Multidimensional Gas Chromatography of Organosulfur Compounds in Coffee and Structure-Odor Analysis of 2-Methyltetrahydrothiophen-3-one.

Organosulfur compounds (OSCs) in coffee remain challenging to analyze by conventional gas chromatography (GC) due to their low concentrations amid coffee's complex matrix and susceptibility to chiral-odor influences. In this study, multidimensional GC (MDGC) methods were developed to profile OSCs in coffee. Conventional GC was compared to comprehensive GC (GC×GC) for untargeted OSC analysis in eight specialty coffees, and GC×GC was found to improve the fingerprinting of OSCs in coffee (50 vs 16 OSCs identified). Of the 50 OSCs, 2-methyltetrahydrothiophen-3-one (2-MTHT) was of high interest due to its chirality and known aroma contribution. Following that, a heart-cutting method for chiral GC (GC-GC) was developed, validated, and applied to the coffees. The mean enantiomer ratio of 2-MTHT was observed to be 1.56 (R/S) in brewed coffees. Overall, MDGC techniques allowed for more comprehensive analyses of coffee OSCs, from which (R)-2-MTHT was found to be the predominant enantiomer with the lower odor threshold.

Characterisation of catechins and their oxidised derivatives in Ceylon tea using multi-dimensional liquid chromatography and high-resolution mass spectrometry.

Tea is a complex food matrix comprising of many structurally diverse compounds, of which catechins and their oxidised derivatives are of particular interest due to their nutritional functionality. However, these catechins and derivatives exist in various isomeric forms with few or no pure standards available, rendering their analysis challenging. A method combining multi-dimensional liquid chromatography (MDLC) and high-resolution mass spectrometry (HRMS) was developed for the characterisation of these compounds using Ceylon tea as a model. Based on a Plackett-Burman (PB) design, flow rate and initial methanol percentage were identified as the most significant factors (p < 0.05) affecting chromatogram coverage and resolution (Rs) for comprehensive two-dimensional LC (LCxLC) and heart-cutting two-dimensional LC (LC-LC) respectively. Central composite design (CCD) was then applied using these parameters for method optimisation and to identify second-order relationships between screened parameters. The optimised LCxLC (flow rate: 2.18 mL/min and initial methanol percentage: 28.0%) and LC-LC (flow rate: 0.86 mL/min and initial methanol percentage for different cuts: A- 10.0%; B- 15.8%; and C- 18.7%) methods were applied to the analysis of Ceylon tea samples from seven regions of Sri Lanka and demonstrated an improved separation of co-eluting isomeric compounds. Finally, with the mass spectral information from HRMS, a total of 31 compounds (eight monomers, 17 dimers, five trimers and one tetramer) were detected and putatively identified in Ceylon tea.

Effect of three milling processes (cyclone-, bead- and stone-millings) on the quality of matcha: Physical properties, taste and aroma.

Analysis of three matcha (cyclone-, bead- and stone-milled) revealed differences in their sizes and surface morphologies. Using liquid chromatography, 4 sugars, 6 organic acids, 18 amino acids and 9 polyphenols were detected in all matcha samples and shown to present in different amount. Moreover, 108 volatile compounds were detected and 30 potential flavour-contributing compounds were quantified by gas chromatography time-of-flight mass spectrometry using headspace-stir bar sorptive extraction-thin-film solid-phase microextraction (HS-SBSE-TFSPME). Sensory evaluation by a trained panel found that the matcha samples possess different notes (cyclone-milled: leafy; bead-milled: fishy; and stone-milled: roasty) which is supported by the volatile compound analysis. Finally, the three matcha were differentiated based on non-volatile and volatile components using principal component analysis, and the correlation between chemical composition and sensory evaluation data was carried out using partial least square regression. In conclusion, milling processes clearly affected the physical, chemical and sensory qualities of matcha.

Combination of solid phase microextraction and low energy electron ionisation gas chromatography-quadrupole time-of-flight mass spectrometry to meet the challenges of flavour analysis.

