Headspace Solid Phase Micro-extraction Combined With Gas Chromatography-mass Spectrometry Research Articles

Development and validation of a high-throughput headspace solid-phase microextraction gas chromatography-mass spectrometry methodology for target and suspect determination of honey volatiles

The determination of volatile compounds is essential for the chemical characterisation of honey's aroma and its correlation to its sensory profile and botanical origin. The present study describes the development, optimization and validation of a new, simple and reliable method for the determination of volatile compounds in honey using headspace solid-phase microextraction combined with gas chromatography/mass spectrometry (HS-SPME-GC-MS). The optimization of the SPME conditions showed that the ratio of honey: water (2:1) and the incubation temperature (60 °C) are the most critical parameters. Gas chromatography was performed with medium polar Varian CP-Select 624 column and the experimental Retention Index for a number of compounds was determined as an additional identification feature for suspect analysis. The simultaneous use of four internal standards chlorobenzene, benzophenone, 2-pentanol and 4-methyl-2-pentanone and matrix matched calibration enhanced method accuracy achieving recoveries 73–114 % and repeatability ranging between 3.9 and 19 % relative standard deviations. Furthermore, the superiority of the HS-SPME to static head space technique was verified exhibiting four-to nine-fold higher sensitivity. Target and suspect screening were applied to 30 Greek honey samples and 53 volatile compounds belonging to different chemical classes, such as alkanes, aldehydes, ketones, alcohols, and esters were identified with quantified concentrations ranging between 3.1 μg kg−1 (Limonene) up to 20 mg kg−1 (Benzeneacetaldehyde). Among the new findings is the detection of Myrtenol in Greek pine honey and 2,3-butanediol in Greek oak honey. The developed analytical protocol can be a valuable tool in order to chemically characterize honey based on the volatile content.

Volatile Organic Compounds Produced by Kosakonia cowanii Cp1 Isolated from the Seeds of Capsicum pubescens R & P Possess Antifungal Activity.

The Kosakonia cowanii Cp1 strain was isolated from seeds of Capsicum pubescens R. & P. cultivated in Michoacan, Mexico. Genetic and ecological role analyses were conducted for better characterization. The results show that genome has a length of 4.7 Mbp with 56.22% G + C and an IncF plasmid of 128 Kbp with 52.51% G + C. Furthermore, pathogenicity test revealed nonpathogenic traits confirmed by the absence of specific virulence-related genes. Interestingly, when fungal inhibitory essays were carried out, the bacterial synthesis of volatile organic compounds (VOCs) with antifungal activity showed that Sclerotinia sp. and Rhizoctonia solani were inhibited by 87.45% and 77.24%, respectively. Meanwhile, Sclerotium rolfsii, Alternaria alternata, and Colletotrichum gloeosporioides demonstrated a mean radial growth inhibition of 52.79%, 40.82%, and 55.40%, respectively. The lowest inhibition was by Fusarium oxysporum, with 10.64%. The VOCs' characterization by headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME-GC-MS) revealed 65 potential compounds. Some of the compounds identified with high relative abundance were ketones (22.47%), represented by 2-butanone, 3-hydroxy (13.52%), and alcohols (23.5%), represented by ethanol (5.56%) and 1-butanol-3-methyl (4.83%). Our findings revealed, for the first time, that K. cowanii Cp1 associated with C. pubescens seeds possesses potential traits indicating that it could serve as an effective biocontrol.

Tracing the Volatilomic Fingerprint of the Most Popular Italian Fortified Wines.

