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Sample records for alder alnus rubra

  1. Alder (alnus crispa) effects on soils in ecosystems of the Agashashok river valley, northwest Alaska

    USGS Publications Warehouse

    Rhoades, C.; Oskarsson, H.; Binkley, D.; Stottlemyer, B.

    2001-01-01

    At the northern limit of the boreal forest biome, alder (Alnus crispa [Ait.] Pursh) shrubs occur in a variety of ecosystems. We assessed the effects of individual alder shrubs on soil properties and understory plant tissue nitrogen in floodplain terraces, valley slopes and tussock tundra ridges. The three ecosystems differed with respect to soil properties and abiotic conditions and supported distinct plant communities. Alder increased resin-exchangeable soil N and NO3 production significantly in each ecosystem. The greatest difference between alder canopy and surrounding soil NO3 measured both under field and laboratory conditions occured in floodplain sites. The shrub effect on soil pH and soil organic matter was greatest on tundra ridges. Alder shrubs also influenced the nitrogen nutrition of plants growing beneath their canopies. Plants growing below alder canopies had higher foliar nitrogen concentration and natural abundance 15N composition and lower carbon to nitrogen ratio than open-grown plants. Similar to soil N availability, understory plant leaf chemistry responded more to alder on floodplains than on slope or tundra ecosystems. This pattern suggests that understory plants rely more heavily on alder-fixed-N in this resource-poor ecosystem.

  2. Alternative statistical methods for interpreting airborne Alder ( Alnus glutimosa (L.) Gaertner) pollen concentrations

    NASA Astrophysics Data System (ADS)

    González Parrado, Zulima; Valencia Barrera, Rosa M.; Fuertes Rodríguez, Carmen R.; Vega Maray, Ana M.; Pérez Romero, Rafael; Fraile, Roberto; Fernández González, Delia

    2009-01-01

    This paper reports on the behaviour of Alnus glutinosa (alder) pollen grains in the atmosphere of Ponferrada (León, NW Spain) from 1995 to 2006. The study, which sought to determine the effects of various weather-related parameters on Alnus pollen counts, was performed using a volumetric method. The main pollination period for this taxon is January-February. Alder pollen is one of the eight major airborne pollen allergens found in the study area. An analysis was made of the correlation between pollen counts and major weather-related parameters over each period. In general, the strongest positive correlation was with temperature, particularly maximum temperature. During each period, peak pollen counts occurred when the maximum temperature fell within the range 9°C-14°C. Finally, multivariate analysis showed that the parameter exerting the greatest influence was temperature, a finding confirmed by Spearman correlation tests. Principal components analysis suggested that periods with high pollen counts were characterised by high maximum temperature, low rainfall and an absolute humidity of around 6 g m-3. Use of this type of analysis in conjunction with other methods is essential for obtaining an accurate record of pollen-count variations over a given period.

  3. A Soil Moisture-Heat Based Early Establishment Model of Riparian White Alder (Alnus rhombifolia)

    NASA Astrophysics Data System (ADS)

    Jablkowski, P.; Johnson, E. A.; Martin, Y. E.

    2013-12-01

    Establishment of fluvially dispersed seeds on accreted gravel-sand bars is limited by water availability in streams. Past establishment models have used the stream/water table recession rate, and maximum root growth rate to determine the elevation limit of seedling establishment. This approach neglects the role of the saturated-unsaturated vadose zone in providing water to recently germinated seedlings, the physical processes that determine the soil moisture content, and the effect moisture deficit has on seedling root growth. This study combines a soil moisture-heat budget and a seedling root growth model that responds to soil moisture availability to find the elevation limit of establishment of white alder (Alnus rhombifolia) on vertically accreted bars along the south fork Eel River in the Angelo Coast Range Reserve, California. To establish successfully, seedling roots must maintain a connection with sufficient moisture to avoid water stress. This will depend on the elevation of the bar, the stream recession rate, the root growth rate, and the diurnal cycle of soil moisture. A one-dimensional moisture-heat budget of the top 15 centimeters of sediment was validated at two locations characterized by sand and clay-gravel textures respectively, using soil moisture and temperature measurements at 5, 10 and 15 cm, net radiation, air temperature, humidity, wind velocity and precipitation measured during spring-summer stream recession. Two patterns in soil water content were apparent: an average daily moisture decrease at each depth driven by stream/water table recession, and a diurnal pattern of isothermal liquid and vapour flux increasing soil water content in the upper 15 cm between 12:00 pm and 5:00 pm PDT. To determine seedling root growth rates, white alder seedlings were grown in growth chambers under a range of reduced matric potentials using polyethylene glycol. Root length measurements were made at 4 hour intervals and a quadratic equation was fit to the root

  4. Factors for converting hazelnut (Corylus avellana L) into black alder (Alnus glutinosa Yalt.) plantations.

    PubMed

    Durkaya, Ali; Durkaya, Birsen

    2009-07-01

    Hazelnut plantations, which are a major source of income for the villagers in the eastern Black sea region are notable to provide sufficient income to the villagers due to price fluctuations and sudden falls witnessed in recent years. Alternative investments in place of hazelnut cultivation are being investigated in order to prevent migration to urban areas and to increase the welfare of the rural population in the region. Black alder plantation investments have been assessed as one of the most essential alternative investment tools within the framework of the study Assessment was carried out by comparing expected possible net present values (NPV). Although value increase occurs 12-18 years later more income can be obtained through black alder than hazelnut plantation. In hazelnut plantations, the best NPV emerged in the lower zone. NPV was positive in the moderate zone but values were close to zero. In upper zone, positive NPV couldn't emerge. As a result, it was understood that black alder plantation investment is an effective alternative for hazelnut plantations.

  5. WATERSHED BIOGEOCHEMISTRY IN THE OREGON COAST RANGE: THE ROLE OF RED ALDER AND SALMON

    EPA Science Inventory

    Variations in plant community composition across the landscape can influence nutrient retention and loss at the watershed scale. A striking example of plant species influence is the role of N2-fixing red alder (Alnus rubra) in the biogeochemistry of Pacific Northwest forests. T...

  6. NITROGEN EXPORT FROM FORESTED WATERSHEDS IN THE OREGON COAST RANGE: THE ROLE OF N2-FIXING RED ALDER

    EPA Science Inventory

    Variations in plant community composition across the landscape can influence nutrient retention and loss at the watershed scale. A striking example of plant species influence is the role of N2-fixing red alder (Alnus rubra) in the biogeochemistry of Pacific Northwest forests. T...

  7. Decrease of ruminal methane production in Rusitec fermenters through the addition of plant material from rhubarb (Rheum spp.) and alder buckthorn (Frangula alnus).

    PubMed

    García-González, R; González, J S; López, S

    2010-08-01

    Roots of rhubarb (Rheum spp.) and bark of alder buckthorn (Frangula alnus) were tested as feed additives for decreasing ruminal methane production released from anaerobic fermentation of a forage-based diet in a rumen-simulating fermenter (Rusitec). Sixteen fermentation units (vessels) were set up for the experiment lasting 19 d. Treated vessels were supplied with 1g/d of rhubarb or alder buckthorn (4 vessels per plant species); another 4 vessels received 12 microM sodium monensin (positive control), and the remaining 4 vessels were controls (no additive). Upon termination of the experimental period, batch cultures were inoculated with the liquid contents of the vessels for examining in vitro fermentation kinetics of cellulose, starch, barley straw, and the same substrate used in the Rusitec cultures. Monensin induced changes in fermentation in agreement with those reported in the literature, and inocula from those cultures decreased the fermentation rate and total gas produced in the gas kinetics study. Rhubarb decreased methane production, associated with limited changes in the profile of volatile fatty acids throughout the duration of the study, whereas digestibility and total volatile fatty acids production were not affected. Rhubarb inocula did not affect gas production kinetics except for cellulose. Alder buckthorn decreased only methane concentration in fermentation gas, and this effect was not always significant. The use of rhubarb (milled rhizomes of Rheum spp.) in the diets of ruminants may effectively modulate ruminal fermentation by abating methane production, thus potentially involving productive and environmental benefits.

  8. Nitrogen mineralization and gaseous nitrogen losses from waterlogged and drained organic soils in a black alder (Alnus glutinosa (L.) Gaertn.) forest

    NASA Astrophysics Data System (ADS)

    Eickenscheidt, T.; Heinichen, J.; Augustin, J.; Freibauer, A.; Drösler, M.

    2014-06-01

    Black alder (Alnus glutinosa (L.) Gaertn.) forests on peat soils have been reported to be hotspots for high nitrous oxide (N2O) losses. High emissions may be attributed to alternating water tables of peatlands and to the incorporation of high amounts of easily decomposable nitrogen (N) into the ecosystem by symbiotic dinitrogen (N2)-fixation of alder trees. Our study addressed the question to what extent drainage enhances the emissions of N2O from black alder forests and how N turnover processes and physical factors influence the production of N2O and total denitrification. The study was conducted in a drained black alder forest with variable groundwater tables at a southern German fen peatland. Fluxes of N2O were measured using the closed chamber method at two drained sites (D-1 and D-2) and one undrained site (U). Inorganic N contents and net N mineralization rates (NNM) were determined. Additionally a laboratory incubation experiment was carried out to investigate greenhouse gas and N2 fluxes at different temperature and soil moisture conditions. Significantly different inorganic N contents and NNM rates were observed, which however did not result in significantly different N2O fluxes in the field but did in the laboratory experiment. N2O fluxes measured were low for all sites, with total annual emissions of 0.51 ± 0.07 (U), 0.97 ± 0.13 (D-1) and 0.93 ± 0.08 kg N2O-N ha-1 yr-1 (D-2). Only 37% of the spatiotemporal variation in field N2O fluxes could be explained by peat temperature and groundwater level, demonstrating the complex interlinking of the controlling factors for N2O emissions. However, temperature was one of the key variables of N2O fluxes in the incubation experiment conducted. Increasing soil moisture content was found to enhance total denitrification losses during the incubation experiment, whereas N2O fluxes remained constant. At the undrained site, permanently high groundwater level was found to prevent net nitrification, resulting in a

  9. Stem Photosynthesis not Pressurized Ventilation is Responsible for Light-enhanced Oxygen Supply to Submerged Roots of Alder (Alnus glutinosa)

    PubMed Central

    ARMSTRONG, WILLIAM; ARMSTRONG, JEAN

    2005-01-01

    • Background and Aims Claims that submerged roots of alder and other wetland trees are aerated by pressurized gas flow generated in the stem by a light-induced thermo-osmosis have seemed inconsistent with root anatomy. Our aim was to seek a verification using physical root–stem models, stem segments with or without artificial roots, and rooted saplings. • Methods Radial O2 loss (ROL) from roots was monitored polarographically as the gas space system of the models, and stems were pressurized artificially. ROL and internal pressurization were also measured when stems were irradiated and the xylem stream was either CO2 enriched or not. Stem photosynthesis and respiration were measured polarographically. Stem and root anatomy were examined by light and fluorescence microscopy. • Key Results Pressurizing the models and stems to ≤10 kPa, values much higher than those reportedly generated by thermo-osmosis, created only a negligible density-induced increase in ROL, but ROL increased rapidly when ambient O2 concentrations were raised. Internal pressures rose by several kPa when shoots were exposed to high light flux and ROL increased substantially, but both were due to O2 accumulation from stem photosynthesis using internally sourced CO2. Increased stem pressures had little effect on O2 transport, which remained largely diffusive. Oxygen flux from stems in high light periods indicated a net C gain by stem photosynthesis. Chloroplasts were abundant in the secondary cortex and secondary phloem, and occurred throughout the secondary xylem rays and medulla of 3-year-old stems. Diurnal patterns of ROL, most marked when light reached submerged portions of the stem, were modified by minor variations in light flux and water level. Low root temperatures also helped improve root aeration. • Conclusions Pressurized gas flow to submerged roots does not occur to any significant degree in alder, but stem photosynthesis, using internally sourced CO2 from respiration and the

  10. Factors affecting distribution of wood, detritus, and sediment in headwater streams draining managed young-growth red alder - Conifer forests in southeast Alaska

    USGS Publications Warehouse

    Gomi, T.; Johnson, A.C.; Deal, R.L.; Hennon, P.E.; Orlikowska, E.H.; Wipfli, M.S.

    2006-01-01

    Factors (riparian stand condition, management regimes, and channel properties) affecting distributions of wood, detritus (leaves and branches), and sediment were examined in headwater streams draining young-growth red alder (Alnus rubra Bong.) - conifer riparian forests (40 years old) remained in channels and provided sites for sediment and organic matter storage. Despite various alder-conifer mixtures and past harvesting effects, the abundance of large wood, fine wood, and detritus accumulations significantly decreased with increasing channel bank-full width (0.5-3.5 m) along relatively short channel distances (up to 700 m). Changes in wood, detritus, and sediment accumulations together with changes in riparian stand characteristics create spatial and temporal variability of in-channel conditions in headwater systems. A component of alder within young-growth riparian forests may benefit both wood production and biological recovery in disturbed headwater stream channels. ?? 2006 NRC.

  11. Headwater riparian invertebrate communities associated with red alder and conifer wood and leaf litter in southeastern Alaska

    USGS Publications Warehouse

    LeSage, C.M.; Merritt, R.W.; Wipfli, M.S.

    2005-01-01

    We examined how management of young upland forests in southeastern Alaska affect riparian invertebrate taxa richness, density, and biomass, in turn, potentially influencing food abundance for fish and wildlife. Southeastern Alaska forests are dominated by coniferous trees including Sitka spruce (Picea sitchensis (Bong.) Carr.), western hemlock (Tsuga heterophylla (Raf.) Sarg.), with mixed stands of red cedar (Thuja plicata Donn.). Red alder (Alnus rubra Bong.) is hypothesized to influence the productivity of young-growth conifer forests and through forest management may provide increased riparian invertebrate abundance. To compare and contrast invertebrate densities between coniferous and alder riparian habitats, leaf litter and wood debris (early and late decay classes) samples were collected along eleven headwater streams on Prince of Wales Island, Alaska, during the summers of 2000 and 2001. Members of Acarina and Collembola were the most abundant taxa collected in leaf litter with alder litter having significantly higher mean taxa richness than conifer litter. Members of Acarina were the most abundant group collected on wood debris and alder wood had significantly higher mean taxa richness and biomass than conifer wood. Alder wood debris in more advanced decay stages had the highest mean taxa richness and biomass, compared to other wood types, while conifer late decay wood debris had the highest densities of invertebrates. The inclusion of alder in young-growth conifer forests can benefit forest ecosystems by enhancing taxa richness and biomass of riparian forest invertebrates. ?? 2005 by the Northwest Scientific Association. All rights reserved.

