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Determination of Teucrium chamaedrys volatiles by using direct thermal desorption-comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

The direct qualification and quantification of the volatile components of Teucrium chamaedrys was studied using a direct thermal desorption (DTD) technique with comprehensive two-dimensional (2D) gas chromatography-time-of-flight mass spectrometry (GC x GC-TOF/MS). The GC x GC separation chromatographically resolved hundreds of components within this sample, and with the separation coupled with TOF/MS for detection, high probability identifications were made for 68 compounds. The quantitative results were determined through the use of internal standards and the desorption of differing amounts of raw material in the injector. The highest yield of volatile compounds (0.39%, w/w) was obtained at 150 degrees C thermal desorption temperature using 1.0mg of dried sample placed in a glass injector liner when studied over the range 1.0-7.0mg. Lowest yield of 0.33% (w/w) was found for the largest sample size of 7.0mg. Relative standard deviation (RSD) for 10 replicates at each size sample were in the range 3.9-21.6%. The major compounds identified were beta-pinene, germacrene D, alpha-pinene, alpha-farnesene, alpha-gurjunene, gamma-elemene and gamma-cadinene. All identified compounds were quantified using total ion chromatogram (TIC) peak areas. DTD is a promising method for quantitative analysis of complex mixtures, and in particular for quantitative analysis of plant samples, which can yield data without the traditional obligation for costly and time-consuming extraction techniques.

Gas Chromatography-Mass Spectrometry↗

Comparison of micro-scale simultaneous distillation-extraction and stir bar sorptive extraction for the determination of volatile organic constituents of grape juice.

Traditional micro-scale simultaneous distillation-extraction (SDE) and stir bar sorptive extraction (SBSE) were compared for their effectiveness in the extraction of volatile organic compounds in a synthetic grape juice and a real grape juice (Huxelrebe, a variety of half Muscat ancestry) from an English vineyard. The novel immersion-mode SBSE method, using stir bars with PDMS sorbent, was optimised using the synthetic grape juice. Although mean percent relative recoveries and reproducibilities (%CV) of the SBSE method were inferior to SDE (28.4 and 8.5%, respectively, against 86.9 and 6.3%), the former method proved to be significantly more sensitive: 126 aroma compounds in Huxelrebe grape juice were identified using SBSE, against 98 using SDE. This allowed the identification of a number of volatile components that have not been reported previously in the juice or wine from the grapes of Muscat varieties.

Beverages↗

Method optimization by solid-phase microextraction in combination with gas chromatography with mass spectrometry for analysis of beer volatile fraction.

A simple and sensitive method for the analysis of beer volatile compounds was optimised using headspace solid-phase microextraction (SPME) and gas chromatography with mass detection. Headspace SPME using a 75 microm Carboxen-polydimethylsiloxane (CAR-PDMS) fiber provided effective sample enrichment and enabled extraction of a wide variety of compounds. The reproducibility depended on the compounds, with a mean value of 1.4% for alcohols, 3.3% for ethers, 6.7% for aldehydes, 3.4% for acids, 1.7% for aromatic compounds, 2.4% for esters, 7.4% for hydrocarbons, 1.8% for alicyclic compounds, and 3.4% for heterocyclic compounds. The optimised methodology can be used to compare volatile profile from different types of beers and eventually to study the evolution of a particular beer during aging.

Beer↗

Analysis of volatiles in water using headspace solid-phase microcolumn extraction.

A rapid solvent-free sample preparation method is presented in which volatilized organic substances are extracted via a solid-phase microcolumn mounted on a gas-tight syringe by the aspiration of an appropriate volume of headspace (tens of millilitres) of the sample under investigation. The microcolumn with the analytes concentrated on an adsorbent material is then transferred to the analytical instrument for desorption and analysis. The instrumental set-up consists of a Twister desorption unit (Gerstel) mounted on an Agilent 6890 GC system equipped with a CIS 4 programmed temperature vaporiser injector and coupled with an Agilent 5973 MS system. The instrumentation is slightly modified in comparison with the analysis made with a twister (stir bar coated with a layer of polydimethylsiloxane) after stir bar sorptive extraction and, thus, its utilization has been extended. For volatiles in water, the method is applicable to the qualitative screening at the microg/l to sub-microg/l level and to the quantitative determination at the ng/l level.

Chromatography, Gas↗

Analysis of Artemisia annua L. volatile oil by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry.

