Citrantifidiene and citrantifidiol: bioactive metabolites produced by Trichoderma citrinoviride with potential antifeedant activity toward aphids

Two novel metabolites with potential antifeedant activity were isolated from cultures of the fungus Trichoderma citrinoviride strain ITEM 4484 grown in solid-state fermentation on sterile rice kernels. The producing strain was identified at species level by sequence analysis of the internal transcribed spacer regions ITS-1 and ITS-2 of the nuclear rDNA and a fragment of the translation elongation factor gene TEF-1alpha. Fractionation by column chromatography and TLC of the culture organic extract, followed by feeding preference tests on the aphid pest Schizaphis graminum (Rondani), allowed the purification of 5.8 and 8.9 mg/kg of culture of two bioactive metabolites, which were named citrantifidiene and citrantifidiol ( 1 and 2). Citrantifidiene and citrantifidiol, whose structures were determined by spectroscopic methods (NMR and MS) are a symmetrical disubstituted hexa-1,3-dienyl ester of acetic acid and a tetrasubstituted cyclohexane-1,3-diol, respectively. The pure metabolites influenced the feeding preference of S. graminum restraining individuals from feeding on wheat leaves dipped in 5% aqueous methanol solution containing 0.57 mg/mL of citrantifidiene or 0.91 mg/mL of citrantifidiol.     

Weed growth interference from temperate cereals: the effect of a hydroxamic-acids-exuding rye (Secale cereale L.) cultivar

Under field conditions, a plot sown with Forrajero-Baer, a rye (Secale cereale L.) cultivar exuding hydroxamic acids through its roots, resulted in 83% less weed biomass than wheat (Triticum aestivum L.) and 76% less than forage oats (Avena strigosa L.). Forage oats reduced broadleaf weed biomass by 40% compared to wheat but failed to suppress wild oats (Avena fatua L.). Rye interference reduced wild oat biomass by 84% and 86% compared to wheat and forage oats, respectively. Bioassays carried out with 2-O-ß-glucopyranosyl-4-hydroxy-l,4-benzoxazin-3-one (DIBOA-glc), the main hydroxamic acid found in rye, its aglucone 2,4-dihydroxy-1,4-benzoxazin-3-one (DIBOA), and its breakdown product benzoxazolin-2-one (BOA) showed inhibition of root and coleoptile growth of A. fatua seedlings at concentrations above 0–25 mM l^?1. These results indicate that hydroxamic acids from Forrajero-Baer rye probably play a significant role in the weed-suppressing ability of this cultivar. Interférence entre la croissance des adventices et les cereales de zones tempérées: l'effet d'un cultivar de seigle (Secale cereale L.) secrétant des acides hydroxamiques Sous conditions de plein champ, une parcelle semée avec Forrajero-Baer, un cultivar de seigle (Secale cereale L.) secrétant des acides hydroxamiques à travers ses racines, a aboutit à une biomasse en adventices de 83% de moins qu'un blé (Triticum aestivum L.) et 76% de moins que de l'avoine fourragère (Avena strigosa L.). Les avoines fourragères réduisent la biomasse des adventices dicotylédones de 40% en comparaison du blé, mais n'éliminent pas les folles avoines (Avena fatua L.). L'inter-férence du seigle a réduit la biomasse de folle avoine par 84% et 86% en comparaison du blé et de l'avoine fourrageé respectivement. Des bioessais conduits avec du 2-O-ß-glucopyrano-glucopyranosyl- 4 -hydroxy- 1,4- benzoxazin -3-one (DIBOA-glc), le principal acide hydroxamique trouvé dans le seigle, son aglycone 2,4-dihydroxy-1-4 benzoxazin 3-one (DIBOA) et son produit de dégradation benzaxazolin-2-one (BOA) ont mis en évidence une inhibition de la croissance des racines et du coléoptile des plantules d'A. fatuaà des concentrations supérieures à 0,25 mM 1^?1. Ces résultats montrent que les acides hydroxamiques du seigle Forrajero-Baer jouent un rôle significatif dans l'aptitude à combattre les adventices de ce cultivar. Beeinträchtigung des Unkrautwachstums durch Getreide: die Wirkung einer Hydroxamsäuren ausscheidenden Sorte des Roggens (Secale cereale L.) In einem Feldversuch war unter der Roggen-Sorge ‘Forrajero-Baer’ (Secale cereale L.), die öber die Wurzeln Hydroxamsäuren ausscheidet, die Unkrautbiomasse 83% geringer als unter Weizen (Triticum aestivum L.) und 76% geringer als unter Sand-Hafer (Avena strigosa L.). Der Sand-Hafer reduzierte die Biomasse dikotyler Unkrautarten im Vergleich zum Weizen um 40%, konnte Flug-Hafer (Avena fatua L.) aber nicht unterdrücken. Der Roggen reduzierte die Biomasse von Flug-Hafer im Vergleich zu Weizen und Sand-Hafer um 84 bzw. 86%. In Biotests hemmten 2-O-β-Gluco-pyranosyl - 4 - hydroxy -1,4- benzoxazin - 3 - on (DOBIA-glc), die hauptsächlich in Roggen gefundene Hydroxamsäure, sein Aglukon 2,4-Hydroxy-l,4-benzoxazin-3-on (DIBOA) und sein Abbauprodukt Benzoxazolin-2-on (BOA) in Konzentrationen über 0,25 mm1^?1 das Wachstum der Wurzeln und der Koleoptile von Avena-fatua-Keimpflanzen. Diese Ergebnisse zeigen, daß Hydroxamsäuren aus der Roggen-Sorte ‘Forrajero-Baer’ offensichtlich eine wichtige Rolle bei der unkrautunterdrückenden Wirkung dieser Sorte spielen.     

