Comparative analysis of volatiles from Drimys brasiliensis Miers and D. angustifolia Miers (Winteraceae) from Southern Brazil

The essential oils obtained from Southern Brazilian native Drimys brasiliensis Miers and Drimys angustifolia Miers were analyzed by GC and GC/MS. The oils from leaves of both species showed predominance of monoterpenoids, while the oils from stem barks were characterized by sesquiterpenoids. Bicyclogermacrene (20.0% in leaves and 25.4% in stem bark) and drimenol (1.4% in leaves and 26.2% in stem bark) were the most abundant in D. angustifolia, and cyclocolorenone (from 16.0% to 32.3% in fresh and dried leaves and almost 50% in stem bark) in D. brasiliensis. The oil from fruits of D. brasiliensis was also analyzed and presented 31.0% of cyclocolorenone. The predominance of this unusual aromadendrane-type sesquiterpene in D. brasiliensis essential oils could be used as a chemosystematic marker.     

Nematicidal Triterpenoids from Lantana camara

A new triterpene, lancamarolide ( 1 ), and seven known triterpenes, oleanonic acid ( 2 ), lantadene A ( 3 ), 11α‐hydroxy‐3‐oxours‐12‐en‐28‐oic acid ( 4 ), betulinic acid ( 5 ), lantadene B ( 6 ), and lantaninilic acid ( 7 ) were isolated from the aerial parts of Lantana camara in the course of bioassay‐guided isolation, and their nematicidal activities against Meloidogyne incognita, the root knot nematode, were carried out. Oleanonic acid was found to be the most active compound and exhibited 80% mortality after 72 h at 0.0625% concentration, which is comparable with that of the standard furadan.     

Biological activity of essential oils from seven Azorean plants against Pseudaletia unipuncta (Lepidoptera: Noctuidae)

Ten essential oils from seven Azorean plant species were evaluated for their insecticidal, ovicidal, feeding‐deterrence and growth inhibition activities against Pseudaletia unipuncta. The oils of Laurus azorica (leaves), and Juniperus brevifolia (leaves) showed strong moderate insecticidal effect on fourth‐instar larvae causing 93.3% and 46.7% mortality, respectively. Juniperus brevifolia (leaves), L. azorica (leaves), Persea indica (leaves), Hedychium gardnerianum (leaves) and Pittosporum undulatum (fruits and leaves) significantly affected the hatching of P. unipuncta eggs (<8% eclosions). Five oils showed significant feeding deterrent activities (L. azorica, 92.4%, J. brevifolia, 93.6%, P. undulatum leaves, 95.5% and fruits, 83.8% and H. gardnerianum, 88.2%). All of the essential oils tested, significantly inhibited the larval growth after 5 days of feeding on the treated diet. Essential oils from L. azorica and J. brevifolia were the most potent growth inhibitors among the oils tested, producing a decrease in the initial larva weight (?14.8 and ?14.5 mg, respectively). Our results indicate that L. azorica (leaves), J. brevifolia (leaves), P. indica (leaves), H. gardnerianum (leaves), and P. undulatum (leaves and fruits) can be exploited for the development of bioactive compounds as a new source of agrochemicals. Further emphasis on isolation and identification of active constituents can be useful to develop new environment‐friendly insect control agents.     

微杆菌Sneb159杀线虫活性物质的分离与鉴定

【目的】有关Microbacterium maritypicum在植物线虫生物防治方面的研究较少,探究菌株M. maritypicum Sneb159的杀线虫活性,明确菌株发酵液中具有杀线虫活性的物质,为生物农药的开发提供理论依据。【方法】本研究检测了菌株Sneb159发酵液对大豆胞囊线虫二龄幼虫的触杀活性;并以触杀活性为追踪,采用有机溶剂萃取、硅胶柱层析及半制备高效液相色谱等技术对菌株Sneb159发酵滤液中的活性物质进行分离纯化;采用核磁共振波谱对纯化物进行结构鉴定。【结果】菌株Sneb159具有杀线虫活性,在24 h和48 h处理组中线虫的死亡率均显著高于对照组。从菌株Sneb159发酵滤液中分离得到杀线虫活性物质A6,经结构鉴定确定该物质为苯乙酰胺。【结论】首次发现M. maritypicum对大豆胞囊线虫的触杀作用,并且明确活性物质为苯乙酰胺。结果表明菌株M. maritypicum Sneb159和苯乙酰胺在大豆胞囊线虫的生物防治方面具有较好的应用潜力。     

