Analysis of terpenoids from hemlock (Tsuga) species by solid-phase microextraction/gas chromatography/ion-trap mass spectrometry

A sampling method for determining the volatile terpenoid composition from single needles of seven Tsuga species was developed using headspace solid-phase microextraction (SPME). A reproducible sampling method for the volatile components was generated by examination of sample storage, method of needle cutting, and headspace sampling duration. Following SPME collection of the volatile compounds from the seven Tsuga species, gas chromatography/ion-trap mass spectrometry was used to identify 51 terpenoids present in the needle headspace. A semiquantitative method was devised to express individual terpenoid amounts as a percentage of all of the identified peaks in the chromatogram. The semiquantitative results permitted facile interspecies comparison using principal component analysis. Two components were able to account for 90% of the variance and were interpreted as a "species" component and a "resistance/susceptibility" component. Three interspecies groupings were evident from the principal component analysis: (1) Tsuga canadensis and Tsuga caroliniana; (2) Tsuga chinesnsis, Tsuga diversifolia, Tsuga heterophylla, and Tsuga sieboldii; and (3) Tsuga mertensiana. The finding that T. mertensiana was grouped alone and far removed from the other species adds to the morphological evidence that this species should be segregated from other Tsuga.     

Characterization of terpenoid volatiles from cultivars of eastern hemlock (Tsuga canadensis)

The volatile terpenoid fraction from needles in 13 cultivars of Tsuga canadensis L. (Carriere) was analyzed by gas chromatography with mass spectrometry (GC-MS). The results of this study are considered along with previously reported results for foliar terpenoid levels of the Asian (T. sieboldii, T. chinensis, T. diversifolia), western North American (T. mertensiana, T. heterophylla), and eastern North American species (T. canadensis, T. caroliniana) of hemlock to draw conclusions about the potential of cultivar host resistance to the hemlock woolly adelgid (Adelges tsugae Annand). It is suggested that hemlocks in eastern North America have adapted their terpenoid chemistry for protection against endemic defoliators and that this has made them vulnerable to non-native, sucking pests such as adelgids and scales. Some cultivars of T. canadensis have a terpenoid profile that resembles that of the resistant noneastern North American species and are candidates for biological screening for resistance. Among the cultivars, the variation in terpenoid chemistry did not absolutely correspond with the considerable differences in morphological characters observed, indicating that the terpenoid chemistry is not definitively coupled with hemlock morphology.     

不同品种和生长期嘉宝果叶片酚类及挥发性物质研究

为研究不同品种和生长期嘉宝果叶片酚类及挥发性物质的含量和组成,分别通过比色法、水蒸气蒸馏法和顶空-气相色谱/质谱联用技术,对沙巴、四季早生、福冈等9个品种嘉宝果老/嫩叶的总酚、总黄酮、精油含量和挥发性成分进行测定。结果表明,沙巴嫩叶的总酚含量(31.87%)最高;阿根廷嫩叶总黄酮含量(24.81%)最高;沙巴老叶精油含量(2.78‰)最高,其次为沙巴嫩叶(2.42‰)。老叶中相对含量在0.05%以上的挥发性化合物有31~44种,均以萜类为主;嫩叶中相对含量在0.05%以上的化合物有28~40种,同样以萜类为主。除沙巴、阿根廷、大红钻老/嫩叶和福冈老叶外,其余老/嫩叶均以倍半萜为优势成分。沙巴老叶主要成分为α-蒎烯、桉叶油醇;沙巴嫩叶为β-蒎烯和α-蒎烯;阿根廷老/嫩叶、大红钻嫩叶和白艾斯老叶为β-蒎烯;福冈老/嫩叶为β-石竹烯;四季早生、大巨红晶、艾斯卡老/嫩叶为β-胡椒烯;乔尼尔老/嫩叶为β-石竹烯、β-胡椒烯。主成分分析结果表明,单萜含氧衍生物、α-蒎烯、单萜烯、β-蒎烯、α-芹子烯是导致不同品种间嘉宝果老叶香气差异的主要物质;倍半萜烯、单萜烯、β-蒎烯、α-蒎烯、β-石竹烯是导致不同品种间嘉宝果嫩叶香气差异的主要物质。综上,沙巴嫩叶总酚含量最高,精油含量较高,活性挥发性物质蒎烯(α-蒎烯+β-蒎烯)相对含量高达62.41%,在抗菌、抗炎、抗氧化、抗肿瘤等方面有潜在的利用价值,在医药领域有极大的研究价值和开发潜力。     

