微波、超声波和水蒸气蒸馏在紫苏籽挥发油分析中的对比研究

采用水蒸气蒸馏法、微波提取和超声波萃取紫苏籽挥发油。运用毛细管气相色谱-质谱联用仪结合计算机检索对所得挥发油成分进行分析和鉴定,用气相色谱峰面积归一法测定各组分的相对质量分数。结果表明,3种方法分别从紫苏籽所得挥发油中鉴定出33、31及29种化合物,各占总峰面积的97.16%、97.38%及96.6%。不同方法所得紫苏籽挥发油化学组成各有异同,但主要成分是正十六酸、(Z,Z,Z)-9,12,15-十八三烯-1-醇和戊基-2-呋喃基酮。     

Varietal and crop year effects on lipid composition of walnut (Juglans regia) genotypes

The FA, unsaponifiable, and volatile constituents of oil from three walnut varieties from two consecutive crop years were studied. The walnut oils (WO) were rich in PUFA and low in saturated FA. The tocopherol fraction consisted mainly of γ-tocopherol. High contents of β-sitosterol were found, together with campesterol and Δ⁵-avenasterol in similar amounts. Methylsterols present in WO were identified as cycloartenol, cyclolaudenol, cycloeucalenol, and 24-methylenecycloartanol. The hydrocarbon fraction was characterized by the predominance of C₁₄–C₂₀ n-alkanes. The major volatiles were aldehydes produced through the linoleic acid oxidative pathway. FA, methylsterols, and some hydrocarbons presented statistically significant differences among varieties. Most of this variation was due to the genotype. The Franquette variety was noteworthy by its higher oil and oleic acid contents. In contrast, tocopherols and volatile compounds showed minor differences among varieties; they were strongly influenced by the crop year. Chemical data were subjected to principal component analysis. The parameters that gave the greatest discrimination between the walnut varieties were oleic and linolenic acids, tetradecane, eicosane, tetracosane, cycloartenol, and 24-methylenecycloartanol. These components presented the major varietal influences and could be useful to determine the identity of walnut genotypes.     

Identification and Field Evaluation of Grape Shoot Volatiles Attractive to Female Grape Berry Moth (<Emphasis Type="Italic">Paralobesia viteana</Emphasis>)

Solid-phase microextraction (SPME) and gas chromatography coupled with electroantennographic detection (GC-EAD) were used to identify volatile compounds from shoots of riverbank grape (Vitis riparia) that attract the female grape berry moth (GBM, Paralobesia viteana). Consistent EAD activity was obtained for 11 chemicals: (Z)-3-hexen-1-yl acetate, (E)-linalool oxide, (Z)-linalool oxide, nonanal, linalool, (E)-4,8-dimethyl-1,3,7-nonatriene, methyl salicylate, decanal, beta-caryophyllene, germacrene-D, and alpha-farnesene. In flight-tunnel tests that involved female GBM and rubber septa loaded with subsets of these 11 compounds, we found that both the 11-component blend and a seven-component blend, composed of (E)-linalool oxide, (Z)-linalool oxide, nonanal, (E)-4,8-dimethyl-1,3,7-nonatriene, decanal, beta-caryophyllene and germacrene-D, elicited equivalent levels of upwind flight as freshly cut grape shoots. The removal of any of the seven compounds from the seven-component blend resulted in a significant decrease in female upwind flight responses. In a field trial with these two synthetic blends, traps equipped with either blend captured more female GBM compared to traps baited with hexane only (control), although the number of females caught was generally low. There were no differences in the number of males captured among treatments. Although in flight-tunnel trials, moths readily flew upwind to both grape shoots and rubber septa loaded with the best lures, they landed on shoots but not on rubber septa. Coupled with relatively low field catches, this suggests that additional host finding cues need to be identified to improve trap efficacy.     

