Determination of volatile compounds in cider spirits by gas chromatography with direct injection

Two analytical methods based on gas chromatography with direct injection are described for the quantitative analysis of volatile compounds (acetals, aldehydes, esters, alcohols, and volatile phenols) in cider brandies. Analytes were divided into major, 15, and minor volatile, 24, compounds depending on their usual concentration in samples. Parameters usually tested for method validation are evaluated. Correlation coefficients are calculated to estimate linearity, obtaining values higher than 0.999. Detection limits range between 0.325 mg/L (1-propanol) and 1.663 mg/L (methanol) among the major volatile compounds and between 0.086 mg/L (ethyl 2-methylbutyrate) and 0.332 mg/L (ethyl tetradecanoate) among the minor volatiles. Mean recoveries ranged between 109% (ethyl lactate) and 95% (1-butanol) for major volatiles and between 109% (1-octen-3-ol) and 94% (ethyl 2-methylbutyrate) for minor volatiles, thus confirming the accuracy of both methods. Reproducibility for major volatiles is < 5.4% (furfural) in all cases and < 9.6% (hexyl acetate) for minor volatiles. Moreover, the accuracy of the methods is evaluated by analyzing a certified whisky and five samples from interlaboratory assays, generally obtaining results in accordance with previous values.     

Synthesis and Biological Properties of 3-(Dihydroxybenzoyloxy)methyl- and 3-(Diacetoxybenzoyloxy)methyl-7α-chlorocephalosporanate Sulfones

We describe the synthesis of tert-butyl esters of 3-(2-hydroxybenzoyloxy)methyl-, 3-(dihydroxybenzoyloxy)methyl-, and 3-(diacetoxybenzoyloxy)methyl-7-chlorocephalosporanic acid sulfones by reaction of tert-butyl ester of 3-bromomethyl-7-chlorocephalosporanic acid sulfone with salts of hydroxy- and acetoxy-substituted benzoic acids. We have investigated the elastase-inhibiting properties of the compounds obtained and also their in vitro cytotoxic activity.     

Determination of the volatile constituents of ChineseCoriandrum sativum L. by gas chromatography—Mass spectrometry with solid-phase microextraction

Summary Fifteen main volatile compounds in ChineseCoriandrum sativum L. were separated and identified by gas chromatography—mass spectrometry (GC-MS) combined with solid-phase microextraction (SPME). Fresh ChineseCoriandrum sativum L. was ground and its volatile compounds were extracted by SPME with a 100 μm polydimethylsiloxane fiber. The fibers were desorbed in a GC injection liner at 250°C for 3 min. More than 15 peaks were separated by headspace SPME-GC-MS analysis. The main compounds in headspace ofCoriandrum sativum L. identified by mass spectrometry included decanal, 2-decenal, 1-decanol,trans-2-decen-1-ol,trans-2-decen-1-al,trans-2-tridecenal etc, which were verified by reference compounds. Their relative contents were calculated on basis of peak areas. SPME extraction conditions and capillary chromatography column used to separate the volatile compounds were investigated.     

In‐tube extraction for the determination of the main volatile compounds in Physalis peruviana L

An analytical procedure based on in‐tube extraction followed by gas chromatography with mass spectrometry has been developed for the analysis of 24 of the main volatile components in cape gooseberry (Physalis peruviana L.) samples. According to their chemical structure, the compounds were organized into different groups: one hydrocarbon, one aldehyde, four alcohols, four esters, and 14 monoterpenes. By single‐factor experiments, incubation temperature, incubation time, extraction volume, extraction strokes, extraction speed, desorption temperature, and desorption speed were determined as 60°C, 20 min, 1000 μL, 20, 50:50 μL/s, 280°C, 100 μL/s, respectively. Quantitative analysis using authentic standards and external calibration curves was performed. The limit of detection and limit of quantification for the analytical procedure were calculated. Results shown the benzaldehyde, ethyl butanoate, 2‐methyl‐1‐butanol, 1‐hexanol, 1‐butanol, α‐terpineol, and terpinen‐4‐ol were the most abundant volatile compounds in analyzed fruits (68.6–585 μg/kg). The obtained data may contribute to qualify cape gooseberry to the group of superfruits and, therefore, increase its popularity.     