Chemical characterization of Azadirachta indica grafted on Melia azedarach and analyses of azadirachtin by HPLC‐MS‐MS (SRM) and meliatoxins by MALDI‐MS

Introduction – Melia azedarach adapted to cool climates was selected as rootstocks for vegetative propagation of Azadirachta indica. Cleft grafting of A. indica on M. azedarach rootstock showed excellent survival. Little is known about the chemistry of grafting. Objective – The roots, stems, leaves and seeds of this graft were examined in order to verify if grafted A. indica would produce limonoids different from those found in non‐grafted plants. Intact matured fruits were also studied to verify if they were free of meliatoxins. Methodology – After successive chromatographic separations the extracts afforded several limonoids. HPLC‐MS/MS and MALDI‐MS were used to develop sensitive methods for detecting azadirachtin on all aerial parts of this graft and meliatoxins in fruits, respectively. Results – The stem afforded the limonoid salannin, which was previously found in the oil seeds of A. indica. Salannin is also found in the root bark of M. azedarach. Thus, the finding of salannin in this study suggests that it could have been translocated from the M. azedarach rootstock to the A. indica graft. HPLC‐MS/MS analyses showed that azadirachtin was present in all parts of the fruits, stem, flowers and root, but absent in the leaves. The results of MALDI‐MS analyses confirmed the absence of meliatoxins in graft fruits. Conclusion – This study showed that A. indica grafted onto M. azedarach rootstock produces azadirachtin, and also that its fruits are free of meliatoxins from rootstocks, confirming that this graft forms an excellent basis for breeding vigorous Neem trees in cooler regions. Copyright © 2010 John Wiley & Sons, Ltd.     

Profiling the Lipophilic Fractions of Pithecellobium dulce Bark and Leaves Using GC/MS and Evaluation of Their Antioxidant,Antimicrobial and Cytotoxic Activities

Pithecellobium dulce has been used in traditional medicine to treat various ailments owing to its restorative properties. The biological activities and chemical profiles of the lipophilic fraction of P. dulce bark and leaves were assessed herein. Fatty acid methyl esters (FAME) and unsaponifiable matter (USM) were prepared and analyzed by GC/MS. A total of 40 compounds were identified in the bark saponifiable fraction, whereas 9 compounds were annotated in the leaves. Palmitic acid methyl ester was the major compound identified accounting for 41.48 % of the bark and 19.03 % of the leaves composition. Besides, linolenic acid methyl ester (22.40 %) and linoleic acid (12.69 %) were annotated in the leaves saponifiable fraction. A total of 63 compounds were detected in the bark USM and 4 compounds were identified in the leaves. Phytol represented the major component in the leaves (52.57 %) followed by lupeol (20.68 %) and lupenone (8.60 %). Meanwhile, n‐dodecane dominated in the bark USM accounting for 24.69 % of the total composition. The leaves and bark lipophilic fractions revealed moderate antioxidant and antibacterial activities. Both extracts showed no antifungal activity. No cytotoxicity was observed for both lipophilic fractions. P. dulce offers a good source of antioxidant compounds that can be introduced to food and pharmaceutical industry.     

Antimicrobial and antiviral activity-guided fractionation from Scutia buxifolia Reissek extracts