鲜、干品红丝线叶挥发油化学成分的GC - MS分析

采用水蒸气蒸馏法分别得到新鲜和干燥红丝线叶挥发油,并结合GC-MS对所得样品的化学成分进行了分析和鉴定,用气相色谱峰面积归一化法测定各组分的相对质量分数。结果显示,从鲜叶挥发油中鉴定出32种成分,占挥发油总峰面积的98.81%,主要成分是反式植醇(43.29%)、橙花叔醇(7.07%)、石竹烯(4.91%)、亚麻酸甲酯(3.81%)和植酮(3.74%)等;从干叶挥发油中鉴定出42种成分,占挥发油总峰面积的96.23%,反式植醇(33.50%)、橙花叔醇(7.75%)、石竹烯(5.14%)、1-辛烯-3-醇(7.20%)、植酮(4.45%)和樟脑(4.07%)等为主要成分。两者的共有成分有23种,其他化学成分及其相对质量分数存在一定差异。     

Female sex pheromone of oriental tobacco budworm,Helicoverpa assulta (Guenee) (Lepidoptera: Noctuidae): Identification and field testing

Analysis of ovipositor washings from virgin femaleHelicoverpa assulta (Guenée) (Lepidoptere: Noctuidae) from Korea by gas chromatography (GC) linked to electroantennography and GC linked to mass spectrometry resulted in the identification of nine compounds, hexadecanal, (Z)-9-hexadecenal, (Z)-11-hexadecenal, hexadecyl acetate, (Z)-9-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, hexadecan-l-ol, (Z)-9-hexadecen-l-ol, and (Z)-11-hexadecen-1-ol. However, ovipositor washings from females from Thailand contained mainly the 16-carbon aldehydes with very small amounts of (Z)-9-hexadecenyl acetate. Field tests conducted in Korea, China, and Thailand indicated that a binary blend of (Z)-9-hexadecenal and (Z)-11-hexadecenal was sufficient for attraction, although the most attractive ratio of compounds varied with location. In Korea a 201 blend of compounds was the most attractive, while in Thailand a 7.51 blend was most attractive. In China both blends of hexadecenal isomers were equally attractive. Addition of the hexadecenyl acetates to the 201 blend of hexadecenals in the ratio of 13.3 increased the trap catch of maleH. assulta compared to lures containing the aldehydes alone in Korea but reduced trap catch in China. Addition of the hexadecenyl acetates to the 7.51 blend of hexadecenals had no significant effect on trap catch in Thailand or China compared to the aldehydes alone. The addition of the 16-carbon alcohols to the aldehydes had a significantly inhibitory effect in all three countries, suggesting they are not pheromone components. Taken together these results indicate thatH. assulta is polymorphic with at least two populations responding to different sex pheromones.     

A multivariate study of the relationship between fatty acids and volatile flavor components in olive and walnut oils

The relationships between FA and the volatile profiles of olive and walnut oils from Argentina were studied using GC and solid-phase microextraction coupled with GC-MS. The major volatiles were aldehydes and hydrocarbons, produced mainly through the oxidative pathways. n-Pentane, nonanal, and 2,4-decadienal were predominant in walnut oils, whereas nonanal, 2-decenal, and 2-undecenal were the most abundant components in olive oils. A multivariate analysis applied to the chemical data emphasized the differences between the oils and allowed us to see a pattern of covariation among the FA and the volatile compounds. The main differences between walnut and olive oils were the presence of larger amounts of short-chain (C₅–C₆) saturated hydrocarbons and aldehydes in the former and the greater quantities of medium-chain (C₇–C₁₁) compounds in olive oil. This can be explained by their different origins, mainly from the linoleic acid in walnut oil or almost exclusively from the oleic acid in olive oil.     

Identification of sex pheromone ofTetanolita mynesalis (Lepidoptera: Noctuidae), a prey species of bolas spider,Mastophora hutchinsoni