Analysis of volatile compounds of wild gilthead sea bream (Sparus aurata) by simultaneous distillation–extraction (SDE) and GC–MS

The volatile compounds of wild gilthead sea bream (Sparus aurata) were analyzed by sensory and instrumental analyses. Simultaneous distillation and extraction (SDE) with dichloromethane were used for extraction of volatile components. According to sensory analysis, the aromatic extract obtained by SDE was representative of sea bream odour. A total of 46 compounds were identified and quantified in sea bream. Aldehydes and alcohols were the most dominant volatiles in sea bream, as they accounted for the largest proportion. Hexanal, heptanal, nonanal, (Z)-4-heptenal, octanal, (E)-2-nonenal, decanal, benzenacetaldehyde, (E,E)-2,4-decadienal, 1-octen-3-ol and (E)-1,5-octadien-3-ol were potent aroma compounds on the basis of odour activity values (OAVs). Within these, decanal (OAV: 1110) and (E)-2-nonenal (OAV: 447.5) were the most powerful contributors to the aroma of the sea bream.     

Isolation and identification of flower oil components from four <Emphasis Type="Italic">Staphylea</Emphasis> L. species

Chemical composition of the hydrodistilled volatile fraction from flowers of four Staphylea L. species (Staphylea colchica Stev., Staphylea elegans Zab., Staphylea holocarpa Hemsl., Staphylea pinnata L.) was determined by the GC/MS method. Compounds in fresh and dried flowers (stored for 1 year) were determined. Mostly, structures of different oxygenated aliphatic hydrocarbons in all four species were found. Different aldehydes, ketones, esters of higher fatty acids, and hexadecanoic acid were identified, with dominating content of tricosane, hexadecanoic acid and also of heneicosane, pentacosane, heptacosane, and nonacosane. In S. pinnata L. (fresh flowers) some nonaliphatic hydrocarbons, and in S. holocarpa Hemsl. (fresh flowers) esters of higher fatty acids were found.     

Conformational comparison of five follicular fluid meiosis-activating sterol-related active and inactive compounds

The crystal structures of five follicular fluid meiosis-activating sterol-related Δ^8,14-sterol compounds are presented. These are 4,4-di­methyl-23-phenyl-24-nor-5α-chola-8,14-dien-3β-ol, C₃₁H₄₄O, 4,4-di­methyl-22-phenyl-23,24-dinor-5α-chola-8,14-dien-3β-ol, C₃₀H₄₂O, (20R)-4,4-di­methyl-22-oxa-5α,20-chol­es­ta-8,14,24-trien-3β-ol, C₂₈H₄₄O₂, 4,4-di­methyl-23-phenyl-22-oxa-24-nor-5α-chola-8,14-dien-3β-ol–water (4/1), 4C₃₀H₄₂O₂·H₂O, and 4,4-di­methyl-5α-cholesta-8,14-dien-3-one, C₂₉H₄₆O. Two of the derivatives are inactive and three are active as agonists. Preliminary structure–activity relationship studies showed that the positions of the double bonds in the skeleton and the structures of the side chains are important determinants for activity. The conformations of the skeletons were compared with double-bond isomers retrieved from the Cambridge Structural Database [Allen & Kennard (1993). Chem. Des. Autom. News, 8 , 1, 31–37]; no significant differences were found. Thus, conformational changes induced by the double bonds are not discriminative with respect to the activity of the compounds. Comparisons of the side-chain conformations of active and inactive structures revealed that the crystal structures were not conclusive as far as correlation of conformation and activity of the side chains were concerned.     

Volatile profile of Echinacea purpurea plants after in vitro endophyte infection

Abstract

The differences in volatile profile of Echinacea purpurea plants not-inoculated (EpC) and inoculated with their endophytes from roots (EpR) and stem/leaves (EpS/L) were analysed and compared by GC-FID/GC–MS in an in vitro model. Non-terpenes and sesquiterpene hydrocarbons were the most abundant classes with an opposite behaviour of EpS/L showing a decreased emission of sesquiterpenes and an increase of non-terpene derivatives. The main compounds obtained from EpS/L were (Z)-8-dodecen-1-ol and 1-pentadecene, while germacrene D and β-caryophyllene were the key compounds in EpC and EpR. For the first time, this work indicates that bacterial endophytes modify the aroma profiles of infected and non-infected in vitro plants of the important medicinal plant E. purpurea. Therefore, our model of infection could permit to select endophytic strains to use as biotechnological tool in the production of medicinal plants enriched in volatile bioactive compounds.     