Associations between the sensory attributes and volatile composition of Cabernet Sauvignon wines and the volatile composition of the grapes used for their production

The sensory properties of wine are influenced by the chemical composition of the grapes used to produce them. Identification of grape and wine chemical markers associated with the attributes perceived by the consumer of the wine will enable better prediction of the potential of a parcel of grapes to produce wine of a certain flavor. This study explores the relationships between Cabernet Sauvignon grape volatile composition and wine volatile profiles with the sensory properties of wines. Twenty grape samples were obtained from nine vineyard sites across three vintages and wines vinified from these parcels using controlled winemaking methods. The volatile composition of the grapes were analyzed by SBSE-GCMS, the wines were analyzed by SPME-GCMS, and these data sets were compared to that obtained from the sensory analysis of the wines. Statistical treatment of the data to account for vintage and region effects allowed underlying relationships to be seen between wine sensory attributes and wine or grape volatile components. The observed associations between grape or wine volatile compounds and wine sensory attributes has revealed target compounds and pathways whose levels may reflect the biochemical effects on grape composition by differing growth conditions during berry development and ripening. The compounds identified in this study may be useful grape or wine markers for potential wine sensory characteristics.     

基于转录组测序的文心兰花香形成分析

文心兰具有很高的观赏价值,但花香形成分子机制研究相对薄弱。本研究以香水文心、黄梦香和白梦香为材料,利用气相色谱-质谱分析其花香挥发物成分。结果表明,3个品种的花香挥发物均以萜类化合物为主,但种类差异较大。盛花期花香挥发物总量由高到低依次为黄梦香、香水文心、白梦香。从转录组数据中共获得459 756个单基因(unigenes),大约40.61%的unigenes被公共数据库注释。MEP和MVA途径中的多数基因在黄梦香中表达量最高,香水文心次之,白梦香最低,与花香挥发物释放总量相符。转录组数据中共筛选出5个显著差异表达的萜类合成酶基因(TPS)。其中,OnTPS4在3个品种中均高表达,说明OnTPS4在3个品种中对香气的形成起重要作用;OnTPS1、OnTPS2和OnTPS5在香水文心中表达偏高,是调控香水文心萜类挥发物形成的重要基因;OnTPS3在黄梦香中表达较高,是调控黄梦香萜类挥发物形成的重要基因。由上述结果可知,MEP和MVA途径的基因表达水平与花香挥发物释放总量相一致,TPS的表达与具体萜类挥发物释放密切相关。 本研究通过花香形成机理研究,为文心兰花香改良提供了依据。     

Composition of the water-soluble fraction of different cheeses

Volatile and nonvolatile compounds present in the water-soluble fraction (WSF) and water-soluble fraction with molecular weight lower than 1000 Da (WSF < 1000 Da) of six Spanish cheeses, Cabrales, Idiazábal, Mahón, Manchego, Roncal, and a goat's milk cheese, were analyzed. Different nitrogen fractions (determined by Kjeldahl method), caseins (by capillary electrophoresis), peptides and amino acids (by HPLC), and volatile components (by dynamic headspace coupled to GC-MS) as well as mineral content in the cheese fractions were analyzed and compared. The different nitrogen and volatile compounds identified in the WSF were characteristic of each cheese variety. Cabrales cheese displayed the highest content of free amino acids and the highest quantity and variety of volatile compounds. The WSF < 1000 Da fraction was less representative, especially for volatile compounds, as some of the components were lost in the ultrafiltration. Alcohols were better recovered than ketones and esters.     

