Studies on the Chemical Constituents of the Volatile Oil of Abies nephrolepis Maxim Leaves

The volatile oil of Abies nephrolepis Maxim leaves growing in Changbai Moutain region was analyzed by OV-1 Capillary column (25×0.25)GC/MS/DS and found to contain 46 chemical constituents, 22 of them which make up 96.8% of the total oil were identified. The major components are α-pinene (15.944%), camphene (20.329%), limonene (29.709%), bornyl acetate (17.083%), etc. Six components from the oil were isolated by N2 protected vectification under vacuum, preparative circle thin-layer chromatography and column chromatography. Limonene, borneol, bornyl acetate and α–bisabolol were idetified by IR and MS.     

Identification of anionic selenium species in Se-rich yeast by electrospray QTOF MS/MS and hybrid linear ion trap/orbitrap MSn

An analytical approach allowing the identification of unknown selenium metabolites in selenium-rich yeast was described. Anion-exchange HPLC of the Se-metabolome fraction co-eluting with salts in size-exclusion chromatography allowed the separation of nine selenium species (excluding isomers and selenate) as monitored by inductively coupled plasma mass spectrometry (ICP MS). The individual fractions were analyzed by electrospray QTOF MS/MS and hybrid linear ion trap/Orbitrap MSn after sample introduction by reversed-phase nanoHPLC and by hydrophilic interaction LC (HILIC), respectively. Out of the nine detected species, eight were identified on the basis of accurate mass measurements and collision induced dissociation/fragmentation information. Seven Se-species (selenohomolanthionine, γ-Glu-selenocystathionine, 2,3-DHP-selenocystathionine, N-acetyl-selenocystathionine, 2,3-DHP-selenohomolanthionine, Se-methyl-selenoglutathione, and 2,3-DHP-Se-methylselenocysteine) were reported for the first time in Se-rich yeast, five of them have never been reported in any biological sample before.     

Streptomycin biosynthesis in Streptomyces griseus II. Adjacent genomic location of biosynthetic genes and one of two streptomycin resistance genes

Abstract A new quinone was isolated from the thermophilic methane-oxidizing bacterium strain H-2; was eluted after ubiquinone-8 on reversed-phase high-performance liquid chromatography (HPLC). Proton-magnetic resonance spectroscopy revealed that one of the isoprene units of a side chain was changed to 4-methyl-3-isopentene. The position of the substituted isoprene unit was localized by MS/MS spectrometry. The new quinone was identified as 2,3-dimethoxy-5-methyl-6-geranylgeranyl- [4-methyl-3-isopentenyl]-farnesyl-1,4-benzoquinone.     

Dehydrodieugenols from Ocotea cymbarum

The trunk wood of Ocotea cymbarum from the Amazon basin contains α-phellandrene, α-pinene, eugenol, dehydrodieugenol and its monomethyl ether, as well as the previously unknown dehydrodieugenol-B (4,5′-diallyl-2′-hydroxy-2,3′-dimethoxydiphenyl ether).     

高β-蒎烯含量思茅松松脂化学特征

采用气-质联用仪对5年生的40个思茅松高产脂嫁接无性系及1个对照松脂的组成成份进行分析,发现10个高β-蒎烯含量的思茅松无性系,与对照相比,松脂松节油化学组成中β-蒎烯平均质量分数(50.25%)约为对照(9.5%)的5倍;△3-蒈烯含量约为对照的3倍;异海松酸含量约为普通思茅松的8倍,可作为高β-蒎烯思茅松选择的重要指标之一。     

Bioactivity of essential oil of Litsea cubeba from China and its main compounds against two stored product insects