Comparison of volatile compound production in fruit body and in mycelium of Pleurotus ostreatus identified by submerged and solid-state cultures

Comparative analyses of the production of volatile compounds by Pleurotus ostreatus JMO.95 fruit body and its corresponding mycelium grown in liquid, on agar surface, and on solid support cultures were carried out by dynamic headspace concentration using gas chromatography/mass spectrometry and gas chromatography sniffing. The aroma produced by fruit body was owing essentially to the presence of octan-3-one and, to a lesser extent, to octan-3-ol. Other compounds, such as oct-1-en-3-ol, oct-1-en, 2-methylbutanol, and α-pinene were also present in low concentrations. Comparison of aromatic spectra of the fruit body with that of mycelia obtained under different culture conditions indicated that the main aromatic compounds present in the P. ostreatus fruit body and mycelium were produced in the same proportions on agar surface and on solid support culture, but not under submerged conditions.     

Structural elucidation of natural 2-hydroxy di- and tricarboxylic acids and esters, phenylpropanoid esters and a flavonoid from Autonoë madeirensis using gas chromatographic/electron ionization, electrospray ionization and tandem mass spectrometric techniques

The chemical composition of Autonoë madeirensis bulbs was characterized as part of a systematic phytochemical study of this species. The compounds reported were mainly identified on the basis of gas chromatography/electron ionization, electrospray ionization and tandem mass spectrometry. The structures of the pure compounds were also characterized by means of other physical and spectroscopic data (m.p., IR, UV, NMR). The compounds identified were 2‐hydroxy di‐ and tricarboxylic acids and esters (malic acid, citric acid and their methyl and ethyl esters), cis‐ and trans‐hydroxycinnamic esters (methyl and ethyl p‐coumarate and methyl ferulate) and a new flavone diglucoside, 7‐O‐[β‐glucosyl‐(1→2)‐O‐β‐glucosyl]apigenin, the interglucosidic linkage (1→2) of which is, to the best of our knowledge, reported for the first time in a diglucoside of apigenin. The results may contribute to the chemotaxonomy of the Autonoë genus and lead to a rapid tool for the systematic characterization of these compounds in plant extracts. Copyright © 2003 John Wiley & Sons, Ltd.     

Characterization of volatile substances in apples from Rosaceae family by headspace solid‐phase microextraction followed by GC‐qMS

The volatile composition of different apple varieties of Malus domestica Borkh. species from different geographic regions at Madeira Islands, namely Ponta do Pargo (PP), Porto Santo (PS), and Santo da Serra (SS) was established by headspace solid‐phase microextraction (HS‐SPME) procedure followed by GC‐MS (GC‐qMS) analysis. Significant parameters affecting sorption process such as fiber coating, extraction temperature, extraction time, sample amount, dilution factor, ionic strength, and desorption time, were optimized and discussed. The SPME fiber coated with 50/30 μm divinylbenzene/carboxen/PDMS (DVB/CAR/PDMS) afforded highest extraction efficiency of volatile compounds, providing the best sensitivity for the target volatiles, particularly when the samples were extracted at 50°C for 30 min with constant magnetic stirring. A qualitative and semi‐quantitative analysis between the investigated apple species has been established. It was possible to identify about 100 of volatile compounds among pulp (46, 45, and 39), peel (64, 60, and 64), and entire fruit (65, 43, and 50) in PP, PS, and SS apples, respectively. Ethyl esters, terpenes, and higher alcohols were found to be the most representative volatiles. α‐Farnesene, hexan‐1‐ol and hexyl 2‐methylbutyrate were the compounds found in the volatile profile of studied apples with the largest GC area, representing, on average, 24.71, 14.06, and 10.80% of the total volatile fraction from PP, PS, and SS apples. In PP entire apple, the most abundant compounds identified were α‐farnesene (30.49%), the unknown compound m/z (69, 101, 157) (21.82%) and hexyl acetate (6.57%). Regarding PS entire apple the major compounds were α‐farnesene (16.87%), estragole (15.43%), hexan‐1‐ol (10.94), and E‐2‐hexenal (10.67). α‐Farnesene (30.3%), hexan‐1‐ol (18.90%), 2‐methylbutanoic acid (4.7%), and pentan‐1‐ol (4.6%) were also found as SS entire apple volatiles present in a higher relative content. Principal component analysis (PCA) of the results clustered the apples into three groups according to geographic origin. Linear discriminant analysis (LDA) was performed in order to detect the volatile compounds able to differentiate the three kinds of apples investigated. The most important contributions to the differentiation of the PP, PS, and SS apples were ethyl hexanoate, hexyl 2‐methylbutyrate, E,E‐2,4‐heptadienal, p‐ethyl styrene, and E‐2‐hexenal.     