  12. New nomenclature combinations in the green alder species complex (Betulaceae)

    PubMed Central

    Chery, Joyce

    2015-01-01

    Abstract The name Alnus viridis (Chaix) DC., based on Betula viridis Chaix (1785), has traditionally been attributed to green alders although it is based on a later basionym. Alnus alnobetula (Ehrh.) K. Koch based on Betula alnobetula Ehrh. (1783) is the correct name for green alders. In light of the increasing use and recognition of the name Alnus alnobetula (Ehrh.) K. Koch in the literature. I herein propose new nomenclatural combinations to account for the Japanese and Chinese subspecies respectively: Alnus alnobetula subsp. maximowiczii (Callier ex C.K. Schneid.) J. Chery and Alnus alnobetula subsp. mandschurica (Callier ex C.K. Schneid.) J. Chery. Recent phylogenetic analyses place these two taxa in the green alder species complex, suggesting that they should be treated as infraspecific taxa under the polymorphic Alnus alnobetula. PMID:26491381

  13. Migration Patterns of Subgenus Alnus in Europe since the Last Glacial Maximum: A Systematic Review

    PubMed Central

    Douda, Jan; Doudová, Jana; Drašnarová, Alena; Kuneš, Petr; Hadincová, Věroslava; Krak, Karol; Zákravský, Petr; Mandák, Bohumil

    2014-01-01

    Background/Aims Recently, new palaeoecological records supported by molecular analyses and palaeodistributional modelling have provided more comprehensive insights into plant behaviour during the last Quaternary cycle. We reviewed the migration history of species of subgenus Alnus during the last 50,000 years in Europe with a focus on (1) a general revision of Alnus history since the Last Glacial Maximum (LGM), (2) evidence of northern refugia of Alnus populations during the LGM and (3) the specific history of Alnus in particular European regions. Methodology We determined changes in Alnus distribution on the basis of 811 and 68 radiocarbon-dated pollen and macrofossil sites, respectively. We compiled data from the European Pollen Database, the Czech Quaternary Palynological Database, the Eurasian Macrofossil Database and additional literature. Pollen percentage thresholds indicating expansions or retreats were used to describe patterns of past Alnus occurrence. Principal Findings An expansion of Alnus during the Late Glacial and early Holocene periods supports the presence of alders during the LGM in southern peninsulas and northerly areas in western Europe, the foothills of the Alps, the Carpathians and northeastern Europe. After glaciers withdrew, the ice-free area of Europe was likely colonized from several regional refugia; the deglaciated area of Scandinavia was likely colonized from a single refugium in northeastern Europe. In the more northerly parts of Europe, we found a scale-dependent pattern of Alnus expansion characterised by a synchronous increase of Alnus within individual regions, though with regional differences in the times of the expansion. In southern peninsulas, the Alps and the Carpathians, by contrast, it seems that Alnus expanded differently at individual sites rather than synchronously in whole regions. Conclusions Our synthesis supports the idea that northern LGM populations were important sources of postglacial Alnus expansion. The

  14. Humus bacteria of Norway spruce stands: plant growth promoting properties and birch, red fescue and alder colonizing capacity.

    PubMed

    Elo; Maunuksela; Salkinoja-Salonen; Smolander; Haahtela

    2000-02-01

    We studied the potential of the humus layer of the Norway spruce stands to supply beneficial rhizobacteria to birch (Betula pendula), alder (Alnus incana) and fescue grass (Festuca rubra), representatives of pioneer vegetation after clear-cutting of the coniferous forest. Axenically grown seedlings of these species were inoculated with the acid spruce humus, pH 3.7-5.3. Actinorhizal propagules, capable of nodulating alder, were present in high density (10(3) g(-1)) in humus of long-term limed plots, whereas plots with nitrogen fertilization contained almost none (

  15. Pityriasis rubra pilaris

    MedlinePlus

    ... Pityriasis rubra pilaris - close-up References James WD, Berger TG, Elston DM. Pityriasis rosea, pityriasis rubra pilaris, ... other papulosquamous and hyperkeratotic diseases. In: James WD, Berger TG, Elston DM, eds. Andrews' Diseases of the ...

  16. Arthropod fauna of rolled alder leaves in Washington State, United States of America (Insecta: Arachnida)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Alders, Alnus spp., growing on the eastern slopes and foothills of the Cascade Range in Washington State, are often infested with shelter-making (primarily leafrolling) Lepidoptera in the families Tortricidae, Gracillariidae, and Choreutidae. Over a 5 year survey period, 5,172 rolled leaves were ex...

  17. Seasonal changes in nodular nitrogenase activity of Alnus glutinosa and Elaeagnus angustifolia.

    PubMed

    Zitzer, S F; Dawson, J O

    1989-06-01

    Root nodule development, and seasonal patterns of nodular nitrogenase and hydrogenase activities were determined for 5- to 8-year old black alder (Alnus glutinosa (L.) Gaertn.) and Russian olive (Elaeagnus angustifolia L.) interplanted with black walnut (Juglans nigra L.) on bottomland and upland sites in central Illinois, USA. Black alder produced nodules at both sites, but Russian olive did so only at the bottomland site. Nodular nitrogenase activity was detectable in both species over a 220-day period. Maximum, midday rates of nitrogenase activity (acetylene reduction) of 15 to 20 micromoles C(2)H(4) per g dry nodule per hour were maintained by black alder for approximately 150 days at both the upland and bottomland sites. Near maximum rates of nodular nitrogenase activity were maintained for a similar period by Russian olive at the lowland site, although specific nitrogenase activity was approximately 25% lower than in black alder owing to a larger proportion of necrotic nodular tissue in Russian olive. In both species, nitrogenase activity increased exponentially with temperature between 10 degrees C and 20 to 25 degrees C. No net hydrogen evolution by nodules of either species was detected at any time during the assay period, indicating efficient hydrogenase systems were operating under the conditions of the field assay. Height of black walnut interplanted with nodulated black alder and Russian olive was greater than that of black walnut grown in pure stands.

  18. The patterns of Corylus and Alnus pollen seasons and pollination periods in two Polish cities located in different climatic regions.

    PubMed

    Puc, Małgorzata; Kasprzyk, Idalia

    2013-01-01

    This study compares phenological observations of Corylus (hazel) and Alnus (alder) flowering with airborne pollen counts of these taxa recorded using volumetric spore traps (2009-2011). The work was carried out in the Polish cities of Szczecin and Rzeszów that are located in different climatic regions. Correlations between pollen concentrations and meteorological data were investigated using Spearman's rank correlation analysis. The timings of hazel and alder pollination and the occurrence of airborne pollen varied greatly and were significantly influenced by meteorological conditions (p < 0.05). The flowering synchronization of hazel and alder pollination in Szczecin and Rzeszów varied over the study period. Hazel and alder trees flowered notably earlier in stands located in places that were exposed to sunlight (insolated) and sheltered from the wind. On the other hand, a delay in the timing of pollination was observed in quite sunny but very windy sites. In Rzeszów, maximum hazel pollen concentrations did not coincide with the period of full pollination (defined as between 25 % hazel and alder and 75 % of flowers open). Conversely, in Szczecin, the highest hazel pollen concentrations were recorded during phenophases of the full pollination period. The period when the highest alder pollen concentrations were recorded varied between sites, with Rzeszów recording the highest concentrations at the beginning of pollination and Szczecin recording alder pollen throughout the full pollination period. Substantial amounts of hazel and alder pollen grains were recorded in the air of Rzeszów (but not Szczecin) before the onset of the respective pollen seasons.

  19. Spatial and temporal controls on Alnus-derived nutrients and stream stoichiometry: Implications for aquatic ecosystem productivity

    NASA Astrophysics Data System (ADS)

    Devotta, D.; Fraterrigo, J.; Walsh, P.; Hu, F.

    2015-12-01

    Predicting how nutrient fluxes that cross ecosystem boundaries will respond to future climate change is one of the greatest challenges for ecology in the 21st century. In southwestern (SW) Alaska, Pacific salmon (Oncorhynchus spp.) and nitrogen (N)-fixation by alder (Alnus spp.) provide key nutrient subsidies to freshwater systems. The importance of alder-derived nutrients (ADN) to aquatic systems will increase as alder cover expands under climate warming and salmon harvesting reduces marine-derived nutrients. We investigate broad-scale spatial and temporal drivers of ADN and stream N:P in 26 streams in SW Alaska. Alder cover and watershed features were measured using satellite images and topographic maps in ArcGIS. Stream water samples were collected in each spring and summer from 2010-2013 and analyzed for dissolved N and total phosphorus (TP). We obtained annual growing season length (AGSL) and sum of growing degree days (GDD) data from weather stations. Elevation was inversely related to alder cover, stream N, and N:P (ρ=-0.802, -0.65, and -0.71 resp., p<0.01, n=208). Alder cover had the largest influence on stream N (mean β estimate=0.402, 90% CIs). Stream N increased with alder cover, under longer AGSL, and lower GDD (interaction effect sizes between alder and stream N=0.196 and -0.185 resp., 90% CIs), suggesting that long growing seasons with minimal heat accumulation during the spring and fall increased ADN export. Higher P was associated with lower temperatures, possibly reflecting reduced P demand under low rates of metabolic activity. Structural equation modeling revealed significant causal relationships among elevation, alder cover, and stream N:P across multiple years (r2=0.94, X2=742.8, df=9, p<0.01). All paths in the model were significant (p<0.01) except between stream N:P and weather (p=0.165). These results demonstrate that spatial variation in alder cover associated with elevation is a stronger regulator of ADN fluxes and stream N:P than

  20. Missing checkerboards? An absence of competitive signal in Alnus-associated ectomycorrhizal fungal communities

    PubMed Central

    Nguyen, Nhu; Cohen, Hannah; Peay, Kabir

    2014-01-01

    A number of recent studies suggest that interspecific competition plays a key role in determining the structure of ectomycorrhizal (ECM) fungal communities. Despite this growing consensus, there has been limited study of ECM fungal community dynamics in abiotically stressful environments, which are often dominated by positive rather than antagonistic interactions. In this study, we examined the ECM fungal communities associated with the host genus Alnus, which live in soils high in both nitrate and acidity. The nature of ECM fungal species interactions (i.e., antagonistic, neutral, or positive) was assessed using taxon co-occurrence and DNA sequence abundance correlational analyses. ECM fungal communities were sampled from root tips or mesh in-growth bags in three monodominant A. rubra plots at a site in Oregon, USA and identified using Illumina-based amplification of the ITS1 gene region. We found a total of 175 ECM fungal taxa; 16 of which were closely related to known Alnus-associated ECM fungi. Contrary to previous studies of ECM fungal communities, taxon co-occurrence analyses on both the total and Alnus-associated ECM datasets indicated that the ECM fungal communities in this system were not structured by interspecific competition. Instead, the co-occurrence patterns were consistent with either random assembly or significant positive interactions. Pair-wise correlational analyses were also more consistent with neutral or positive interactions. Taken together, our results suggest that interspecific competition does not appear to determine the structure of all ECM fungal communities and that abiotic conditions may be important in determining the specific type of interaction occurring among ECM fungi. PMID:25548729

  1. Can an Alder Disease Influence the Controls of Ecosystem Water Flux?

    NASA Astrophysics Data System (ADS)

    Rohrs-Richey, J. K.; Mulder, C. P.; Ruess, R. W.; Winton, L. M.; Stanosz, G. R.

    2007-12-01

    In Alaska, nitrogen-fixing shrubs (Alnus spp.) comprise a large component of the vegetation and are important for water and energy flux in the Alaskan tundra, the Interior boreal forest, and south-central Alaska. Recently there has been high incidence and severity of a canker disease on Alnus which alters small scale controls (e.g., leaves, branches) of water and carbon flux and may have ecosystem scale effects in severely diseased areas. The fungal pathogen, Valsa melanodiscus (anamorph =Cytospora umbrina), kills active xylem and phloem, causes long, girdling cankers on stems, and is frequently associated with stem mortality in the thin leaf alder (Alnus tenuifolia) and green alder (Alnus crispa). We are just beginning to understand how this canker disease affects the physiology of its host and the implications for water loss and carbon fixation. An inoculation experiment at the University of Alaska is currently being conducted on well-watered and water-limited green alders to: 1) monitor the response of the water transport system to infection and canker development; 2) assess the ability of colonized alders to adjust water use efficiency; and 3) measure the effect of canker development on photosynthesis. Only 4 weeks after inoculation, stems (3-5 mm diam.) with incipient cankers had an overall reduction in total daily water loss and up to 50 percent decrease in daily peak water loss. Stems with incipient cankers were also unable to attain the maximum photosynthetic rate of healthy stems, and had lower light saturation points and quantum efficiencies. Further quantification of these relationships is underway. This study, in combination with recent field measurements of sapflow, will allow us to estimate the impact of varying degrees of disease severity on stand-level water flux. Alders are a keystone species and are currently responding to climate change by expanding into the Alaska tundra, increasing abundance in northern Alaska, and migrating into river

  2. Localization of the porous partition responsible for pressurized gas transport in Alnus glutinosa (L.) Gaertn.

    PubMed

    Buchel, H B; Grosse, W

    1990-09-01

    The pressurized gas transport which improves the oxygen supply of the roots of the wetland tree black alder (Alnus glutinosa (L.) Gaertn.), is based on the existence of a thermo-osmotically active porous tissue partition in the lower part of the trunk with pore diameters in the range of, or smaller than, the mean free path length of the gas molecules (e.g., 70 nm for O(2) at 20 degrees C and 100 kPa). Anatomical studies have shown that only the cambial layer or the phellogen of the lenticels have intercellular spaces small enough to be responsible for thermo-osmotic activity. The final localization of the thermo-osmotically active partition and the determination of the pore sizes were done by diffusion and effusion experiments with basal trunk pieces of 3- to 4-year-old trees. The mean pore sizes of the intercellular system were not smaller than 100 nm in diameter in the cambial layer separating the bark from the wood, but 14 +/- 7 nm in diameter in the phellogen underlying the lenticels. Because of these small pores, the phellogen of the lenticels is the significant thermo-osmotically active partition for the transport of air to the root system in black alder.

  3. Morphological measurements and ITS sequences show that the new alder rust in Europe is conspecific with Melampsoridium hiratsukanum in eastern Asia.

