Static Headspace Solid-phase Microextraction Research Articles

The olfactory component of floral display in Asimina and Deeringothamnus (Annonaceae)

Floral scent is a key component of floral display, and probably one of the first floral attractants linking insect pollinators to the radiation of Angiosperms. In this article, we investigate floral scent in two extra-tropical genera of Annonaceae. We discuss floral scent in the context of differing pollination strategies in these genera, and compare their scent to that of a close tropical relative. Floral volatiles were collected for Annona glabra, Asimina and Deeringothamnus whole flowers and dissected floral organs, using a standardized static-headspace solid phase microextraction method. Scents were analyzed using gas chromatography-mass spectrometry, and identified using known standards. The floral scents of these species are highly dynamic, varying between floral organs, sexual stages and species. Maroon-flowered species of Asimina produce 'yeasty' odors, dominated by fermentation volatiles and occasionally containing sulfurous or nitrogenous compounds. White-flowered species of Asimina and Deeringothamnus produce pleasant odors characterized by lilac compounds, benzenoids and hydrocarbons. Annona glabra produces a strong, fruity-acetonic scent dominated by 3-pentanyl acetate and 1,8-cineole. The fermented/decaying scents of maroon-flowered species of Asimina suggest mimicry-based pollination strategies similar to aroids and stapeliads, whereas the pleasant scents of white-flowered species of Asimina suggest honest, reward-based pollination strategies. The scent of Annona glabra is typical of specialized beetle pollination systems common to tropical Annonaceae.

Characterisation of volatile compounds in Tunisian fenugreek seeds

Abstract In this study, we intend to develop a simple and fast analytical procedure to identify the volatile compounds implicated in the odour of Tunisian fenugreek (Trigonella foenum-graceum L.) seeds. Two procedures, solvent extraction and static headspace solid-phase microextraction (SHS-SPME), have been used under different conditions. The volatile compounds extracted were systematically identified using gas chromatography–mass spectrometry, based on their mass spectrum and Kovats index on two columns of different polarity. A total of 67 compounds were identified, some of them being reported for the first time in fenugreek seeds (e.g. several pyrazines, 2,5-dimethyl-4-hydroxy-3(2H)-furanone or 1-epi-cubenol). Methanol was found to be the preferred solvent for high and medium boiling point volatile compounds, such as sotolone and nitrogen compounds. For SHS-SPME, the fibre coated with divinylbenzene/carboxen/polydimethylsiloxane 2 cm was the most suitable for extracting volatile compounds from ground seeds. The efficiency of this fibre was confirmed by direct gas chromatography–olfactometry, with a global odour similar to that of fenugreek seeds.

Volatile flavour constituent patterns of Terras Madeirenses red wines extracted by dynamic headspace solid‐phase microextraction

A suitable analytical procedure based on static headspace solid-phase microextraction (SPME) followed by thermal desorption gas chromatography-ion trap mass spectrometry detection (GC-(ITD)MS), was developed and applied for the qualitative and semi-quantitative analysis of volatile components of Portuguese Terras Madeirenses red wines. The headspace SPME method was optimised in terms of fibre coating, extraction time, and extraction temperature. The performance of three commercially available SPME fibres, viz. 100 mum polydimethylsiloxane; 85 mum polyacrylate, PA; and 50/30 mum divinylbenzene/carboxen on polydimethylsiloxane, was evaluated and compared. The highest amounts extracted, in terms of the maximum signal recorded for the total volatile composition, were obtained with a PA coating fibre at 30 degrees C during an extraction time of 60 min with a constant stirring at 750 rpm, after saturation of the sample with NaCl (30%, w/v). More than sixty volatile compounds, belonging to different biosynthetic pathways, have been identified, including fatty acid ethyl esters, higher alcohols, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, and monoterpenols/C(13)-norisoprenoids.

