Cigarette smoke composition. Part 2. Method for determining major components in smoke of cigarettes that heat instead of burn tobacco

A method is described for determining major constituents in the smoke of a cigarette that heats, but does not burn, tobacco. Dual, simultaneous separations are performed in a single gas chromatographic oven to determine water, glycerol, nicotine, and propylene glycol in a rapid and cost-effective manner. A materials balance of new cigarette smoke total particulate matter was attempted from both Cambridge filter and electrostatic precipitation smoke collection data. Serious deficiencies were found when Cambridge filter smoke collection was applied for this purpose. Electrostatic precipitation smoke collection eliminated these problems. The data obtained by electrostatic precipitation smoke collection indicate that water, glycerol, nicotine, and propylene glycol make up about 94% of new cigarette smoke total particulate matter.     

Polar constituents from the aerial parts of Origanum vulgare L. Ssp. hirtum growing wild in Greece

From the polar extracts of Origanum vulgare L. ssp. hirtum 19 compounds have been isolated. The structures and relative stereochemistry have been elucidated by spectroscopic analysis and determined as apigenin, luteolin, chrysoeriol, diosmetin, quercetin, eriodictyol, cosmoside, vicenin-2, caffeic acid, p-menth-3-ene-1,2-diol 1-O-beta-glucopyranoside, thymoquinol 2-O-beta-glucopyranoside, thymoquinol 5-O-beta-glucopyranoside, thymoquinol 2,5-O-beta-diglucopyranoside, 12-hydroxyjasmonic acid, 12-hydroxyjasmonic acid 12-O-beta-glucopyranoside, lithospermic acid B, rosmarinic acid, 10-epi-lithospermic acid, and epi-lithospermic acid B. The three latter products display unusual stereochemistry of the 3,4-hydroxyphenyllactic acid unit(s), which to the authors' best knowledge has never been reported before in similar compounds. Moreover, lithospermic acid B (and its stereoisomers), p-menth-3-ene-1,2-diol 1-O-beta-glucopyranoside, 12-hydroxyjasmonic acid, and 12-hydroxyjasmonic acid 12-O-beta-glucopyranoside were isolated for the first time from Origanum species.     

Alfalfa (Medicago sativa L.) flavonoids. 1. Apigenin and luteolin glycosides from aerial parts

Nine flavones and adenosine have been identified in aerial parts of alfalfa, and their structures were established by spectral (FABMS and NMR) techniques. Five of the identified compounds, including apigenin 7-O-[beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[2-O-feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[2-O-feruloyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], apigenin 7-O-[2-O-p-coumaroyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], and luteolin 7-O-[2-O-feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, have not been reported before in the plant kingdom. Additionally, five known compounds, including apigenin 7-O-beta-D-glucuronopyranoside, apigenin 4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[beta-D- glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], luteolin 7-O-beta-D-glucuronopyranoside, and adenosine, were identified.     

Alfalfa (Medicago sativa L.) flavonoids. 2. Tricin and chrysoeriol glycosides from aerial parts.

Ten flavone glycosides have been isolated and identified in aerial parts of alfalfa. These included six tricin, one 3'-O-methyltricetin, and three chrysoeriol glycosides. Most of these compounds were acylated with ferulic, coumaric, or sinapic acids, and acylation occurred on the terminal glucuronic acid. Eight of these compounds, including 7-O-beta-D-glucuronopyranosyl-3'-O-methyltricetin, 7-O-beta-D-glucuronopyranosyl-4'-O-beta-D-glucuronopyranosidechrysoeriol, 7-O-[2'-O-feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]chrysoeriol, 7-O-[2'-O-feruloyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]chrysoeriol, 7-O-[2'-O-sinapoyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, 7-O-[2'-O- feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, 7-O-[2'-O-p-coumaroyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, and 7-O-[2'-O-feruloyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, have not been reported previously in the plant kingdom. Two previously identified alfalfa flavones, 7-O-beta-D-glucuronopyranosidetricin and 7-O-[beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, were also isolated.     