    PubMed

    Hantula, J; Kurkela, T; Hendry, S; Yamaguchi, T

    2009-01-01

    Three species of Melampsoridium have been reported to infect hosts in genus Alnus. An epidemic of foliar rust affecting A. glutinosa and A. incana began in Europe in the mid-1990s, and the associated pathogen was identified as Melampsoridium hiratsukanum based on morphology. In this investigation we analyzed the morphology and genetic variation of alder rusts from Europe and Japan and the host specificity of the European epidemic rust. Our results showed that two rusts occur on the leaves of alders native to northern Europe; in Scotland an endemic rust indistinguishable from M. betulinum occurs, whereas alders in areas of Europe affected by the current epidemic were infected by M. hiratsukanum. M. hiratsukanum from naturally infected alder in Finland produced aecia on all Larix species tested but did not infect Betula leaves.

  4. Absence of net long-term successional facilitation by alder in a boreal Alaska floodplain.

    PubMed

    Stuart Chapin, F; Conway, Alexandra J; Johnstone, Jill F; Hollingsworth, Teresa N; Hollingsworth, Jamie

    2016-11-01

    Long-term experiments provide a way to test presumed causes of successional or environmentally driven vegetation changes. Early-successional nitrogen (N)-fixing plants are widely thought to facilitate productivity and vegetation development on N-poor sites, thus accounting for observed vegetation patterns later in succession. We tested this facilitative impact on vegetation development in a 23-yr field experiment on an Interior Alaska (USA) floodplain. On three replicate early-successional silt bars, we planted late-successional white spruce (Picea glauca) seedlings in the presence and absence of planted seedlings of an early-successional N-fixing shrub, thinleaf alder (Alnus incana). Alder initially facilitated survivorship and growth of white spruce. Within six years, however, after canopy closure, alder negatively affected spruce survivorship and growth. Our three replicate sites followed different successional trajectories. One site was eliminated by erosion and supported no vegetation development during our study. The other two sites, which differed in site moisture, diverged in vegetation composition. Structural equation modeling (SEM) suggested that, in the drier of these two sites, alder inhibited spruce growth directly (presumably by competition) and indirectly through effects mediated by competition with other woody species. However, at the wetter site, alder had both positive and negative effects on spruce growth, with negative effects predominating. Snowshoe hares (Lepus americanus) in alder thickets further reduced height growth of spruce in the wetter site. We conclude that net effects of alder on white spruce, the late-successional dominant, were primarily inhibitory and indirect, with the mechanisms depending on initial site moisture. Our results highlight the importance of long-term research showing that small differences among initial replicate sites can cause divergence in successional trajectories, consistent with individualistic distributions

  5. Comparative phylogenies and host specialization in the alder ectomycorrhizal fungi Alnicola, Alpova and Lactarius (Basidiomycota) in Europe

    PubMed Central

    2011-01-01

    Background Mycorrhizal fungi form intimate associations with their host plants that constitute their carbon resource and habitat. Alnus spp. (Betulaceae) are known to host an exceptional species-poor and specialized ectomycorrhizal (ECM) fungal community compared to other tree species, but the host-specificity pattern and its significance in terms of fungal diversification and speciation remain poorly documented. The degree of parallel speciation, host switching, and patterns of biogeography were explored in the historical associations between alders and three ECM taxa of Basidiomycetes: Alnicola (Agaricales), Alpova (Boletales), and Lactarius (Russulales). The aim was to develop an evolutionary framework on host specificity and diversification of Basidiomycetes in this highly specialized plant-fungus symbiosis. Results Sporocarps of Alnicola (220), Lactarius (61) and Alpova (29) were collected from stands of the four European alder species (A. alnobetula including the endemic subsp. suaveolens in Corsica, A. cordata, A. glutinosa, A. incana) in Western Europe (mainly in France and Austria), from 1995 to 2009. Specimens were morphologically identified to the species level. From these, 402 sequences of four DNA regions (ITS, rpb2, gpd, and the V9 domain of the mit-SSU rDNA) were successfully obtained and analyzed in addition with 89 sequences available in GenBank and UNITE databases. Phylogenetic analyses were conducted on all sequence data sets (individual and combined) using maximum likelihood reconstruction and Bayesian inference. Fungal phylogenies are compared and discussed in relation to the host, with a focus on species boundaries by associating taxonomic, systematic and molecular information. Conclusions Patterns of host specificity and phylogenies of Alnicola and Lactarius suggest coevolution as a basal factor of speciation in relation with the subgeneric diversification of Alnus, possibly due to the very selective pressure of the host. A second element of

  6. Pityriasis rubra pilaris following exposure to dolomite.

    PubMed

    Iraji, Fariba; Siadat, Amir H

    2013-07-01

    In this case report, we present a 30-year-old man who developed pityriasis rubra pilaris (PRP) following exposure to Dolomite. The diagnosis of PRP was confirmed histologically and the patient was successfully treated with acitretin and cyclosporine.

  7. Leaf photosynthetic characteristics of seedlings of actinorhizal Alnus spp. and Elaeagnus spp.

    PubMed

    Côté, B; Carlson, R W; Dawson, J O

    1988-06-01

    Single leaf photosynthetic characteristics of Alnus glutinosa, A. incana, A. rubra, Elaeagnus angustifolia, and E. umbellata seedlings conditioned to ambient sunlight in a glasshouse were assessed. Light saturation occurred between 930 and 1400 μmol m(-2)s(-1) PAR for all species. Maximum rates of net photosynthesis (Pn) measured at 25°C ranged from 12.8 to 17.3 μmol CO2m(-2)s(-1) and rates of dark respiration ranged from 0.74 to 0.95 μmol CO2m(-2)s(-1). These values of leaf photosynthetic variables are typical of early to midsuccessional species. The rate of Pn measured at optimal temperature (20°C) and 530μmol m(-2)s(-1) PAR was significantly (p<0.01) correlated with leaf nitrogen concentration (r=0.69) and negatively correlated with the mean area of a leaf (r=-0.64). We suggest that the high leaf nitrogen concentration and rate of Pn observed for Elaeagnus umbellata and to a lesser degree for E. angustifolia are genetic adaptations related to their crown architecture.

  8. Performance of ectomycorrhizal alders exposed to specific Canadian oil sands tailing stressors under in vivo bipartite symbiotic conditions.

    PubMed

    Beaudoin-Nadeau, Martin; Gagné, André; Bissonnette, Cyntia; Bélanger, Pier-Anne; Fortin, J André; Roy, Sébastien; Greer, Charles W; Khasa, Damase P

    2016-07-01

    Canadian oil sands tailings are predominately sodic residues contaminated by hydrocarbons such as naphthenic acids. These conditions are harsh for plant development. In this study, we evaluated the effect of inoculating roots of Alnus viridis ssp. crispa and Alnus incana ssp. rugosa with ectomycorrhizal fungi in the presence of tailings compounds. Seedlings were inoculated with 7 different strains of Paxillus involutus and Alpova diplophloeus and were grown under different treatments of NaCl, Na2SO4, and naphthenic acids in a growth chamber. Afterwards, seedling survival, height, dry biomass, leaf necrosis, and root mycorrhization rate were measured. Paxillus involutus Mai was the most successful strain in enhancing alder survival, health, and growth. Seedlings inoculated with this strain displayed a 25% increase in survival rate, 2-fold greater biomass, and 2-fold less leaf necrosis compared with controls. Contrary to our expectations, A. diplophloeus was not as effective as P. involutus in improving seedling fitness, likely because it did not form ectomycorrhizae on roots of either alder species. High intraspecific variation characterized strains of P. involutus in their ability to stimulate alder height and growth and to minimize leaf necrosis. We conclude that in vivo selection under bipartite symbiotic conditions is essential to select effective strains that will be of use for the revegetation and reclamation of derelict lands.

  9. Hardwood price reporting. Forest Service research paper

    SciTech Connect

    Sohngen, B.L.; Haynes, R.W.

    1994-02-01

    The prices for red alder (Alnus rubra) hardwood logs are published and analyzed for reliability, consistency, and robustness. Timberland managers can use these prices to make decisions about land management. They show that values for red alder logs have been increasing steadily for the last 11 years.

  10. Nonconventional Remission of Miliaria rubra during Heat Acclimation: Case Report,

    DTIC Science & Technology

    1987-01-01

    red papules on a mildly erythunatous skin. Although usually classfied as a minor skin disorder, miliaria rubra may be the precursor of impetigo...miliaria rubra from miliaria crystillina, miliaria pustulosa and miliaria profunda (3). Most reports of miliaria rubra originated in the Pacific

  11. New Polybenzimidazole Architectures by Diels Alder Polymerization

    DTIC Science & Technology

    2012-02-14

    REPORT New Polybenzimidazole Architectures By Diels Alder Polymerization. Final Report 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: Due to their high...substituents to improve processability, are desirable. This project was a proof of principle study to determine if Diels - Alder polymerization of monomers...AND ADDRESSES U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 15. SUBJECT TERMS Polybenzimidazole, Diels Alder

  12. Economic considerations in establishing European alder in herbaceous cover on surface-mined land

    SciTech Connect

    Ringe, J.M.; Graves, D.H.

    1985-12-09

    Herbicides are a practical tool for selectively controlling vegetative competition during tree seedling establishment. A study to investigate the effects of eight herbicide treatments on the survival and height growth of European alder (Alnus glutinosa) seedlings established in herbaceous cover indicated a positive treatment effect, but very little difference between the herbicide treatments themselves. Since the costs of the herbicides varied considerably, similar results could be obtained using the different herbicides, but at substantially different costs. Biological data were combined with the economic data to derive a modified benefit/cost ratio. This ratio facilitates herbicide treatment choice by comparing the amount of added survival or growth obtained per dollar spent on herbicides. 5 references, 6 tables.

  13. Growth and photosynthesis of plants in response to environmental stress. [Raphanus sativus; Glycine max; Salix nigra; Alnus serrulata; Populus tremuloides

    SciTech Connect

    Greitner, C.S.

    1991-01-01

    Environmental stresses generally decrease photosynthetic rates and growth of plants, and alter biomass partitioning. Nutrient deficiency and drought cause root:shoot ratios to increase, whereas the air pollutant ozone (O[sub 3]) causes an opposite shift in carbon allocation. Plants in nature usually grow under suboptimal conditions; therefore plants were raised with O[sub 3] combined with other stresses to analyze the mechanisms whereby multiple stresses influence gas exchange and growth. Physiological and growth responses to stress were determined for radish (raphanus sativus), soybean (Glycine max) willow (Salix nigra), alder (Alnus serrulata) and aspen (Populus tremuloides) in laboratory and field trials. In willow, high-nutrient status plants had more visible injury, but a smaller decline in leaf area with O[sub 3] than did low-nutrient plants. Ultrastructure of host plant cells in alder root nodules was disrupted by O[sub 3], suggesting that this air pollutant can affect the ability of plants to acquire nutrients via symbiosis. Biomass and root:shoot ratios decreased with O[sub 3] in radish and soy-bean. Shifts in stable carbon isotope ratios were caused by O[sub 3], and this technique was used to integrate the effects of O[sub 3] on gas exchange over time. In aspen, O[sub 3] enhanced photosynthesis and foliar areas in young leaves of well-watered aspen, partially compensating for declines in older leaves. This effect was more pronounced in plants raised at a high nitrogen level than in N-deficient plants. Carboxylation efficiency decreased in older, but increased in younger leaves with O[sub 3]. Prior exposure to drought reduced effects of O[sub 3] on photosynthesis and leaf area.

  14. Short-term influence of nitrate on acetylene reduction, photosynthesis and nodule respiration of black alder seedlings

    SciTech Connect

    Cazell, B.H.; Samuelson, L.J.; Seiler, J.R. )

    1990-05-01

    Black alder (Alnus glutinosa L. Gaernt.) has shown significant benefits in several silvicultural applications such as nurse-trees. However, little is known concerning the nitrate/N-fixing interactions. Our objections were to examine the effects of three nitrate levels on acetylene reduction (AR), net photosynthesis (Ps) and nodule respiration (NR). Fifteen month-old black alder rooted cuttings were inoculated with one strain of Frankia inoculum (ARgN22D) at six months, maintained under 16h photoperiod at ambient greenhouse conditions, and fertilized for two months prior to study with a modified Crone's N-free solution. At study initiation seedlings were fertilized for six days with 0, 7.5 or 15 mM NO{sub 3}{sup {minus}}. Measurements of AR, Ps and NR were collected on the second, fourth and sixth day of NO{sub 3}{sup {minus}} application. By day four AR was significantly lowered by 75% for the 15 mM NO{sub 3}{sup {minus}} treatment when compared with the controls. On day six, Ps and NR were lowered significantly by 29% and 59%, respectively, for the 15 mM NO{sub 3}{sup {minus}} treatments when compared to control values. Results suggest any benefit from black alder N-fixation might be negated by nitrate fertilization.

  15. Landscape genomics and a common garden trial reveal adaptive differentiation to temperature across Europe in the tree species Alnus glutinosa.

    PubMed

    De Kort, Hanne; Vandepitte, Katrien; Bruun, Hans Henrik; Closset-Kopp, Déborah; Honnay, Olivier; Mergeay, Joachim

    2014-10-01

    The adaptive potential of tree species to cope with climate change has important ecological and economic implications. Many temperate tree species experience a wide range of environmental conditions, suggesting high adaptability to new environmental conditions. We investigated adaptation to regional climate in the drought-sensitive tree species Alnus glutinosa (Black alder), using a complementary approach that integrates genomic, phenotypic and landscape data. A total of 24 European populations were studied in a common garden and through landscape genomic approaches. Genotyping-by-sequencing was used to identify SNPs across the genome, resulting in 1990 SNPs. Although a relatively low percentage of putative adaptive SNPs was detected (2.86% outlier SNPs), we observed clear associations among outlier allele frequencies, temperature and plant traits. In line with the typical drought avoiding nature of A. glutinosa, leaf size varied according to a temperature gradient and significant associations with multiple outlier loci were observed, corroborating the ecological relevance of the observed outlier SNPs. Moreover, the lack of isolation by distance, the very low genetic differentiation among populations and the high intrapopulation genetic variation all support the notion that high gene exchange combined with strong environmental selection promotes adaptation to environmental cues.

  16. Ecotoxicological effects evoked in hydrophytes by leachates of invasive Acer negundo and autochthonous Alnus glutinosa fallen off leaves during their microbial decomposition.