During our screening program for agrochemicals from Chinese medicinal herbs and wild plants, the essential oil of Litsea cubeba fruits was found to possess strong contact toxicity against the cigarette beetle Lasioderma serricorne adults and the booklouse Liposcelis bostrychophila, with LD₅₀ values of 27.33 μg/adult and 71.56 μg/cm², respectively, and also showed strong fumigant toxicity against the two stored product insects with LC₅₀ values of 22.97 and 0.73 mg/L, respectively. The essential oil obtained by hydrodistillation was investigated by GC MS. The main components of the essential oil were identified to be E-citral (geranial) (27.49%), Z-citral (neral) (23.57%) and d-limonene (18.82%) followed by β-thujene (3.34%), β-pinene (2.85%), α-pinene (2.57%), 6-methyl-5-hepten-2-one (2.40%) and linalool (2.36%). Citral (Z/E-citral), d-limonene, β-pinene, α-pinene and linalool were separated and purified by silica gel column chromatography and preparative thin layer chromatography, and further identified by means of physicochemical and spectrometric analysis. Citral and linalool showed strong contact toxicity against L. serricorne and L. bostrychophila (LD₅₀ = 11.76, 12.74 μg/adult and 20.15, 99.97 μg/cm², respectively) and fumigant toxicity against L. serricorne and L. bostrychophila (16.54, 18.04 mg/L air and 0.14, 0.71 mg/L air, respectively). Otherwise, citral, d-limonene and linalool were strongly repellent against the cigarette beetle L. serricorne as the essential oil whereas β-pinene and α-pinene exhibited weaker repellency against the cigarette beetle compared with the positive control, DEET. Moreover, except α-pinene and linalool, the other three compounds as well as the essential oil exhibited comparable repellency against the booklouse relative to DEET.     

Headspace-SPME of <Emphasis Type="Italic">in vitro</Emphasis> shoot-cultures and micropropagated plants of <Emphasis Type="Italic">Lavandula viridis</Emphasis>

In this work the volatiles emitted from in vitro shoot-cultures and micropropagated plants of Lavandula viridis L’Hér. were characterized and compared with those obtained from the field-grown mother-plant, using headspace solid phase micro-extraction following by capillary gas chromatography coupled to mass spectrometry (HS-SPME-GC/MS). The headspace composition consisted mainly in oxygenated monoterpenes (66.7–79.2 %), where the major constituents emitted by the mature field-grown mother-plant, in vitro shoot-cultures and micropropagated plants were 1,8-cineole (74.0, 51.9 and 57.8 %) and camphor (2.9, 15.3 and 8.7 %), respectively. The headspace of in vitro shoot-cultures and micropropagated plants showed greater amount of α-pinene, camphene, β-pinene, β-selinene and selina-3,7(11)-diene, when compared with the field-grown mother-plant.     

Chemical classification of the essential oils of the Iranian Salvia species in comparison with their botanical taxonomy

The essential oils of eight Salvia species collected from different localities in Iran were analyzed by gas chromatography/mass spectrometry (GC/MS). The analytical results were compared with those previously published for related Iranian sage species in order to identify chemical markers for these species. Salvia eremophila, S. hypoleuca, and S. reuteriana are endemic, while S. atropatana, S. chloroleuca, S. santolinifolia, S. aegyptiaca, and S. macrosiphon also grow wild in neighboring countries. We categorized the Iranian Salvia species into four main chemotypes according to their essential-oil constituents: those which are dominated by 1) monoterpenes, 2) mono- and sesquiterpenes, or 3) sesquiterpenes as the major constituents, and 4) those containing low-molecular-weight acids, aldehydes, and esters, and green-leaf volatiles (GLVs). Likely due to the chemical diversity of different Salvia chemotypes, this categorization was supported by principal component analysis (PCA) for the group sampled here, but not for the values reported in the literature. We identified the following chemical markers: α-pinene, β-pinene, 1,8-cineol, linalool, and borneol in monoterpene-rich species, or β-caryophyllene, germacrene D, bicyclogermacrene, spathulenol, and caryophyllene oxide in sesquiterpene-rich species. Among these, α-pinene, β-caryophyllene, and germacrene D are the most common and abundant in the Salvia species investigated. In accordance with their close biological taxonomy, the chemical similarity of the essential oils of S. santolinifolia and S. eremophila is so high that we may consider them chemically identical.     

Studies on the Components of the Essential oil from Adcnosma indianum (Lour.) Merr

This paper presents the chemical constituents of the essential oil of Adenosma indianum (Lour.) Merr. by GC and GC/MS/DS. Fivty-four components which were isolated and quantified. Thirtyfive components have been identified. The main components are α-pinene, β-pinene, limonene, p-cymene, 1,4-cineol, linalool, fenchone, o-methylanisole and δ-guaiene.     

