Identification of potent odourants in wine and brewed coffee using gas chromatography-olfactometry and comprehensive two-dimensional gas chromatography

Volatile constituents in wine and brewed coffee were analyzed using a combined system incorporating both GC-olfactometry (GC-O) and comprehensive two-dimensional GC-flame ionization detection (GC×GC-FID). A column set consisting of a 15m first dimension ((1)D; DB-FFAP (free fatty acid phase)), and a 1.0m (2)D column (DB-5 phase) was applied to achieve the GC×GC separation of the volatile extracts isolated by using solid phase extraction (SPE). While 1D GC resulted in many overlapping peaks, GC×GC allowed resolution of co-eluting compounds which coincided with the odour region located using GC-O. Character-impact odourants were tentatively identified through data correlation of GC×GC contour plots across results obtained using either time-of-flight mass spectrometry (TOFMS), or with flame photometric detection (FPD) for sulfur speciation. The odourants 2-methyl-2-butenal, 2-(methoxymethyl)-furan, dimethyl trisulfide, 2-ethyl-5-methyl-pyrazine, 2-octenal, 2-furancarboxaldehyde, 3-mercapto-3-methyl-1-butanol, 2-methoxy-3-(2-methylpropyl)-pyrazine, 2-furanmethanol and isovaleric acid were suspected to be particularly responsible for coffee aroma using this approach. The presented methodology was applied to identify the potent odourants in two different Australian wine varietals. 1-Octen-3-ol, butanoic acid and 2-methylbutanoic acid were detected in both Merlot and a Sauvignon Blanc+Semillon (SV) blend with high aroma potency. Several co-eluting peaks of ethyl 4-oxo-pentanoate, 3,7-dimethyl-1,5,7-octatrien-3-ol, (Z)-2-octen-1-ol, 5-hydroxy-2-methyl-1,3-dioxane were likely contributors to the Merlot wine aroma; while (Z)-3-hexen-1-ol, β-phenylethyl acetate, hexanoic acid and co-eluting peaks of 3-ethoxy-1-propanol and hexyl formate may contribute to SV wine aroma character. The volatile sulfur compound 2-mercapto-ethyl acetate was believed to contribute a fruity, brothy, meaty, sulfur odour to Australian Merlot and SV wines.     

Gas chromatography-olfactometry

GC-olfactometry (GC-O) refers to the use of human assessors as a sensitive and selective detector for odour-active compounds. The aim of this technique is to determine the odour activity of volatile compounds in a sample extract, and assign a relative importance to each compound. Methods can be classified into three types: detection frequency, dilution to threshold and direct intensity. Dilution to threshold methods measure the potency of odour-active compounds by using a series of extract dilutions, whereas detection frequency and direct-intensity methods measure odour-active compound intensity, or relative importance, in a single concentrated extract. Factors that should be considered to improve the value of GC-O analysis are the extraction method, GC instrument conditions, including the design and operation of the odour port, methods of recording GC-O data and controlling the potential for human assessor bias using experimental design and a trained panel. Considerable emphasis is placed on the requirement for multidimensional GC analysis, and on best practice when using human assessors.     

Thermal validation of a simple moving boundary model to determine the frying time of a thin potato crisp

A simple moving boundary model was redesigned to describe the immersion frying of a thin cut potato crisp of thickness 2 mm. The model took into account the effects of a variable oil convection heat transfer coefficient. In the model, the centre temperature was defined as a value of a region rather than a point. The model also predicted the effect of some shift in the location of the thermocouple on the measurements. Experiments at oil temperatures of 170, 180 and 190 °C were conducted to verify whether or not the model predictions were accurate. Good agreement was found between the experimental and predicted values, which were generally within the t ₉₉(0.01) confidence interval of the experimental data. Received on 3 November 1998     

The combination of gas chromatography-olfactometry and multidimensional gas chromatography for the characterisation of essential oils

A research area of great interest to the flavour industry is the analysis of odour active compounds in essential oils. In this paper, a methodology is presented for the identification of character-impact odorants in essential oil samples using (a) gas chromatography-olfactometry (GC-O); (b) comprehensive two-dimensional gas chromatography (GC x GC) combined to time-of-flight mass spectrometry (TOFMS) and (c) heart-cut multidimensional gas chromatography-olfactometry (MDGC-O). The specific advantages and limitations of each technique are discussed. The advantage of combining these techniques in a strategy to identify character-impact odorants is demonstrated using examples from coriander leaf (Coriandrum sativum) and hop (Humulus lupulus) essential oils. In particular, resolution of co-eluting regions of compounds and evaluation of their individual odour activity is discussed. In coriander leaf, only E-2-dodecenal was found to contribute to a co-eluting odour region, E-2-dodecen-1-ol and 1-dodecanol being present below detection threshold. Using MDGC on a hop essential oil sample, eight significant peaks were resolved from an 18 s heart-cut where a potent odorant was perceived during GC-O.     