The bolas spider,Mastophora hutchinsoni, attracts adult males of four species of nocturnally active Lepidoptera through aggressive chemical mimicry of those species' sex pheromones. Here we report the identification of the sex pheromone of one prey species, the smoky tetanolita (Tetanolita mynesalis). In sex pheromone gland extracts, only two peaks stimulated an electrophysiological response as measured by a coupled gas chromatography-electroantennographic detection analysis. These two peaks had retention times identical to (3Z,6Z,9Z)-heneicosatriene (3Z,6Z,9Z-21:H) and (3Z,9Z)-cis-6,7-epoxy-heneicosadiene (3Z,9Z-cis-6,7-epoxy-21:H), respectively, and mass spectra identical to these two compounds. It was determined that 0.23±0.16 and 0.56±0.26 ng of 3Z,6Z,9Z-21:H and 3Z,9Z-cis-6,7-epoxy-21:H, respectively, were present in pheromone gland extracts from individual females. A 1:1 blend of 3Z,6Z,9Z-21:H and 3Z,9Z-6S,7R-epoxy-21:H was an effective attractant for adult males from feral populations. Blend ratios of these two components from 2:1 to 1:2 were equally effective as attractants. Greater deviation from the optimal blends resulted in diminished trap catches. The enantiomer 3Z,9Z-6R,7S-epoxy-21:H not only was not effective in attracting males, its presence in the effective blend shut down trap catches. These results indicate that the pheromone blend consists of 3Z,6Z,9Z-21:H and 3Z,9Z-6S,7R-epoxy-21:H. This is the first report of a hydrocarbon/epoxide pheromone for a prey species of this bolas spider. Sex attractants or pheromones for the other three prey species are composed of aldehydes or acetates.     

Avian Exocrine Secretions. I. Chemical Characterization of the Volatile Fraction of the Uropygial Secretion of the Green Woodhoopoe, Phoeniculus purpureus

Using gas chromatography-mass spectrometry in conjunction with auxiliary techniques such as solid phase microextraction and determination of double bond positions by means of dimethyl disulfide derivatization, 45 constituents of the uropygial secretion of the green woodhoopoe, Phoeniculus purpureus, have been identified. The majority of these constituents are long-chain branched and unbranched alkanes, and (Z)-alkenes such as (Z)-9-tricosene, and a number of unidentified wax esters. The more volatile fraction of the secretion contained short-chain fatty acids, aldehydes, aliphatic and heterocyclic aromatic amines, ketones, and dimethyl sulfides. This group of volatile compounds is responsible for the obnoxious odor of the secretion and also for its defensive action against predators.     

A high-field1H nuclear magnetic resonance study of the minor components in virgin olive oils

High-field (600 MHz) nuclear magnetic resonance (NMR) spectroscopy was applied to the direct analysis of virgin olive oil. Minor components were studied to assess oil quality and genuineness. Unsaturated and saturated aldehyde resonances, as well as those related to other volatile compounds, were identified in the low-field region of the spectrum by two-dimensional techniques. Unsaturated aldehydes can be related to the sensory quality of oils. Other unidentified peaks are due to volatile components, because they disappear after nitrogen fluxing. The statistical analysis performed on the intensity of these peaks in several oil samples, obtained from different olive varieties, allows clustering and identification of oils arising from the same olive variety. Diacylglycerols, linolenic acid, other volatile components, water, acetic acid, phenols, and sterols can be detected simulteneously, suggesting a useful application of high-field NMR in the authentication and quality assessment of virgin olive oil.     

Emission of Volatile Aldehydes from DAG-Rich and TAG-Rich Oils with Different Degrees of Unsaturation During Deep-Frying

The purpose of the present study was to compare the emission of volatile aldehydes from diacylglycerol-rich oils (DAG-OILs) and triacylglycerol-rich oils (TAG-OILs) with different degrees of unsaturation of fatty acid moieties during the deep-frying of sliced potatoes. To examine the effect of fatty acid composition, four kinds of oils with different fatty acid compositions were selected: rape seed (RS); sunflower oil as a high oleic (HO); safflower oil as high linoleic (HL); and, perilla oil as high linolenic (HLn) oils. The emissions of volatile aldehydes were determined during the deep-frying of sliced potatoes by using the above fresh test oils or deteriorated RS oils. The statistical analysis showed no significant difference in volatile aldehyde emission and profile between the DAG-OIL and TAG-OIL with the fatty acid composition of RS, HL, and HLn. Although a statistically significant difference was noted in the volatile aldehyde emission between the DAG-OIL and TAG-OIL with HO, this difference was extremely small when compared to the variations found in the oils with four types of fatty acid composition. Finally, no difference was found in the volatile aldehyde emissions between the deteriorated DAG-OIL and TAG-OIL, although volatile aldehyde emissions increased with frying time. In addition, the acrylamide contents in potato chips prepared with RS–DAG or RS–TAG were at comparable levels.     

