Conversion of Some Saturated Fatty Acids,Aldehydes, and Alcohols into γ- and δ-Lactones

A series or γ- and δ-lactones could be found in the thermal oxidative products of normal saturated acids, aldehydes, and alcohols (C₉, C₁₀, and C₁₂, respectively) heated at 180°C in the presence of 0.1% KMnO₄. Their lactones were identified by gas chromatography, infrared spectroscopy, and mass spectroscopy. And they could be detected also in the volatile compounds occurred by heating of C₁₀ acid, aldehyde, and alcohol mixed with pork fat. So it was expected that lactones in meat fat flavor described in the earlier papers could be secondary products converted from saturated acids, aldehydes, and alcohols formed by oxidative degradation of meat fats. This process was presumed to be one of the mechanisms of the lactone formation.

It was discussed that lactones might be derived through mono or dihydroperoxides of acids, aldehydes, and alcohols.     

Volatiles from winter wheat: Identification of additional compounds and effects of tissue source

Sixteen volatile compounds have been identified in oil prepared from winter wheat by reduced pressure steam distillation-extraction. Most of these compounds were found in relatively small quatities (0.5%, or less) with the exception of pentadecanal. Comparisons were also made of the relative amounts of C₉ alcohols and aldehydes obtained from fresh versus frozen plants, cut versus intact plants and leaves versus culms.     

An analysis of the volatile flavour compounds in a soft raw goat milk cheese

The major components of the musty cow rind cheeses were identified in a soft raw goat milk cheese as heptan-2-one, nonan-2-one, their corresponding secondary alcohols, some esters and sulfur compounds. Their production was associated with the manufacturing process and its influence on the microbial activity. However a specificity in goat cheese compounds was displayed concerning in particular limonene and some ketones, alcohols and aldehydes.     

Study of the volatile compounds produced by Debaryomyces hansenii NRRL Y-7426 during the fermentation of detoxified concentrated distilled grape marc hemicellulosic hydrolysates

The volatile compounds produced by Debaryomyces hansenii NRRL Y-7426 during the fermentation of detoxified concentrated distilled grape marc hemicellulosic hydrolysates was analysed by GC?CMS. Thirty-five compounds corresponding to ten groups of volatile compounds: terpenes, higher alcohols, C₆ alcohols, aldehydes, volatile acids, acetates, ethyl esters, volatile phenols, sulphur compounds and hydrocarbons were identified. The supplementation with commercial nutrients increased the concentration of 2-phenylethanol, a commercial flavour and fragrance compound, with a rose-like odour, employed in cosmetics and food industries; and other positive compounds to the aroma such as terpenes and ethyl esters. Non-supplemented media produced the highest content in higher alcohols, volatile acids, sulphur compounds and in the majority of hydrocarbons detected, meanwhile supplementation with vinasses hardly produced volatile compounds. Only four volatile compounds contributed directly to the aroma according to the OAVs values higher than 1. Finally, a PCA analysis allowed accounting for 100?% of the variance.     

Lipophilic compounds in femoral secretions of males and females of the El Hierro giant lizard Gallotia simonyi (Lacertidae)

Many lizards use femoral gland secretions in reliable intraspecific communication. Based on mass spectra, obtained by GC–MS, we found 57 lipophilic compounds in femoral secretions of males and females of El Hierro giant lizards, Gallotia simonyi (fam. Lacertidae). Compounds included steroids (mainly cholesterol) and fatty acids ranging between n-C₁₆ and n-C₂₂ (mainly hexadecanoic and octadecanoic acids), followed by aldehydes, alcohols, ketones, squalene and waxy esters. There were important intersexual differences in the presence, abundance and number of compounds (more numerous in males). Males had higher proportions of the most odoriferous compounds (fatty acids and aldehydes), while females had higher proportions of more stable compounds (steroids, waxy alcohols, waxy esters and terpenoids). This suggests sexual differences in function of femoral secretions. In addition, some compounds could reflect the physiological state, allowing monitoring health of lizards from secretions samples, which is especially important given the critical conservation status of this lizard.     

A detailed identification study on high-temperature degradation products of oleic and linoleic acid methyl esters by GC-MS and GC-FTIR

GC-MS and GC-FTIR were complementarily applied to identify oxidation compounds formed under frying conditions in methyl oleate and linoleate heated at 180°C. The study was focused on the compounds that originated through hydroperoxide scission that remain attached to the glyceridic backbone in fats and oils and form part of non-volatile molecules. Twenty-one short-chain esterified compounds, consisting of 8 aldehydes, 3 methyl ketones, 4 primary alcohols, 5 alkanes and 1 furan, were identified. In addition, twenty non-esterified volatile compounds, consisting of alcohols, aldehydes and acids, were also identified as major non-esterified components. Furanoid compounds of 18 carbon atoms formed by a different route were also identified in this study. Overall, the composition of the small fraction originated from hydroperoxide scission provides a clear idea of the complexity of the new compounds formed during thermoxidation and frying.     