Assessment of PCDD/Fs and PCBs in Sediments from the Spanish Northern Atlantic Coast

Fluid catalytic cracking of heavy ends to high-value liquid fuels is a common unit operation in oil refineries. In this process, the heavy feedstock that contains sulfur is cracked to light products. Sulphur content is hence redistributed in the liquid and gaseous products and coke of the catalyst used in this process. The coke is later burnt in the regenerator releasing sulfur into the discharged flue gas as SO₂. In the present work, comprehensive emission inventories for a fluid catalytic cracking unit in a typical oil refinery are prepared. These inventories are based on calculations that assume complete combustion of catalyst coke in the regenerator. Yearly, material balances for both SO₂ and particulate matters emissions are carried out taking into account seasonal variations in the operation of the process unit. The results presented in this article reflect the variation of sulfur in feedstock originating from various units in the refinery. The refinery operations are not dependant on seasons but controlled by market-driven conditions to maximize the profit. The seasonal impact on refinery emissions is minimal due to its operation at optimum capacity fulfilling the international market demand. The data presented and analyzed here can be used to assess the hazardous impact of SO₂ and particulate matter emissions on surrounding areas of the refinery.     

Evaluation of phenolic compounds in virgin olive oil by direct injection in high-performance liquid chromatography with fluorometric detection

Hydrophilic phenols are the most abundant natural antioxidants of virgin olive oil (VOO), in which tocopherols and carotenes are also present. The prevalent classes of hydrophilic phenols found in VOO are phenyl alcohols, phenolic acids, secoiridoids such as the dialdehydic form of decarboxymethyl elenolic acid linked to (3,4-dihydroxyphenyl)ethanol or (p-hydroxypheny1)ethanol (3,4-DHPEA-EDA or p-HPEA-EDA) and an isomer of the oleuropein aglycon (3,4-DHPEA-EA), lignans such as (+)-1-acetoxypinoresinol and (+)-pinoresinol, and flavonoids. A new method for the analysis of VOO hydrophilic phenols by direct injection in high-performance liquid chromatography (HPLC) with the use of a fluorescence detector (FLD) has been proposed and compared with the traditional liquid-liquid extraction technique followed by the HPLC analysis utilizing a diode array detector (DAD) and a FLD. Results show that the most important classes of phenolic compounds occurring in VOO can be evaluated using HPLC direct injection. The efficiency of the new method, as compared to the liquid-liquid extraction, was higher to quantify phenyl alcohols, lignans, and 3,4-DHPEA-EA and lower for the evaluation of 3,4-DHPEA-EDA and p-HPEA-EDA.     

Comparative effects of food-derived polyphenols on the viability and apoptosis of a human hepatoma cell line (HepG2)

Consumption of fruits and vegetables, which are rich in polyphenols, has been associated with a reduced risk of chronic diseases such as cancer. Dietary polyphenols have antioxidant and antiproliferative properties that might explain their beneficial effect on cancer prevention. The aim of this study was to investigate the effects of different pure polyphenols [quercetin, chlorogenic acid, and (-)-epicatechin] and natural fruit extracts (strawberry and plum) on viability or apoptosis of human hepatoma HepG2 cells. The treatment of cells for 18 h with quercetin and fruit extracts reduced cell viability in a dose-dependent manner; however, chlorogenic acid and (-)-epicatechin had no prominent effects on the cell death rate. Similarly, quercetin and strawberry and plum extracts, rather than chlorogenic acid and (-)-epicatechin, induced apoptosis in HepG2 cells. Moreover, quercetin and fruit extracts arrested the G1 phase in the cell cycle progression prior to apoptosis. Quercetin and strawberry and plum extracts may induce apoptosis and contribute to a reduced cell viability in HepG2 cells.     