The aim of the current study was to provide a useful platform to identify characteristic molecular markers related to the authenticity of Italian fortified wines. For this purpose, the volatilomic fingerprint of the most popular Italian fortified wines was established using headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME/GC-MS). Several volatile organic compounds (VOCs), belonging with distinct chemical groups, were identified, ten of which are common to all the analyzed fortified Italian wines. Terpenoids were the most abundant chemical group in Campari bitter wines due to limonene's high contribution to the total volatilomic fingerprint, whereas for Marsala wines, alcohols and esters were the most predominant chemical groups. The fortified Italian wines VOCs network demonstrated that the furanic compounds 2-furfural, ethyl furoate, and 5-methyl-2-furfural, constitute potential molecular markers of Marsala wines, while the terpenoids nerol, α-terpeniol, limonene, and menthone isomers, are characteristic of Vermouth wines. In addition, butanediol was detected only in Barolo wines, and β-phellandrene and β-myrcene only in Campari wines. The obtained data reveal an adequate tool to establish the authenticity and genuineness of Italian fortified wines, and at the same time constitute a valuable contribution to identify potential cases of fraud or adulteration to which they are subject, due to the high commercial value associated with these wines. In addition, they contribute to the deepening of scientific knowledge that supports its valorization and guarantee of quality and safety for consumers.

Differences in the Volatilomic Urinary Biosignature of Prostate Cancer Patients as a Feasibility Study for the Detection of Potential Biomarkers.

Prostate cancer (PCa) continues to be the second most common malignant tumour and the main cause of oncological death in men. Investigating endogenous volatile organic metabolites (VOMs) produced by various metabolic pathways is emerging as a novel, effective, and non-invasive source of information to establish the volatilomic biosignature of PCa. In this study, headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME/GC-MS) was used to establish the urine volatilomic profile of PCa and identify VOMs that can discriminate between the two investigated groups. This non-invasive approach was applied to oncological patients (PCa group, n = 26) and cancer-free individuals (control group, n = 30), retrieving a total of 147 VOMs from various chemical families. This included terpenes, norisoprenoid, sesquiterpenes, phenolic, sulphur and furanic compounds, ketones, alcohols, esters, aldehydes, carboxylic acid, benzene and naphthalene derivatives, hydrocarbons, and heterocyclic hydrocarbons. The data matrix was subjected to multivariate analysis, namely partial least-squares discriminant analysis (PLS-DA). Accordingly, this analysis showed that the group under study presented different volatomic profiles and suggested potential PCa biomarkers. Nevertheless, a larger cohort of samples is required to boost the predictability and accuracy of the statistical models developed.

Effects of Trellis Systems on the Vegetative Growth and Fruit Quality of Muscat-Flavored Table Grapes

The selection of appropriate grapevine trellis systems is of great importance for regulating vine vigor, forming grape yield, improving fruit quality, and labor-saving field management in the North China Plain. The effects of two trellis systems on the viticultural characteristics and fruit quality of three table grape cultivars: RuiduHongyu (RDHY), RuiduXiangyu (RDXY), and Red Globe (RG) were investigated. The two trellis systems were: (i) T trellis, with shoots positioned horizontally and downwards; and (ii) V trellis, with shoots positioned upright with an inclined angle. Headspace-solid-phase micro-extraction combined with gas chromatography mass spectrometry (HS-SPME-GC-MS) was used to determine the compositions and contents of the monoterpenes in the fruit. The results showed that for RDHY and RG, the T trellis showed better shoot growth consistency. The sugar–acid ratios of RDHY in 2019 and RDXY in 2021 under the T trellis were significantly higher than those under the V trellis. In 2020 and 2021, RDHY showed significantly higher total anthocyanin, flavonoid, and proanthocyanidin concentrations under the T trellis. The total monoterpene content in RDHY berries was significantly higher under the T trellis. The aromatic profiles of RDHY and RDXY grapes were similar and were mainly composed of citrus, other floral, other fruit, and rose aromatic characteristics. Among them, the main aromatic characteristics varied greatly among the different treatments. In conclusion, the Eurasian table grape cultivars with muscat flavor showed a more moderate and controllable vine vigor, consistent shoot growth, better fruit quality and taste, and greater accumulation of polyphenolic compounds and monoterpenes under the T trellis system.

Influence of Cold Pre-Fermentation Maceration on the Volatilomic Pattern and Aroma of White Wines.