Artemisia annua L. is an annual herb native of Asia, it has been used for many centuries for the treatment of fever and malaria. In this paper, analysis of the volatile oil of Artemisia annua L. was performed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC x GC-TOF MS). Three hundred and three components were tentatively identified and terpene compounds are the main components of Artemisia annua L. volatile oil. Artemisinic acid is tentatively qualified.

Artemisia annua↗

Determination of hydroxycinnamic acids and volatile phenols in wort and beer by isocratic high-performance liquid chromatography using electrochemical detection.

The suitability of a simple and rapid isocratic RP-HPLC method with amperometric electrochemical detection for the simultaneous detection and quantification of hydroxycinnamic acids and their corresponding aroma-active volatile phenols in wort and beer is reported. The technique gives good specificity and sensitivity, and can therefore be used for routine monitoring of hydroxycinnamic acids in wort and the development of volatile phenolic flavour compounds during the beer production process and subsequent conservation.

Beer↗

Quantitative determination of wine highly volatile sulfur compounds by using automated headspace solid-phase microextraction and gas chromatography-pulsed flame photometric detection. Critical study and optimization of a new procedure.

The quantitative determination of wine volatile sulfur compounds by automated headspace solid-phase microextraction (HS-SPME) with a carboxen-polydimethylsiloxane (CAR-PDMS) fiber and subsequent gas chromatography-pulsed flame photometric detection (GC-PFPD) has been evaluated. The direct extraction of the sulfur compounds in 5 ml of wine has been found to suffer from matrix effects and short linear ranges, problems which could not be solved by the use of different internal standards or by multiple headspace SPME. These problems were attributed to saturation of the fiber and to competitive effects between analytes, internal standards and other wine volatiles. Another problem was the oxidation of analytes during the procedure. The reduction in sample volume by a factor 50 (0.1 ml diluted with water or brine) brought about a reduction in the amount of sulfur compounds taken in the fiber by a factor just 3.3. Consequently, a new procedure has been proposed. In a sealed vial containing 4.9 ml of saturated NaCl brine, the air is thoroughly displaced with nitrogen, and the wine (0.1 ml) and the internal standards (0.02 ml) are further introduced with a syringe through the vial septum. This sample is extracted at 35 degrees C for 20 min. This procedure makes a satisfactory determination possible of hydrogen sulfide, methanethiol, ethanethiol, dimethyl sulfide, diethyl sulfide and dimethyl disulfide. The linear dynamic ranges cover the normal ranges of occurrence of these analytes in wine with typical r2 between 0.9823 and 0.9980. Reproducibility in real samples ranges from 10 to 20% and repeatability is better than 10% in most cases. The method accuracy is satisfactory, with errors below 20% for hydrogen sulfide and mostly below 10% for the other compounds. The proposed method has been applied to the analysis of 34 Spanish wines.

Automation↗

Cytotoxic effects of volatile anesthetics with free radicals undergoing laparoscopic surgery.

BACKGROUND: Free radicals induced by several diseases can trigger oxidative stress, leading to the production of malondialdehyde (MDA) and protein carbonyl content (CB). Volatile agents are able to increase the extent of oxidative status. However, the effects of these agents together with pneumoperitonium (Pp) have not been reported. We aimed to investigate the role of volatile anesthetics and ischemic injury during Pp on free radicals and scavenging enzymes in laparoscopic abdominal surgery. METHODS AND MATERIALS: Forty patients were examined. Patients were randomly divided into four groups in order to receive sevoflurane-fentanyl (SF = 10), sevoflurane-N(2)O (SN = 10), desflurane-fentanyl (DF = 10), and desflurane-N(2)O (DN = 10), respectively. Tidal volume and ventilation frequency were kept unchanged during the operation. Intraabdominal pressure was remained constant at 12 mm Hg. Baseline values in venous blood samples were preoperatively taken and blood was also taken postoperatively at the 6th and the 24th hours. After collection of blood samples into citrate (3.5 mg/mL blood) containing glass tubes, erythrocyte sediments were prepared for the analyses. Then malondialdehyde levels, protein carbonyl content, and sulfhydryl (SH) groups were measured. RESULTS: The levels of MDA and protein carbonyl content were significantly higher at the 6th hour rather than the 24th hour postoperatively with desflurane anesthesia. In addition, SH groups were significantly different between the 6th hour and the 24th hour measurements (P < 0.05). In our study, desflurane caused a statistically significant increase in MDA levels and protein carbonyl content and a decrease in SH groups. When the two groups were compared, in the case of MDA and CB values, a significant increase was observed in the 6th and the 24th hour, where there was a decrease in SH groups in the desflurane group (P < 0.05). These parameters did not change in the sevoflurane group (P > 0.05). CONCLUSION: We concluded that desflurane was affected by desflurane with low flow anesthesia in patients undergoing laparoscopic abdominal surgery. Significant influence on oxidative stress and antioxidant mechanics was not seen with sevoflurane anesthesia. Our studies support that oxidant and antioxidant defense mechanisms were altered in the desflurane group and this alteration improved after a combination of desflurane-N(2)O.