Studies on the Chemical Constituents of Fruits of Lindera glauca (Sieb. et Zuec.) Bl. and Their Uses

The paper presents the chemical constituents of fruits of Lindera glauca (Sieb. et Zucc.) B1. By applying the techniques of fractional distillation, column chromatography, GC, TLC, PC, chemical methods and spectroscopic data (IR, NMR and MS), the following chemical constituents in essential oils from the fruits and the fatty acids of fatty oil from seed have been identified: There are 13 components in essential oil—α-pinene (0.03%), β-pinene (2.75%), camphene (2.27%), ocimene (77.99%), nonyl aldehyde (1.08%), capric aldehyde (0.30%), 1,8-cincol (2.47%), borneol (0.21%), citral (0.42%), β-cymene (0.63%), safrole (2.60%), bornyl acetate (0.60%), γ-patehoulene (0.69%); 6 fatty acids in fatty oilcaprylic acid (0.28%), eapric acid (55.27%), lauric acid (32.21%), myristic acid (1.18%), palmitie acid (2.72%) and stearie acid (8.94%). In addtion, the use of essential oil of fruit and fatty oil of seed has been studied.     

Composition and Chemical Variability of the Essential Oil from Aerial Parts of Cladanthus scariosus,an Endemic Species to the Moroccan High Atlas

Cladanthus scariosus (Ball) Oberpr. & Vogt is endemic to Moroccan High Atlas. It is known under the vernacular names Irezghi or Irezgui. Three essential oil samples have been isolated from aerial parts and analyzed by combination of chromatographic and spectroscopic techniques [gas chromatography (GC) in combination with retention indices (RI), gas chromatography-mass spectrometry (GC/MS) and ¹³C-NMR spectroscopy]. The compositions of oil samples were dominated by monoterpenes: α-pinene sabinene, and terpinen-4-ol. Chamazulene and dihydrochamazulene isomers as well as various hemiterpene esters and analogs have been identified. To evidence a chemical variability, statistical analysis performed on 13 oil sample compositions allowed partitioning into three groups, mainly differentiated by their contents of sabinene, camphor, borneol, terpinen-4-ol, and germacrene D.     

Chemical composition, antioxidant activity and inhibitory effects of essential oil of Eucalyptus teretecornis grown in north-western Himalaya against Alternaria alternata

The essential oil obtained from fresh leaves of Eucalyptus teretecornis (family Myrtaceae) was analysed by gas chromatography/mass spectrometry (GC/MS). Twenty eight compounds were identified and ??-pinene (22.55%), ??-pinene (22.50%), 1,8-cineole (19.84%), limonene (5.62%), ??-fenchol (3.10%), ??-phellandrene (2.90%), ??-eudesmol (2.66%) and 4-(2-methylcyclohex-1-enyl)-but-2-enal (2.34%) were the main components. The antifungal activity of the essential oil was assayed against Alternaria alternata using bioautography. Two main bioactive components namely a₁ (R _f ?=?0.27) and a₂ (R _f ?=?0.33) were observed that produced inhibition zone of 4?mm and 8?mm in diameter respectively. The minimum inhibitory amount (MIA) of a₁ and a₂ against A. alternata was determined as 28???g and 10???g, respectively using bioautography assay. Components corresponding to a₁ and a₂ were determined as ??-fenchol (oxygenated monoterpene) and ??-eudesmol (oxygenated sesquiterpene) respectively using GC/MS analysis. The antioxidant activity of the essential oil and its bioactive fraction was evaluated by DPPH radical scavenging assay, ??-carotene/linoleic acid bleaching assay, reducing power assay and metal chelating assay. In addition fraction of the essential oil that showed antioxidant activity was analyzed using GC/MS and ??-fenchol, 4-terpineol and carvacrol were the main components.     

Essential oil composition of Angelica archangelica L. (Apiaceae) roots and its antifungal activity against plant pathogenic fungi

This study reports the results of gas chromatography–mass spectrometry (GC–MS) analyses of the essential oil of Angelica archangelica L. (Apiaceae) roots, as well as its in vitro antifungal activity against 10 plant pathogenic fungi. Moreover, the essential oil was evaluated for its antifungal activity using the agar dilution method, and also minimum inhibitory concentrations and minimum fungicidal concentrations were determined. The major compounds identified by GC–MS were α-pinene (21.3%), δ-3-carene (16.5%), limonene (16.4%), and α-phellandrene (8.7%). The oil showed in vitro antifungal activity against some species of the Fusarium genus, Botrytis cinerea, and Alternaria solani. Our study indicates that the oil of A. archangelica could be used as a control agent for plant pathogenic fungi in natural formulations.     