Antimicrobial and antiviral activities of the fractions from Scutia buxifolia stem bark and leaves were evaluated. Best antimicrobial results occurred with the ethyl acetate (EA) and n-butanolic (NB) fractions from the leaves against Micrococcus sp. (minimal inhibitory concentration—MIC = 62.5 μg/ml), and NB fraction from stem bark and leaves against Klebsiella pneumoniae and Enterococcus faecalis (MIC = 62.5 μg/ml). The most active fractions were selected and fractioned into silica column to perform an in vitro antibiofilm assay, which evidenced subfractions EA2 and EA3 as the more active against Candida albicans (biofilm inhibitory concentration—BIC = 582 ± 0.01 μg/ml) and Staphylococcus aureus (BIC = 360 ± 0.007 μg/ml), respectively. The NB (selectivity index—SI = 25.78) and the EA (SI = 15.97) fractions from the stem bark, and the EA (SI = 14.13) fraction from the leaves exhibited a potential antiviral activity towards Herpes Simplex Virus type 1 whereas EA2 and EA3 subfractions from leaves (SI = 12.59 and 10.06, respectively), and NB2 subfraction from stem bark (SI = 12.34) maintained this good activity. Phenolic acids and flavonoids (gallic acid, chlorogenic acid, caffeic acid, rutin, isoquercitrin, quercitrin and quercetin) were identified by HPLC and may be partially responsible for the antimicrobial and antiherpes activities observed. The results obtained in this study showed that Scutia buxifolia has antibiofilm and anti-herpetic activities and that these properties are reported for the first time for this species.     

Aroma Profile of Rubus ulmifolius Flowers and Fruits During Different Ontogenetic Phases

The chemical composition of spontaneous volatile emission from Rubus ulmifolius flowers and fruits during different stages of development was evaluated by HS‐SPME‐GC/MS. In total, 155 chemical compounds were identified accounting 84.6 – 99.4% of whole aroma profile of flowers samples and 92.4 – 96.6% for fruit samples. The main constituents were α‐copaene, β‐caryophyllene, germacrene D, (E,E)‐α‐farnesene, 1,7‐octadien‐3‐one,2‐methyl‐6‐methylene, tridecane, (E)‐2‐hexenol acetate, (E)‐3‐hexenol acetate and cyperene. The results give a chemotaxonomic contribution to the characterization of the VOCs emitted from flowers and fruits during their ontogenic development.     

Total Tocopherols,Carotenoids, and Fatty Acids Content Variation of Pistacia atlantica from Different Organs’ Crude Oils and Their Antioxidant Activity during Development Stages

The current study investigated the effect of developmental stages on the chemical composition and the antioxidant activity of fifteen crude oil samples obtained from Pistacia atlantica Desf. leaves, galls, and fruits. Twelve fatty acids were detected by GC/FID, linolenic acid (C18 : 3) was the major fatty acid detected in leaves crude oils that registered [41.73 % (P<0.05)] on the last stage. The best content of tocopherols and carotenoids was recorded at the last stage for leaves and galls oils, respectively, with values of [1.530±0.01, 0.52±0.01 (P<0.05) mg α‐tocopherol equivalent/g DW] and [86.60±0.95, 69.15±0.13 (P<0.05) μg β‐carotene equivalent/g DW]. For fruits oils, the content varied depending on the levels of fruits maturation. The results from DPPH, FRAP, and ABTS assays revealed that the antioxidant activity increased with the increasing content of tocopherols and carotenoids in leaves and galls oils during development stages, and varied for fruits oils depending on the ripening stages. Moreover, according to PCA analysis, the best phytoconstituent content and antioxidant activity were attributed to P. atlantica Desf. fruit's crude oils. Also, a strong relationship was found between the antioxidant activity and bioactive phytochemical components, such as tocopherols, carotenoids, and omega‐three fatty acid, which confirmed that P. atlantica Desf. crude oils present a valuable source of natural antioxidant that could be used for pharmaceutical and food industries purposes.     

New Constituents from the Low Polar Fraction of the Fruits of Crataegus dahurica and Their Anti‐Inflammatory Activity in RAW264.7 Cells

The fruit of Crataegus dahurica Koehne was used to treat the disease of infantile indigestion and dyspepsia as an ethnic medicine and food. As a continuous work on finding the active constituents from the edible herbs, four new biphenyl derivatives ( 1 – 4 ), together with two known compounds ( 5 and 6 ), were obtained from the petroleum ether fraction of the fruits of C. dahurica. Their structures were determined by the extensive 1D and 2D NMR spectra and HR‐MS spectrometry. Furthermore, the anti‐inflammatory activities of all the isolated compounds were investigated, in which compound 4 showed moderately inhibitory effects on NO production in RAW264.7 cells without inducing cytotoxicity.     