    PubMed

    Krevš, Alina; Darginavičienė, Jūratė; Gylytė, Brigita; Grigutytė, Reda; Jurkonienė, Sigita; Karitonas, Rolandas; Kučinskienė, Alė; Pakalnis, Romas; Sadauskas, Kazys; Vitkus, Rimantas; Manusadžianas, Levonas

    2013-02-01

    Throughout 90-day biodegradation under microaerobic conditions, invasive to Lithuania species boxelder maple (Acer negundo) leaves lost 1.5-fold more biomass than that of autochthonous black alder (Alnus glutinosa), releasing higher contents of N(tot), ammonium and generating higher BOD(7). Boxelder maple leaf leachates were characterized by higher total bacterial numbers and colony numbers of heterotrophic and cellulose-decomposing bacteria than those of black alder. The higher toxicity of A. negundo aqueous extracts and leachates to charophyte cell (Nitellopsis obtusa), the inhabitant of clean lakes, were manifested at mortality and membrane depolarization levels, while the effect on H(+)-ATPase activity in membrane preparations from the same algae was stronger in case of A. glutinosa. Duckweed (Lemna minor), a bioindicator of eutrophic waters, was more sensitive to leaf leachates of A. glutinosa. Fallen leaves and leaf litter leachates from invasive and native species of trees, which enter water body, affect differently microbial biodestruction and aquatic vegetation in freshwater systems.

  17. Ecotoxicity effects triggered in aquatic organisms by invasive Acer negundo and native Alnus glutinosa leaf leachates obtained in the process of aerobic decomposition.

    PubMed

    Manusadžianas, Levonas; Darginavičienė, Jūratė; Gylytė, Brigita; Jurkonienė, Sigita; Krevš, Alina; Kučinskienė, Alė; Mačkinaitė, Rimutė; Pakalnis, Romas; Sadauskas, Kazys; Sendžikaitė, Jūratė; Vitkus, Rimantas

    2014-10-15

    The replacement of autochthonous tree species by invasive ones in coastal zones of freshwater bodies induces additional alteration of hydrochemical and microbiological characteristics due to decomposition of fallen leaves of non-indigenous species, which can lead to ecotoxic response of the littoral biota. Leaves of invasive to Lithuania boxelder maple (Acer negundo) and autochthonous black alder (Alnus glutinosa) lost more than half of biomass and released stable amount of DOC (60-70 mg/L) throughout 90-day mesocosm experiment under aerobic conditions. This, along with the relatively small BOD7 values detected after some variation within the first month confirms effective biodegradation by fungi and bacteria. The ambient water was more enriched with different forms of N and P by decomposing boxelder maple than by alder leaves. During the first month, both leachates were more toxic to charophyte (Nitellopsis obtusa) at mortality and membrane depolarization levels, while later to two crustacean species. Biomarker response, H(+)-ATPase activity in membrane preparations from N. obtusa, was stronger for A. negundo. Generally, boxelder maple leaf leachates were more toxic to tested hydrobionts and this coincides with previous study on leaves of the same pair of tree species conducted under microaerobic conditions (Krevš et al., 2013).

  18. Can We Use Tree Rings of Black Alder to Reconstruct Lake Levels? A Case Study for the Mecklenburg Lake District, Northeastern Germany

    PubMed Central

    van der Maaten, Ernst; van der Maaten-Theunissen, Marieke; Buras, Allan; Scharnweber, Tobias; Simard, Sonia; Kaiser, Knut; Lorenz, Sebastian; Wilmking, Martin

    2015-01-01

    In this study, we explore the potential to reconstruct lake-level (and groundwater) fluctuations from tree-ring chronologies of black alder (Alnus glutinosa L.) for three study lakes in the Mecklenburg Lake District, northeastern Germany. As gauging records for lakes in this region are generally short, long-term reconstructions of lake-level fluctuations could provide valuable information on past hydrological conditions, which, in turn, are useful to assess dynamics of climate and landscape evolution. We selected black alder as our study species as alder typically thrives as riparian vegetation along lakeshores. For the study lakes, we tested whether a regional signal in lake-level fluctuations and in the growth of alder exists that could be used for long-term regional hydrological reconstructions, but found that local (i.e. site-specific) signals in lake level and tree-ring chronologies prevailed. Hence, we built lake/groundwater-level reconstruction models for the three study lakes individually. Two sets of models were considered based on (1) local tree-ring series of black alder, and (2) site-specific Standardized Precipitation Evapotranspiration Indices (SPEI). Although the SPEI-based models performed statistically well, we critically reflect on the reliability of these reconstructions, as SPEI cannot account for human influence. Tree-ring based reconstruction models, on the other hand, performed poor. Combined, our results suggest that, for our study area, long-term regional reconstructions of lake-level fluctuations that consider both recent and ancient (e.g., archaeological) wood of black alder seem extremely challenging, if not impossible. PMID:26317768

  19. Metal cotolerance to copper, lead, and zinc in Festuca rubra

    SciTech Connect

    Wong, M.H.

    1982-10-01

    Tillers of red fescue (Festuca rubra) were collected from three copper-contaminated sites: Prescot (Lancashire, near the copper refinery factory), Great Orme (Clwyd, copper mine), and Ecton (Staffordshire, copper mine), as well as from an uncontaminated area (Festuca rubra S59). By comparing their indexes of tolerance, it was discovered that tillers from Ecton which contained a rather high level of copper, lead, and zinc were tolerant to all three metals. This variety of F. rubra would be useful for reclaiming nonferrous mine spoils which contain a high level of the three commonly occurring heavy metals, i.e., copper, lead and zinc.

  20. Bounding salt marsh nitrogen fluxes: development of an ecohydrological salt marsh model

    EPA Science Inventory

    A mass-balance approach to characterize nitrogen flux in a 2-hectare, meso-haline saltmarsh yielded extensive flow and water chemistry data. However, a significant, unevenly distributed population of the nitrogen fixer Alnus rubra (red alder) in the 20-hectare upland catchment l...

  1. From the forest to the sea and back again: Biogeochemistry in the Oregon Coast Range

    EPA Science Inventory

    Variations in plant community composition across the landscape can influence nutrient retention and loss at the watershed scale. A striking example of plant species influence is the role of N2-fixing red alder (Alnus rubra) in the biogeochemistry of Pacific Northwest forests. A...

  2. Linking landscape characteristics and stream nitrogen in the Oregon Coast Range: Empirical modeling of water quality monitoring data

    EPA Science Inventory

    Background sources of nitrogen (N) provide a challenge for setting stream nutrient criteria in the Pacific Northwest US. Red alder (Alnus rubra), an early successional nitrogen fixing tree, and sea salt inputs can strongly influence stream N concentrations observed in individual...

  3. Bevacizumab-induced pityriasis rubra pilaris-like eruption

    PubMed Central

    Brown, Shannon; Fletcher, J. Wesley

    2016-01-01

    Pityriasis rubra pilaris is a rare inflammatory disorder characterized by follicular papules on an erythematous base often exhibiting islands of unaffected skin, follicular plugging, and palmoplantar hyperkeratosis. While vitamin A deficiency and autoimmune reactions have been hypothesized as possible etiologies of this condition, pityriasis rubra pilaris-like eruptions secondary to medications are extremely rare. To our knowledge, only three other cases have been reported, and pityriasis rubra pilaris has never been reported in association with bevacizumab. We present a 70-year-old man who developed erythroderma both clinically and histologically consistent with pityriasis rubra pilaris 10 days after intravitreal injection of bevacizumab for age-related macular degeneration. As immune-modulating drugs grow in their application for a host of diseases, recognition of associated medication complications is important. PMID:27365893

  4. Alder, Nitrogen, and Lake Ecology: Terrestrial-Aquatic Linkages in the Postglacial History of Lone Spruce Pond, Southwestern Alaska

    PubMed Central

    Axford, Yarrow; Kaufman, Darrell S.

    2017-01-01

    Diatoms, combined with a multiproxy study of lake sediments (organic matter, N, δ15N, δ13C, biogenic silica, grain size, Cladocera and chironomids, Alnus pollen) from Lone Spruce Pond, Alaska detail the late-glacial to Holocene history of the lake and its response to regional climate and landscape change over the last 14.5 cal ka BP. We show that the immigration of alder (Alnus viridis) in the early Holocene marks the rise of available reactive nitrogen (Nr) in the lake as well as the establishment of a primarily planktonic diatom community. The later establishment of diatom Discostella stelligera is coupled to a rise of sedimentary δ15N, indicating diminished competition for this nutrient. This terrestrial-aquatic linkage demonstrates how profoundly vegetation may affect soil geochemistry, lake development, and lake ecology over millennial timescales. Furthermore, the response of the diatom community to strengthened stratification and N levels in the past confirms the sensitivity of planktonic diatom communities to changing thermal and nutrient regimes. These past ecosystem dynamics serve as an analogue for the nature of threshold-type ecological responses to current climate change and atmospheric nitrogen (Nr) deposition, but also for the larger changes we should anticipate under future climate, pollution, and vegetation succession scenarios in high-latitude and high-elevation regions. PMID:28076393

  5. Association pityriasis rubra pilaire et myasthénie

    PubMed Central

    Agharbi, Fatima Zahra; Elbekkal, Amal; Baybay, Hanane; Meziane, Mariame; Mikou, Ouafae; Mernissi, Fatima Zahra

    2011-01-01

    Le pityriasis rubra pilaire est un trouble de kératinisation rare dont l’étiopathogénie reste inconnue mais dont l'association avec autres pathologies a été déjà rapportée. Nous rapportons l'observation d'une jeune patiente qui présente un pityriasis rubra pilaire associé à une myasthénie. Traitée par Néostigmine et thymectomie avec bonne évolution sur le plan neurologique. Vu son désir de grossesse un traitement systémique de son pityriasis rubra pilaire n'a pas pu être instauré et l’évolution sous dermocorticoïdes n’était pas très favorable. PMID:22187589

  6. Control of endophytic Frankia sporulation by Alnus nodule metabolites.

    PubMed

    Hay De-Bettignies, Anne-Emmanuelle; Boubakri, Hasna; Buonomo, Antoine; Rey, Marjolaine; Meiffren, Guillaume; Cotin-Galvan, Laetitia; Comte, Gilles; Herrera-Belaroussi, Aude

    2017-01-10

    A unique case of microbial symbiont capable of dormancy within its living host cells has been reported in actinorhizal symbioses: some Frankia strains, named Sp+, are able to sporulate inside plant cells, contrarily to Sp- strains. The presence of metabolically slowed down bacterial structures in host cells alters our understanding of symbiosis based on reciprocal benefits between both partners, and its impact on the symbiotic processes remains unknown. The present work reports a metabolomic study of Sp+ and Sp- nodules (from Alnus glutinosa), in order to highlight variabilities associated with in-planta sporulation. A total of 21 amino acids (AA), 44 sugars and organic acids (SOA), and 213 secondary metabolites (M) were detected using UV and mass spectrometric-based profiling. Little change was observed in primary metabolites, suggesting that in-planta sporulation would not strongly affect the primary functionalities of the symbiosis. One secondary metabolite (M27) was detected only in Sp+ nodules. It was identified as Gentisic acid 5-O-β-D-xylopyranoside, previously reported as involved in plant defenses against microbial pathogens. This metabolite significantly increased Frankia in-vitro sporulation, unlike another metabolite significantly more abundant in Sp- nodules (M168 = (5R)-1,7-bis-(3,4-) dihydroxyphenyl)-heptane-5-O-β-D-glucopyranoside). All these results suggest that the plant could play an important role in Frankia ability to sporulate in-planta, and allow us to discuss a possible sanction emitted by the host against less cooperative Sp+ symbionts.

  7. Controls on methane emissions from Alnus glutinosa saplings.

    PubMed

    Pangala, Sunitha R; Gowing, David J; Hornibrook, Edward R C; Gauci, Vincent

    2014-02-01

    Recent studies have confirmed significant tree-mediated methane emissions in wetlands; however, conditions and processes controlling such emissions are unclear. Here we identify factors that control the emission of methane from Alnus glutinosa. Methane fluxes from the soil surface, tree stem surfaces, leaf surfaces and whole mesocosms, pore water methane concentrations and physiological factors (assimilation rate, stomatal conductance and transpiration) were measured from 4-yr old A. glutinosa trees grown under two artificially controlled water-table positions. Up to 64% of methane emitted from the high water-table mesocosms was transported to the atmosphere through A. glutinosa. Stem emissions from 2 to 22 cm above the soil surface accounted for up to 42% of total tree-mediated methane emissions. Methane emissions were not detected from leaves and no relationship existed between leaf surface area and rates of tree-mediated methane emissions. Tree stem methane flux strength was controlled by the amount of methane dissolved in pore water and the density of stem lenticels. Our data show that stem surfaces dominate methane egress from A. glutinosa, suggesting that leaf area index is not a suitable approach for scaling tree-mediated methane emissions from all types of forested wetland.