Chirality and biosynthesis of lilac compounds in Actinidia arguta flowers

Biosynthesis of lilac compounds in ‘Hortgem Tahi’ kiwifruit (Actinidia arguta) flowers was investigated by treating inflorescences with d₅-linalool. The incorporation of the deuterium label into 8-hydroxylinalool, 8-oxolinalool, the lilac aldehydes, alcohols, and alcohol epoxides was followed by GC-MS and enantioselective GC-MS. Both (R)- and (S)-linalool were produced naturally by the flowers, but 8-hydroxylinalool, 8-oxolinalool, and the lilac aldehydes and alcohols occurred predominantly as the (S) and 5′(S)-diastereoisomers, respectively. The enantioselective step in the biosynthesis of the lilac aldehydes and alcohols was concluded to be the oxidation of linalool to (S)-8-hydroxylinalool. In contrast, the lilac alcohol epoxides had a 5′(R):(S) ratio, the same as for linalool, which suggests that either these compounds are not synthesised from the 5′(S)-configured lilac aldehydes and alcohols, or that if indeed they are, then it is by an enantioselective step that favours utilisation of the 5′(R)-configured compounds.     

Volatile constituents of wood-rotting basidiomycetes

Phytochemical investigation of the hydrodistillation products of the basidiomycetes Fomitopsis pinicola, Piptoporus betulinus, Gloeophyllum odoratum and Trametes suaveolens led to the identification of numerous mono- and sesquiterpenes as well as many aliphatic alcohols, aldehydes and ketones and some aromatic compounds. In addition, some diterpenes were identified as constituents of Fomitopsis pinicola. The absolute configuration of some terpenes was determined     

Application of Axial-haloketone Rule to Lactones

Antifungal activities were examined and compared for some 40 kinds of aliphatic and aromatic aldehydes, alcohols, phenolic compounds, ether compounds and hydrocarbons from essential oils and for some related compounds, using seven fungi.     

Antimicrobial Browning-Inhibitory Effect of Flavor Compounds in Seaweeds

Since ancient times, the antimicrobial properties of seaweeds have been recognized. However, antimicrobial activities of volatile compounds in seaweeds have not been explored so far. Here, essential oils from seaweeds including green, brown and red algae such as Laminaria japonica, Kjellmaniella crassifolia, Gracilaria verrucosa and Ulva pertusa were prepared by using SDE (simultaneous distillation and extraction) apparatus. Volatile compounds in the essential oils were identified as aldehydes, ketones, carboxylic acids, alcohols and hydrocarbons by comparison of GC-retention times and MS data with those of authentic specimens. Flavor compounds such as (3Z)-hexenal, (2E)-hexenal and (2E)-nonenal in some essential oils showed strong antimicrobial activities against Escherichia coli TG-1, and Erwinia carotovora. Inhibition of browning can be achieved during either of two stages, namely, oxidation reaction by tyrosinase or subsequent non-enzymatic polymerization. Tyrosinase activity was measured by monitoring absorbance at 475 nm originating from dopachrome formed from L-DOPA. Many kinds of aliphatic carboxylic acids, aldehydes and alcohols were used as inhibitors for PPO activity. The results indicated that the α,β-unsaturated carbonyl compounds strongly inhibit tyrosinase activity. When seaweeds are damaged or macerated, the α,β-unsaturated aldehydes such as (2E)-hexenal and (2E)-nonenal are biosynthesized via the corresponding (3Z)-unsaturated aldehydes from linolenic acid and arachidonic acid. The flavor compounds that are formed could be valuable as safe antimicrobial browning-inhibitory agents of edible seaweed origin.     

Biotransformation of monoterpenoids by suspension cultures of Lavandula angustifolia

Suspension cultures of Lavandula angustifolia reduced monoterpenoid aldehydes and structurally related compounds to their corresponding primary alcohols. Acyclic primary monoterpenoid alcohols were further metabolized to unidentified compounds. Cyclic, secondary, tertiary and aromatic alcohols were not metabolized.     