Aroma compounds play a key role in wine quality due to their importance in wine aroma. The aim of the present study is to investigate the influence of cold pre-fermentative maceration (CPM) treatment on aromatic and sensory properties of white wines from four grape varieties (Tempranillo Blanco, Maturana Blanca, Viura and Garnacha Blanca) during two consecutive years (2019 and 2020). A total of 62 aroma compounds belonging to different chemical families were identified using headspace solid-phase microextraction combined with gas chromatography mass spectrometry (HS-SPME/GC-MS). CPM treatment enhanced the total relative concentration of alcohols, esters and acids compared to control wines. Regarding sensorial properties, esters made the greatest contribution to the studied white wines, mainly through the development of floral and fruity notes. On the other hand, CPM treatment did not significantly influence the total relative concentration of terpenoids, and different trends were observed according to grape variety and vintage. The obtained results showed differences in the wine's aromatic complexity according to the grape variety, the vintage and the treatment applied and suggested that CPM treatment could represent a suitable approach to manipulate the aromatic profile and enhance the aromatic quality and complexity of wine.

Key Aromatic Volatile Compounds from Roasted Cocoa Beans, Cocoa Liquor, and Chocolate

The characteristic aromas at each stage of chocolate processing change in quantity and quality depending on the cocoa variety, the chemical composition of the beans, the specific protein storage content, and the polysaccharides and polyphenols determining the type and quantity of the precursors formed during the fermentation and drying process, leading to the formation of specific chocolate aromas in the subsequent roasting and conching processes. Bean aroma is frequently profiled, identified, and semiquantified by headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPMEGC-MS) and by gas chromatography olfactometry (GC-O). In general, the flavors generated in chocolate processing include fruity, floral, chocolate, woody, caramel, earthy, and undesirable notes. Each processing stage contributes to or depletes the aroma compounds that may be desirable or undesirable, as discussed in this report.

Analyzing Volatile Compounds of Young and Mature Docynia delavayi Fruit by HS-SPME-GC-MS and rOAV.

This study focused on the examination of the volatile compounds and fragrance properties of the young and mature fruit of Docynia delavayi. Headspace solid-phase microextraction combined with gas chromatography−mass spectrometry (HS-SPME-GC-MS) was applied for identifying 42 volatile compounds, with young and mature fruit containing 36 and 42 compounds, respectively. Heat map cluster analysis, principal component analysis (PCA), orthogonal partial least squares discriminant analysis (OPLS-DA), and independent sample t-testing were used to analyze sample differences. Based on a variable importance in projection (VIP) > 1 and p < 0.05, 23 key volatile compounds such as octanal, geranylacetone, butyl acetate, and dihydro-β-ionone were screened. β-Ionone and phenethyl acetate made the largest contribution to the aroma of D. delavayi after analyzing the relative odor activity value (rOAV) of the key volatile compounds and their aroma descriptors. Young D. delavayi fruit exhibited a prominent woody scent, while mature D. delavayi fruit had more intense floral and rosy aromas. The findings may lay a foundation for comprehensively developing and utilizing D. delavayi fruit.

Flavor and Functional Analysis of Lactobacillus plantarum Fermented Apricot Juice

The small white apricot is a juicy, delicious fruit with a short shelf life. Slight fermentation can significantly promote the flavors and nutrient value of apricot juice. This study used high-performance liquid chromatography (HPLC) and headspace solid-phase microextraction combined with gas chromatography–mass spectrometry (HS-SPME-GC-MS) to examine the physicochemical properties, nutritive value and flavor substances of apricot juice fermented by Lactobacillus plantarum LP56. Fermentation significantly increased lactic acid bacteria (LAB) and their product lactic acid, adding probiotic benefits to fermented apricot juice. In addition, the total phenolic compounds and antioxidant capacity increased, while the levels of soluble solids and organic acids decreased. Gallic acid, 3-caffeoylquinic acid and rutin mainly contributed to the antioxidant activity of fermented apricot juice. Alcohols, aldehyde, acid, ester, etc., were the main volatile compounds. Among the flavors, 12 substances with high odor activity values (OAV &gt; 1) were the key aroma-producing compounds with fruit, pine and citrus flavors. In conclusion, this study shows that L. plantarum LP56 fermentation can improve the nutritional value and aroma characteristics of apricot juice.