  8. Hydrogenase in actinorhizal root nodules and root nodule homogenates.

    PubMed Central

    Benson, D R; Arp, D J; Burris, R H

    1980-01-01

    Hydrogenases were measured in intact actinorhizal root nodules and from disrupted nodules of Alnus glutinosa, Alnus rhombifolia, Alnus rubra, and Myrica pensylvanica. Whole nodules took up H2 in an O2-dependent reaction. Endophyte preparations oxidized H2 through the oxyhydrogen reaction, but rates were enhanced when hydrogen uptake was coupled to artificial electron acceptors. Oxygen inhibited artifical acceptor-dependent H2 uptake. The hydrogenase system from M. pensylvanica had a different pattern of coupling to various electron acceptors than the hydrogenase systems from the alders; only the bayberry system evolved H2 from reduced viologen dyes. PMID:6989799

  9. The impact of a pulsing groundwater table on greenhouse gas emissions in riparian grey alder stands.

    PubMed

    Mander, Ülo; Maddison, Martin; Soosaar, Kaido; Teemusk, Alar; Kanal, Arno; Uri, Veiko; Truu, Jaak

    2015-02-01

    Floods control greenhouse gas (GHG) emissions in floodplains; however, there is a lack of data on the impact of short-term events on emissions. We studied the short-term effect of changing groundwater (GW) depth on the emission of (GHG) carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) in two riparian grey alder (Alnus incana) stands of different age in Kambja, southern Estonia, using the opaque static chamber (five replicates in each site) and gas chromatography methods. The average carbon and total nitrogen content in the soil of the old alder (OA) stand was significantly higher than in the young alder (YA) stand. In both stands, one part was chosen for water table manipulation (Manip) and another remained unchanged with a stable and deeper GW table. Groundwater table manipulation (flooding) significantly increases CH4 emission (average: YA-Dry 468, YA-Manip 8,374, OA-Dry 468, OA-Manip 4,187 μg C m(-2) h(-1)) and decreases both CO2 (average: OA-Dry 138, OA-Manip 80 mg C m(-2) h(-1)) and N2O emissions (average: OA-Dry 23.1, OA-Manip 11.8 μg N m(-2) h(-1)) in OA sites. There was no significant difference in CO2 and CH4 emissions between the OA and YA sites, whereas in OA sites with higher N concentration in the soil, the N2O emission was significantly higher than at the YA sites. The relative CO2 and CH4 emissions (the soil C stock-related share of gaseous losses) were higher in manipulated plots showing the highest values in the YA-Manip plot (0.03 and 0.0030 % C day(-1), respectively). The soil N stock-related N2O emission was very low achieving 0.000019 % N day(-1) in the OA-Dry plot. Methane emission shows a negative correlation with GW, whereas the 20 cm depth is a significant limit below which most of the produced CH4 is oxidized. In terms of CO2 and N2O, the deeper GW table significantly increases emission. In riparian zones of headwater streams, the short-term floods (e.g. those driven by extreme climate events) may significantly enhance

  10. Antiscalant properties of Spergularia rubra and Parietaria officinalis aqueous solutions

    NASA Astrophysics Data System (ADS)

    Cheap-Charpentier, Hélène; Gelus, Dominique; Pécoul, Nathalie; Perrot, Hubert; Lédion, Jean; Horner, Olivier; Sadoun, Jonathan; Cachet, Xavier; Litaudon, Marc; Roussi, Fanny

    2016-06-01

    The formation of calcium carbonate in water has important implications in industry. Chemical antiscalant is usually used to control scale depositions. Plant extracts have been recently used as new green antiscalant agents, as they can be easily prepared and are environmentally friendly. In this study, stock aqueous solutions of Spergularia rubra and Parietaria officinalis, two plants used in traditional medicine to treat or prevent urolithiasis, were obtained by infusion. The antiscaling properties of these extracts towards CaCO3 formation were tested by using chronoamperometry and Fast Controlled Precipitation methods. The aqueous solution of S. rubra was further fractionated to isolate compounds of lower polarity. Their efficiency towards CaCO3 precipitation was characterized by Fast Controlled Precipitation method. The inhibiting efficiency of this fractionated solution was greater than that of the stock aqueous solution.

  11. Synthesis of Antitumor Lycorines by Intramolecular Diels-Alder Reaction.

    PubMed

    Pérez, Dolores; Burés, Gema; Guitián, Enrique; Castedo, Luis

    1996-03-08

    Pharmacologically interesting lycorines were obtained by a short, efficient method based on an intramolecular Diels-Alder reaction between an alpha-pyrone and an alkyne, followed by loss of CO(2) in a retro Diels-Alder reaction. The cyclization precursors (pyrones 9) were obtained in good yields in two or three steps from the corresponding homophthalic acid or anhydride.

  12. Evaluation of Various Therapeutic Measures in Striae Rubra

    PubMed Central

    Karia, Umesh Karsandas; Padhiar, Bela Bhemabhai; Shah, Bela Jaswantbhai

    2016-01-01

    Background: Striae are linear atrophic depressions that form in areas of dermal damage in the skin. As on date, no consensus or protocol exists for the treatment of stria rubra. Topical retinoids, chemical peels, microdermabrasion, radiofrequency, photothermolysis, intense pulsed light and lasers are some of the modalities used. Aims and Objective: To compare the efficacy of various therapeutic modalities in striae rubra. Methods: This prospective cohort study comprised of a total of fifty patients from August-2012 to October-2013 in a tertiary care center in Western India, Gujarat having striae rubra. They were randomly divided into five groups of ten patients each. Patients were evaluated on the basis of visual assessment, both by doctor as well as the patient. Group I was given topical tretinoin (0.1% w/w) gel applied once at night, Group II-microdermabrasion (MDA) combined with trichloroacetic acid (TCA) (30%) peel, Group III-mesotherapy, Group IV-Q-switched Nd: YAG laser, and Group V-combination treatment of microdermabrasion, salicylic acid peel and retinol (yellow) peel. Patients were treated at an interval of 15 days for 2 months and then at monthly intervals. Objective assessment was done at 2nd month, 6th month, and at the end of 1st year. Results: Patients in Group I treated with topical tretinoin showed the least response with 80% (8) of them showing minimal clinical improvement (0–25%) as compared to patients in Group V in which 60% (6) patients showed moderate clinical improvement (50–75%). While majority of the patients in Group II, III, and IV showed mild clinical improvement (25–50%). Conclusions: Striae rubra is a common cause of concern for adolescent population. Combination treatment with microdermabrasion, salicylic acid and retinol yellow peel gave superior results as compared to other therapeutic options. Mild to moderate improvement was seen with Nd: YAG laser, mesotherapy and MDA + TCA whereas minimal improvement were seen with

  13. Taxonomic implications of Rhodotorula rubra isolates from polluted sea water in Rio de Janeiro, Brazil.

    PubMed

    Hagler, A N; Mendonça-Hagler, L C

    1979-04-01

    Sixty two strains of Rhodotorula rubra which were all isolated from marine and estuarine waters of Rio de Janeiro were found variable for 19 to 32 carbon assimilation tests used in yeast taxonomy. Two R. rubra strains which had latent assimilation of maltose and melizitose appeared to be intermediate with R. pilimanae. Strains of R. glutinis var dairenensis which differed from R. rubra only by weak assimilation of nitrate appeared to be intermediated between these two species. Our physiological tests suggested that R. rubra, R. pilimanae, and part of R. glutinis should be combined and this was supported by DNA base composition and coezyme Q data existing in the literature.

  14. Occultocarpon, a new monotypic genus of Gnomoniaceae on Alnus nepalensis from China

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new monotypic genus Occultocarpon and its species, O. ailaoshanense, was discovered on the bark of branches of Alnus nepalensis (Betulaceae) in Yunnan, China. A phylogeny based on three genes (LSU, rpb2, tef1-a) reveals that O. ailaoshanense belongs to the Gnomoniaceae (Diaporthales, Ascomycetes) ...

  15. Spatiotemporal models for predicting high pollen concentration level of Corylus, Alnus, and Betula

    NASA Astrophysics Data System (ADS)

    Nowosad, Jakub

    2016-06-01

    Corylus, Alnus, and Betula trees are among the most important sources of allergic pollen in the temperate zone of the Northern Hemisphere and have a large impact on the quality of life and productivity of allergy sufferers. Therefore, it is important to predict high pollen concentrations, both in time and space. The aim of this study was to create and evaluate spatiotemporal models for predicting high Corylus, Alnus, and Betula pollen concentration levels, based on gridded meteorological data. Aerobiological monitoring was carried out in 11 cities in Poland and gathered, depending on the site, between 2 and 16 years of measurements. According to the first allergy symptoms during exposure, a high pollen count level was established for each taxon. An optimizing probability threshold technique was used for mitigation of the problem of imbalance in the pollen concentration levels. For each taxon, the model was built using a random forest method. The study revealed the possibility of moderately reliable prediction of Corylus and highly reliable prediction of Alnus and Betula high pollen concentration levels, using preprocessed gridded meteorological data. Cumulative growing degree days and potential evaporation proved to be two of the most important predictor variables in the models. The final models predicted not only for single locations but also for continuous areas. Furthermore, the proposed modeling framework could be used to predict high pollen concentrations of Corylus, Alnus, Betula, and other taxa, and in other countries.

  16. Spatiotemporal models for predicting high pollen concentration level of Corylus, Alnus, and Betula.

    PubMed

    Nowosad, Jakub

    2016-06-01

    Corylus, Alnus, and Betula trees are among the most important sources of allergic pollen in the temperate zone of the Northern Hemisphere and have a large impact on the quality of life and productivity of allergy sufferers. Therefore, it is important to predict high pollen concentrations, both in time and space. The aim of this study was to create and evaluate spatiotemporal models for predicting high Corylus, Alnus, and Betula pollen concentration levels, based on gridded meteorological data. Aerobiological monitoring was carried out in 11 cities in Poland and gathered, depending on the site, between 2 and 16 years of measurements. According to the first allergy symptoms during exposure, a high pollen count level was established for each taxon. An optimizing probability threshold technique was used for mitigation of the problem of imbalance in the pollen concentration levels. For each taxon, the model was built using a random forest method. The study revealed the possibility of moderately reliable prediction of Corylus and highly reliable prediction of Alnus and Betula high pollen concentration levels, using preprocessed gridded meteorological data. Cumulative growing degree days and potential evaporation proved to be two of the most important predictor variables in the models. The final models predicted not only for single locations but also for continuous areas. Furthermore, the proposed modeling framework could be used to predict high pollen concentrations of Corylus, Alnus, Betula, and other taxa, and in other countries.

  17. Performance of an age series of Alnus-cardamom plantations in the Sikkim Himalaya: nutrient dynamics.

    PubMed

    Sharma, G; Sharma, R; Sharma, E; Singh, K K

    2002-03-01

    Nutrient cycling, nutrient use efficiency and nitrogen fixation in an age series of Alnus-cardamom plantations were studied in the eastern Himalaya. The impact of stand age (5, 10, 15, 20, 30 and 40 years) on the nutrient dynamics of mixtures of N2-fixing (Alnus nepalensis) and non-N2-fixing (large cardamom) plants was assessed. Foliar nutrient concentrations of Alnus decreased with advancing age groups of plantations and showed an inverse relationship with stand age. Annual N fixation increased from the 5-year-old stand (52 kg ha(-1)), peaking in the 15-year-old stand (155 kg ha(-1)) and then decreased with increasing plantation age. Nitrogen and phosphorus uptake was lowest in the 40-year-old stand, and highest in the 15- and 5-year-old stand, respectively. Nutrient storage in understorey cardamom was very high: up to 31 % N and 59 % P of the stand total in the 15-year-old stand. Nutrient use efficiency was higher (with faster turnover times) in younger stands and decreased (with slower turnover times) in older plantations. Nitrogen retranslocation showed a strong positive relationship with stand age, while that of P was inversely related to stand age. Nutrient standing stock, uptake and return were also highest in the 15-year-old stand. Nitrogen and P cycling in Alnus-cardamom plantations was functionally balanced. Nutrient cycling and dynamics indicated that Alnus-cardamom plantations performed sustainably up to 15-20 years. The management practice should be altered to incorporate replantation after this age.

  18. Effects of surface inactivation, high temperature drying and preservative treatment on surface roughness and colour of alder and beech wood

    NASA Astrophysics Data System (ADS)

    Aydin, Ismail; Colakoglu, Gursel

    2005-10-01

    Although extensive research has been conducted in wood surface quality analysis, a unified approach to surface quality characterisation does not exist. Measurements of the variation in surface roughness and surface colour are used widely for the evaluation of wood surface quality. Colour is a basic visual feature for wood and wood-based products. Colour measurement is one of the quality control tests that should be carried out because the colour deviations are spotted easily by the consumers. On the other hand, a common problem faced by plywood manufacturers is panel delamination, for which a major cause is poor quality glue-bonds resulting from rough veneer. Rotary cut veneers with dimensions of 500 mm × 500 mm × 2 mm manufactured from alder ( Alnus glutinosa subsp. barbata) and beech ( Fagus orientalis Lipsky) logs were used as materials in this study. Veneer sheets were oven-dried in a veneer dryer at 110 °C (normal drying temperature) and 180 °C (high drying temperature) after peeling process. The surfaces of some veneers were then exposed at indoor laboratory conditions to obtain inactive wood surfaces for glue bonds, and some veneers were treated with borax, boric acid and ammonium acetate solutions. After these treatments, surface roughness and colour measurements were made on veneer surfaces. High temperature drying process caused a darkening on the surfaces of alder and beech veneers. Total colour change value (Δ E*) increased linear with increasing exposure time. Among the treatment solutions, ammonium acetate caused the biggest colour change while treatment with borax caused the lowest changes in Δ E* values. Considerable changes in surface roughness after preservative treatment did not occur on veneer surfaces. Generally, no clear changes were obtained or the values mean roughness profile ( Ra) decreased slightly in Ra values after the natural inactivation process.

  19. Covalently crosslinked diels-alder polymer networks.

    SciTech Connect

    Bowman, Christopher; Adzima, Brian J.; Anderson, Benjamin John

    2011-09-01

    This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis of the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.

  20. Reduced atmospheric CO2 inhibits nitrogen mobilization in Festuca rubra.

    PubMed

    Thornton, Barry; Paterson, Eric; Kingston-Smith, Alison H; Bollard, Andrea L; Pratt, Shona M; Sim, Allan

    2002-09-01

    In defoliated grasses, where photosynthesis is reduced due to removal of leaf material, it is well established that remobilization of nitrogen occurs from both older remaining leaves and roots towards the younger growing leaves. In contrast, little is known about the movement of nitrogen within intact grass plants experiencing prolonged inhibition of photosynthesis. We tested the following hypotheses in Festuca rubra L. ssp. rubra cv. Boreal: that both reduction of the atmospheric CO2 concentration and defoliation (1) induce mobilization of nitrogen from roots and older leaves towards growing leaves and (2) elicit similar directional change in the abundance of proteins in roots and older leaves relevant to the process of nitrogen mobilization including, glutamine synthetase (GS), EC 6.3.1.2; papain, EC 3.4.22.2; chymopapain, EC 3.4.22.6; ribulose bisphosphate carboxylase/oxygenase (Rubisco), EC 4.1.1.39; and the light harvesting complex of photosystem II (LHCPII). After growth at ambient atmospheric CO2 concentration, plants of F. rubra were subject to atmospheres containing either ambient (350 micro l l-1) or deplete (< 20 micro l l-1) CO2. Concurrently, plants were either left intact or defoliated on one occasion. Steady state 15N labelling coupled with a series of destructive harvests over a 7-day period enabled changes in the nitrogen dynamics of the plants to be established. Proteins pertinent to the process of nitrogen mobilization were quantified by immunoblotting. Irrespective of defoliation, plants in ambient CO2 mobilized nitrogen from older to growing leaves. This mobilization was inhibited by deplete CO2. Greater concentration of Rubisco and reduced chymopapain abundance in older remaining leaves of intact plants, in deplete compared with ambient CO2, suggested the inhibition of mobilization was due to inhibition of protein degradation, rather than to the export of degradation products. Both deplete CO2 and defoliation induced nitrogen mobilization from

  1. Amino acids of the cell wall of Nocardia rubra.

    PubMed

    Beaman, B L; Kim, K S; Salton, M R; Barksdale, L

    1971-11-01

    Two classes of preparations of cell walls of Nocardia rubra strain 721-A, digested by trypsin and pepsin with or without subsequent extraction in alkaline ethanol, when examined by electron microscope and analyzed quantitatively for amino acid content differ in ultrastructure and constituent amino acids. Evidence suggests that the lipid-associated amino acids (as peptide or protein) occupy a location superficial to the basal peptido-glycan layer of this nocardia. Their removal is associated with the loss of a characteristic pattern of the outer envelope.