Triterpenoid saponins from the shells of Argania spinosa seeds

Two new oleanene saponins were isolated from the MeOH extract of the shell of Argania spinosa.They possess protobassic acid and 16alpha-protobassic acid as aglycons. The disaccharide moiety linked to C-3 of the aglycon is made up of two glucose units; the pentasaccharide moiety linked to C-28 is made up of arabinose, xylose, and three rhamnose units. Their structures were elucidated by 1D and 2D NMR experiments including (1)H-(1)H (DQF-COSY, 1D TOCSY, and 2D HOHAHA) and (1)H-(13)C (HSQC and HMBC) spectroscopy along with mass spectrometry.     

Biodegradability of Disinfectants in Surface Waters from Buenos Aires: Isolation of an Indigenous Strain Able to Degrade and Detoxify Benzalkonium Chloride

Biodegradability of chlorhexidine (CH), triclosan (TC), and benzalkonium chloride (CBA) has been tested in 18 surface water sampling points in the urban area of Buenos Aires. Sampling points were located in both the Reconquista and the Matanza-Riachuelo basins as well as in the La Plata River. High tolerance to the three disinfectants was found and indigenous strains capable of degrading CBA and TC were isolated. Neither tolerance nor biodegradation were correlated with sewage pollution. A strain that degrades CBA was identified as belonging to the genus Pseudomonas using the API20NE system and 16SRNA sequencing. In batch assays, the strain was capable of degrading 100, 200, and up to 500 mg L^?1 of CBA in 10, 25, and 46 h respectively with specific growth rates (μ) of 0.56, 0.30, and 0.14 h^?1. The efficiency of the process was between 99.5–98.0% in terms of compound removal and between 93.8–89.1% in terms of chemical oxygen demand (COD). The detoxification of the compound as a result of the biodegradation was assessed using Pseudokirchneriella subcapitata, Vibrio fischeri, and Lactuca sativa as test organisms.     

Feedbacks between vegetation pattern and resource loss dramatically decrease ecosystem resilience and restoration potential in a simple dryland model

Conceptual frameworks of dryland degradation commonly include ecohydrological feedbacks between landscape spatial organization and resource loss, so that decreasing cover and size of vegetation patches result in higher water and soil losses, which lead to further vegetation loss. However, the impacts of these feedbacks on dryland dynamics in response to external stress have barely been tested. Using a spatially-explicit model, we represented feedbacks between vegetation pattern and landscape resource loss by establishing a negative dependence of plant establishment on the connectivity of runoff-source areas (e.g., bare soils). We assessed the impact of various feedback strengths on the response of dryland ecosystems to changing external conditions. In general, for a given external pressure, these connectivity-mediated feedbacks decrease vegetation cover at equilibrium, which indicates a decrease in ecosystem resistance. Along a gradient of gradual increase of environmental pressure (e.g., aridity), the connectivity-mediated feedbacks decrease the amount of pressure required to cause a critical shift to a degraded state (ecosystem resilience). If environmental conditions improve, these feedbacks increase the pressure release needed to achieve the ecosystem recovery (restoration potential). The impact of these feedbacks on dryland response to external stress is markedly non-linear, which relies on the non-linear negative relationship between bare-soil connectivity and vegetation cover. Modelling studies on dryland vegetation dynamics not accounting for the connectivity-mediated feedbacks studied here may overestimate the resistance, resilience and restoration potential of drylands in response to environmental and human pressures. Our results also suggest that changes in vegetation pattern and associated hydrological connectivity may be more informative early-warning indicators of dryland degradation than changes in vegetation cover.     

Ultrasonographic measurement of abomasal volume, location, and emptying rate in calves

OBJECTIVE: To develop and validate an ultrasonographic method for measuring abomasal volume, location, and emptying rate in suckling calves. ANIMALS: 9 male Holstein calves < 40 days of age. PROCEDURE: Before and after calves were fed different volumes of milk replacer or 2 L of oral electrolyte solutions, ultrasonographic measurements of abomasal dimensions (width, length, and height) were obtained by applying a 3.5-MHz sector probe to the ventral aspect of the abdomen in the transverse and sagittal planes. Abomasal volume was calculated from the ultrasonographic measurements by modeling the abomasum as an ellipsoid and by use of a power exponential equation to calculate the half-time of abomasal emptying (t1/2). RESULTS: Preprandial abomasal volume was 20 to 137 mL. All 3 abomasal dimensions increased during feeding and after suckling, and the abomasum was symmetrically located about the midline of the ventral aspect of the abdomen. Strong linear relationships were identified between ultrasonographic and suckled volumes, between ultrasonographic and scintigraphic heights, and between ultrasonographic and scintigraphic lengths. Ultrasonographic t1/2 was linearly related to scintigraphic t1/2; the latter is regarded as the gold standard measure of gastric emptying rate. CONCLUSIONS AND CLINICAL RELEVANCE: Ultrasonographic evaluation of the abomasum appears to provide a practical, rapid, noninvasive, and accurate method for determination of abomasal volume, location, and emptying rate in suckling calves.