Adult↗

Quantitative determination of volatile organic compounds in indoor dust using gas chromatography-UV spectrometry.

A novel technique, gas chromatography-UV spectrometry (GC-UV), was used to quantify volatile organic compounds (VOCs) in settled dust from 389 residences in Sweden. The dust samples were thermally desorbed in an inert atmosphere and evaporated compounds were concentrated by solid phase micro extraction and separated by capillary GC. Eluting compounds were then detected, identified, and quantified using a diode array UV spectrophotometer. Altogether, 28 compounds were quantified in each sample; 24 of these were found in more than 50% of the samples. The compounds found in highest concentrations were saturated aldehydes (C5-C10), furfuryl alcohol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2-furaldehyde, and benzaldehyde. Alkenals were also found, notably 2-butenal (crotonaldehyde), 2-methyl-propenal (methacrolein), hexenal, heptenal, octenal, and nonenal. The concentrations of each of the 28 compounds ranged between two to three orders of magnitude, or even more. These results demonstrate the presence of a number of VOCs in indoor dust, and provide, for the first time, a quantitative determination of these compounds in a larger number of dust samples from residents. The findings also illustrate the potential use of GC-UV for analysing volatile compounds in indoor dust, some of which are potential irritants (to the skin, eyes or respiratory system) if present at higher concentrations. The potential use of GC-UV for improving survey and control of the human exposure to particle-bound irritants and other chemicals is inferred.

Air Pollution, Indoor↗

Production of volatile organic sulfur compounds (VOSCs) by basidiomycetous yeasts.

Thirty-seven basidiomycetous yeasts belonging to 30 species of seven genera were grown on media containing l-cysteine or l-methionine as sole nitrogen sources with the objective of evaluating volatile organic sulfur compound (VOSC) production. The headspace of yeast cultures was analyzed by the solid-phase microextraction (SPME) sampling method, and volatile compounds were quantified and identified by GC-MS techniques. Ten strains assimilating L-methionine produced the following VOSCs: 3-(methylthio)-1-propanol, methanethiol, S-methyl thioacetate, dimethyl disulfide, dimethyl trisulfide, allyl methyl sulphide and 4,5-dihydro-3(2H)-thiophenone. Production was <1 mgl(-1) except for 3-(methylthio)-1-propanol of which between 40 and 400 mgl(-1) was synthesized. Higher alcohols (isobutyl alcohol, isoamyl alcohol and active amyl alcohol) and esters (ethyl acetate, ethyl propionate, n-propyl acetate, isobutyl acetate, n-propyl propionate, n-butyl acetate, isoamyl acetate, amyl acetate, isoamyl propionate, amyl propionate and 2-phenylmethyl acetate) were also sporadically produced. This is the first report of VOSCs production by basidiomycetous yeasts. Consequently, basidiomycetous yeasts may be considered an interesting new group of microbial VOSCs producers for the flavor industry.

Basidiomycota↗

Use of volatile fatty acids from an acid-phase digester for denitrification.

This study investigates the ability of naturally-produced volatile fatty acids (VFAs) to act as a carbon source for the removal of nitrate-Nitrogen concentrations in the range of 20 to 200 mg/L. The VFAs were generated from an anaerobic digester treating a 1:1 mixture of starch-rich industrial and municipal wastewater. The experiments were carried out at an ambient temperature of 22+/-2 degrees C using 600 mL batch reactors containing VFA-rich effluent from the digester and prepared primary sludge. Nitrates added in the form of a 1 M potassium nitrate solution were observed to completely disappear in conjunction with significant recovery of pH and alkalinity (i.e. biological denitrification). In all cases, denitrification followed zero-order kinetics with an average rate constant of 2.67 mg/[Lh] and a mean specific denitrification rate of 0.0111 g NOx-N/g volatile suspended solids (VSS) per day. The denitrifier population had a preference for acetic acid which occurred in the largest quantity and was exhausted the most rapidly. The next two most abundant VFAs were butyric acid and propionic acid, which were consumed only after acetate concentrations began to decline. The third "choice" of the denitrifiers was valeric acid, thus it appears that denitrifying bacteria have a sequential preference for VFAs. In addition, they prefer VFAs over other more complex soluble organic carbon forms.