  2. Effects of Alder Mine on the Water, Sediments, and Benthic Macroinvertebrates of Alder Creek, 1998 Annual Report.

    SciTech Connect

    Peplow, Dan

    1999-05-28

    The Alder Mine, an abandoned gold, silver, copper, and zinc mine in Okanogan County, Washington, produces heavy metal-laden effluent that affects the quality of water in a tributary of the Methow River. The annual mass loading of heavy metals from two audits at the Alder Mine was estimated to exceed 11,000 kg per year. In this study, water samples from stations along Alder Creek were assayed for heavy metals by ICP-AES and were found to exceed Washington State's acute freshwater criteria for cadmium (Cd), copper (Cu), selenium (Se), and zinc (Zn).

  3. The pentadehydro-Diels–Alder reaction

    PubMed Central

    Wang, Teng; Naredla, Rajasekhar Reddy; Thompson, Severin K.; Hoye, Thomas R

    2016-01-01

    In the classic Diels–Alder (DA) [4+2] cycloaddition reaction1, the overall degree of unsaturation of the 4π (diene) and 2π (dienophile) pairs of reactants dictates the oxidation state of the newly formed six-membered carbocycle. For example, in the classic DA reaction, butadiene and ethylene combine to produce cyclohexene. More recent developments include variants in which the hydrogen atom count in the reactant pair and in the resulting product is reduced by2, for example, four in the tetradehydro-DA (TDDA) and by six in the hexadehydro-DA (HDDA3,4,5,6,7) reactions. Any oxidation state higher than tetradehydro leads to the production of a reactive intermediate that is more highly oxidized than benzene. This significantly increases the power of the overall process because trapping of the benzyne intermediate8,9 can be used to increase the structural complexity of the final product in a controllable and versatile manner. In this manuscript, we report an unprecedented net 4π+2π cycloaddition reaction that generates a different, highly reactive intermediate known as an α,3-dehydrotoluene. This species is at the same oxidation state as a benzyne. Like benzynes, α,3-dehydrotoluenes can be captured by various trapping agents to produce structurally diverse products that are complementary to those arising from the HDDA process. We call this new cycloisomerization reaction a pentadehydro-Diels–Alder (PDDA) reaction—a nomenclature chosen for chemical taxonomic rather than mechanistic reasons. In addition to alkynes, nitriles (RC≡N), although non-participants in aza-HDDA reactions, readily function as the 2π-component in PDDA cyclizations to produce, via trapping of the α,3-(5-aza)dehydrotoluene intermediates, pyridine-containing products. PMID:27088605

  4. A Diels-Alder Route to Angularly Functionalized Bicyclic Structures

    PubMed Central

    Kim, Woo Han; Lee, Jun Hee; Aussedat, Baptiste; Danishefsky, Samuel J.

    2010-01-01

    A Diels-Alder based route to trans-fused angularly functionalized bicyclic structures has been developed. This transformation features the use of a tetrasubstituted dienophile in the cycloaddition step. PMID:20717474

  5. The hetero-Diels-Alder approach to spiroketals.

    PubMed

    Rizzacasa, Mark A; Pollex, Annett

    2009-03-21

    The hetero-Diels-Alder reaction can provide spiroketal systems with excellent stereoselectivity. This perspective article will briefly outline the scope and limitations of this approach for the production of naturally occurring spiroketals and derivatives.

  6. Two new species of Lactarius associated with Alnus acuminata subsp. arguta in Mexico.

    PubMed

    Montoya, Leticia; Bandala, Victor M; Garay, Edith

    2014-01-01

    In pure stands of Alnus acuminata subsp. arguta trees from Sierra Norte de Puebla (central Mexico) two undescribed ectomycorrhizal species of Lactarius were discovered. Distinction of the two new species is based on morphological characters and supported with phylogenetic analyses of the nuclear ribosomal DNA ITS region and part of the gene that encodes for the second largest subunit of RNA polymerase II (rpb2). The phylogenies inferred recovered the two species in different clades strongly supported by posterior probabilities and bootstrap values. The new Lactarius species are recognized as part of the assemblage of ectomycorrhizal fungi associated with Alnus acuminata. Information about these taxa includes the morphological variation achieved along 16 monitories 2010-2013. Descriptions are provided. They are accompanied by photos including SEM photomicrographs of basidiospores and information on differences between them and other related taxa from Europe and the United States.

  7. Evidence that some Frankia sp. strains are able to cross boundaries between Alnus and Elaeagnus host specificity groups.

    PubMed

    Bosco, M; Fernandez, M P; Simonet, P; Materassi, R; Normand, P

    1992-05-01

    Phenotypic and genotypic methods were used to prove the existence of Frankia strains isolated from an Elaeagnus sp. that are able to cross the inoculation barriers and infect Alnus spp. also. Repeated cycles of inoculation, nodulation, and reisolation were performed under axenic conditions. Frankia wild-type strain UFI 13270257 and three of its coisolates did exhibit complete infectivity and effectiveness on Elaeagnus spp. and Hippophaë rhamnoides and variable infectivity on Alnus spp. Microscopical observation of host plant roots showed that these strains are able to infect Alnus spp. by penetrating deformed root hairs. Reisolates obtained from nodules induced on monoxenic Alnus glutinosa, Alnus incana, and Elaeagnus angustifolia resembled the parent strains in host infectivity range, in planta and in vitro morphophysiology, isoenzymes, and nif and rrn restriction fragment length polymorphisms, thus fulfilling Koch's postulates on both host plant genera. Alnus and Elaeagnus group-specific polymerase chain reaction DNA amplifications, DNA-DNA hybridizations, and partial gene sequences coding for 16S rRNA provided evidence for the genetic uniformity of wild-type strains and their inclusion into one and the same genomic species, clearly belonging to the Elaeagnus group of Frankia species.

  8. Toxicity and antioxidant capacity of Frangula alnus Mill. bark and its active component emodin.

    PubMed

    Brkanac, Sandra Radić; Gerić, Marko; Gajski, Goran; Vujčić, Valerija; Garaj-Vrhovac, Vera; Kremer, Dario; Domijan, Ana-Marija

    2015-12-01

    In the present study toxicity of Frangula alnus Mill. bark, widely used as laxative, was investigated. Human peripheral blood lymphocytes (HPBLs) were treated with F. alnus bark extract or emodin (emodin is bark component with laxative property), and cytotoxicity, genotoxicity and parameters of oxidative stress were assessed. Also, polyphenol content of bark extract and antioxidant activity of the extract and emodin measured by DPPH, ABTS and FRAP methods were examined. The bark extract (500 μg/ml) produced cell death and DNA damage, while level of ROS changed at 250 μg/ml. Emodin induced cell death and DNA damage at 150 μg/ml and 200 μg/ml, respectively, and the increase of ROS was observed at 25 μg/ml. These results suggest that both, bark extract and emodin, are cyto/genotoxic to HPBLs and that oxidative stress is involved in the mechanism of their toxicity. The results on antioxidant activity showed that, unlike emodin, bark extract possess moderate antioxidant capacity (44.6%, 46.8% and 2.25 mmol Fe(2+)/g measured by DPPH, ABTS and FRAP assay, respectively) that can be related to relatively high phenolic content (116.07 mg/g). However, due to toxicological properties use of F. alnus bark as well as emodin-containing preparations should be taken with caution.

  9. Predicting crown weight and bole volume of five western hardwoods. Forest Service general technical report

    SciTech Connect

    Snell, J.A.K.; Little, S.N.

    1983-03-01

    Regression equations are presented for estimating biomass of five western hardwoods: red alder (Alnus rubra), giant chinkapin (Castanopsis chrysophylla), big leaf maple (Acer macrophyllum), Pacific madrone (Arbutus memziesii), and tan oak (Lithocarpus densiflorus). Estimators are given for total crown biomass, cumulative proportions for separating crown weight into foliage and four timelag fuel diameter classes, bark weight, and bole volume (inside bark) to any specified top diameter. With one exception, the equation uses diameter at breast height as the only independent variable.

  10. Identifying, cloning and structural analysis of differentially expressed genes upon Puccinia infection of Festuca rubra var. rubra.

    PubMed

    Ergen, Neslihan Z; Dinler, Gizem; Shearman, Robert C; Budak, Hikmet

    2007-05-15

    Differentially expressed genes in response to rust infection (Puccinia sp.) in creeping red fescue (Festuca rubra var. rubra) were identified and quantified using the mRNA differential display technique. The differentially induced genes were identified as homologs of mitogen-activated protein kinase (MAPK) 3 of Arabidopsis thaliana, stem rust resistance protein Rpg1 of barley and Hsp70 of Spinacia oleracea. The change in the steady state expression levels of these genes in response to rust infection was tested by Northern blot analysis and further quantified by real-time PCR. A steady accumulation of transcripts in the course of rust infection was observed. Full-length transcript of a fescue MPK-3 was obtained by RACE PCR. Its corresponding cDNA encodes a protein with a predicted MW of 42.5 kDa which was mapped onto the structural model of homologs MAPK to illustrate the corresponding MAPK signature motifs. This study, for the first time, presents evidence on the rust infection dependent metabolic pathways in creeping red fescue.

  11. The hexadehydro-Diels–Alder reaction

    PubMed Central

    Hoye, Thomas R.; Baire, Beeraiah; Niu, Dawen; Willoughby, Patrick H.; Woods, Brian P.

    2012-01-01

    Summary o-Benzynes (arynes) are among the most versatile of all reactive (short-lived) intermediates in organic chemistry. These species can be trapped to give products that are valuable from the perspective of both fine (pharmaceuticals) and commodity (agrochemicals, dyes, polymers, etc.) chemicals. Here we show a fundamentally new strategy that unites a de novo generation of benzynes, through the title hexadehydro-Diels–Alder (HDDA) reaction, with their in situ elaboration into structurally complex benzenoid products. In the HDDA reaction a 1,3-diyne is engaged in a [4+2] cycloisomerization with a third (pendant) alkyne–the diynophile–to produce the highly reactive benzyne intermediate. The metal- and reagent-free reaction conditions for this simple, thermal transformation are notable. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed. PMID:23060191

  12. SYSTEMIC BLASTOMYCOSIS IN A CAPTIVE RED RUFFED LEMUR (VARECIA RUBRA).

    PubMed

    Rosser, Michael F; Lindemann, Dana M; Barger, Anne M; Allender, Matthew C; Hsiao, Shih-Hsuan; Howes, Mark E

    2016-09-01

    A 5-yr-old, intact male red ruffed lemur ( Varecia rubra ) presented for evaluation as the result of a 1-wk history of lethargy and hyporexia. Physical examination findings included thin body condition, muffled heart sounds, harsh lung sounds, and liquid brown diarrhea. Complete blood count and serum biochemistry showed an inflammatory leukogram, mild hyponatremia, and mild hypochloremia. Orthogonal trunk radiographs revealed a severe alveolar pattern in the right cranial lung lobes with cardiac silhouette effacement. Thoracic ultrasound confirmed a large, hypoechoic mass in the right lung lobes. Fine-needle aspiration of the lung mass and cytology revealed fungal yeast organisms, consistent with Blastomyces dermatitidis. Blastomyces Quantitative EIA Test on urine was positive. Postmortem examination confirmed systemic blastomycosis involving the lung, tracheobronchial lymph nodes, spleen, kidney, liver, cerebrum, and eye. To the authors' knowledge, this is the first report of blastomycosis in a prosimian species.

  13. Pityriasis rubra pilaris-like eruption following insulin therapy initiation

    PubMed Central

    Badri, Talel; Zaouak, Anissa; Lakhoua, Ghozlane; Koubaa, Wafaa; Fennich, Sami; Zaiem, Ahmed

    2016-01-01

    Pityriasis rubra pilaris (PRP) is a chronic disorder of keratinization of unclear pathogenesis. PRP-like eruptions induced by drugs have rarely been described. A previously healthy 29-year-old man presented with a generalized, rapidly spreading, erythematosquamous dermatosis, that started three days after initiation of subcutaneous insulin therapy for diabetes mellitus type 1. Clinical and histopathological features were consistent with a PRP-like eruption, possibly due to insulin therapy. The patient was switched to insulin analogue therapy and a complete healing of all lesions was achieved after two months. No recurrence was seen after one year of follow-up. Other possible etiologies of PRP were excluded. The mechanism leading to the occurrence of drug-induced PRP-like eruptions are not clear. Since PRP may occur in the context of immunological anomalies, it is possible that diabetes mellitus type 1 may have been a predisposing condition for the development of PRP in this case. PMID:27867741

  14. Change in ATP-binding cassette B1/19, glutamine synthetase and alcohol dehydrogenase gene expression during root elongation in Betula pendula Roth and Alnus glutinosa L. Gaertn in response to leachate and leonardite humic substances.

    PubMed

    Tahiri, Abdelghani; Delporte, Fabienne; Muhovski, Yordan; Ongena, Marc; Thonart, Philippe; Druart, Philippe

    2016-01-01

    Humic substances (HS) are complex and heterogeneous compounds of humified organic matter resulting from the chemical and microbiological decomposition of organic residues. HS have a positive effect on plant growth and development by improving soil structure and fertility. They have long been recognized as plant growth-promoting substances, particularly with regard to influencing nutrient uptake, root growth and architecture. The biochemical and molecular mechanisms through which HS influence plant physiology are not well understood. This study evaluated the bioactivity of landfill leachate and leonardite HS on alder (Alnus glutinosa L. Gaertn) and birch (Betula pendula Roth) during root elongation in vitro. Changes in root development were studied in relation to auxin, carbon and nitrogen metabolisms, as well as to the stress adaptive response. The cDNA fragments of putative genes encoding two ATP-binding cassette (ABC) transporters (ABCB1 and ABCB19) belonging to the B subfamily of plant ABC auxin transporters were cloned and sequenced. Molecular data indicate that HS and their humic acid (HA) fractions induce root growth by influencing polar auxin transport (PAT), as illustrated by the modulation of the ABCB transporter transcript levels (ABCB1 and ABCB19). There were also changes in alcohol dehydrogenase (ADH) and glutamine synthetase (GS) gene transcript levels in response to HS exposure. These findings confirmed that humic matter affects plant growth and development through various metabolic pathways, including hormonal, carbon and nitrogen metabolisms and stress response or signalization.