In vitro antioxidant properties and phenolic composition of Salvia virgata Jacq. from Turkey

Antioxidant activities and phenolic compositions of the active fractions of Salvia virgata Jacq. (Lamiaceae) from Turkey were examined. The aerial part of S. virgata was extracted with different solvents in an order of increasing polarity such as hexane, ethyl acetate, methanol, and 50% aqueous methanol using a Soxhlet apparatus. Water extract was also prepared from S. virgata by reflux. All solvent fractions were investigated for their total phenolic contents, total flavonoids, flavonols, qualitative-quantitative compositions (by HPLC-PDA analysis), iron(III) reductive activities, free radical scavenging activities (using DPPH*), and effect upon linoleic acid peroxidation activities; also, the peroxidation level was determined by the TBA method. The results of activity tests given as IC50 values were estimated from nonlinear algorithm and compared with standards, viz., butylated hydroxytoluene, ascorbic acid, and gallic acid. Polar fractions were found to be more active for free radical activity whereas nonpolar fractions protected the peroxidation of linoleic acid. Rosmarinic acid was the most abundant component in the extracts, followed by caffeic acid and lutelin-7- O-glycoside.     

Polycyclic aromatic hydrocarbons in liquid smoke flavorings obtained from different types of wood. Effect of storage in polyethylene flasks on their concentrations

Smoke flavorings are widely used as an alternative to the traditional smoking techniques. Smoke generation conditions can determine the level of polycyclic aromatic hydrocarbons (PAHs) in the smoke and, consequently, in these preparations. In this paper, the influence of the wood source on the formation of PAHs is studied. For this purpose, five liquid smoke flavorings, obtained from different types of wood, were used. Sample aliquots, including deuterated internal standards, were subjected to an alkaline treatment, extracted by liquid-liquid partition and cleaned up by means of silica tubes, followed by gas chromatography-mass spectrometry analysis. The results reveal that the flavoring obtained from poplar wood presents the highest number and concentrations of both total and carcinogenic PAHs, even though the levels of these latter are very low. It has also been observed that the storage of smoke flavorings in polyethylene flasks reduces the concentration of some PAHs.     

Influence of the moisture content on the composition of the liquid smoke produced in the pyrolysis process of Fagus sylvatica L. wood.

The pyrolysis of several samples of sawdust of Fagus sylvatica L. wood with different moisture contents was carried out, keeping all other smoke generation parameters constant. However, parameters such as smoke production length and maximum temperature reached were affected by the moisture content of the sample and varied in the different pyrolytic runs. The acidity and the composition of the liquid smokes obtained were determined, this latter by means of gas chromatography/mass spectrometry and gas chromatography with flame ionization detection. The acidity and composition of the liquid smoke produced were affected not only by the moisture content of the sawdust sample but also by the smoke generation length and by the temperature of the process. The highest yields in components were produced from samples with low moisture content that underwent a short pyrolytic process. Some compounds, with important properties from an organoleptic and preservative point of view, were not generated from samples with high moisture content. Equations that closely relate yield of the total components or of groups of components or of individual components with parameters such as moisture content, length of the process, and temperature were obtained; these equations predict yield data of liquid smoke components with a satisfactory degree of approximation.     

Water-deficit impact on fatty acid and essential oil composition and antioxidant activities of cumin (Cuminum cyminum L.) aerial parts

This study is designed to examine the effect of water deficit on growth, fatty acid and essential oil composition, and antioxidant activities of Cuminum cyminum aerial part extracts. Plants were treated with different levels of water deficit: control (C), moderate water deficit (MWD), and severe water deficit (SWD). Plant growth (height, fresh and dry matter weights) as well as yield components were significantly increased under moderate water deficit and conversely reduced at severe level. Total fatty acid content decreased significantly with severity of constraint. Drought reduced considerably the proportions of major fatty acids and the unsaturated to saturated fatty acid ratio. The essential oil yield was 0.14% (based on the dry weight); it increased by 2.21-fold at MWD but decreased by 42.8% under SWD in comparison to the control. Drought results in the modification of the essential oil chemotype from 1-phenyl-1-butanol to 1-phenyl-1,2-ethanediol. Antioxidant activities of the acetone extracts were determined by two complementary test systems, namely, DPPH and β-carotene/linoleic acid. The highest activity was exhibited by moderately stressed plants and was reduced significantly under SWD. In control plants, the total phenolic amount was 10.23 mg GAE/g DW, which increased by 1.5-fold under MWD and decreased by 42% under SWD.     