Application of liquid chromatography-mass spectrometry to the investigation of poisoning by Oenanthe crocata

Liquid chromatography-mass spectrometry (LC-MS) analysis of methanol extracts of Oenanthe crocata roots revealed that oenanthotoxin co-eluted with another major polyalkyne, 2,3-dihydro-oenanthotoxin, using the existing high performance liquid chromatography (HPLC) method (isocratic elution from C18 with aqueous methanol) for investigating Oenanthe poisoning. Positive ES or APCI gave [(M+H)-H(2)O](+) and its methanol adduct as major ion species for oenanthotoxin, whereas 2,3-dihydro-oenanthotoxin formed [M+H](+) and its methanol adduct. The two polyalkynes could be chromatographically resolved on C18 by gradient elution with aqueous acetonitrile. This provides superior analysis for oenanthotoxin using HPLC with photodiode array (PDA) detection alone, but for LC-MS/MS aqueous acetonitrile was less suitable due to poor ionisation and, with APCI, an increase in the relative abundance of a [M-1](+) species, which could confuse compound assignment. HPLC-PDA and LC-MS/MS methods using an aqueous acetonitrile or aqueous methanol mobile phase, respectively, were successful when applied to the analysis of the stomach contents of a pony suspected to have eaten O. crocata. Relevant product ion spectra, by ion trap MS/MS, accurate mass data and complete sets of (1)H and (13)C NMR spectral assignments are given for the two compounds.     

Alternative pathway for the formation of 4,5-dihydroxy-2,3-pentanedione, the proposed precursor of 4-hydroxy-5-methyl-3(2H)-furanone as well as autoinducer-2, and its detection as natural constituent of tomato fruit

The formation of 4-hydroxy-5-methyl-3(2H)-furanone (HMF, norfuraneol) by spinach ribosephosphate isomerase was reinvestigated. Incubation experiments using D-ribose-5-phosphate and D-ribulose-5-phosphate clearly revealed a spontaneous nonenzymatic formation of the hydroxy-furanone from the ketose-phosphate under physiological conditions at 35 degrees C and pH 7.5, whereupon up to 1.3% of D-ribulose-5-phosphate was transformed to HMF within 15 h. 4,5-Dihydroxy-2,3-pentanedione was deduced as ultimate precursor of HMF, since addition of o-phenylenediamine to the incubation mixture led to lower amounts of HMF and to the formation of 3-(1,2-dihydroxyethyl)-2-methylquinoxaline, which was identified by means of high pressure liquid chromatography with diode array detection (HPLC-DAD), HPLC-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) and NMR spectroscopy. Additionally, the spontaneous formation of 4,5-dihydroxy-2,3-pentanedione was demontrated by its conversion to the respective alditol acetate using either NaBH(4) or NaBD(4) for the reduction. Comparative gas chromatography-mass spectrometry (GC-MS) analysis revealed the incorporation of two deuterium atoms and confirmed the dicarbonyl structure. Application of 1-13C-D-ribulose-5-phosphate as well as 5-13C-D-ribulose-5-phosphate and analysis of the derived quinoxaline derivatives by HPLC-ESI-MS/MS demonstrated the formation of the methyl-group at C-5 of the carbohydrate phosphate in consequence of a nonenzymatic phosphate elimination. Application of o-phenylenediamine into ripe tomatoes led to the detection of 3-(1,2-dihydroxyethyl)-2-methylquinoxaline by means of HPLC-MS/MS analysis implying the genuine occurrence of 4,5-dihydroxy-2,3-pentanedione in this fruit.     

Potential semiochemicals in urine from free ranging wolverines (Gulo gulo Pallas, 1780)

Urine deposition has been observed as an important scent-marking behaviour among wolverines (Gulo gulo, Mustelinae, Mustelidae). Solid phase microextraction (SPME) of headspace volatiles of the urine from free ranging wolverines were examined by gas chromatography–mass spectrometry (GC–MS). Urine samples were collected directly from the bladder of live-trapped animals or from frozen samples deposited in snow. Nineteen potential semiochemicals were identified in the headspace from 22 urine samples. The composition of these volatile compounds varied by type and amount with each sample, but a number of chemicals were regularly found in many samples. The most commonly found constituents were the ketones; 2-heptanone, 4-heptanone and 4-nonanone; and the terpenes: α-pinene, β-pinene, limonene, linalool and geraniol. Mammalian urinary discharge of ingested α-pinene, β-pinene, limonene and other hydrocarbon terpenes is unusual, as these compounds are usually oxidized before excretion. The source of the hydrocarbon monoterpenes likely includes conifer needles, as they have been found in wolverine scat.     