储藏玉米陈化机理及挥发物与品质变化的关系

为了找寻挥发性物质与玉米储藏品质指标的关系,探讨玉米品质变化机理.对重庆地区不同储藏时间的玉米,采用项空气相色谱-质谱联用法测定其挥发性物质,同时测定其生理、生化指标,研究挥发性物质的种类和含量及其与储藏时间、生理、生化指标的相关性.研究结果表明:不同储藏时间的玉米挥发性物质种类基本相同,只是在量上存在差异.随着储藏时间的延长,玉米的总挥发性物质以及单个挥发性物质含量逐渐增加.总挥发性物含量、丙酮、对环己二烯、环戊乙炔、乙酸、己醛的含量与储藏时间、生理生化指标呈较高相关性,可作为玉米储存品质变化的评判指标.储存玉米的挥发性物质主要是由脂质的氧化和水解产生的.     

Volatile metabolites from actinomycetes

Twenty-six Streptomyces spp. were screened for their volatile production capacity on yeast starch agar. The volatile organic compounds (VOCs) were concentrated on a porous polymer throughout an 8-day growth period. VOCs were analyzed by gas chromatography with flame ionization detection and identified or characterized by gas chromatography-mass spectrometry. A total of 120 VOCs were characterized by retention index and mass spectra. Fifty-three compounds were characterized as terpenoid compounds, among which 18 could be identified. Among the VOCs were alkanes, alkenes, alcohols, esters, ketones, sulfur compounds, and isoprenoid compounds. Among the most frequently produced compounds were isoprene, acetone, 1-butanol, 2-methyl-1-propanol, 3-methyl-3-buten-1-ol, 3-methyl-1-butanol, 2-methyl-1-butanol, cyclopentanone, dimethyl disulfide, dimethyl trisulfide, 2-phenylethanol, and geosmin. The relationship between the excretion of geosmin and the production of spores was examined for one isolate. A good correlation between headspace geosmin and the number of spores was observed, suggesting that VOCs could be used to indicate the activity of these microorganisms in heterogeneous substrates.     

Volatile metabolites from Salvia fruticosa as antifungal agents in soilborne pathogens

The volatile metabolites of Salvia fruticosa plants, growing wild in 15 localities scattered across Greece, were analyzed by means of GC and GC-MS. The essential oil content ranged from 0.69 to 4.68%, and the results of the analyses showed a noticeable variation in the amounts of the five main components [1,8-cineole, alpha-thujone, beta-thujone, camphor, and (E)-caryophyllene]. The antifungal activities of the essential oils from two localities, belonging in two different groups of cluster and principal component analysis, and their main components (1,8-cineole and camphor) were evaluated in vitro against five phytopathogenic fungi. Both oils were slightly effective against Fusarium oxysporum f. sp. dianthi and Fusarium proliferatum, whereas against Rhizoctonia solani, Sclerotinia sclerotiorum, and Fusarium solani f. sp. cucurbitae the oils exhibited high antifungal activities.     

贮藏过程中京甜紫花糯2号玉米软罐头的主要挥发性风味成分的变化

采用顶空固相微萃取和气相色谱-质谱联用（HS-SPME-GC/MS）技术,测定京甜紫花糯2号玉米软罐头贮存10个月的挥发性物质,并对主要挥发性物质的变化进行探讨;同时对京甜紫花糯2号玉米软罐头蒸煮香气和不良气味进行感官评定,使用偏最小二乘回归分析法（PLSR）研究感官测定结果与仪器测定结果的相关性。结果显示,京甜紫花糯...     

Effects of abscisic acid and calcium on tomato fruit aroma volatiles

Aroma volatiles are derived from precursors, such as amino acids, fatty acids and carotenoids in tomato fruit. Volatiles enhance the main flavor components in the fruit, particularly sugars. Abscisic acid (ABA) is derived from the carotenoid pathway and there may be an indirect connection to this pathway. Therefore, the purpose of this study was to examine the influence of ABA on tomato fruit volatiles. This study identified five flavor volatile compounds that were consistently present in “Mt. Fresh Plus” tomato fruit tissue. They were 2-methyl furan, (E)-2-hexeanl, 1-hexanol, hexenal, and 6-methyl-5-hepten-2-one. ABA treatments did not have an effect on volatile concentrations in “Mt. Fresh Plus” tomato fruit. Majority of the volatiles identified did not differ between the ABA treated plants and the ABA control plants. However, ABA treatments did significantly decrease (E)-2-hexenal. These results indicated that ABA treatments did not have a major effect on the aroma volatile profile of the fruit.     