Analysis of Volatile Compounds in Beef Fat by Dynamic‐Headspace Solid‐Phase Microextraction Combined with Gas Chromatography–Mass Spectrometry

A solid-phase microextraction (SPME) technique has been applied to the determination of the volatile compounds, including diterpenoids and lactones, in cooked beef fat. The ability of static-headspace SPME to extract lactones was disappointing, regardless of the type of SPME fiber or the temperature used. Dynamic-headspace SPME extraction with 50-/30-microm divinylbenzene-Carboxen on a polydimethylsiloxane fiber at 100 degrees C, by contrast, enabled the analysis of volatiles, including delta-lactones, gamma-lactones, and diterpenoids, with 50-/30-microm divinylbenzene-Carboxen on a polydimethylsiloxane fiber at 100 degrees C. Fifty-three compounds were identified from only 0.20 g of rendered beef fat, and 76% of these showed reliable peak size repeatability: the coefficient of variation was less than 10% on the total ion chromatograms obtained from gas chromatography-mass spectrometry (GC-MS) analysis. Some lactones showed higher CV values (>10%), but single-ion mode GC-MS analysis reduced them to 10% or less. In a study of beef samples available to the Japanese market, our analytical procedure revealed significantly higher levels of 1-hexanol, octadecane, ethyl tetradecanoate, gamma-nonalactone, but lower levels of delta-decalactone, delta-dodecalactone, and neophytadiene, in Japanese Black cattle than in beef imported from Australia.

Enantiomeric monoterpene emissions from natural and damaged Scots pine in a boreal coniferous forest measured using solid-phase microextraction and gas chromatography/mass spectrometry

In order to develop a valuable method for accurate screening of biogenic emissions from undisturbed living plants or for plant-insect interactions, solid-phase microextraction (SPME) has been combined with dynamic branch enclosure cuvettes and enantioselective GC/MS. The study was conducted at Hyytiälä forest station, Finland within a boreal coniferous forest dominated by Scots pine ( Pinus sylvestris). The SPME method was optimized for monoterpenes by testing three fibre coatings: polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB) and carbowax/divinylbenzene (CW/DVB) and determining the optimum exposure time. The PDMS/DVB fibre was found to be most suitable and was used to characterize emissions of P. sylvestris enclosed in dynamic branch enclosure cuvettes by exposure for 1 min followed by desorption and separation on a β-cyclodextrin column installed in the GC/MS oven. Dynamic cuvette measurements have been compared to static headspace SPME samples of the emission of detached needles from the same tree species and a portable dynamic air sampler (PDAS)-SPME for sampling the ambient air around the same trees. The method developed has allowed an accurate characterization of the gaseous emission of P. sylvestris and the identification of 17 isoprenoids comprising chiral and achiral monoterpenes. Two chemotypes of Scots pine can be differentiated through their emission of (+)-δ-3-carene. While SPME-dynamic cuvette, portable dynamic sampler and absorbent results agreed well, significant differences in enantiomeric ratios were observed in natural emissions and those of damaged leaves. Therefore, in enantioselective studies of plant–insect and/or plant–plant interactions, the two enantiomers of a given monoterpene should be treated as two separate substances.

Solid‐phase microextraction gas chromatography/mass spectrometry: a new method for species identification of truffles

This study describes a rapid method to identify different truffle species by analysis of their volatile compound fraction using static headspace solid-phase microextraction gas chromatography/mass spectrometry. The volatile organic compounds (VOCs) were extracted using a new 2-cm 50/30 microm DVB/CAR/PDMS fiber placed for 10 min in the headspace of the truffle sample with the vial maintained at 20 degrees C (in a thermostatically controlled analysis room). The mass spectra of the VOC chromatograms were represented as 'fingerprints' of the analysed samples. Next, stepwise factorial discriminant analysis afforded a limited number of characteristic fragment ions that allowed a classification of the truffle species studied. This new method provides an effective approach to rapid quality control and identification of truffle species by analysis of their volatile fraction. Moreover, this method offers the advantage of minimizing thermal, mechanical, and chemical modifications of the truffles, thereby reducing the risk of analytical artifacts.

Determination of flavor components in Sicilian goat cheese by automated HS-SPME-GC

This investigation is based on the gas chromatographic analysis of the volatile fraction of Sicilian goat cheese. Volatile analytes were extracted through static headspace solid phase microextraction (HS-SPME) with the sup- port of a modern automatic instrument designed specifically for this sampling procedure. Component identification was carried out by GC-MS and the employment of internal standard compounds. In the preliminary part of this research, different fibres and capillary columns were tested and their effectiveness compared in order to optimize solute extraction and separation. Furthermore, the HS-SPME sampling conditions were properly tuned in order to maximize solute absorp- tion. Evaluations were also made on the SPME instrumentation and its capability to supply reproducible data. The optimized method was applied to the investigation of six goat cheese samples and their aroma profiles were evaluated, leading to the identification of 44 components. Copyright © 2005 John Wiley & Sons, Ltd.