ω-苯基-(2S)-N-叔丁氧羰基氨基酸乙酯的制备

格氏试剂和N-叔丁氧羰基焦谷氨酸乙酯反应生成中间体ω-苯基-δ-氧代-(2S)-N-叔丁氧羰基氨基酸乙酯, 分别用对甲基苯磺酰肼和醋酸硼氢化钠结合的一锅法还原或Pd/C催化氢化还原中间体得到ω-苯基-(2S)-N-叔丁氧羰基氨基酸乙酯.     

N-[5-(2-氯苯基)-2-呋喃甲酰氨基硫羰基]-L-α-氨基酸乙酯的合成与生物活性测定

设计并合成了9种未见文献报道的N-(5-邻氯苯基-2-呋喃甲酰氨基硫羰基)-L-α-氨基酸乙酯衍生物, 其结构经IR, ¹H NMR, MS和元素分析测试确证. MTT法测试结果表明大部分目标化合物对白血病K562细胞系的增殖具有明显的抑制作用.     

Analysis of volatiles emitted by potato plants by means of a Colorado beetle electroantennographic detector

An electroantennographic detector based on the antenna of the Colorado potato beetle (Leptinotarsa decemlineata Say, 1824) was used to investigate volatile organic compounds emitted by injured potato plants (Solanum tuberosum L., 1753). Samples were collected on charcoal traps using the CLSA method. Analyses were performed with a GC-EAD-FID setup as well as a GC-MS system. The experiments revealed that several groups of compounds are perceptible to the Colorado potato beetle. The ability of the Colorado potato beetle to detect green leaf odours (e.g. (Z)-3-hexen-1-ol and (E)-2-hexenal), linalool and some terpenes has been noticed before [Visser et al., J. Chem. Ecol. 5 (1979) 13]. In this work the presence of (Z)-3-hexen-1-ol, (E)-2-hexenal and linalool in the potato odour could be confirmed. Moreover, β-myrcene, benzeneethanol, and several sesquiterpenes (e.g. caryophyllene and germacrene-D) were identified. The GC-EAD experiments reveal that apart from the green leaf odours and linalool prominent reactions of the Colorado bettle antenna are induced by benzeneethanol and the sesquiterpene fraction.     

Reaction of arylidene-2-naphthylamines with the ethyl ester of (2-quinolyl)-β-oxopropionic acid

The reaction of arylidene-2-naphthylamines with the ethyl ester of (2-quinolyl)--oxopropionic acid results in the synthesis of ethyl esters of 1-(2-quinolyl)-3-arylbenzo[f]quinoline-2-carboxylic acids. All the theoretically possible intermediate reaction products were isolated: the amino esters of 2-quinoline--oxopropionic acid, the hydroxy esters of tetrahydro- and esters of dihydrobenzo[f]quinoline-2-carboxylic acid, as well as the by-products — the ethyl ester of 2-quinolyl--(R-benzylidene)--oxopropionic acid. The IR, UV, and mass spectra of the synthesized compounds are discussed.Institute of Physical Organic Chemistry, Belorussian Academy of Sciences, Minsk 220603. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1406–1410, October, 1994. Original article submitted October 5, 1994.     