Degradation of diphenylether by Pseudomonas cepacia

The microbial degradation of hard coal implies the cleavage of diaryl ether linkages in the coal macromolecule. We investigated the biodegradation of diphenylether as a model compound representing this substructure of coal. A bacterial strain isolated from soil and identified as Pseudomonas cepacia, was able to grow with diphenylether as sole source of carbon. During microbial growth, three metabolites were detected in the culture supernatant by high pressure liquid chromatography. As product of ring hydroxylation and subsequent rearomatization, 2,3-dihydroxydiphenylether was identified by UV, mass and nuclear magnetic resonance spectrometry and gas chromatography analyses. The cleavage of the ether linkage led to the formation of phenol and 2-pyrone-6-carboxylic acid, the latter being not further degraded by Pseudomonas cepacia. The possible cleavage mechanism of the ether linkage is discussed.Non-standard abbreviations DPE diphenylether - PCA 2-pyrone-6-carboxylic acid - GC gas chromatography - MS mass spectrometry - HPLC high pressure liquid chromatography     

Dr. Alfred Jeske 75 jahre

The chemical composition, phytotoxic and antifungal activities of the essential oils isolated by hydrodistillation from the needles of Tunisian Aleppo pine harvested from different provenances were evaluated. The chemical composition analysed by gas chromatography/mass spectrometry (GC/MS) revealed variability among provenances displaying interesting chemotypes, (Z)-caryophyllene (16.16–28.9%), β-myrcene (8.5–22.9%), α-pinene (11.7–13.14%), β-pinene (3.13–11.8%), bicyclogermacrene (5.2–12.37%), α-terpinolene (8.11–11.01%) and α-humulene (2.85–5.2%), which were the main components in the oil. Antifungal ability of Aleppo pine oils was tested by disc agar diffusion against 10 phytopathogenic fungi. Weak antifungal activity was observed for the essential oils isolated. Furthermore, in contrast, the herbicidal activity investigated for three common weeds in Tunisian cereal crops was very strong and seed germination was inhibited at a low concentration and their herbicidal effects were higher than those of a commercial herbicide.     

Carcinogenic liver fluke Opisthorchis viverrini oxysterols detected by LC–MS/MS survey of soluble fraction parasite extract

Liquid chromatography in tandem mass spectrometry (LC–MS/MS) has emerged as an informative tool to investigate oxysterols (oxidized derivatives of cholesterol) in helminth parasite associated cancers. Here, we used LC–MS/MS to investigate in soluble extracts of the adult developmental stage of Opisthorchis viverrini from experimentally infected hamsters. Using comparisons with known bile acids and the metabolites of estrogens, the LC–MS data indicated the existence of novel oxysterol derivatives in O. viverrini. Most of these derivatives were ramified at C-17, in similar fashion to bile acids and their conjugated salts. Several were compatible with the presence of an estrogen core, and/or hydroxylation of the steroid aromatic ring A, hydroxylation of both C-2 and C-3 of the steroid ring and further oxidation into an estradiol-2,3-quinone.     

Volatile Organic Compounds and Their Roles in Bacteriostasis in Five Conifer Species

In order to make clear the functions of plant volatile organic compounds (VOCs) on bacteriostasis and air decontamination, we analyzed the composition and content of VOCs in Pinus tabulaeformis Carr., P. bungeana Zucc., Sabina chinensis Antoine, Picea koraiensis Nakai, and Cedrus deodara G. Don under near-natural conditions using the thermal-desorption cold trap gas chromatography/mass spectrometer technique. The effects of the VOCs on airborne microorganisms were investigated using the method of natural sedimentation. Results showed that the major VOCs were as follows: limonene, β-pinene, α-pinene,and α-caryophyllene in Pinus tabulaeformis and P. bungeana; limonene, borneol acetate, β-pinene, myrcene, and tricylene in S. chinensis; limonene, α-pinene, myrcene, camphene, and β-pinene in Picea koraiensis; and limonene, 2, (10)-pinene, α-pinene, and myrcene in C. deodara. These VOCs and the corresponding foliar extracts inhibited the growth of bacteria and stimulated the growth of fungi. Experimental data using monomers of the VOCs demonstrated that limonene, β-pinene, and three aldehydes could significantly inhibit bacterial growth, suggesting an inhibitory effect of VOCs on the growth of airborne microorganisms in the five conifer species. The bacteriostasis and air-decontaminating effects of plant VOCs are further discussed in terms of their chemical composition.