The flavour analysis of volatile compounds remains challenging not only because of their diversity in properties and dynamic range, but also due to the high background noise from food matrix constituents. To improve sensitivity and specificity for a multiclass range of compounds, a combination of solid phase micro-extraction (SPME) devices and low energy electron ionisation (LE-EI) was proposed for the analysis of 36 volatile compounds, using coffee as a model matrix. From a pre-evaluation of devices and extraction modes, the combined use of direct immersion-stir bar sorptive extraction and headspace-thin-film SPME (SBSE-TFSPME) was selected to increase compound recovery, and further optimised for extraction temperature (88 °C) and time (110 min). Furthermore, to complement sample preparation by improving method specificity, a LE-EI technique was developed by evaluating the effect of ionisation energy, source temperature, and emission current on the formation of the diagnostic molecular ions and their preservation. This LE-EI method (15 eV, 150 °C, 0.3 µA) was validated with SBSE-TFSPME as a complete workflow in coffee matrices, and was found to possess good repeatability (intra-day RSD: 1.6-7.3 %), intermediate precision (inter-day RSD: 4.1-12.2 %), and linearity (R2 > 0.98). Even for complex coffee samples, the method detection limit reached the pg/mL range (e.g. 2,4,5-trimethylthiazole was detected at 15 pg/mL). In conclusion, this study provided insights on the potential of SPME and LE-EI to improve the sensitivity and specificity of analysis for a range of volatile compounds from food and other complex matrices.

Identification of key odorants in honeysuckle by headspace-solid phase microextraction and solvent-assisted flavour evaporation with gas chromatography-mass spectrometry and gas chromatograph-olfactometry in combination with chemometrics.

At present, the identification of honeysuckle aroma depends on experienced tasters, which results in inconsistencies due to human error. The key odorants have the potential to distinguish the different species and evaluate the quality of honeysuckle. Hence, in this study, a more scientific approach was applied to distinguish various honeysuckles. The volatile compounds of different species and parts of honeysuckle were separately extracted by headspace-solid phase microextraction (HS-SPME) and solvent assisted flavor evaporation (SAFE). Compounds with greater volatility such as aldehydes, limonene, γ-terpinene, and terpinolene were preferentially extracted by HS-SPME. As a complementary extraction method to HS-SPME, SAFE was found to recover comparatively more polar compounds such as eugenol, decanoic acid, and vanillin. Subsequently, key odorants with the highest flavour dilution (FD) factors were detected by aroma extract dilution analysis (AEDA). These were benzaldehyde, 4-ethylphenol, decanoic acid, vanillin, 3-methyl-2-butenal, and ß-ionone in honeysuckle flowers and γ-octalactone, 4-ethyl phenol, and vanillin in honeysuckle stem. Finally, principal component analysis (PCA) was conducted to analyze not only the key odorants of species and parts of honeysuckle but also their different origins. The results of PCA suggested that the species of honeysuckle contributed much more to variations in aroma rather than their origins. In conclusion, the application of the key odorants combined with PCA was demonstrated as a valid approach to differentiate species, origins, and parts of honeysuckle.

Improved detection of key odourants in Arabica coffee using gas chromatography-olfactometry in combination with low energy electron ionisation gas chromatography-quadrupole time-of-flight mass spectrometry.

Four Arabica coffees (Brazil, Colombia, Ethiopia, and Guatemala) yield highly variant odours, attesting to the complexities of coffee aroma that command advanced analytical tools. In this study, their volatiles were extracted using solvent-assisted flavour evaporation (SAFE) and headspace solid-phase microextraction (HS-SPME). Due to matrix complexity, some trace odourants were detected in SAFE extracts by aroma extract dilution analysis (AEDA) but remained difficult to quantify by gas chromatography-mass spectrometry (GC-MS). This prompted the application of low energy electron ionisation (EI) coupled with GC-quadrupole time-of-flight (GC-QTOF). Optimal low EI GC-QTOF parameters (EI energy: 15 eV, acquisition rate: 3 Hz) were applied to achieve improved molecular ion signal intensity and reproducibility (relative standard deviation < 10%) across five compounds, which resulted in good linearity (R2 ≥ 0.999) and lowered detection levels (e.g. 0.025 ±â€¯0.005 ng/mL for 4-hydroxy-5-methyl-3(2H)-furanone). Therefore, this method potentially improves the measurement of trace odourants in complex matrices by increasing specificity and sensitivity.