Volatile components in crabmeats of Charybdis feriatus

The volatile components of different meats (legs with claws, body, and carapace) of a popularly consumed edible crab in Asia, Charybdis feriatus, were investigated. Samples were extracted by simultaneous steam distillation-solvent extraction and analyzed by gas chromatography/mass spectrometry. Among 177 compounds detected, 130 were positively identified. Seventy-six compounds were previously reported in other crab species. A greater number of naphthalenes were detected in this crab compared with other crabs in the literature. Aromatic compounds, alcohols, and sulfur-containing compounds were the three predominant groups with >15 components. Carapace tissue contained a greater number of volatile components in each group, except for sulfur-containing compounds. Most of the common components in the leg meat and the body meat were found at similar levels (p > 0.05). Carapace tissue generally had the highest quantity of common components among the meats. The higher levels of volatile components present in the carapace tissue might account for its stronger flavor compared with the other meats. Furthermore, the higher number of aldehydes and lower number of sulfur-containing compounds detected in the carapace meat might contribute to its unique flavor.     

Seasonal and phenological variations of the essential oil from the narrow endemic species Artemisia molinieri and its biological activities

The volatile components of the aerial parts of Artemisia molinieri, an endemic wormwood of southern France, were analyzed by GC and GC-MS. Among the 69 compounds identified, major components were ascaridole (19-76%), alpha-terpinene (traces-36%), p-cymene (1-17%), 1,8-cineole (0.3-8%), and germacrene D (0.6-15%). Quantitative variations have been characterized following the season, the phenological cycle, and the aging of the plants. Bioassays have been performed on a sample of essential oil, which has shown a strong inhibition of the growth of both tested yeasts (Candida albicans and Saccharomyces cerevisiae var. chevalieri) and minor activity on both tested Gram-negative bacteria (Escherichia coli and Enterococcus hirae). The oils have shown interesting antioxidant activities on the basis of alpha-tocopherol as reference compound, up to 400-1200%.     

Volatile compounds from potato-like model systems

The volatile reaction products of aqueous mixtures comprising combinations of methionine, glucose, linoleic acid, and starch heated in a modified Likens-Nickerson apparatus were extracted and analyzed by gas chromatography-mass spectrometry (GC-MS). The majority of volatile compounds were formed from linoleic acid degradation, hexanal, 2,4-decadienal, and 2-pentylfuran being identified in the greatest amounts. Dimethyl disulfide and dimethyl trisulfide were detected in every system containing methionine. 3-(Methylthio)propanal (methional) and other sulfur compounds were detected when methionine was heated with another precursor. No binding of volatile compounds to starch was observed; rather, starch appeared to act as an additional source of reactive carbohydrate. Almost all the components identified have been identified among the aroma components of cooked potato. No pyrazines, pyridines, or thiazoles were identified, probably due to the relatively low temperature/high moisture conditions.     

Aroma potential of two bairrada white grape varieties: Maria Gomes and Bical

Maria Gomes and Bical are the main white grape varieties in Portuguese Bairrada Appellation, which represent 80% and 15%, respectively, of white vineyard. To estimate their aroma potentialities, free and potential volatile components from the musts were examined. The free volatile components were extracted using a liquid-liquid continuous method and were analyzed by gas chromatography-mass spectrometry. The potential volatile compounds were determined after elimination of the free components by heat and enzymatic treatments. Principal component analysis was used to establish relations between the compounds and the varieties and also the form (free or in potential). Maria Gomes has 11.5 mg/L volatile compounds, of which 33% are in free form; Bical has 4.4 mg/L volatile compounds, of which 46% are in free form. A total of 59 compounds was identified and quantified. In Maria Gomes, the sum of the terpenoids is within the perception limits for hotrienol (0.21 mg/L) and linalool (0.20 mg/L). In Bical, benzyl alcohol and phenylethylethanol represent 20% of the volatile compounds. Considering that the volatile composition pattern of Maria Gomes and Bical varieties are different, wine-making technologies should be developed specifically for each variety.     

Influence of the species and geographical location on volatile composition of Spanish oak wood (Quercus petraea Liebl. and Quercus robur L.)