Online monitoring of higher alcohols and esters throughout beer fermentation by commercial Saccharomyces cerevisiae and Saccharomyces pastorianus yeast

Higher alcohols and esters are among the predominant classes of volatile organic compounds (VOCs) that influence the quality of beer. The concentrations of these compounds are determined through a specific yeast strain selection and fermentation conditions. The effect of yeast strains on the formation of higher alcohols and esters throughout fermentations (at 20°C) was investigated. Flavour-relevant esters (ethyl acetate, isoamyl acetate, ethyl hexanoate and ethyl octanoate) and higher alcohols (isoamyl alcohol, isobutyl alcohol and phenylethyl alcohol) were monitored throughout the fermentation using proton transfer reaction–time of flight–mass spectrometry (PTR-ToF-MS) coupled with an automated sampling system for continuous measurements. Compound identification was confirmed by analysis of samples using gas chromatography–mass spectrometry (GC–MS). Results demonstrated the specific time points where variation in higher alcohol and ester generation between yeast strains occurred. In particular, the concentrations of isoamyl acetate, ethyl octanoate and isoamyl alcohol between yeast strains were significantly different over the first 2 days of fermentation; whereas, after Day 3, no significant differences were observed. The two Saccharomyces pastorianus strains produced comparable concentrations of the key higher alcohols and esters. However, the key higher alcohol and ester concentrations varied greatly between the two S. cerevisiae strains. The use of PTR–ToF–MS to rapidly measure multiple yeast strains provides new insights on fermentation for brewers to modify the sensory profile and optimise quality.     

Multiple component isolation in preparative multidimensional gas chromatography with characterisation by mass spectrometry and nuclear magnetic resonance spectroscopy

The preparative scale isolation of multiple components from an essential oil matrix is described using multidimensional gas chromatography (prep-MDGC) which allows their further characterisation by mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy. Menthol, linalyl acetate, carvone and geraniol were isolated individually, and were also collected in various combinations. It was demonstrated to be possible to collect multiple selected components from numerous repeat injections of the sample, to permit increased mass recovery from an external cryotrap collection device. Peak retention times remained reproducible (<0.3 s) over the repeated injections and switching events. This methodology may be utilised to confirm peak identity or to produce unique mixed-component reference standards, for instance to allow their identification in other samples using GC/MS, or identify them in comprehensive two-dimensional gas chromatography (GC × GC) analysis.     

Evidence for the quantum birth of our universe

We present evidence for a nonsingular origin of the Universe with intial conditions determined by quantum physics and relativistic gravity. In particular, we establish that the present temperature of the microwave background and the present density of the Universe agree well with our predictions from these intial conditions, after evolution to the present age using the Einstein-Friedmann equation. Remarkably, the quantum origin for the Universe naturally allows its evolution at exactly the critical density. We also discuss the consequences of these results to some fundamental aspects of quantum physics in the early Universe.     

Identification of character-impact odorants in coriander and wild coriander leaves using gas chromatography-olfactometry (GCO) and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC x GC-TOFMS)

The essential oil of coriander leaves (Coriandrum sativum) and wild coriander leaves (Eryngium foetidum) grown in Fiji was obtained by steam distillation. The aroma profiles were characterised using gas chromatography-olfactometry (GCO) and CharmAnalysis. The character-impact odorants were identified using comprehensive two-dimensional gas chromatography (GC x GC) combined with time-of-flight mass spectrometry (TOFMS). During GCO analysis, the co-elution of E-2-alkenals and E-2-alken-1-ols resulted in the perception of 'odour-clusters'. The most important odorants in C. sativum were found to be Z-2-decenal, a co-eluting odour-cluster (E-2-dodecenal, E-2-dodecen-1-ol, and 1-dodecanol), beta-ionone, eugenol, and E-2-decenal. E-2-decen-1-ol was the most abundant compound in C. sativum (26.0% TIC) but only contributed 0.39% of the total odour activity. The most abundant compound in E. foetidum was E-2-dodecenal (63.5% TIC), which also contributed the most odour activity (52.9%). Other important odorants were either eugenol or a trimethylbenzaldehyde isomer, beta-ionone, Z-4-dodecenal, dodecanal, and E-2-tetradecenal. GC x GC-TOFMS allowed the identification of 42 and 20 compounds not previously reported in the literature for C. sativum and E. foetidum, respectively. In particular, beta-ionone was determined to be an important odorant in both samples but could not be identified with GC-qMS.     

Difference frequency generation of 8-microm radiation in orientation- patterned GaAs

First-order quasi-phase-matched difference frequency generation of narrowband tunable mid-infrared light is demonstrated in orientation-patterned GaAs. The all-epitaxial orientation-patterned crystal is fabricated by a combination of molecular beam epitaxy and hydride vapor phase epitaxy. Lasers at 1.3 and 1.55 microm were mixed to give an idler output at 8 microm, with power and wavelength tuning consistent with theoretical estimates, indicating excellent material uniformity over the 19-mm-long and 500-microm-thick device.     

Measurement of the nonlinear coefficient of orientation-patterned GaAs and demonstration of highly efficient second-harmonic generation

Quasi-phase-matched (QPM) GaAs structures, 0.5 mm thick, 10 mm long, and with 61-mum grating periods, were grown by a combination of molecular-beam epitaxy and hydride vapor phase epitaxy. These were characterized by use of mid-IR second-harmonic generation (SHG) with a ZnGeP(2) (ZGP) optical parametric oscillator as a pump source. The SHG efficiencies of QPM GaAs and QPM LiNbO(3) were directly compared, and a ratio of nonlinear coefficients d(14)(GaAs)/d(33) (LiNbO(3))=5.01+/-0.3 was found at 4.1-mum fundamental wavelength. For input pulse energies as low as 50muJ and approximately 60-ns pulse duration, an internal SHG conversion efficiency of 33% was measured in QPM GaAs.