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert-butyl hydroperoxide/Fe2+

The lipid ester core aldehydes formed during a rapid oxidation (7.8 M tert-butyl hydroperoxide, 90 min at 37°C) of the triacylglycerols of purified corn and sunflower oils were isolated as dinitrophenylhydrazones by preparative thin-layer chromatography and identified by reversed-phase high-performance liquid chromatography with on-line electrospray ionization mass spectrometry and by reference to standards. A total of 113 species of triacylglycerol core aldehydes were specifically identified, accounting for 32–53% of the 2,4-dinitrophenylhydrazine (DNPH)-reactive material of high molecular weight representing 25–33% of the total oxidation products. The major core aldehyde species (50–60% of total triacylglycerol core aldehydes) were the mono(9-oxo)nonanoyl- and mono(12-oxo)-9,10-epoxy dodecenoyl- or (12-oxo)-9-hydroxy-10,11-dodecenoyl-diacylglycerols. A significant proportion of the total (9-oxo)nonanoyl and epoxidized (12-oxo)-9,10-dodecenoyl core aldehydes was found in complex combinations with hydroperoxy or hydroxy fatty acyl groups (6–10% of total triacylglycerol core aldehydes). Identified were also di(9-oxo)nonanoylmonoacylglycerols (0.5% of total) and tri(9-oxo)nonanoylglycerols (trace). The identification of the oxoacylglycerols was consistent with the products anticipated from tert-butyl hydroperoxide oxidation of the major species of corn and sunflower oil triacylglycerols (mainly linoleoyl esters). However, the anticipated (13-oxo)-9,11-tridecadienoyl aldehyde-containing acylglycerols were absent because of further oxidation of the dienoic core aldehyde. A significant proportion of the unsaturated triacylglycerol core aldehydes contained tert-butyl groups linked to the unsaturated fatty chains via peroxide bridges (2–9%). The study demonstrates that rapid peroxidation with tert-butyl hydroperoxide consitutes an effective method for enriching natural oils and fats in triacylglycerol core aldehydes for biochemical and metabolic testing.     

Major Sex Pheromone Components of the Australian Gum Leaf Skeletonizer Uraba lugens: (10E,12Z)-Hexadecadien-1-yl Acetate and (10E,12Z)-Hexadecadien-1-ol

Two sex pheromone components of the gum leaf skeletonizer, Uraba lugens (Lepidoptera: Nolidae), recently established in New Zealand, were identified. Gas chromatography (GC) electroantennographic detection analyses of female pheromone gland extracts gave three compounds that consistently elicited antennal responses. Chemical analyses, using GC and GC-mass spectrometry, in conjunction with 4-methyl-1,2,4-triazoline-3,5-dione and dimethyldisulfide derivatizations, identified these compounds as (10E,12Z)-hexadecadien-1-yl acetate (E10,Z12-16:Ac), (10E,12Z)-hexadecadien-1-ol (E10,Z12-16:OH), and (Z)-11-hexadecen-1-yl acetate (Z11-16:Ac). A trapping trial in Queensland, Australia, in 2002, indicated that a blend of the two major components E10,Z12-16:Ac and E10,Z12-16:OH could attract gum leaf skeletonizer males. In the same trial, E10,Z12-16:Ac alone trapped large numbers of an unidentified nolid, Nola spp. Further trials in Auckland, New Zealand established that these two components were sufficient and necessary for trap catch of males; adding minor gland components, (10E,12E)-hexadecadien-1-yl acetate (E10,E12-16:Ac), Z11-16:Ac, or octadecan-1-ol (18:OH), to the two-component lure did not result in increased trap catches. Behavioral observations and gland analyses of the Auckland population revealed that female moths begin calling soon after emergence, with peak calling and pheromone production occurring 7 hr into the scotophase. Analysis of gland extract at two-hourly intervals during the first activity period showed that the ratio of E10,Z12-16:Ac to E10,Z12-16:OH (mean of 86: 14, respectively) and pheromone titer were fairly constant. No qualitative or quantitative differences in pheromone components were detected between gland extracts from Tasmanian univoltine and Auckland bivoltine populations of U. lugens.     