Removal of VOCs from wood by introducing activators to form hydroxyl radicals in-situ generation platform

Wood contains abundant extractives and volatile oils, resulting in the emission of hazardous volatile organic compounds (VOCs) and unpleasant odors. The homogeneous Fe2+ catalyzed Fenton reaction remains an attractive advanced oxidation process (AOPs) for the degradation of hazardous organic contaminants, but limited by due to the poor permeability of wood and wide distribution of extractives, the effective removal of wood extractives remained a challenge. Herein, a facile approach toward forming an in-situ ·OH radical generation platform was proposed by introducing EDTA-Fe2+ chelating agent into parenchyma cells and resin canals of wood by vacuum impregnation. Oxidation process was carried out using a “respiratory impregnation” method that imitated human respiration. The Electron paramagnetic resonance (EPR) analysis reveals that·OH was generated in-situ as the primary reactive species. Various controlling factors, including Fe2+ concentration, pH value, and H2O2 concentration were evaluated. The removal rate of VOCs was estimated by headspace solid-phase micro-extraction combined with gas chromatography-mass spectrometry (HS-SPME/GC-MS). The best results (89.5% removal without cycling treatment) were observed at pH = 3, H2O2 = 20 mM and Fe2+ = 200 mM. This work improves the feasibility of using the Fenton system to remove VOCs from wood products.

Chemical constituents, antibacterial, acaricidal and anti-inflammatory activities of the essential oils from four Rhododendron species

As the ornamental plants and traditional medicines, Rhododendron przewalskii, R. anthopogonoides, R. thymifolium, and R. capitatum are widely distributed in western China. In this paper, the essential oils from these four species were extracted by supercritical extraction and the components were analyzed using headspace solid phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME-GC-MS), the antibacterial, acaricidal and anti-inflammatory activities were investigated. Results showed that R. thymifolium (RTEO) contained the highest yield of 0.99% with 246 compounds, followed by R. capitatum (RCEO, 0.81%) with 290 chemicals, R. anthopogonoides (RAEO, 0.57%) with 302 compounds and R. przewalskii (RPEO, 0.30%) with 294 components. They also exhibited the safety at given doses and have the anti-inflammatory in vitro and in vivo tests via inhibiting the cytokines productions, the acaricidal and antibacterial activities also were found. 4-Hydroxy-3-methylacetophenone from RPEO, α-pinene and β-pinene from RAEO, β-farnesene and germacrone from RTEO, and benzylacetone from RCEO, as main and active components, inhibited the NO content in RAW 264.7 cells induced by LPS. These results indicated that four essential oils have certain medicinal value and laid the foundation for the development of these species as raw materials for the pharmaceutical and perfume industries.

Effects of Fruit Bagging Treatment with Different Types of Bags on the Contents of Phenolics and Monoterpenes in Muscat-Flavored Table Grapes

The effects of fruit bagging treatments with seven different types of bags on the physicochemical characteristics of three table grape cultivars: RuiduZaohong (RDZH), RuiduHongyu (RDHY), and RuiduHongmei (RDHM) were investigated. Headspace-solid-phase micro-extraction combined with gas chromatography mass spectrometry (HS-SPME-GC-MS) was used to determine the compositions of monoterpenes in the fruit. The results showed that the total soluble solids in RDZH and RDHY fruits treated with the transparent, mesh, yellow, white, and blue bags were significantly higher than the control. The sugar–acid ratio of RDZH was optimized under the transparent bag and yellow bag treatments, and both significantly increased the sugar-acid ratio of RDHY and RDHM. Additionally, mesh bag, transparent bag, and white bag improved the contents of phenolics to a certain extent. The most abundant volatiles were linalool, geraniol, β-myrcene, β-cis-ocimene, and β-trans-ocimene, of which linalool was the main aroma component. The least squares discriminant analysis results showed that linalool, 4-terpineol, and terpinolen could be used to distinguish the main contribution of different bagging treatments for RDZH. Trans-isogeraniol, α-terpineol, and terpinolen could be used for RDHY. Trans-isogeraniol, β-myrcene, and terpinolen could be used for RDHM. In conclusion, transparent and white bags promoted the accumulation of phenolics and monoterpenes while pink and blue bags showed inhibitory effects.