The influence of the species and geographical origin on the volatile composition of wood samples from 80 Spanish oaks (55 Quercus petraea Liebl. and 25 Quercus robur L.) has been studied. Oak volatile components were isolated by simultaneous distillation-extraction and analyzed by gas chromatography-mass spectrometry. cis- and trans-beta-methyl-gamma-octalactones were the main constituents, the cis stereoisomer being predominant. Other important volatile components were furfural, 5-methylfurfural, guaiacol, eugenol, vanillin, or syringaldehyde. The main differences were established between species, Quercus petraea being significantly richer in volatile compounds than Quercus robur; however, the variability found among trees was high. Differences among geographical provenances were much less important than those found between species.     

Flavor Volatiles of Rice During Cooking Analyzed by Modified Headspace SPME/GC‐MS

The flavor volatiles in three Japanese rice cultivars, Nihonbare, Koshihikari, and Akitakomachi, during cooking were directly extracted by using a modified headspace solid‐phase microextraction (SPME) method and analyzed by gas chromatography‐mass spectrometry (GC‐MS). A total of 46 components were identified, including aldehydes, ketones, alcohols, and heterocyclic compounds, as well as fatty acids and esters, phenolic compounds, hydrocarbons, etc. The amount of key odorant compounds increased with cooking, while the amount of low‐boiling volatiles decreased. The similarities and differences of the three rice cultivars were determined through a comparison of their volatile components. Nihonbare was characterized by a higher amount of indole but an absence of the chemical class of fatty acid esters. In contrast, both Koshihikari and Akitakomachi had a higher amount of 4‐vinylphenol and an abundance of those esters. Koshihikari and Akitakomachi were quite similar in regard to those flavor volatiles. Furthermore, the observations in the research may suggest that the volatile components at cooking stage (I) were the representatives of the flavor volatiles of uncooked rice, while the volatile constituents at cooking stage (IV) were the representatives of the flavor volatiles of cooked rice.     

Volatile composition and contribution to the aroma of spanish honeydew honeys. Identification of a new chemical marker

Honeydew honeys from holm-oak, oak, and forest were isolated for aroma compounds by simultaneous distillation-extraction and analyzed by gas chromatography-mass spectrometry. In all, 66 volatile components were identified and quantified. trans-Oak lactone, a characteristic volatile component of oak wood, is proposed as a new chemical marker for the plant origin of honeydew honeys. Other compounds, such as aminoacetophenone and propylanisol, could be considered characteristic of holm-oak honeydew honeys. A total of 15 volatile compounds presented odor activity values (OAVs) greater than 1, with phenylacetaldehyde and beta-damascenone being those with the highest OAVs.     

Amelioration of odorous components in spent mushroom compost

Volatile sulfur compounds, as well as other volatiles found in the headspace above spent mushroom compost (SMC), were analyzed by gas chromatography and mass spectrometry. Data from these techniques as well as organoleptic evaluation of both the SMC and the chromatographic eluant indicated that the volatile sulfur compounds and cresol were important odorous components in SMC; cresol was reported as a musty, cattle-feces aroma. Samples consisted of headspaces from untreated SMC as well as SMC stirred with 1% (by weight) powered activated carbon (PAC). SMC stirred with and without PAC reduced headspace volatile concentrations, but the stirred with added PAC further decreased concentrations of important malodorants such as volatile sulfur compounds and cresol.     

Characterization of volatiles in bullock's heart (Annona reticulata L.) fruit cultivars from Cuba

Volatile compounds were isolated from four cultivars of bullock's heart fruit (Cenizo, Rojo, Verde, and De Ojo) by simultaneous steam distillation-solvent extraction. Compounds were identified by HRGC and capillary GC-MS. One hundred and eighty compounds were identified in the aroma extracts, of which alpha-pinene, beta-pinene, myrcene, limonene, terpinen-4-ol, and germacrene D were found to be the major constituents. Fruit from cv. De Ojo containing the highest concentration of total volatile and the highest major terpenoid content had the highest custard-like and overall fruity aroma intensity. The presence of many terpenic compounds is thought to contribute to the unique flavor of the bullock's heart fruit.