Chemodiversity and Antiproliferative Activity of the Essential Oil of Schinus molle Growing in Jordan

The leaves and unripe and fully‐grown fruits of Schinus molle were collected from three geographical regions of Jordan: Amman (the Mediterranean), Madaba (Irano‐Turanean), and Sahab (Saharo‐Arabian). The hydrodistilled volatile oils of fresh and dried leaves and fruits were analyzed by gas chromatography‐mass spectrometry (GC/MS). The actual composition of the emitted volatiles was determined using Solid Phase Micro‐Extraction (SPME). α‐ and β‐Phellandrenes were the major components in all the analyzed samples. Quantitative differences were observed in the obtained essential oils (0.62–5.25 %). Additionally, cluster analysis was performed. Biologically, the antiproliferative activity of the essential oil, ethanol, and water extracts of the fruits and leaves was screened on Caco2, HCT116, MCF7, and T47D cell lines. The essential oil and ethanol extracts exhibited a dose‐dependent inhibition of cell growth with IC₅₀ ranging between 21 and 65 μg/mL. The water extract did not exhibit any antiproliferative activity against the investigated cell lines.     

Chemical Constituents of Daphne giraldii Nitsche

In a search for structurally interesting substances from traditional Chinese medicines, eight compounds were isolated from an ethanolic extract of the stem bark of Daphne giraldii Nitsche. On the basis of one- and two-dimensional nuclear magnetic resonance and mass spectrometry data, and chemical methods, their structures were determined to be 2H-1-benzopyran-2-one-8-hydroxy-7-O-β-D-glucopyranosyl-5-（2-oxo- 2H-1-benzopyran-7-hydroxy-8-yloxy） （compound 1）, 1-pentanone, 1-（4-hydroxyphenyl）-5-phenyl （compound 2）, octadecyl caffeate （compound 3）, （＋）syringaresinol-4,4＇-diglycoside （compound 4）, daphnetin-8-O-β-D- glucopyranoside （compound 5）, p-hydroxybenzoic acid （compound 6）, 7,7＇-dihydroxy-[6, 8＇-bi-2H-benzopyran]- 2, 2＇-dione （compound 7）, and daphnorin （compound 8）, respectively. Of the compounds isolated, compounds 1 and 2, which we named daphnolin and daphnolon, respectively, were new, and the others were obtained from this plant for the first time.     

Piptadenin,a Novel 3,4‐Secooleanane Triterpene and Piptadenamide,a New Ceramide from the Stem Bark of Piptadeniastrum africanum (Hook.f.) Brenan

Piptadenin ( 1 ), a new triterpene along with piptadenamide ( 10 ), a new ceramide, have been isolated from the AcOEt‐soluble fraction of the MeOH extract of the stem bark of Piptadeniastrum africanum along with nine known compounds, 1‐O‐[(3β,22β)‐3,22‐dihydroxy‐28‐oxoolean‐12‐en‐28‐yl]‐β‐d ‐glucopyranose ( 2 ), 22β‐hydroxyoleanic acid ( 3 ), oleanic acid ( 4 ), lupeol ( 5 ), betulinic acid ( 6 ), 5α‐stigmasta‐7,22‐dien‐3β‐ol ( 7 ), 5α‐stigmasta‐7,22‐dien‐3‐one ( 8 ), (3β)‐stigmast‐5‐en‐3‐yl β‐d ‐glucopyranoside ( 9 ) and 2,3‐dihydroxypropyl hexacosanoate ( 11 ). Except for compound 11 , all the isolated compounds are reported for the first time from this plant. The structures of the isolated compounds were elucidated by spectroscopic data including 1D and 2D NMR. The pure compounds 1 – 11 were subjected to the pharmacological screening and compounds 2 , 5 – 7 and 9 exhibited potent urease inhibitory activity with IC₅₀ value of 25.8, 28.9, 30.1, 31.8 and 32.7 μm , respectively, whereas compound 1 showed moderate activity (IC₅₀ = 98.7 μm ). The potent urease inhibitory activity supplemented the previous literature reports and medicinal uses of this plant.     