Analysis of flavor-related compounds in fermented persimmon beverages stored at different temperatures

Storage temperature plays a very important role in the flavor development of fermented beverages. In this study, fermented persimmon beverage was stored for one year to study the changes in flavor-related compounds during storage at different temperatures. Fresh persimmon beverage and fermented beverages stored at 10, 20, and 30 °C had different tastes, distinguished by electronic tongue (ET). The fermented beverage was sweet when stored at 10 °C and salty when stored at 20 °C or above. A total of 658 nonvolatile metabolites were identified, among which quercetin and epicatechin were detected by a liquid chromatography-mass spectrometry (LC-MS) based metabolomics approach from four fermented beverage samples. The volatile compounds in the beverages were determined by headspace solid phase microextraction, combined with gas chromatography-mass spectrometry (HS-SPME-GC-MS) and gas phase-ion migration spectroscopy (GC-IMS), respectively showing totals of 47 and 69 compounds in the four beverage samples. As detected by both methods, ethyl acetate, ethyl hexanoate, ethyl octanoate, ethanol, and acetic acid were all found in beverages stored at different temperatures and the results showed that a higher storage temperature resulted an increase in the number of volatile compounds in the beverage. However, fermented persimmon beverage stored at low temperatures had a better taste and flavor characteristics.

Correlation analysis of normal and moldy beef jerky microbiota with Volatile compounds

In this study, the microbial composition and volatile flavor components of normal beef jerky (NBJ) and moldy beef jerky (MBJ) from three different regions were examined using high-throughput sequencing (HTS) and headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME-GC-MS) to explore the effects of microbial and environmental factors on MBJ, and the correlation between core microorganisms and volatile compounds were revealed using Spearman rank correlation analysis (|r | >1, P < 0.05). At the genera level, Aspergillus, Xeromyces and Wallemia were the dominant fungi. While Nicotiana_Otophora, Staphylococcus, Bacillus, Brochothrix and Acinetobacter were the dominant bacterial genera. 82 volatile compounds were identified in beef jerky from different regions. The correlation heat map between microorganisms and volatile compounds showed that eight core microbial genera had significant effects on the flavor quality of beef jerky after mold (VIP>1, P < 0.05), including five fungal and 3 bacteria, namely Arthrobacter, Xerochrysium, Dryomyces, Aspergillus, Colletotrichum, Bacillus, Staphylococcus and Salvia_pomifera. Bacillus, Staphylococcus, Salvia_pomifera and Colletotrichum had significant effects (P < 0.05) on 18 compounds, which may be classified as key microorganisms that affect beef jerky spoilage. Our study provides a theoretical reference for solving the problem of MBJ.

Effective degradation of VOCs from wood by Fe2+ chelate activated dual oxidant (H2O2-PS)

Wood is rich in extractives and volatile oils that emit unpleasant odors and some harmful volatile organic compounds (VOCs). Chemical oxidation technologies processes high efficiency on the destruction of aqueous organic components via oxidation by radicals, however, wood block treatment scenarios suffer from the low availability of radicals in aqueous conditions owing to the special structure of the wood blocks, limitations of mass transfer and the short life of free radicals. Herein, ethylenediaminetetraacetic acid (EDTA) is selected as a chelating agent to synthesize EDTA-Fe2+ chelate, thus introducing Fe2+ into the wood by vacuum impregnation. The Fe2+ is evenly distributed and immobilized in the wood to form a chemical oxidation system via in-situ activation of the dual oxidant (H2O2-PS), which truncates the contact distance between free radicals and extractives/volatile oils thus enhancing the removal efficiency. Various controlling factors, including EDTA/Fe2+ molar ratio, Fe2+dosage, PS/H2O2 molar ratio, and persulfate (PS) dosage are evaluated. The degradation products of VOCs by headspace solid-phase micro-extraction combined with gas chromatography-mass spectrometry (HS-SPME/GC-MS) indicate that the wood VOC removal rate is ∼80%. The Electron paramagnetic resonance (EPR) analysis further reveals that SO4−· and ·OH are the primary reactive species. The characterization of wood properties illustrates that the process has no destructive effect. The results of this work may provide a theoretical basis for feasibility of the practical application of the EDTA-Fe2+/H2O2-PS system.