Solid-phase microextraction of volatile components from natural grassland plants.

The volatile components from nine plants growing on natural grasslands in Auvergne, central France, selected for the broad qualitative and quantitative diversity of their terpenoid fractions, were analyzed by high-resolution gas-phase chromatography and mass spectrometry (HRGC-MS) after static headspace solid-phase microextraction (SHS-SPME). SHS-SPME allowed all the plant material to be analyzed under the same conditions despite its wide-ranging composition. This is not always possible with other extraction methods. Using an apolar poly(dimethylsiloxane) (PDMS) phase, numerous terpenoid hydrocarbons, together with alcohols, cyclic ethers, and esters, were extracted. Its ease of use and the high resolution of the chromatographic profiles obtained make SHS-SPME well suited to the rapid characterization of the main components of the volatile fraction of plants. Of the nine plants studied, four (Meum athamanticum, Pimpinella saxifraga, Achillea millefolium, and Thymus pulegioides) exhaled more than 60 different volatile components. Certain terpenes present in large amounts in these plants might help link dairy products to grazing pasture, thus improving food traceability.

A comparison of solid-phase microextraction (SPME) fibres for measurement of hexanal and pentanal in cooked turkey

Static headspace solid-phase microextraction (SPME) was evaluated for the quantitative measurement of hexanal in cooked turkey samples. Three fibre materials Carboxen/PDMS, PDMS/DVB and Carbowax/DVB with fibre thickness of 75, 65 and 65 μm, respectively, were compared for linearity, limit of detection, and repeatability of response to hexanal in cooked turkey samples. In terms of reproducibility and linearity of response the PDMS/DVB fibre was the most effective of the three fibres studied while Carboxen/PDMS was the most sensitive, with a limit of detection for hexanal of 2 ng/g. The use of 2-methyl pentanal as an internal standard facilitated the accurate measurement of hexanal and pentanal in oxidised turkey homogenates. In fresh and oxidised cooked turkey samples a high correlation between both hexanal and pentanal levels determined by SPME/GC and lipid oxidation measured as 2-thiobarbituric reactive substances (TBARS) was obtained.

438 Optimization of a SPME Method for Flavor Characterization in Fresh-cut Cantaloupe

Fresh-cut melons in many consumer-ready packages are notorious for “wetting” and accumulation of standing juices. These conditions likely create undesirable flavor and aroma changes. We initiated a study to investigate flavor changes in stored fresh-cut cantaloupe. One objective was to optimize solid phase microextraction (SPME) to evaluate organoleptic compounds. Static head-space SPME analyses were performed on fresh-cut cantaloupe cubes (≈2.5 mm, 5 mm, or 2.5 cm), expressed juice, and homogenized slurries. SPME fiber (100 μm PDMS vs. 75 μm Carboxen/PDMS) exposure time (5, 7.5, 10, 12.5, 15, 17.5, 20 min) was evaluated at 40 °C with various head-space: product ratios, plus or minus NaCl to produce typical chromatograms. Fibers were desorbed in an HP5890 GC with a DB-624 or DB-5 column for 45-min runs and an HP6890 GC (DB-5) equipped with a 5973 MS detector for 35-min runs. Albeit qualitative, the best chromatograms were obtained with 7-ml slurries, stirred with NaCl, exposed to a 10 0μm PDMS SPME fiber for 12.5 min. The 100 μm PDMS fiber produced better chromatograms considering the fact that many important flavor volatiles are low-molecular-weight polar esters and alcohols. These conditions were subsequently used to analyze numerous fresh-cut cantaloupe samples stored various times (0 to 9 days). Over 100 peaks were identified, many of which changed through storage and some are suspected as probable agents responsible for undesirable flavor changes. Our analyses are progressing in an attempt to authenticate compounds associated with flavor-related changes in numerous fresh-cut cantaloupe varieties from various growing regions.