Concentration of isoflavones and other phenolics in the aerial parts of Trifolium species

Some species of the genus Trifolium are well-known for their content of isoflavones, which are natural compounds showing health-promoting activities. Until recently, only a few species of this genus have been characterized with respect to their composition. In the present study, 57 Trifolium species have been analyzed for their contents of isoflavones, phenolic acids, flavonoids, and clovamides. The cluster analysis of experimental data allowed us to identify a number of species, which should be of interest as potential sources of these metabolites. The isoflavone contents of the three species ( T. heldreichianum, T. scabrum, and T. subterraneum) had extremely high amounts of these compounds, reaching 7-9% of dry matter, and the concentration in a number of other species was higher or at least comparable to the amounts occurring in T. pratense, one of the major isoflavone sources for the nutraceutical industry. Several species contained high amounts of all four analyzed groups of phenolics (isoflavones, phenolic acids, flavonoids, and clovamides). These species may also be of great interest as the association of several groups of active molecules is highly desired for effective disease prevention.     

Identification and synthesis of new volatile molecules found in extracts obtained from distinct parts of cooked chicken

Several chicken parts (skin, fat, juice) were cooked in different ways (roasting, simmering) and investigated separately for their volatile composition. In-depth GC/MS analysis of the separate fractions revealed several unknown molecules. Mass spectra interpretation allowed us to identify nine molecules for the first time in chicken, including cyclic aldehydes, cyclic ketones, and new δ-lactones containing an unsaturated linear chain. Identification was confirmed by chemical synthesis followed by comparison of the mass spectra and linear retention indices. The natural occurrence of five of these molecules is reported here for the first time in a natural product.     

Essential oils from dalmatian sage (Salvia officinalis l.): variations among individuals, plant parts, seasons, and sites.

The factors affecting oil yield and quality of essential oils from Dalmatian sage (Salvia officinalis L.) are analyzed. Distillations of oils from individual plants and GC analyses revealed the presence of three chemotypes with different proportions of alpha- and beta-thujone (alpha/beta 10:1, 1.5:1, and 1:10). Different accessions could also be classified as having high (39-44%), medium (22-28%), or low (9%) total thujone contents. Flowering parts of S. officinalis had higher oil contents (1.6 versus 1.1%) and beta-pinene levels (27 versus 10%) than leaves and lower thujone levels (16 versus 31%). Major seasonal changes were found in the composition of oil distilled from a flowering type of Dalmatian sage, but oil yields from healthy, established plants did not vary greatly. Total thujone levels were lowest (25%) around flowering in spring and summer, so autumn or winter was the best harvest time to obtain oils with high thujone levels.     

Dynamics of yield components and essential oil production in a commercial hybrid sage (Salvia officinalis x Salvia fruticosa cv. Newe Ya'ar no. 4).

The fresh yields, the essential oil content, and the quality of a sage hybrid (Salvia officinalis x Salvia fruticosa, cv. Newe Ya'ar No. 4, Lamiaceae) as affected by development and harvest time were determined. Marked increases in plant height and in the number of nodes developed per plant together with a modest increase in leaf size were accompanied by dramatic increases (more than 20-fold) in the fresh yields throughout a 50-day growth period. No major changes in the essential oil content per fresh weight and its composition were detected throughout the growth period. In contrast, the compositions of the essential oils obtained from stems, as compared to leaves and leaf-primordia, had marked differences. Developmentally controlled changes in the extractives from individual leaf pairs from the same plant were also noted. In upper young leaves, the oxygenated diterpene manool and the sesquiterpene hydrocarbons alpha-humulene and beta-caryophyllene constituted up to 20%, 8%, and 4% of the total extractives, respectively. In older leaves, the abundance of these components steadily dropped to roughly half their levels in young leaves. Conversely, the proportions of the monoterpenes, particularly the ketones camphor and alpha-thujone, steadily increased with leaf position. Minor changes in the levels of other extractives were also recorded. These studies imply independent regulatory patterns for di-, sesqui-, and monoterpenes in this sage hybrid, and suggest possible agrotechnical means to obtain preferred chemical compositions of its essential oil.     