  15. meta-Tyrosine in Festuca rubra ssp. commutata (Chewings fescue) is synthesized by hydroxylation of phenylalanine.

    PubMed

    Huang, Tengfang; Rehak, Ludmila; Jander, Georg

    2012-03-01

    m-Tyrosine is a non-protein amino acid that is structurally similar to the common protein amino acids p-tyrosine and phenylalanine. Copious amounts of m-tyrosine can be found in root exudates of the fine fescue cultivar, Festuca rubra L. ssp. commutata (Chewings fescue). The phytotoxicity of m-tyrosine may contribute to the allelopathic potential of F. rubra. m-Tyrosine in Euphorbia myrsinites (donkey-tail spurge), was previously shown to be synthesized via transamination of m-hydroxyphenylpyruvate. Here we show that m-tyrosine biosynthesis in F. rubra occurs through direct hydroxylation of phenylalanine in the root tips, perhaps through the activity of a cytochrome P450 enzyme. Hence, E. myrsinites and F. rubra, the only two plant species known to produce m-tyrosine, use distinct biosynthetic pathways that likely arose independently in evolutionary history.

  16. Permuting Diels-Alder and Robinson Annulation Stereopatterns.

    PubMed

    Peng, Feng; Dai, Mingji; Angeles, Angie R; Danishefsky, Samuel J

    2012-01-01

    Controlled isomerization of the double bond of certain Diels-Alder reactions provides substrates that, upon oxidation, give rise to products whose gross structure corresponds to that of a Robinson annulation. In these cases, the stereochemistry of the Robinson annulation product reflects the fact that the initial combination occurred in a Diels-Alder mode. Using these principles, we have synthesized carissone and cosmosoic acid. In the latter case, our total synthesis raised serious questions as to the accuracy of the assigned structure of the natural product.

  17. Effect on tumor necrosis factor-α production and antioxidant ability of black alder, as factors related to its anti-inflammatory properties.

    PubMed

    Acero, Nuria; Muñoz-Mingarro, Dolores

    2012-06-01

    Alders exhibit several uses in different areas and also offer some nutritional and medicinal values. The bark and leaves from black alder [Alnus glutinosa (L.) Gaertn] are used in folk medicine for the treatment of inflammatory processes and other health disorders. This study assessed if an extract of A. glutinosa stem bark exhibits some biological properties linked to improving the inflammatory state, which could partly justify its ethnopharmacological use. Therefore, various aspects of antioxidant activity as well as the effect on tumor necrosis factor-α (TNF-α) production were evaluated. The phytochemical study revealed the presence of terpenes, saponins, tannins, flavonoids, and anthraquinones (by high-performance thin-layer chromatography). The betulinic acid content in the extract, determined by reversed-phase high-performance liquid chromatography (validated method), was 0.72±0.027%. In addition, high amounts for total phenols as well as flavonoids were determined. The extract exhibited a 2,2'-diphenylpicrylhydrazyl radical scavenging capacity similar to that of ascorbic acid and had a significant effect on superoxide anion scavenging, superior to that of ascorbic acid. It was also able to protect HeLa cells from induced oxidative stress. In the TNF-α assay, levels of this citokine were depressed by the extract in HL-60 cells. To test the effect of the extract on cell proliferation, a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay was performed. According to the results, the antioxidant properties displayed by the extract of A. glutinosa stem bark, together with the effect on TNF-α levels, suggest that these activities, linked to a successful reduction in inflammatory processes, may support, in part, its ethnopharmacological use.

  18. Effect on Tumor Necrosis Factor-α Production and Antioxidant Ability of Black Alder, as Factors Related to Its Anti-Inflammatory Properties

    PubMed Central

    Acero, Nuria

    2012-01-01

    Abstract Alders exhibit several uses in different areas and also offer some nutritional and medicinal values. The bark and leaves from black alder [Alnus glutinosa (L.) Gaertn] are used in folk medicine for the treatment of inflammatory processes and other health disorders. This study assessed if an extract of A. glutinosa stem bark exhibits some biological properties linked to improving the inflammatory state, which could partly justify its ethnopharmacological use. Therefore, various aspects of antioxidant activity as well as the effect on tumor necrosis factor-α (TNF-α) production were evaluated. The phytochemical study revealed the presence of terpenes, saponins, tannins, flavonoids, and anthraquinones (by high-performance thin-layer chromatography). The betulinic acid content in the extract, determined by reversed-phase high-performance liquid chromatography (validated method), was 0.72±0.027%. In addition, high amounts for total phenols as well as flavonoids were determined. The extract exhibited a 2,2′-diphenylpicrylhydrazyl radical scavenging capacity similar to that of ascorbic acid and had a significant effect on superoxide anion scavenging, superior to that of ascorbic acid. It was also able to protect HeLa cells from induced oxidative stress. In the TNF-α assay, levels of this citokine were depressed by the extract in HL-60 cells. To test the effect of the extract on cell proliferation, a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay was performed. According to the results, the antioxidant properties displayed by the extract of A. glutinosa stem bark, together with the effect on TNF-α levels, suggest that these activities, linked to a successful reduction in inflammatory processes, may support, in part, its ethnopharmacological use. PMID:22424456

  19. Temporal and spatiotemporal autocorrelation of daily concentrations of Alnus, Betula, and Corylus pollen in Poland.

    PubMed

    Nowosad, J; Stach, A; Kasprzyk, I; Grewling, Ł; Latałowa, M; Puc, M; Myszkowska, D; Weryszko-Chmielewska, E; Piotrowska-Weryszko, K; Chłopek, K; Majkowska-Wojciechowska, B; Uruska, A

    The aim of the study was to determine the characteristics of temporal and space-time autocorrelation of pollen counts of Alnus, Betula, and Corylus in the air of eight cities in Poland. Daily average pollen concentrations were monitored over 8 years (2001-2005 and 2009-2011) using Hirst-designed volumetric spore traps. The spatial and temporal coherence of data was investigated using the autocorrelation and cross-correlation functions. The calculation and mathematical modelling of 61 correlograms were performed for up to 25 days back. The study revealed an association between temporal variations in Alnus, Betula, and Corylus pollen counts in Poland and three main groups of factors such as: (1) air mass exchange after the passage of a single weather front (30-40 % of pollen count variation); (2) long-lasting factors (50-60 %); and (3) random factors, including diurnal variations and measurements errors (10 %). These results can help to improve the quality of forecasting models.

  20. Incompatibility and pollen competition in Alnus glutinosa: Evidence from pollination experiments.

    PubMed

    Steiner, W; Gregorius, H R

    1999-03-01

    Different types of incompatibility systems were found to operate simultaneously in Alnus glutinosa in the course of numerous pollination experiments, including self-pollination and pollination with controlled pollen mixtures. Isozyme genetic markers were used to identify the pollen parent of each offspring from the mixed pollination experiments, thus allowing specification of the fertilization success of each pollen parent. In a first step, these results were compared with observations on in vitro pollen germination experiments. This comparison allows for exploration of the explanatory value of different germination media as models of germination conditions on stigmas. In most cases, the data suggest that the in vitro germination conditions resemble the fertilization conditions in vivo, at least in the sense that they favor the same pollen parents. By providing a generic and operable definition of the two basic types of incompatibility, eliminating (inability to fertilize ovules) and cryptic (resulting in lowered fertilization success of a pollen parent under competition), evidence was detected for the existence of both types of incompatibility in Alnus glutinosa, where eliminating incompatibility occurred as self-incompatibility only. However, since this incompatibility seems to act primarily via pollen elimination, seed production is not likely to be negatively affected in natural populations, even for comparatively large amounts of self-pollination.

  1. High stereoselectivity on low temperature Diels-Alder reactions

    PubMed Central

    da Silva Filho, Luiz Carlos; Lacerda Júnior, Valdemar; Constantino, Mauricio Gomes; da Silva, Gil Valdo José; Invernize, Paulo Roberto

    2005-01-01

    We have found that some of the usually poor dienophiles (2-cycloenones) can undergo Diels-Alder reaction at -78°C with unusually high stereoselectivity in the presence of niobium pentachloride as a Lewis acid catalyst. A remarkable difference in reaction rates for unsubstituted and α- or β-methyl substituted 2-cycloenones was also observed. PMID:16542029

  2. 61. Photocopy of Engine Room Floor Plan, White Alder. The ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    61. Photocopy of Engine Room Floor Plan, White Alder. The Niagara Shipbuilding Corp. Engineering Department, Buffalo, New York. Coast Guard Headquarters Drawing No. 540-WAGL-1604-10, dated February 1943; revised January 1963. Original drawing property of the U.S. Coast Guard. - U.S. Coast Guard Cutter WHITE HEATH, USGS Integrated Support Command Boston, 427 Commercial Street, Boston, Suffolk County, MA

  3. N2-fixing red alder indirectly accelerates ecosystem nitrogen cycling

    USGS Publications Warehouse

    Perakis, Steven S.; Matkins, Joselin J.; Hibbs, David E.

    2012-01-01

    Symbiotic N2-fixing tree species can accelerate ecosystem N dynamics through decomposition via direct pathways by producing readily decomposed leaf litter and increasing N supply to decomposers, as well as via indirect pathways by increasing tissue and detrital N in non-fixing vegetation. To evaluate the relative importance of these pathways, we compared three-year decomposition and N dynamics of N2-fixing red alder leaf litter (2.34 %N) to both low-N (0.68 %N) and high-N (1.21 %N) litter of non-fixing Douglas-fir, and decomposed each litter source in four forests dominated by either red alder or Douglas-fir. We also used experimental N fertilization of decomposition plots to assess elevated N availability as a potential mechanism of N2-fixer effects on litter mass loss and N dynamics. Direct effects of N2-fixing red alder on decomposition occurred primarily as faster N release from red alder than Douglas-fir litter, but direct increases in N supply to decomposers via fertilization did not stimulate decomposition of any litter. Fixed N indirectly influenced detrital dynamics by increasing Douglas-fir tissue and litter N concentrations, which accelerated litter N release without accelerating mass loss. By increasing soil N, tissue N, and the rate of N release from litter of non-fixers, we conclude that N2-fixing vegetation can indirectly foster plant-soil feedbacks that contribute to the persistence of elevated N availability in terrestrial ecosystems.

  4. Nutritional and functional potential of Beta vulgaris cicla and rubra.

    PubMed

    Ninfali, Paolino; Angelino, Donato

    2013-09-01

    Swiss chard (Beta vulgaris cicla, BVc) and beetroot (Beta vulgaris rubra, BVr) are vegetables of the Chenopodiaceae family, widely consumed in traditional western cooking. These vegetables represent a highly renewable and cheap source of nutrients. They can be cultivated in soils with scarce organic material and little light and water. BVc and BVr have a long history of use in folk medicine. Modern pharmacology shows that BVc extracts possess antihypertensive and hypoglycaemic activity as well as excellent antioxidant activity. BVc contains apigenin flavonoids, namely vitexin, vitexin-2-O-rhamnoside and vitexin-2-O-xyloside, which show antiproliferative activity on cancer cell lines. BVr contains secondary metabolites, called betalains, which are used as natural dyes in food industry and show anticancer activity. In this light, BVc and BVr can be considered functional foods. Moreover, the promising results of their phytochemicals in health protection suggest the opportunity to take advantage of the large availability of this crop for purification of chemopreventive molecules to be used in functional foods and nutraceutical products.

  5. Antithrombotic Effect and Mechanism of Radix Paeoniae Rubra

    PubMed Central

    Xie, Pingyao; Cui, Lili; Shan, Yuan

    2017-01-01

    The compounds of Radix Paeoniae Rubra (RPR) were isolated and identified by bioassay-guided method, and antithrombotic effects and mechanism were investigated by the acute blood stasis rat model. The RPR extract was evaluated by APTT, TT, PT, and FIB assays in vitro. Results indicated that RPR extract exhibited the anticoagulant activity. In order to find active compounds, six compounds were isolated and identified, and four compounds, paeoniflorin (Pae), pentagalloylglucose (Pen), albiflorin (Ali), and protocatechuic acid (Pro), exhibited the anticoagulant activity in vitro. Therefore, the antithrombosis effects of RPR extract and four active compounds were investigated in vivo by measuring whole blood viscosity (WBV), plasma viscosity (PV), APTT, PT, TT, and FIB. Meanwhile, the levels of TXB2, 6-Keto-PGF1α, eNOS, and ET-1 were detected. Results suggested that RPR extract and four active compounds had the inhibition effect on thrombus formation, and the antithrombotic effects were associated with the regulation of vascular endothelium active substance, activating blood flow and anticoagulation effect. PMID:28299338

  6. Phylogeography of the ant Myrmica rubra and its inquiline social parasite

    PubMed Central

    Leppänen, Jenni; Vepsäläinen, Kari; Savolainen, Riitta

    2011-01-01

    Widely distributed Palearctic insects are ideal to study phylogeographic patterns owing to their high potential to survive in many Pleistocene refugia and—after the glaciation—to recolonize vast, continuous areas. Nevertheless, such species have received little phylogeographic attention. Here, we investigated the Pleistocene refugia and subsequent postglacial colonization of the common, abundant, and widely distributed ant Myrmica rubra over most of its Palearctic area, using mitochondrial DNA (mtDNA). The western and eastern populations of M. rubra belonged predominantly to separate haplogroups, which formed a broad secondary contact zone in Central Europe. The distribution of genetic diversity and haplogroups implied that M. rubra survived the last glaciation in multiple refugia located over an extensive area from Iberia in the west to Siberia in the east, and colonized its present areas of distribution along several routes. The matrilineal genetic structure of M. rubra was probably formed during the last glaciation and subsequent postglacial expansion. Additionally, because M. rubra has two queen morphs, the obligately socially parasitic microgyne and its macrogyne host, we tested the suggested speciation of the parasite. Locally, the parasite and host usually belonged to the same haplogroup but differed in haplotype frequencies. This indicates that genetic differentiation between the morphs is a universal pattern and thus incipient, sympatric speciation of the parasite from its host is possible. If speciation is taking place, however, it is not yet visible as lineage sorting of the mtDNA between the morphs. PMID:22393482

  7. Performance of an age series of alnus-cardamom plantations in the Sikkim Himalaya: productivity, energetics and efficiencies.