Anaerobiosis↗

Hydroperoxide-lyase activity in mint leaves. Volatile C6-aldehyde production from hydroperoxy-fatty acids.

The extraction of 13-hydroperoxide-lyase activity from mint leaves as well as its use for C6-aldehyde production was studied in this work. The enzyme cleaves 13(S)-hydroperoxy-C18 fatty acids into C6-aldehyde and C12-oxo-acid. Two mint species were tested: Mentha veridis and Mentha pulegium. The headspace injection method coupled to gas chromatography was used for volatile compound analysis. The optimal conditions for temperature and pH were, respectively, 15 and 7 degrees C. We also studied the specific synthesis of hexanal and hexenals respectively from 13(S)-hydroperoxy-linoleic acid and 13(S)-hydroperoxy-linolenic acid. Considerable quantities of aldehyde (up to 2.58 micromol) were produced after 15 min of cleavage reaction in 2 ml stirred at 100 rpm, especially in presence of extract of M. veridis. The conversion yields decreased from 52.5% as maximum to 3.3% when using initial hydroperoxide concentrations between 0.2 and 15 mM. An unsaturated aldehyde, the 3(Z)-hexenal was produced from 13(S)-hydroperoxy-linolenic acid. The 3(Z)-isomer was unstable and isomerized in part to 2(E)-hexenal. In this work, we observed a very limited isomerization of 3(Z)-hexenal to 2(E)-hexenal, since the reaction and the volatile purge were carried out successively in the same flask without delay or any contact with the atmosphere. These aldehydes contribute to the fresh green odor in plants and are widely used in perfumes and in food technology. Their importance increases especially when the starting materials are of natural biological origin as used in this work. GC-MS analysis allowed the identification of the products.

Aldehyde-Lyases↗

Design and laboratory testing of a chamber device to measure total flux of volatile organic compounds from the unsaturated zone under natural conditions.

To determine if an aquifer contaminated with volatile organic compounds (VOCs) has potential for natural remediation, all natural processes affecting the fate and transport of VOCs in the subsurface must be identified and quantified. This research addresses the quantification of air-phase volatile organic compounds (VOCs) leaving the unsaturated zone soil gas and entering the atmosphere-including the additional flux provided by advective soil-gas movement induced by barometric pumping. A simple and easy-to-use device for measuring VOC flux under natural conditions is presented. The vertical flux chamber (VFC) was designed using numerical simulations and evaluated in the laboratory. Mass-balance numerical simulations based on continuously stirred tank reactor equations (CSTR) provided information on flux measurement performance of several sampling configurations with the final chamber configuration measuring greater than 96% of model-simulated fluxes. A laboratory device was constructed to evaluate the flux chamber under both diffusion-only and advection-plus-diffusion transport conditions. The flux chamber measured an average of 82% of 15 diffusion-only fluxes and an average of 95% of 15 additional advection-plus-diffusion flux experiments. The vertical flux chamber has the capability of providing reliable measurement of VOC flux from the unsaturated zone under both diffusion and advection transport conditions.

Air Movements↗

Effect of organic additives on the mitigation of volatility of 1-nitro-3,3'-dinitroazetidine (TNAZ): next generation powerful melt cast able high energy material.