Organ- and season-dependent variation in the essential oil composition of Salvia officinalis L. cultivated at two different sites.

More than 50 compounds were identified in essential oils from stems and leaves of Salvia officinalis L. plants harvested in July, in Arouca, in northern Portugal. About 40 of those compounds were also present in flower essential oils, collected from the same plants. alpha-Thujone was the major compound, representing about 55, 30, and 18% of the essential oils from stems, leaves, and flowers, respectively. Significant percentage variations in the main compound classes of the essential oils from shoots sampled over the year were recorded at two different sites in northern Portugal. From December to April, oxygenated monoterpenes (MO) decreased from approximately 67-72% to values of 42-43% of the essential oils. During the same time interval, the percentage of monoterpene hydrocarbons (MH) rose from 8-11% to 17-22%. At both sites, sesquiterpene hydrocarbons (SH) rose from approximately 7% in February to 19-22% in April, decreasing thereafter to approximately 9% in July. Oxygenated sesquiterpenes (SO) increased from a minimum of approximately 5% in July to a maximum of 8-11% in February, decreasing thereafter. The compounds that mostly accounted for the essential oil composition variation were alpha-pinene, beta-pinene, and camphene, as MH; alpha-thujone and camphor, as MO; alpha-humulene and beta-caryophyllene, as SH; and viridiflorol, as SO.     

Chemical composition and extraction yield of the extract of Origanum vulgare obtained from sub- and supercritical CO2

In this work sub- and supercritical CO(2) were used to obtain extracts from two origanum samples, one commercial, and another cultivated under agronomic control. The experiments were performed in the temperature range of 293-313 K and from 100 to 200 bar in pressure, employing around 26 g of origanum samples. Results show that the commercial sample provides a higher yield of extract if compared to the other sample. It is also achieved that a raise in temperature at constant pressure leads to an increase in the extraction yield despite solvent density changes. Chemical analyses were carried out in a GC-MSD, allowing the identification of around 24 compounds by use of the library of spectra of the equipment and injection of some standard compounds for both commercial and cultivated origanum samples. It was also found that the distribution of chemical components as a function of extraction time differs appreciably between the origanum species. The chromatographic analysis permitted the identification of thymol and cis-sabinene hydrate as the most prominent compounds present in commercial oregano sample and carvacrol and cis-sabinene hydrate in the cultivated Origanum vulgare.     

Recovery efficiency of nitrogen from liquid and solid fractions of pig slurry obtained using different separation technologies

The characteristics of solid (SF) and liquid (LF) fractions resulting from solid–liquid separation of pig slurry depend on the separation technique used. It can be assumed that the separation technique will also affect the nitrogen (N) availability to plants. A pot experiment was performed with ryegrass to compare the N‐recovery efficiency of SFs and LFs obtained with four frequently used separation techniques (centrifugation [Cent], sediment settling during 20 h [Sed], enhanced settling during 20 h by addition of cationic polyacrylamide [Sed+PAM], sieving [Siev], sieving followed by treatment of the resulting liquid fraction by PAM addition [Siev+PAM]) with the untreated slurry (US) and an unfertilized control. Increases (2–17%) of ryegrass dry matter yield (DMY) were obtained in LF treatments relative to US. However, this increase was statistically significant only for the Siev+PAM‐L treatment. A significant decrease of ryegrass DMY was observed in SF treatments relative to US. All treatments with SFs led to similar values of DMY while only small differences were observed between treatments receiving LFs. A significant correlation (R² = 0.968) was observed between the total DMY and the NH$ _4^+ $ ‐ N : N_tot ratio of the fraction applied suggesting that this is a major parameter to be considered when comparing separation techniques. Overall, the separation techniques showed only a weak effect on the dry matter yields and on the N ‐ recovery efficiency from LF and SF although they strongly affected the nutrient concentration and speciation in each fraction.     