Composition,Antifungal and Antiproliferative Activities of the Hydrodistilled Oils from Leaves and Flower Heads of Pterocephalus nestorianus Nábělek

This article reports the first study of the chemical composition, and antifungal and antiproliferative properties of the volatile extracts obtained by hydrodistillation of the flower heads and leaves of the traditional Kurdish medicinal plant Pterocephalus nestorianus Nábělek , collected in the wild. A total of 55 constituents, 43 of the flower heads’ oil (PFO) and 46 of the leaves’ oil (PLO), respectively, were identified by GC/MS, constituting 99.68% and 99.04% of the two oils, respectively. The oils were obtained in 0.15% and 0.10% yields (w/w), respectively, on air‐dried vegetable material. The prevalent constituents of the PFO were α‐terpineol (2.41%), α‐linalool (6.42%), 6,10,14‐trimethylpentadecan‐2‐one (2.59%), myristic acid (24.65%), and lauric acid (50.44%), while the major components of PLO were (E)‐hex‐2‐enal (2.26%), (E)‐hex‐2‐en‐1‐ol (2.04), myristic acid (34.03%), and lauric acid (50.35%). The two oils showed significant inhibitory and fungicidal activities against the medically important fungi Candida albicans, Candida tropicalis, Microsporum canis, and Trichophyton mentagrophytes, with minimum inhibitory concentration ranging from 0.7 to 3.3 mg/ml and minimum fungicidal concentration varying from 1.4 to 6.6 mg/ml. The antiproliferative activity of the two oils was assayed against one normal and six human tumor cell lines. Both oils showed selective cytotoxic activity, with IC₅₀ values ranging from 1.4 to 3.3 μg/ml.     

Cytotoxic Compounds from the Leaves of Garcinia polyantha

A new compound, named banganxanthone C (=12‐(1,1‐dimethylprop‐2‐en‐1‐yl)‐5,10‐dihydroxy‐9‐methoxy‐2‐methyl‐2‐(4‐methylpent‐3‐en‐1‐yl)‐2H,6H‐pyrano[3,2‐b]xanthen‐6‐one; 4 ), together with five known compounds, were isolated from the leaves of Garcinia polyantha. The structures of the compounds were elucidated on the basis of 1D‐ and 2D‐NMR spectroscopy. Among the known compounds, two were xanthones, one was a pentacyclic triterpene, one sterol, and one benzophenone derivative. Isoxanthochymol ( 2 ) and 4‐[(2E)‐3,7‐dimethylocta‐2,6‐dien‐1‐yl]‐1,5,8‐trihydroxy‐3‐methoxy‐9H‐xanthen‐9‐one ( 3 ) exhibited significant antiproliferative activity against the leukemia cell line TPH‐1 with IC₅₀ inhibition values of 1.5 and 2.8 μg/ml, respectively. The cytotoxic activity was found to be related to apoptosis induction.     

Thinning Jeffrey pine stands to reduce susceptibility to bark beetle infestations in California,U.S.A.

• 1 Bark beetles (Coleoptera: Curculionidae, Scolytinae) are commonly recognized as important tree mortality agents in coniferous forests of the western U.S.A.
• 2 High stand density is consistently associated with bark beetle infestations in western coniferous forests, and therefore thinning has long been advocated as a preventive measure to alleviate or reduce the amount of bark beetle‐caused tree mortality.
• 3 The present study aimed to determine the effectiveness of thinning to reduce stand susceptibility to bark beetle infestations over a 10‐year period in Pinus jeffreyi forests on the Tahoe National Forest, California, U.S.A. Four treatments were replicated three times within 1‐ha square experimental plots. Treatments included thinning from below (i.e. initiating in the smallest diameter classes) to a residual target basal area (cross‐sectional area of trees at 1.37 m in height) of: (i) 18.4 m²/ha (low density thin); (ii) 27.6 m²/ha (medium density thin); (iii) 41.3 m²/ha (high density thin); and (iv) no stand manipulation (untreated control).
• 4 Throughout the present study, 107 trees died as a result of bark beetle attacks. Of these, 71% (75 trees) were Abies concolor killed by Scolytus ventralis; 20.6% (22 trees) were Pinus ponderosa killed by Dendroctonus ponderosae; 4.7% (five trees) were P. jeffreyi killed by Dendroctonus jeffreyi; 1.8% (two trees) were P. jeffreyi killed by Ips pini; 0.9% (one tree) were P. jeffreyi killed by Orthotomicus (= Ips) latidens; 0.9% (one tree) were P. ponderosa killed by both Dendroctonus brevicomis and D. ponderosae; and 0.9% (one tree) were P. jeffreyi killed by unknown causes.
• 5 In the low density thin, no pines were killed by bark beetles during the 10‐year period. Significantly fewer trees (per ha/year) were killed in the low density thin than the high density thin or untreated control. No significant treatment effect was observed for the percentage of trees (per year) killed by bark beetles.