1-Nitro-3,3'-dinitroazetidine (TNAZ) was synthesized based on the lines of reported method. Thermolysis studies on synthesized and characterized TNAZ using differential scanning calorimetry (DSC) and hyphenated TG-FT-IR techniques were undertaken to generate data on decomposition pattern. FT-IR of decomposition products of TNAZ revealed the evolution of oxides of nitrogen and HCN containing species suggesting the cleavage of C/N-NO(2) bond accompanied with the collapse of ring structure. The effect of incorporation of 15% additives namely, 3-amino-1,2,4-triazole (AT), 3,5-diamino-1,2,4-triazole (DAT), carbohydrazide (CHZ), 5,7-dinitrobenzofuroxan (DNBF), bis (2,2-dinitropropyl) succinate (BNPS), triaminoguanidinium nitrate (TAGN), 2,4,6-trinitrobenzoic acid (TNBA) and nitroguanidine (NQ) on the volatility of TNAZ was investigated by undertaking thermogravimetric analysis. The TG pattern brings out the potential of BNPS and TAGN as additives to mitigate the volatility of TNAZ. The influence of additives on thermal decomposition of pattern of TNAZ was also investigated by DSC. The DSC results indicated that the additives did not have appreciable effect on the melting point of TNAZ. Scanning electron microscopic (SEM) studies were carried out to investigate the effect of additives on morphology of TNAZ. This paper also discusses the possible mechanism involved in between the TNAZ and TAGN and BNPS. It appears that the formation of charge transfer complex formation between the TNAZ and TAGN/BNPS. The effect of addition of high explosives such as CL-20, HMX and RDX on thermo-physical characteristics of TNAZ is also reported in this paper.

Azetidines↗

Analysis of adsorption equilibrium of volatile chlorinated organic compounds to dry soil.

Adsorption is one of the main mechanisms of soil contamination by hazardous volatile chlorinated organic compounds. The adsorption equilibriums of six volatile organic chlorinated compounds to three dry soils were investigated using batch adsorption experiments. The adsorption equilibriums for the dry soils could be expressed by the Dubinin-Astakhov equation. The equation's parameters were analyzed with the characteristic values of the soils and compounds. No correlation between the values of the affinity coefficients, beta, and the molecular volume, Mv, was found. W(0) could be expressed by the functions of a pore volume of less than 10 nm, V(<10 nm), or the specific surface area, S. The adsorbed amount could be estimated using equations relating E(0), V(<10 nm) (or S), and beta. The predicted amounts agreed well with the measured data.

Adsorption↗

Dynamic determination of the concentration of volatile alcohols in a fixed bed of zeolite 13X by FT-IR.

A series of dynamic adsorptions of volatile methanol, ethanol, and iso-propanol (IPA) onto zeolite 13X were studied. Instead of traditional gas chromatography (GC), a gas-phase Fourier Transformation-IR (FT-IR) spectrometer was used to measure the evolution of concentrations of these volatile alcohols due to its quick response to the instantaneous changes of the gas concentration. Even though it has rarely been used in dynamic adsorption experiments in the literature, an FT-IR equipped with a constant-temperature gas cell was shown to be adequate to obtain breakthrough curves. In this study, the experiments were carried out at different gas flow rates and feed concentrations for each type of alcohol. Significant influences of the operating conditions on the breakthrough time, the shape of the breakthrough curve, and the uptake of each alcohol were found. A simple mathematical model proposed by Yoon and Nelson was applied to fit the experimental data. Good consistency between the experimental data and the regressed breakthrough curves was observed.

Adsorption↗

Headspace solvent microextraction-gas chromatography-mass spectrometry for the analysis of volatile compounds from Foeniculum vulgare Mill.

A novel and rapid headspace solvent microextraction followed by gas chromatography-mass spectrometry (HSME-GC-MS) for the analysis of the volatile compounds of Foeniculum vulgare Mill is described. HSME parameters including extracting solvent, extraction temperature and time, headspace volume and particle size were optimized. As a result, benzyl alcohol was finally used for the extraction at 70 degrees C for 20 min with headspace volume of 12.1 ml and particle size of 120 mesh. Under the determined conditions, the powered samples of Foeniculum vulgare Mill were directly applied for the analysis. A comparison of HSME-GC-MS, solid phase microextraction (SPME)-GC-MS and steam distillation (SD)-GC-MS methods was made and showed that the HSME-GC-MS method was simple, inexpensive and effective and can be used for the analysis of volatile compounds in traditional Chinese medicines (TCMs).

Foeniculum↗

Diffusible and volatile compounds produced by an antagonistic Bacillus subtilis strain cause structural deformations in pathogenic fungi in vitro.

An efficient antagonistic strain of Bacillus subtilis, originally isolated from the rhizosphere of established tea bushes, was found to cause structural deformities in six pathogenic fungi under in vitro culture conditions. This effect was attributed to the production of diffusible and volatile antifungal compounds. Out of the selected test fungi four were phytopathogenic, while the remaining two were of clinical importance. The bacterial strain successfully restricted the growth of all test fungi in dual cultures, and induced morphological abnormalities such as mycelial and conidial deviations. The inhibitory effect caused by volatiles was greater than that by diffusible compounds.

Antibiosis↗