for the preparation of Pyrex (borosilicate) wall-coated open tubular (WCOT) gas chromatography columns with the polar stationary phases Superox™-4 (4 · 10 6 molecular weight polyethylene glycol) and SP-1000 (nitroterephthalic acid derivative of Carbowax 2OM), was successfully adapted to the preparation of fused-silica WCOT columns with these phases. Pretreatment of the fused-silica tubing with Superox-4 increased the surface energy, improved the wettability of the surface for polar phases and deactivated the fused-silica surface. The polar stationary phases, Superox-4 and SP-1000, were statically coated onto the Superox-4-treated surface. These polar WCOT columns were found to be efficient, thermally stable, and low in surface activity.

Preparation of wall-coated open tubular glass (pyrex) capillary columns with polar stationary phases, using superox™-4 as a surface pretreating and deactivating agent

Abstract Wall-coated open tubular (WCOT) glass (Pyrex) capillary columns were prepared with three different polar stationary phases (Carbowax 20M, Superox™-4, and SP-1000) using Superox-4 as a surface pretreating and deactivating agent. Methods for the laboratory preparation and practical application of these columns are given. Columns prepared by this technique were efficient, thermally stable, and low in surface activity. The Superox-4 pretreatment and deactivation technique produced high quality polar WCOT columns, and no surface roughening procedure was required. The technique offered a substantial decrease in column preparation time. In addition, columns prepared by this technique were comparable to those from commercial suppliers or those produced by conventional preparation techniques.

Determination of solanesol in tobacco by capillary gas chromatography

A gas chromatographic (GC) method has been developed for solanesol, a long-chain (C45 terpenoid alcohol of tobacco. The method separates and quantities solanesol as its volatile trimethylsilyl derivative. After saponification of the tobacco sample with methanolic potassium hydroxide to liberate bound solanesol, total solanesol was determined on a wide-bore fused-silica SE-54 capillary column. The reproducibilities of both the extraction and GC methods were found to be excellent. As an example of application, six tobacco varieties, used in a low-solanesol tobacco breeding study, were analyzed. In these tobaccos, free solanesol content varied from 70 to 90% of the total solanesol, which ranged from 1.9 to 2.8% of dry weight.

Capillary gas chromatography of carbolines : Application to cigarette smoke

Abstract A method was developed for the gas chromatographic analysis of carbolines (pyridoindoles) on fused-silica glass capillary columns, coated with SuperoxTM-4. Separation characteristics are presented for all four possible isomers of carboline and several methyl-, methoxy- and dihydro-derivatives fo β-carboline (norharman). These gas chromatographic techniques were utilized in the development of a rapid method for the analysis of norharman and harman (1-methyl-β-carboline) in cigarette smoke condensate. Levels of norharman and harman found in the smoke of a research reference cigarette were 11.2 and 3.6 μg/cigarette, respectively. Commercial non-filter cigarettes gave similar values, while filtered brands gave lower values. The identification of α-carboline in cigarette smoke is reported.

Capillary gas chromatography of dihydroxybenzoic, -phenylacetic and -phenylpropionic acids

Abstract All six possible ring-substittued dimethoxy and dihyroxy isomers of phynylacetic and β-phenylpropionic acids were prepared. The gas chromatographic (GC) separation, on an SE-54 coated fused-silica capillary column, of all 24 isomers (as their trimethylsilyl derivatives) is presented for the first time, as well as the first reported synthesis of 2,6-dihydroxyphenylacetic acid. The GC elution sequence of silylated dihydroxyphenylacetic and dihydroxyphenylpropionic acids is compaed to that of dihydroxybenzoic acids. Mass spectral (MS) fragmentation patterns of the silylated isomers reflect positions of the substituents and can be used to characterize isomers. The data presented wil allow the determination of these isomeric acids, based on their MS and GC data, relative to common, commercially available isomers. The developed data were applied to identifications of unknown phenolic acids of tobacco smoke.

Toxicity of Synthetic Sucrose Esters Against the Tobacco Aphid (Homoptera: Aphididae)

Four synthetic sucrose esters were evaluated in the laboratory and field to determine their insecticidal activity on the tobacco aphid, Myzus nicotianae Blackman. Synthetic sucrose esters provided ...

Characterization of the amino acids of antifungal peptides from B. subtilis by cold on-column injection capillary GC/MS

Abstract Recent studies have shown that the cell-free culture liquor of Bacillys sublitis inhibits the growth of the peach brown rot fungus, Monilinia fructicola. Bacillus sublitis and other related bacilli are known to produce a variety of peptide antibiotics, including cyclic peptides of the Iturin family. Fractionation of the culture liquor yeilded two major components which were shown to be cyclic peptides of the Iturin type. Specific capilliary GC/MS methodology was developed for the characterization of the amino acids, including β-amino aliphatic acids, resulting from the hydrolyses of these cyclic antifungal peptides. After cold on-column injection, the N- pentafluoropropionyl- D,L -amino acid n- propyl esters were separated on a fused silica Chirasil-Val III ™ column and characterized by mass spectrometry on a Hewlett Packard 5985B GC/MS system equipped with an open-split interface. MS data used to characterize the long-chain aliphatic β-amino acids in the peptides are discussed.

Increasing Selenium in Cigarettes and Smoke: Transfer to Smoke

The selenium content of some American tobaccos and cigarettes was determined. The quantities of added selenium that were transferred from cigarettes to inhaled, mainstream smoke were examined for several commercial and experimental cigarettes of different tar levels. For high-tar cigarettes, as much as 10% of added selenium was found in mainstream smoke, while low-tar cigarettes delivered about 3% of added selenium. Transfer rates of selenium to mainstream smoke are reported for various levels of fortification (0-25 micrograms/cigarette) and the rationale for selenium fortification is discussed. Based on highly favorable reports in the literature on the antitumor activity of selenium, the fortification of tobacco with selenium may become a viable way of producing a safer tobacco product. It is proposed that such selenium-fortified smoking products be developed and evaluated extensively.

Comparison of the Volatile Flower Oils of Nicotiana rustica and N. forgetiana

ABSTRACT The volatile constituents obtained by vacuum-steam distillation of the flowers of Nicotiana rustica and of N. forgetiana were profiled by capillary GC and characterized by GC/MS. Compounds comprising 74% of N. rustica flower oil and 72% of N. forgetiana flower oil were identified. Seventeen compounds were observed in N. rustica oil, with the alkaloid, nicotine (25.92%), and the sesquiterpene, aromadendrene (11.26%) being the major constituents. Of the 14 compounds observed in N. forgetiana oil, no constituents exceeded 10% of the total amount. Farnesyl acetone (4.97%), β-pinene (4.19%), acoradiene (3.81%) and (Z)-3-hexenyl acetate (3.97%) were present in highest concentrations. Twelve compounds were common to the oils of both species, although seven of these were aliphatic C21-C25 hydrocarbons. These hydrocarbons occurred in significantly greater amounts in N. forgetiana. (Z)-3-Hexenol was die only component found at a level exceeding 5% in both species.