传统烹饪与软包装无锡酱排骨的挥发性风味成分对比

采用固相微萃取(SPME)法和同时蒸馏萃取(SDE)法与气相色谱-质谱联用(GC-MS)技术,提取分析传统烹饪无锡酱排骨的挥发性风味成分。与软包装无锡酱排骨进行比较,前者共鉴定出71种化合物,后者共鉴定出76种,共同检测到的物质有31种。两者在醛类及含氮、含硫及其杂环类化合物上的差异较为显著,是两种排骨样品风味差异的主要原因,而茴香等香辛料使用量的差异可能是导致传统烹饪与软包装无锡酱排骨风味差异的另一原因。     

塑料水管中挥发性有机物的迁移研究

介绍了高密度聚乙烯管(PE-HD)、交联聚乙烯管(PE-X)和硬质聚氯乙烯管(PVC-U)中的挥发性有机成分向水中的迁移测定研究。PE-HD中主要的迁移成分是2,4-二-间-丁基-苯酚(2,4.-DTBP),是酚类抗氧化剂的降解产物,除此之外降解产物还有醋、乙醛、酮、芳香烃和菇类化合物。根据塑料管接触水的极限臭味值(TON)估测,在测试的7种PE-HD管材中有5种PE-HD管的TON-4; 2种PE-HD管释放到水中挥发性有机物(VOC)的总量基本恒定;PEX管迁移实验显示大量的VOC迁移到水中(TON-5),其中一些迁移的VOC成分不确定;HPVC管向水中迁移的挥发性物质很少。     

赣南脐橙花挥发油的化学成分分析

用常规水蒸气蒸馏法提取出赣南脐橙鲜花的挥发油,经气相色谱-质谱联机分析,共分离出40多个峰,鉴定出了其中35种化合物。挥发油主要成分是3,7-二甲基-1,6-己二烯-3-醇(质量分数20.16%,以下均为质量分数)、3,7,11-三甲基-1,6,10-十二碳-三烯-3-醇(12.75%)、3,7,11-三甲基-2,6,10-十二碳三烯-1-醇(9.63%)、吲哚(5.34%)、2-氨基苯甲酸甲酯(3.81%)、二十三烷(3.58%)、4-亚甲基-1-(1-甲基乙基)-双环[3,1,0]己烷(3.49%)、(R)-1,4-二甲基-3-环己烯-1-醇(3.48%),所鉴定的成分占挥发油总质量的94.58%。     

Effect of cultivation area and climatic conditions on volatiles of virgin olive oil

To elucidate the influence of the cultivation area and climatic conditions on volatiles of virgin olive oil from Gemlik cultivar, an investigation was carried out. Five Turkish geographical zones (Bal?kesir, Ayd?n, Manisa, Antalya and Hatay) were chosen. From these areas, fruits were collected at the same maturity stage and processed using a small experimental olive oil mill, applying identical processing conditions for all olive samples. Headspace solid‐phase microextraction (HS‐SPME) technique coupled to GC/MS was used for volatile analysis. Twenty‐seven compounds were identified and characterised, representing 96.40–98.74% of the total GC area. The major volatile representing about 50% was the (E)‐2‐hexenal. This compound was found in higher concentrations on olive oils from Antalya than from Hatay area. Hexanal was the second most abundant volatile compound and varied between 13.89 and 28.96%. Comparing the olive growing areas Hatay and Antalya, the hexanal concentration was about 29 and 14%, respectively. Generally, a significant difference in the composition of volatile compounds between the oils from the same olive cultivar and from different geographic regions was recorded. The results suggest that climatic factors, latitude and longitude affect the formation of volatiles.     