Chemical Composition of Lipids from Peat-Forming Leafy Mosses of Eutrophic Swamps of Western Siberia and Altai

The molecular composition of lipids in three samples of leafy mosses (Aulacomnium palustre, Warnstorfia fluitans, and Calliergon giganteum) has been determined. The revealed acyclic compounds included normal and isoprenoid alkanes, isoprenoid alkenes, normal and isoprenoid ketones, carboxylic acids and their esters, alcohols, and aldehydes. Among cyclic compounds, bi-, tri- and tetracyclic polycycloaromatic hydrocarbons (PAHs), bicyclic and pentacyclic terpenoids, steroids and tocopherols have been observed. The identified organic compounds consisted mainly of carbocyclic acids and n-alkanes with the prevalence of C₂₇ homologues. A. palustre is characterized by a reduced content of isoprenoid compounds, alcohols, and ketones, while the content of unsaturated acids, pentacyclic terpenoids, and aldehydes is rather heightened. A. palustre differs from W. fluitans and C. giganteum in the steroid composition and contains eremophylene, a sesquiterpenoid, which is absent in the mosses of the family Amblystegiaceae. Compared to C. giganteum, W. fluitans has a higher content of lycopadiene, carboxylic acids, n-alkanes, phyt-2-ene, aldehydes, esters, squalene, diploptene, α-tocopherol, and triphenyl phosphates.     

The alteration of intracellular enzymes. II. The relation between the surface and the biological activities of altering agents

1. The ability of homologous series of alcohols, ketones, and aldehydes to cause alteration of intracellular catalase increases approximately threefold for each methylene group added, thus following Traube's rule. Equiactive concentrations of alcohols (methanol to octanol) varied over a 4,000-fold range, yet the average corresponding surface tension was 42 ± 2 dynes/cm., that for ketones 43 ± 2, and for aldehydes (above C₁) 41 ± 3. 2. Above C₈ the altering activity of alcohols ceased to follow Traube's rule, and at C₁₈ was nil. Yet the surface activities of alcohols from nonanol to dodecanol did follow Traube's rule. These two facts show that the interface which is being affected by these agents is not the cell surface, for if it were, altering activity should not fall off between C₉ and C₁₂ where surface activity is undiminished; they show also that micelle formation by short range association of hydrocarbon "tails," usually invoked to explain decrease in biological activity of compounds above C₈, is not responsible for this effect in these experiments, in which permeability of the cell membrane probably is involved. 3. The most soluble alcohols and aldehydes (alcohols C₁ to C₈; aldehydes C₁, C₂), but not ketones, cause, above optimal concentration, an irreversible inhibition of yeast catalase. 4. The critical concentration of altering agent (i.e., that concentration just sufficient to cause doubling of the catalase activity of the yeast suspension) was independent of the concentration of the yeast cells. 5. Viability studies show that the number of yeast cells killed by the altering agents was not related to the degree of activation of the catalase produced. While all the cells were invariably killed by concentrations of altering agent which produced complete activation, all the cells had been killed by concentrations which were insufficient to cause more than 50 per cent maximal activation. Further, the evidence suggested that the catalase may be partially activated by concentrations of altering agent which cause no decrease in viability at all. Hence alteration, unlike death, may not be all-or-none per cell. 6. The fact that the biological criterion being examined was the activation of a water-soluble enzyme rules out the possibility that the reason for the logarithmic increase in altering activity with chain length was increase in concentration of the altering agent in some intracellular fat phase. It is concluded that these surface-active agents cause enzyme alteration by becoming adsorbed at some intracellular interface and thus causing, directly or indirectly, the modification of catalase properties. 7. It is considered that these data support, but do not provide critical proof for, the interfacial hypothesis, which states that catalase is present at the intracellular interface in question, but is desorbed into solution as a consequence of the alteration process.     

Basic and Neutral Compounds in the Cooked Odor from Antarctic Krill

The cooked odor concentrate from precooked krill was obtained by a simultaneous distillation and extraction system. The resulting odor concentrate was separated into basic, carbonyl and carbonyl-free fractions. Each fraction was analyzed by gas chromatography and gas chromatography-mass spectrometry. Fifty seven compounds, including 3 pyridines, 10 pyrazines, 6 thiazoles, 3 dihydro-4H-1,3,5-dithiazines, 11 aldehydes, 10 ketones, 4 alcohols, 6 hydrocarbons and 4 other compounds were identified. Twenty two of these compounds were newly found as the odor components of krill. The low molecular aldehydes, which are known to be a part of the precursors of the secondary formation of the cooked odor, were also investigated by thin layer chromatography. Ethanal, propanal and butanal were newly detected.     

Identification of volatile metabolites from rice fermented by the fungusMonascus purpureus (Ang-kak)

Eighty volatile compounds that create typical ang-kak aroma have been identified in samples of rice grains fermented byMonascus purpureus and in cultivation media afterM. purpureus fermentation. These volatile metabolites include alcohols, aldehydes, ketones, esters and terpenoid compounds. Identification has been performed by means of GC-MS after sample distillation and extraction with dichloromethane.     