微波辐射下合成3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-酮衍生物

在微波辐射和对甲基苯磺酸的催化作用下, 5-芳基-1,3-环己二酮与邻氨基苯甲腈进行缩合反应, 得到了N-取代的2-氨基苯甲腈衍生物, 在K₂CO₃和Cu₂Cl₂的催化作用下进一步合环, 得到3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-酮衍生物, 用LiAlH₄还原羰基得到3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-醇衍生物. 新合成化合物的结构均经元素分析、红外光谱和核磁共振光谱予以确认.     

Use of solid-phase microextraction as a sampling technique for the characterization of volatile compounds emitted from Chinese daffodil flowers

Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) has been applied to the determination of volatile compounds emitted from living daffodil flowers. The SPME conditions were optimized and applied to headspace extraction of the volatile compounds. The volatile compounds adsorbed on the fiber were desorbed and analyzed by GC-MS. We identified 27 compounds in the flower emission, which mainly included acetic acid phenethyl ester (31.68%), E-ocimene (17.15%), acetic acid benzyl ester (11.53%), neo-allo-ocimene (6.94%), allo-ocimene(5.34%), α-linalool (5.26%), 1,8-cineole(3.70%), benzenepropyl acetate (1.98%), and 3-methyl-2-buten-1-ol acetate(1.88%). The volatile compounds emitted by the flower excised from the daffodil were also analyzed by the present method, and the results showed that n-pentadecane, n-hexadecane, n-octadecane, and acetic acid phenethyl ester might be biomarker compounds of living daffodil flowers. To our knowledge, this is the first report on the volatile compounds emitted from Chinese daffodil flowers. The text was submitted by the authors in English.     

Comparative study of the whisky aroma profile based on headspace solid phase microextraction using different fibre coatings

A dynamic headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to ion trap mass spectrometry (GC-(IT)MS) method was developed and applied for the qualitative determination of the volatile compounds present in commercial whisky samples which alcoholic content was previously adjusted to 13% (v/v). Headspace SPME experimental conditions, such as fibre coating, extraction temperature and extraction time, were optimized in order to improve the extraction process. Five different SPME fibres were used in this study, namely, poly(dimethylsiloxane) (PDMS), poly(acrylate) (PA), Carboxen-poly(dimethylsiloxane) (CAR/PDMS), Carbowax-divinylbenzene (CW/DVB) and Carboxen-poly(dimethylsiloxane)-divinylbenzene (CAR/PDMS/DVB). The best results were obtained using a 75 microm CAR/PDMS fibre during headspace extraction at 40 degrees C with stirring at 750 rpm for 60 min, after saturating the samples with salt. The optimised methodology was then applied to investigate the volatile composition profile of three Scotch whisky samples--Black Label, Ballantines and Highland Clan. Approximately seventy volatile compounds were identified in the these samples, pertaining at several chemical groups, mainly fatty acids ethyl esters, higher alcohols, fatty acids, carbonyl compounds, monoterpenols, C13 norisoprenoids and some volatile phenols. The ethyl esters form an essential group of aroma components in whisky, to which they confer a pleasant aroma, with "fruity" odours. Qualitatively, the isoamyl acetate, with "banana" aroma, was the most interesting. Quantitatively, significant components are ethyl esters of caprilic, capric and lauric acids. The highest concentration of fatty acids, were observed for caprilic and capric acids. From the higher alcohols the fusel oils (3-methylbutan-1-ol and 2.phenyletanol) are the most important ones.     

Determination of the Free Radical Scavenging Activity of Lycium Extracts

Lycium species growing in Turkey have not so far been studied sufficiently. For this reason, non-polar and polar extracts obtained from the fruits of Lycium barbarum L. and L. Ruthenicum Murray (Solanaceae) were assessed both in vitro for their potential as free radical scavenger crude extracts and their phenolic composition. Fruits of Lycium species were sequentially extracted with petroleum ether, ethyl acetate, methanol, n-butanol, and water in a Soxhlet extractor. All the extracts were assessed for the scavenging of the nitrogen-centered free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH^.) by in vitro method. Furthermore, the composition of each extract was investigated both in terms of its Folin-Ciocalteau reactive components and its qualitative content. The phenolic compounds within the extracts were determined as benzoic acid and hydroxycinnamic acid derivatives, flavonoids, and anthocyanins according to their retention time and UV spectral data by HPLC-DAD system.