香薷籽及其油脂中挥发油成分的分析研究

对香薷籽、香薷油脂及其粕中的挥发性成分进行了提取,在同一条件下分别进行气相色谱分析,对其结果作了比较。香薷籽中的挥发油,采用气相色谱-质谱联用法分析其成分,检出30种化学成分,确认了26种化合物,其含量占全油的96.79%。主要化学成分为脱氢香薷酮(84.62%),3-氨基吡唑﹙5.373%﹚,香薷酮﹙2.97%﹚,β-波旁烯﹙1.41%﹚,2,5-二甲基-3-乙烯基-1,4-己二烯﹙1.36%﹚,反式-2,4-癸二烯醛﹙1.06%﹚。     

NMR,GC–MS and ESI-FTICR-MS Profiling of Fatty Acids and Triacylglycerols in Some Botswana Seed Oils

In the search for non-traditional seed oils, physicochemical parameters, fatty acid (FA) and triacylglycerol (TAG) profiles for five Botswana seed oils, obtained by Soxhlet extraction, were determined. GC–MS and ¹H-NMR analyses showed the FA profiles for mkukubuyo, Sterculia africana, and manketti, Ricinodendron rautanenii, seed oils dominated by linoleic and oleic acids, 26.1, 16.7 and 51.9, 24.4%, respectively, with S. africana containing significant amounts of cyclic FAs (19.9%). Mokolwane, Hyphaene petersiana, seed oil was typically lauric; 12:0 and 14:0 acids were 25.9 and 13.4%, respectively. Morama, Tylosema esculentum, seed oil resembled olive oil; 18:1 (47.3%) and 18:2 (23.4%) acids dominated. Moretologa-kgomo, Ximenia caffra, seed oil had 45.8% of 18:1 FA, plus significant amounts of very long chain FAs: 26:1 (5.8%), 28:1 (13.9%), 30:1 (3.9%), and acetylenic acids, 9a-18:1 (1.5%) and 9a, 11t-18:2 (16.0%). TAG classes and regiochemistry were determined with ESI-FTICR-MS, and ¹³C-NMR spectra, respectively. Morama showed seven major TAG classes with C54:4 and C54:3 dominating; mokolwane had 16 major classes with C32:0, C38:0 and C42:2 dominating; manketti had 11 major classes with C54:7, C54:6 and C54:4 dominating; mkukubuyo had 12 major classes with C52:4, C52:3 and C54:4 dominating; moretologa-kgomo had 30 major TAG classes with C64:5, C64:3 and C62:3 dominating. Saturated FAs were generally distributed over the sn-1(3) position for morama, manketti, and moretologa-kgomo but at the sn-2 position for mokolwane and mkukubuyo. These findings indicate that morama and manketti seed oils can be developed for food uses, whilst moretologa-kgomo and mkukubuyo seed oils only for nonfood uses.     

Photolyse von 13(S)-Hydroperoxy-9(Z), 11(E)-octadecadiensäuremethylester in Gegenwart von Sauerstoff — Analyse der niedermolekularen Reaktionsprodukte

Photolysis of methyl 13(S)-Hydroperoxy-9(Z),11(E)-Octadecadienoate in the Presence of Oxygen — Analysis of the Low Molecular Reaction Products A solution of methyl 13(S)-hydroperoxy-9(Z),11(E)-octadecadienoate in n-pentane was irradiated in the presence of oxygen at 15°C with light at wavelengths greater than 230 nm. After 2 hours 3.5 mol-% volatile aldehydes and esters and in addition 5 mol-% low molecular acids were isolated. Four major products were identified: hexanal, caproic acid, azelaic acid monomethyl ester and methyl 6-heptenoate.     

菊花和菊花蕾挥发性成分的GC/MS分析

研究了对比杭菊花和杭白菊花蕾挥发油的化学成分。采用水蒸气蒸馏法提取杭菊花和杭白菊花蕾挥发油,用气相色谱-质谱联用技术对其化学成分进行分离鉴定,鉴定出菊花主要化学成分27种(75.85%),菊花蕾主要化学成分21种(61.25%)。结果表明:杭菊花和杭白菊花蕾挥发油的主要成分为单萜烯类、倍半萜烯类及其含氧衍生物等,但其化学成分种类有明显的差别,在入药及保健品开发时均需认真紧慎对待。