GC-MS法测定阳荷花挥发油的成分

为分析阳荷Zingiber striolatum Diels.花挥发油中的成分,采用水蒸气蒸馏的方法提取阳荷花中的挥发性成分,应用气相色谱-质谱联用法对化学成分进行鉴定,用峰面积归一化法测定各个化合物在挥发油中的相对百分含量。检测出59个化学成分,鉴定了其中55个化学成分总提物的95.54%。其中烯烃类占49.08%,醇类化合物占22.39%,醛类化合物占6.07%,酯类占4.72%,氧化物占4.25%,酮类化合物占2.26%,,还含有少量的烷烃占2.19%,苯的衍生物占1.81%。     

Enantiomer Distribution of Major Chiral Volatile Organic Compounds in Selected Types of Herbal Honeys

In this article, volatile organic compounds in 14 honey samples (rosemary, eucalyptus, orange, thyme, sage, and lavender) were identified. Volatile organic compounds were extracted using a solid phase microextraction method followed by gas chromatography connected with mass spectrometry analysis. The studied honey samples were compared based on their volatile organic compounds composition. In total, more than 180 compounds were detected in the studied samples. The detected compounds belong to various chemical classes such as terpenes, alcohols, acids, aldehydes, ketones, esters, norisoprenoids, benzene and furane derivatives, and organic compounds containing sulfur and nitrogen heteroatom. Ten chiral compounds (linalool, trans‐linalool oxide, cis‐linalool oxide, 4‐terpineol, α‐terpineol, hotrienol, and four stereoisomers of lilac aldehydes) were selected for further chiral separation. Chirality 26:670‐674, 2014. © 2014 Wiley Periodicals, Inc.     

Chemical degradation of liposomes by serum components detected by NMR

Interaction between serum components and liposomes is an oxygen-dependent exothermic process. We studied the interaction of 100 nm extruded liposomes (bearing positive, negative or no charge) with foetal calf serum by 1H NMR and 13C NMR, in order to further our understanding of these reactions. Studies of aqueous or organic extracts obtained after 2 h, 1 day or 1 week, showed hydrolysis to be a degradation process concomitant with the interaction with serum. Oxidation was identified as additional to hydrolysis in the process of degradation. Oxidation produced aldehydes, acids and alcohols, although aldehydes and alcohols were prone to further decomposition and only appeared transiently. Alkenes and other oxidized compounds predominated in those products derived from oxidation. In stearylamine-containing liposomes some aldehydes and a nitroderivative were found as degradation products. Such metabolites are apolar and their presence might explain the intrinsic toxicity of this kind of liposome in cell cultures. The work described in the present study revealed the chemical degradation of liposomes in the serum used. In all cases the results obtained were compared with liposomes not incubated with serum.     

Gas Chromatographic and Mass Spectral Analyses of Heated Flavor Compounds of Beef Fats

The volatile compounds from beef fats heated under the cooking condition-145°C, l0 min-were isolated, and nonacidic compounds separated from them were further fractionated into five fractions by silicic acid column chromatography. The odor of nonacidic compounds significantly resembled the heated flavor of beef fats. Several carbonyl compounds, hydrocarbons, alcohols, lactones and pyrazine compounds in the fractionated compounds were identified with the techniques of gas chromatography and gas chromatography-mass spectrometry. Their possible contribution to the heated beef fat flavor was discussed. The typical heated flavor could probably be ascribed to a proper combination of aldehydes, ketones, esters and sulfur-containing compounds.     

ACOMPARATIVE STUDY ON THE ELECTROANTENOGRAM RESPONSES OF THREE APHID SPECIES TO PLANT VOLATILES

Abstract  Electroantennogram responses (EAGs) to 39 plant volatiles from Aphis glycines, A. gossypii and Myzus persicae were recorded. The olfactory system of these three aphid species differentially responded to green leaf, aromatic, mono-and sequiterpene chemicals. The EAG depolarizatin to green leaf chemicals and their isomers were more pronounced than to terpenes, alcohols and aldehydes, 6 carbon atom compounds being the most effective. It was shown that there was certain difference in the olfactory spectra of these three aphid species to plant volatiles. Higher responses in A. glycines and A. gossypii were elicited by the leaf aldehydes and esters than by the corresponding alcohols, which are in contrast with those in M. persicue . The activity of aphid olfactory system was related to molecular structures of the compounds. The responses to saturated alcohols and aldehydes were higher than those to unsaturated. The responses of spring emigrants of A. glycines to terpene derivatives (alcohols, aldehydes and esters) were higher than those of A. gossypii , but were lower to terpene hydrocarbons. The dissimilarity in olfactory spectra of the aphid species reflected the evolution of their host plant selection specificity. In the evolution, their chemosensory system adapted to perceive host plants. The shapes of the EAGs evoked by the various components were consistently different, with the slowest recovery for geraniol, 1-decanol and (±)-β-cit-ronellol, and ware related to number of carbon atoms in straight chain saturated alcohols.