Differentiation of wines according to grape variety and geographical origin based on volatiles profiling using SPME-MS and SPME-GC/MS methods.

Among methods to detect wine adulteration, profiling volatiles is one with a great potential regarding robustness, analysis time and abundance of information for subsequent data treatment. Volatile fraction fingerprinting by solid-phase microextraction with direct analysis by mass spectrometry without compounds separation (SPME-MS) was used for differentiation of white as well as red wines. The aim was to differentiate between varieties used for wine production and to also differentiate wines by country of origin. The results obtained were compared to SPME-GC/MS analysis in which compounds were resolved by gas chromatography. For both approaches the same type of statistical procedure was used to compare samples: principal component analysis (PCA) followed by linear discriminant analysis (LDA). White wines (38) and red wines (41) representing different grape varieties and various regions of origin were analysed. SPME-MS proved to be advantageous in use due to better discrimination and higher sample throughput.

Degradation of phytosterols during storage of enriched margarines.

Oxidative changes of phytosterols were recently studied in vegetable oils and some food products. Cholesterol-lowering properties of phytosterols and phytostanols are the main driver for formulating functional foods containing these compounds. Margarines enriched in plant stanols were stored at two typical temperatures for up to 18weeks. Analysed margarines contained four phytosterols: brassicasterol, campesterol, sitosterol, avenasterol and two phytostanols: sitostanol, campestanol. The content of phytosterols and phytostanols in margarines changed from 79mg/g in a control sample to 63mg/g and 55mg/g in samples stored for 18weeks at 4°C and 20°C, respectively. At the end of storage, contents of sitostanol decreased by 23% and 30%, while the amounts of oxidised sterols increased by 35% and 100%, respectively, for both temperatures. 7-Hydroxy derivatives dominated among all oxidised phytosterols and their content increased threefold at the end of storage. Epoxy derivatives exhibited a maximum after 6weeks of storage at 20°C and thereafter decreased constantly.

Volatile compounds responsible for aroma of Jutrzenka liquer wine.

Jutrzenka is a sweet liquer wine produced in Poland from the grape variety of the same name, developed in Poland to withstand the harsh climate of winery regions. Jutrzenka wine has a characteristic aroma with strong fruity and flowery notes, which make it unique among other liquer wines as demonstrated in sensory profile analysis. The work was aimed at characterization of volatile compounds in this wine, with the emphasis on characterization of compounds responsible for its unique aroma. Gas chromatography-olfactometry (GC-O) was applied to identify the key odorants using aroma extract dilution analysis (AEDA) approach. To facilitate free and bound terpenes and C(13)-norisoprenoids identification solid phase extraction (SPE) was used followed by GC/MS. Among identified key odorants ß-damascenone was the compound having the highest FD (4096), followed by isoamyl alcohol, 4-mercapto-4-methyl-2-pentanone (FD=2048), methional, linalool, ethyl decanoate (FD=1024) and ethyl hexanoate, furaneol (FD=512). Other significant compounds were ethyl 2-methyl propanoate, ethyl 2-methylbutanoate and phenyl ethyl alcohol. Determination of odor activity values (OAV) showed the highest values for ß-damascenone (566), 4-mercapto-4-methyl-2-pentanone (288) ethyl hexanoate (32) and linalool (7). Jutrzenka exhibited also a rich profile of free, and to lesser extent bound terpenes.

Odor active compounds content in spices and their microencapsulated powders measured by SPME.

Within this study, main odorants of marjoram and thyme (linalool and thymol) were determined in spices and microencapsulated powders using solid-phase microextraction (SPME). Analyses were conducted on selected batches of spices before and after decontamination and on microencapsulated powders prepared for technological purposes (improvement of aroma in decontaminated spices). Conditions of SPME analyses were determined for individual compounds and matrices. Determination of total and surface contents of compounds and the percentage dependencies between encapsulated and surface aroma made it possible to identify the best powders in terms of their quality.