     

Nematicidal activity of <Emphasis Type="Italic">Paecilomyces</Emphasis> spp. and isolation of a novel active compound

Many species of Paecilomyces are entomogenous fungi and several are efficacious toward nematodes. To study the potential of Paecilomyces species in controlling nematodes, fungal extracts of 40 Paecilomyces spp. were evaluated for their nematicidal activity against Bursaphelenchus xylophilus and Panagrellus redivivus. The extracts of six Paecilomyces spp. exhibited the nematicidal activity against P. redivivus, and 11 species exhibited the nematicidal activity against B. xylophilus. The methanol extract of strain 1.01761 incubating on Czapek solid medium killed more than 95% P. redivivus in 24 h at 5 mg/ml, and the filtrate of strain 1.01788 cultured in Sabouraud’s broth medium resulted in 90% mortality of B. xylophilus in 24 h at 5 mg/ml. A novel nematicidal compound 4-(4′-carboxy-2′-ethyl-hydroxypentyl)-5,6-dihydro-6-methylcyclobuta[b]pyridine-3,6-dicarboxylic acid, was isolated from Paecilomyces sp. YMF1.01761. The LD₅₀ value of the compound within 24 h against P. redivivus was 50.86 mg/L, against Meloidogyne incognita was 47.1 mg/L, and against B. xylophilus was 167.7 mg/L.     

A Prospective of Multiple Biopharmaceutical Activities of Procyanidins-Rich Uapaca togoensis Pax Extracts: HPLC-ESI-TOF-MS Coupled with Bioinformatics Analysis

The article reports the chemical composition, antioxidant, six key enzymes inhibitory and antimicrobial activities of two solvent extracts (water and methanol) of leaves and stem bark of Uapaca togoensis. For chemical composition, methanol extract of stem bark exhibited significant higher total phenolic (129.86 mg GAE/g) and flavanol (10.44 mg CE/g) contents. Methanol extract of leaves and water extract of stem bark showed high flavonoids (20.94 mg RE/g) and phenolic acid (90.40 mg CAE/g) content, respectively. In addition, HPLC-ESI-TOF-MS analysis revealed that U. togoensis was rich in procyanidins. The methanol and water extracts of stem bark had overall superior antioxidant activity; however, only methanol extract of stem bark showed higher inhibition of cholinesterase (AChE: 2.57 mg GALAE/g; BChE: 4.69 mg GALAE/g), tyrosinase (69.53 mg KAE/g) and elastase (2.73 mmol CE/g). Potent metal chelating ability was showed by water extract of leaves (18.94 mg EDTAE/g), higher inhibition of amylase was detected for water extracts of leaves (0.94 mmol ACAE/g) and stem bark (0.92 mmol ACAE/g). The tested extracts have shown wide-spectrum antibacterial properties and these effects have shown to be more effective against Aspergillus ochraceus, Penicillium funiculosum, Trichoderma viride, Bacillus cereus, Escherichia coli and Pseudomonas aeruginosa. The results revealed that the antioxidant, enzyme inhibitory and antimicrobial activities depended on the extraction solvents and the parts of plant. Bioinformatics analysis on the 17 major compounds showed modulation of pathway associated with cancer. In brief, U. togoensis might be valuable as potential source of natural agents for therapeutic application.     

Polyprenylated Xanthones from Garcinia lancilimba Showing Apoptotic Effects against HeLa‐C3 Cells

Three new prenylated xanthones, 1 – 3 , along with ten known compounds, were isolated from the stem bark of Garcinia lancilimba. Their structures were elucidated by extensive spectroscopic analysis, including 1D‐ and 2D‐NMR spectra, as well as HR‐MS experiments. Some of these compounds showed apoptotic effects or growth‐inhibition effects against HeLa cells expressing a caspase sensor protein.