Characterization of the Volatile Profile of Cultivated and Wild-Type Italian Celery (Apium graveolens L.) Varieties by HS-SPME/GC-MS

Celery (Apium graveolens L.) is a vegetable belonging to the Apiaceae family that is widely used for its distinct flavor and contains a variety of bioactive metabolites with healthy properties. Some celery ecotypes cultivated in specific territories of Italy have recently attracted the attention of consumers and scientists because of their peculiar sensorial and nutritional properties. In this work, the volatile profiles of white celery “Sedano Bianco di Sperlonga” Protected Geographical Indication (PGI) ecotype, black celery “Sedano Nero di Torricella Peligna” and wild-type celery were investigated using head-space solid-phase microextraction combined with gas-chromatography/mass spectrometry (HS-SPME/GC-MS) and compared to that of the common ribbed celery. Exploratory multivariate statistical analyses were conducted using principal component analysis (PCA) on HS-SPME/GC-MS patterns, separately collected from celery leaves and petioles, to assess similarity/dissimilarity in the flavor composition of the investigated varieties. PCA revealed a clear differentiation of wild-type celery from the cultivated varieties. Among the cultivated varieties, black celery “Sedano Nero di Torricella Peligna” exhibited a significantly different composition in volatile profile in both leaves and petioles compared to the white celery and the prevalent commercial variety. The chemical components of aroma, potentially useful for the classification of celery according to the variety/origin, were identified.

Multi-Statistical Approach for the Study of Volatile Compounds of Industrial Spoiled Manzanilla Spanish-Style Table Olive Fermentations.

Table olives can suffer different types of spoilage during fermentation. In this work, a multi-statistical approach (standard and compositional data analysis) was used for the study of the volatile organic compounds (VOCs) associated with altered (butyric, sulfidic, and putrid) and non-altered (normal) Manzanilla Spanish-style table olive fermentations. Samples were collected from two industrial fermentation yards in Seville (Spain) in the 2019/2020 season. The VOC profiles of altered (n = 4) and non-altered (n = 6) samples were obtained by headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME-GC-MS). Ninety-one VOCs were identified and grouped into alcohols (30), esters (21), carbonyl compounds (12), acids (10), terpenes (6), phenols (6), sulfur compounds (2), and others (4). The association of the VOCs with spoilage samples depended on the standard or compositional statistical methodology used. However, butyric spoilage was strongly linked by several techniques to methyl butanoate, ethyl butanoate, and butanoic acid; sulfidic spoilage with 2-propyl-1-pentanol, dimethyl sulfide, methanol, 2-methylbutanal, 2-methyl-2-butenal, ethanol, 2-methyl-3-buten-2-ol, and isopentanol, while putrid was mainly related to D-limonene and 2-pentanol. Our data contribute to a better characterisation of non-zapatera spoiled table olive fermentations and show the convenience of using diverse statistical techniques for a most robust selection of spoilage VOC markers.

Effects of different preheat treatments on volatile compounds of camellia (Camellia oleifera Abel.) seed oil and formation mechanism of key aroma compounds.