Influence of drying methods and agronomic variables on the chemical composition of mate tea leaves (Ilex paraguariensis A. St.-Hil) obtained from high-pressure CO2 extraction

The main objective of this work is to assess the influence of two drying methods (microwave and vacuum oven) and some agronomic variables (plant fertilization conditions and sunlight intensity) on the characteristics of mate tea (Ilex paraguariensis) leaves extracts obtained from high-pressure carbon dioxide extractions performed in the temperature range from 20 to 40 degrees C and from 100 to 250 bar. Samples of mate were collected in an experiment conducted under agronomic control at Ervateira Bar?o LTDA, Brazil. Chemical distribution of the extracts was evaluated by gas chromatography coupled with a mass spectrometer detector (GC/MS). In addition to extraction variables, results showed that both sample drying methods and agronomic conditions exert a pronounced influence on the extraction yield and on the chemical distribution of the extracts.     

Formation of polycyclic aromatic hydrocarbons in the smoke from heated model lipids and food lipids.

The contents of polycyclic aromatic hydrocarbons (PAHs) in the smoke from model lipids and food lipids during heating were determined and the mechanism of PAH formation was studied. A Rancimat oil stability analyzer was used as a model system for heating model lipids and food lipids at 220 degrees C for 2 h and for adsorption of smoke. The various lipid degradation products and PAHs in the smoke were identified and quantified by a GC/MS technique. Results showed that model lipids were more susceptible to smoke formation than food lipids during heating, but the PAH levels were lower for the former than latter. Methyl linolenate produced the highest amount of PAHs, followed by methyl linoleate, methyl oleate, and methyl stearate. Also, soybean oil generated a larger amount of PAHs than canola oil or sunflower oil. Benzene-like compounds were found to be possible precursors for PAHs formation. Several PAH derivatives were also present in heated model lipids and food lipids.     

Effects of extraction methods on phenolic contents and antioxidant activity in aerial parts of Potentilla atrosanguinea Lodd. and quantification of its phenolic constituents by RP-HPLC

The effects of different solvent systems (methanol, ethanol, acetone, and their 50% aqueous concentrations) and extraction procedures (microwave, ultrasound, Soxhlet and maceration) on the antioxidant activity of aerial parts of Potentilla atrosanguinea were investigated by three different bioassays: 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assays and ferric reducing antioxidant potential (FRAP). The 50% aqueous ethanol extracts exhibited strong antioxidant activity measured in terms of Trolox equivalent antioxidant capacity (TEAC) [(54.34 to 122.96, 29.82 to 101.22 and 13.64 to 41.43) mg of Trolox/g] with ABTS (*+), DPPH (*) and FRAP assays, respectively. In general, TEAC of Soxhlet extracts was found to be 1.8 and 3 times higher than ultrasound and maceration but slightly (1.2 times) higher than microwave. A positive correlation (r(2) = 0.931 to 0.982) was observed between total polyphenol (TPC) and total flavonoid (TFC) contents which ranged between 26.7 to 30.7 mg/g gallic acid equivalent and 16.8 to 20.8 mg/g quercetin equivalent respectively, with antioxidant activity. In addition, some of its bioactive phenolic constituents which contribute largely toward antioxidant potential such as chlorogenic acid, catechin, caffeic acid, p-coumaric acid and quercetin were also quantified in different extracts by RP-HPLC.     

Chemical composition and structural features of the macromolecular components of plantation Acacia mangium wood

The wood of Acacia mangium, a prominent fast-growing plantation species used in the pulp-and-paper industry and, so far, poorly investigated for its chemical structure, was submitted to a detailed characterization of its main macromolecular components. Lignin (28% wood weight) isolated by mild acidolysis and characterized by permanganate oxidation, 1H and 13C NMR, and GPC, showed a very low content of syringylpropane-derived units (S:G:H of 48:49:3), a high degree of condensation, a low content of beta-O-4 ( approximately 0.40-0.43 per C6) structures, and a Mw of 2230. Glucuronoxylan (14% wood weight) isolated by alkaline (KOH) or by dimethyl sulfoxide extraction was characterized by methylation analysis, 1H NMR, and GPC. About 10% of the xylopyranose (Xylp) units constituting the linear backbone were substituted at O-2 with 4-O-methylglucuronic acid residues. Almost half of the Xylp units (45%) were O-2 (18%), O-3 (24%) or O-2,3 (3%) acetylated. X-ray diffraction analysis of cellulose (46% wood weight), isolated according to the Kürschner-Hoffer method, showed a degree of crystallinity of 67.6%.