Determination of trichothecenes in wheat grain without sample cleanup using comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

An application of comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC x GC-ToF MS) use for the analysis of trichothecene mycotoxins is described. Trichothecenes belonging to group A (scirpentriol, HT-2, T-2, 15-monoacetoxyscirpenol (15-MAS), 4,15-diacetylscirpenol (DAS), triacetoxyscirpenol (TAS)) and those belonging to group B (deoxynivalenol (DON), 3-acetyldeoxynivalenol, fusarenone-X, nivalenol) were analyzed and quantified as trifluoroacetic acid anhydride (TFAA) and trimethylsilyl (TMS) derivatives, respectively. The application has been developed for the determination of trichothecenes in wheat grain, after extraction, without any cleanup step. The separation of trichothecenes from matrix constituents was possible due to the vast peak capacity of comprehensive two-dimensional gas chromatography. Despite the presence of uncleaned matrix constituents signal-to-noise ratios for 25 pg of injected trichothecenes ranged from 11:1 to 78:1. Identification of compounds was based on their full spectra. The linearity in a range of 25-2,500 pg was generally 0.999 except for 3-acetyldeoxynivalenol deoxynivalenol and fusarenone-X. RSD for peak areas was <9% for all analyzed toxins.

Inhibition of stigmasterol oxidation by antioxidants in purified sunflower oil.

A study was conducted to analyze the effect of the antioxidants butylated hydroxytoluene, alpha-tocopherol, ethanolic extracts of rosemary, and green tea on stigmasterol resistance against degradation and formation of its oxidation products in purified triacylglycerols (TAG) from sunflower oil. The content of stigmasterol and its oxidation products 7alpha- and 7beta-hydroxy, alpha- and beta-epoxy, triol, and 7-ketostigmasterol were determined during incubation at 60 degrees C for 3, 6, and 9 days. In addition, peroxide value and fatty acid composition were also determined in the samples. Correlation between the levels of the accumulated stigmasterol oxides and peroxide value of the TAG with antioxidants during incubation was significant only for rosemary extract (R = 0.6799, p < 0.05). The lack of correlation precludes the use of peroxide values to determine the level of sterol oxidation products in the used model system. Correlation between stigmasterol content and the level of stigmasterol oxides was significant for all samples (R = 0.8874, p < 0.05). The total increase of the stigmasterol oxidation products was the lowest in samples with alpha-tocopherol, but the content of stigmasterol-triol increased the most in this sample. In all the analyzed samples, alpha-epoxy-stigmasterol was formed in the highest amounts among the analyzed stigmasterol oxidation products.

Determination of geosmin, 2-methylisoborneol, and a musty-earthy odor in wheat grain by SPME-GC-MS, profiling volatiles, and sensory analysis.

Geosmin and 2-methylisoborneol-compounds responsible for the musty-earthy off-odor of wheat grain, were isolated by SPME and analyzed by GC-MS. Carboxen/PDMS/DVB fiber coating was selected because of its highest extraction efficiency. Concentrations of geosmin and 2-methylisoborneol as low as 0.001 microg/kg were detected in SIM mode using ion trap mass spectrometer. Apart from GC-MS determination of geosmin and 2-methylisoborneol, various methods for evaluating the musty-earthy off-odor caused by these compounds in wheat grain are presented. Sensory profile analysis differentiated wheat grain into sound and off-flavored, but the method was tedious. Similar groupings, however, were obtained using more rapid methods such as comparison of volatile profiles using SPME-fast GC with PCA projection of data and metal oxide (MOS) based electronic nose.

Estimation of the main dill seeds odorant carvone by solid-phase microextraction and gas chromatography.

Solid-phase microextraction (SPME) was examined for its suitability for isolation of volatiles from seeds of dill in comparison with the traditional steam distillation procedure. Two main dill seeds volatiles, carvone and limonene, were taken into consideration. Two Supelco SPME fibers were used for the extraction: polyacrylic (PAc) and polydimethylsiloxane (PDMS). The time required to saturate the fibers was 3 min, while distillation took 3 h. Gas chromatography (GC) separation was reduced to 5 min by use of microcapillary column HP-5 cross-linked 5% Ph Me Siloxane. The standards of limonene and carvone were used to prepare calibration curves. PAc fiber responses were described by quadratic curves while PDMS responded linearly. Six varieties of dill were examined by distillation and SPME with both fibers. The good results were achieved for carvone by SPME-PDMS with significant regression between distillation and SPME. This compound can be measured in dill seeds samples within 10 min. The SPME-PDMS were also tested for its application to chiral resolution of carvone and limonene enantiomers in dill seeds oil. The enantiomeric separation was done with two chiral columns. The enantiomeric ratios measured by SPME were just the same as with distillation.