In this study, volatile compounds of camellia seed oil (CSO) prepared by different preheat treatments (microwave, frying, roasting, and steaming) were identified by headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME/GC-MS). A total of 107 volatile compounds were identified in CSO samples, including aldehydes (16), alcohols (6), ketones (3), heterocyclic compounds (26), esters (23), hydrocarbons (15), and others (17). Among them, untreated CSO is mainly hydrocarbons, roasting and steaming CSO are mainly aldehydes and alcohols, while microwave and roasting CSO are dominated by aldehydes and heterocyclic compounds. Fourteen volatile compounds with high relative odor activity value (ROAV≥1) were selected as key aroma compounds (KACs). Principal Component Analysis (PCA) and Cluster Analysis (CA) were performed on 14 KACs, which determined that there were 3, 3, 3, 7, and 6 characteristic aroma compounds (CACs) in untreated, microwaved, frying, roasting, and steaming CSO. Additionally, the potential formation pathways and mechanism of KACs were discussed. PRACTICAL APPLICATIONS: Flavor is an important factor for consumers to choose edible oils, and it is also one of the indicators of oil quality. Different flavors of CSO can cater to the needs of different consumers. CSO manufactories can choose different preheat treatments to produce CSO with various flavors to meet different customers' need. CSO with new flavor can extend its market share and increase its value.

Effects of different brewing processes on the volatile flavor profiles of Chinese vinegar determined by HS-SPME-AEDA with GC-MS and GC-O

Effects of different brewing processes, such as the solarization process (i.e. with or without), selection of different types of rice as a raw material (i.e. normal or sticky rice), and addition of flavoring materials (i.e. presence or absence of spices or sugar), on the aroma profiles of three types of Chinese vinegars were investigated. These three vinegars were the Longmen aromatic sweet rice vinegar (LASRV), Longmen aromatic rice vinegar (LARV), and Longmen rice vinegar (LRV). Headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME-GC-MS) and HS-SPME-aroma extract dilution analysis combined with gas chromatography-olfactometry (HS-SPME-AEDA-GC-O) were used to identify and quantify the volatile compounds, as well as the aroma-active compounds in the Longmen vinegars. Among the total of 68 volatile compounds that were identified, 49 were confirmed by their corresponding chemical standards. The results showed that the LASRV sample contained higher concentrations of acids, alcohols, esters, sulfides, acetal, and aromatic hydrocarbons because of effects of the solarization process and the presence of added sugar. The LARV sample was found to contain more aldehydes, pyrazines, ketones, phenols, lactone, and oxazoles, which might be contributed by the solarization process, as well as the addition of spices.

Identification of the Volatile Compounds and Observation of the Glandular Trichomes in Opisthopappus taihangensis and Four Species of Chrysanthemum.

Opisthopappus taihangensis (Ling) Shih, a wild relative germplasm of chrysanthemum, releases a completely different fragrance from chrysanthemum species. We aimed to identify the volatile compounds of the leaves of O. taihangensis and four other Chrysanthemum species using headspace solid-phase micro-extraction combined with gas chromatography-mass spectrometry (HS-SPME-GC/MS). In total, 70 compounds were detected, and terpenoids accounted for the largest percentage in these five species. Many specific compounds were only emitted from O. taihangensis and not from the other four species. In particular, 1,8-cineole could be responsible for the special leaf fragrance of O. taihangensis as it accounted for the largest proportion of the compounds in O. taihangensis but a small or no proportion at all in other species. The glandular trichomes (GTs) in the leaves are the main organs responsible for the emission of volatiles. To explore the relationship between the emissions and the density of the GTs on the leaf epidermis, the shape and density of the GTs were observed and calculated, respectively. The results showed that the trichomes have two shapes in these leaves: T-shaped non-glandular trichomes and capitate trichomes. Histochemical staining analyses indicated that terpenoids are mainly emitted from capitate glandular trichomes. Correlation analysis showed that the volatile amount of terpenoids is highly related to the density of capitate trichomes. In O. taihangensis, the terpenoids content and density of capitate trichomes are the highest. We identified the diversity of leaf volatiles from O. taihangensis and four other Chrysanthemum species and found a possible relationship between the content of volatile compounds and the density of capitate trichomes, which explained the cause of the fragrance of O. taihangensis leaves.