    PubMed

    Sharma, G; Sharma, E; Sharma, R; Singh, K K

    2002-03-01

    Biomass, net primary productivity, energetics and energy efficiencies were estimated in an age series of Alnus-cardamom plantations in the eastern Himalaya. The impact of stand age (5, 10, 15, 20, 30 and 40 years) on the performance of mixtures of N2-fixing (Alnus nepalensis) and non-N2-fixing (large cardamom) plants was studied. Large cardamom (Amomum subulatum) is the most important perennial cash crop in the region and is cultivated predominantly under Alnus trees. Net primary productivity was lowest (7 t ha(-1) per year) in the 40-year-old stand and was more than three times higher (22 t ha(-1) per year) in the 15-year-old stand. Agronomic yield of large cardamom peaked between 15 and 20 years of age. Cardamom productivity doubled from the 5- to the 15-year-old stand, and then decreased with plantation age to reach a minimum in the 40-year-old stand. Performance of cardamom in association of N2-fixing Alnus remained beneficial until 20 years of age. Annual net energy fixation was highest (444 x 10(6) kJ ha(-1) per year) in the 15-year-old stand, being 1.4 times that of the 5-year-old stand and 2.9-times that of the 40-year-old stand. Inverse relationships of production efficiency, energy conversion efficiency and energy utilized in N2-fixation against stand age, and a positive relationship between production efficiency and energy conversion efficiency suggest that the younger plantations are more productive. The Alnus-cardamom plantation system will be sustainable by adopting a rotational cycle of 15 to 20 years.

  8. Application of the aza-Diels-Alder reaction in the synthesis of natural products.

    PubMed

    Cao, Min-Hui; Green, Nicholas J; Xu, Sheng-Zhen

    2017-03-22

    The Diels-Alder reaction that involves a nitrogen atom in the diene or dienophile is termed the aza-Diels-Alder reaction. As well as the powerful all-carbon Diels-Alder reaction, the aza-Diels-Alder reaction has also played an important role in the total synthesis of natural products. Herein, we review various natural products using an aza-Diels-Alder reaction as a key step to their total synthesis, and divide the syntheses into inter- and intra-molecular aza-Diels-Alder reactions and a retro-aza-Diels-Alder reaction. Inter- and intra-molecular aza-Diels-Alder reactions involve an imine as an electron deficient dienophile and an imine as an electron deficient azadiene. The significance of the aza-Diels-Alder reaction for the construction of a six-membered ring containing nitrogen is tremendous, but the development of asymmetric, in particular catalytic enantioselective intramolecular aza-Diels-Alder reaction in the total synthesis of natural products remains highly challenging, and will no doubt see enormous advances in the future.

  9. Bioactivity guided isolation of anticancer constituents from leaves of Alnus sieboldiana (Betulaceae).

    PubMed

    Ludwiczuk, A; Saha, A; Kuzuhara, T; Asakawa, Y

    2011-04-15

    The leaves of the Japanese Alnus sieboldiana have been extracted with n-hexane and then with methanol. A bioactivity-guided approach based on MTT assay for growth inhibition and quantitative real-time PCR for TNF-α inhibitory activity was taken to identify the active compounds in EtOAc soluble fraction of the methanol extract. From this active fraction, seven compounds have been isolated and four compounds (pinosylvin, galangin, quercetin and methyl gallate) have been examined for their dose-response effect on the viability of A549 cells and on TNF-α inhibitory activity. Based on MTT assay, all of the four examined compounds inhibit growth of human lung cancer cells. Among four tested compounds only galangin (3,5,7-trihydroxyflavone) significantly inhibited TNF-α gene expression in A549 cells (IC₅₀ = 94 μM). Taken together, this finding suggests that galangin may be useful in cancer prevention.

  10. The ectomycorrhizas of Lactarius cuspidoaurantiacus and Lactarius herrerae associated with Alnus acuminata in Central Mexico.

    PubMed

    Montoya, Leticia; Bandala, Victor M; Garay-Serrano, Edith

    2015-08-01

    Two pure Alnus acuminata stands established in a montane forest in central Mexico (Puebla State) were monitored between 2010 and 2013 to confirm and recognize the ectomycorrhizal (EcM) systems of A. acuminata with Lactarius cuspidoaurantiacus and Lactarius herrerae, two recently described species. Through comparison of internal transcribed spacer (ITS) of nuclear ribosomal DNA sequences from basidiomes and ectomycorrhizas sampled in the forest stands, we confirmed their ectomycorrhizal association. The phytobiont was corroborated by comparing ITS sequences obtained from EcM root tips and leaves collected in the study site and from other sequences of A. acuminata available in Genbank. Detailed morphological and anatomical descriptions of the ectomycorrhizal systems are presented and complemented with photographs.

  11. KINETICS OF LEAF TEMPERATURE FLUCTUATION AFFECT ISOPRENE EMISSION FROM RED OAK (QUERCUS RUBRA) LEAVES

    EPA Science Inventory

    Because the rate of isoprene (2-methyl-1,3-butadiene) emission from plants is highly temperature-dependent, we investigated the natural fluctuations on leaf temperature and the effects of rapid temperature change on isoprene emission of red oak (Quercus rubra L.) leaves at the to...

  12. Chloroplast DNA variation of Quercus rubra L. in North America and comparison with other Fagaceae.

    PubMed

    Magni, C R; Ducousso, A; Caron, H; Petit, R J; Kremer, A

    2005-02-01

    Quercus rubra is one of the most important timber and ornamental tree species from eastern North America. It is a widespread species growing under variable ecological conditions. Chloroplast DNA variation was studied by PCR-RFLP (polymerase chain reaction-restriction fragment length polymorphism) in 290 individuals from 66 populations sampled throughout the natural range. A total of 12 haplotypes were detected, with one found in 75% of the trees. Population differentiation is relatively low (G(ST) = 0.46), even when similarities between haplotypes are taken into account (N(ST) = 0.50), pointing to a weak phylogeographical structure. Furthermore, no spatial structure of genetic diversity could be detected. The genetic differentiation increased northwards, reflecting the postglacial history of Q. rubra. The unusual aspect of this study was the low level of chloroplast DNA genetic differentiation in Q. rubra compared to that typically observed in other oak species. Palynological evidence indicates that during the last glacial maximum, Q. rubra had one major distribution range with populations located relatively far to the north, resulting in only modest movement northwards when climate improved, whereas European white oaks were largely restricted to the southern European peninsulas and experienced extensive movements during the postglacial period. The contrasted geographical features and levels of tree species richness of both continents might further explain why congeneric species sharing similar life history traits have genetic structures that are so different.

  13. Draft genome sequence of Xylella fastidiosa supsp. multiplex strain Griffin-1 from Quercus rubra in Georgia

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The draft genome sequence of Xylella fastidiosa subsp. multiplex Strain Griffin-1 isolated from a red oak tree (Quercus rubra) in Georgia, U.S.A. is reported. The bacterium has a genome size of 2,387,314 bp with 51.7% G+C content and comprises 2,903 predicted open reading frames (ORFs), and 50 RNA g...

  14. Forecasting model of Corylus, Alnus, and Betula pollen concentration levels using spatiotemporal correlation properties of pollen count.

    PubMed

    Nowosad, Jakub; Stach, Alfred; Kasprzyk, Idalia; Weryszko-Chmielewska, Elżbieta; Piotrowska-Weryszko, Krystyna; Puc, Małgorzata; Grewling, Łukasz; Pędziszewska, Anna; Uruska, Agnieszka; Myszkowska, Dorota; Chłopek, Kazimiera; Majkowska-Wojciechowska, Barbara

    The aim of the study was to create and evaluate models for predicting high levels of daily pollen concentration of Corylus, Alnus, and Betula using a spatiotemporal correlation of pollen count. For each taxon, a high pollen count level was established according to the first allergy symptoms during exposure. The dataset was divided into a training set and a test set, using a stratified random split. For each taxon and city, the model was built using a random forest method. Corylus models performed poorly. However, the study revealed the possibility of predicting with substantial accuracy the occurrence of days with high pollen concentrations of Alnus and Betula using past pollen count data from monitoring sites. These results can be used for building (1) simpler models, which require data only from aerobiological monitoring sites, and (2) combined meteorological and aerobiological models for predicting high levels of pollen concentration.

  15. Niche separation in Varecia variegata rubra and Eulemur fulvus albifrons: II. Intraspecific patterns.

    PubMed

    Vasey, Natalie

    2002-06-01

    Based on a year-long field study in northeastern Madagascar, I summarize annual patterns of niche use (food patch size, diet, forest height, and forest site) in two sympatric lemurs, Varecia variegata rubra and Eulemur fulvus albifrons. Furthermore, I examine intraspecific patterns of niche use according to sex, season, and reproductive stage in these two lemurs that differ in terms of energetic investment in reproduction. Lemurs as a group provide a special opportunity to test hypotheses concerning sex differences in niche use. Due to their body size monomorphism and seasonal, synchronous pattern of breeding, it is possible to directly evaluate whether sex differences in diet reflect high energetic investment in reproduction by females. Results confirm the hypothesis that intraspecific variation in niche use (e.g., sex differences, seasonal differences) would be more pronounced in V. v. rubra than in E. f. albifrons, due in large measure to the former's relatively high energetic investment in reproduction: 1a) Dietary sex differences in V. v. rubra are most pronounced during costly reproductive stages and involve acquisition of low-fiber, high-protein plant foods. Females of both species consume more seasonally available low-fiber protein (young leaves, flowers) relative to conspecific males during the hot dry season, but only in V. v. rubra females is this pattern also evident during gestation and lactation. 1b) The diets of female V. v. rubra and female E. f. albifrons are more similar to each other than are the diets of conspecific males and females in the case of V. v. rubra. This is not uniformly the case for female E. f. albifrons. This finding confirms a hypothesis put forward in Vasey ([2000] Am J Phys Anthropol 112:411-431) that energetic requirements of reproductive females drive niche separation more than do the energetic requirements of males. 1c) Both species synchronize most or all of lactation with seasonal food abundance and diversity. E. f

  16. Myrionecta Rubra Population Genetic Diversity and Its Cryptophyte Chloroplast Specificity in Recurrent Red Tides in the Columbia River Estuary

    SciTech Connect

    Herfort, Lydie; Peterson, Tawnya D.; McCue, Lee Ann; Crump, Byron C.; Prahl, Fredrick G.; Baptista, Antonio M.; Campbell, Victoria; Warnick, Rachel; Selby, Mikaela; Roegner, G. Curtis; Zuber, Peter A.

    2011-01-04

    For at least a decade, annually recurring blooms of the photosynthetic ciliate, Myrionecta rubra have been observed in the Columbia River estuary in late summer. In an effort to understand the dynamics of these blooms, we investigated the genetic variability of M. rubra and its cryptophyte plastids within three large estuarine blooms formed in consecutive years (2007-2009), and conducted a broader spatial survey along the coasts of Oregon/Washington. Analysis of the ‘18S-28S’ sequences specific for Mesodiniidae uncovered at least 7 variants of M. rubra within the Columbia River coastal margin in spring and summer, but only one of these M. rubra variants was implicated in estuary bloom formation. Using a multigene approach, we show that the bloom-forming variant of M. rubra appears to harbor the same cryptophyte chloroplast in recurring blooms. Analyses of chloroplast 16S rRNA, cryptophyte RuBisCO and Photosystem II D2 genes together suggest that the plastid is derived from Teleaulax amphioxeia. Free-living cells of this species and of other cryptophytes were practically absent from the bloom patches in the estuary main channels based on 18S rDNA sequence analyses. The respectively low and high proportions of T. amphioxeia nuclei and chloroplasts signals found in the M. rubra bloom of the Columbia River estuary in successive years supports the notion of a transient association between T. amphioxeia and the bloom-forming M. rubra variant, with loss of cryptophyte nuclei. The genetic variability of M. rubra uncovered here is relevant to the controversy in the literature regarding the cryptophyte /M. rubra association.

  17. Succession on subalpine placer mine spoil: Effects of revegetation with Alnus viridis, Alaska, U.S.A.

    USGS Publications Warehouse

    Densmore, R.V.

    2005-01-01

    Alnus viridis seedlings were planted on placer mine spoil in an Alaskan subalpine watershed to bypass a seedling establishment bottleneck for A. viridis, and to evaluate the interaction between A. viridis and the dominant riparian woody plants, Salix alaxensis and Populus balsamifera. The study area was divided into 11 replicate blocks, each on a homogeneous recontoured spoil pile. Blocks were divided into two 0.01 ha plots, and treatments without (control) and with 84 planted A. viridis seedlings were randomly assigned to plots. After 10 years, the Alnus treatment had a dense stand of A. viridis 1–2 m tall, while the control had fewer, smaller seedlings. Compared to the control, planted A. viridis had a neutral effect on S. alaxensis and inhibited P. balsamifera at the seedling establishment stage, but facilitated the growth of established plants of both species, with many plants overtopping the A. viridis canopy. Compared to the control, S. alaxensis plants in the Alnus treatment had higher levels of foliar N and δ15N values closer to those of A. viridis, indicating the importance of N fixation by A. viridis. Planting A. viridis accelerated the rate of succession by stimulating growth of woody dominants.

  18. Homopterans and an invasive red ant, Myrmica rubra (L.), in Maine.

    PubMed

    McPhee, Katherine; Garnas, Jeffrey; Drummond, Frank; Groden, Eleanor

    2012-02-01

    Myrmica rubra (L.), is an invasive ant that is spreading across eastern North America. It is presently found in over 40 communities in Maine and areas in Vermont, New Hampshire, Massachusetts, New York, and several provinces in the Canadian Maritimes and Ontario. In addition to disrupting native ant faunas, invasive ants also have been shown to influence homopteran abundance and species composition. We conducted surveys of Homoptera in infested and noninfested sites and conducted manipulative experiments to quantify the effects of M. rubra on homopteran abundance and composition in the summers of 2003, 2006, and 2007 on Mount Desert Island, ME. In 2003, Homoptera family-level richness was higher in infested sites compared with noninfested sites with two out of three sampling methods. Homopteran abundance in infested compared with noninfested sites depended upon the site. The sites with the highest population of M. rubra were associated with significant differences in Homoptera population abundance. In 2006 and 2007, two out of three host plants sampled had significantly higher abundances of the aphids, Aphis spiraephila Patch and Prociphilus tessellatus Fitch. An ant exclusion field experiment on the native plant, meadowsweet (Spiraea alba Du Roi), resulted in higher abundances of A. spiraephila with M. rubra tending compared with native ant tending. A predator exclusion field experiment was conducted on meadowsweet using adult ladybeetles, Hippodamia convergens Guérin-Méneville, larval green lacewings, Chyrsoperla carnea Stephens, and no predators. Predator impacts on aphid populations were reduced in the presence of M. rubra with C. carnea and moderately reduced with H. convergens.

  19. Enhancement of heavy metal phytoremediation by Alnus firma with endophytic Bacillus thuringiensis GDB-1.

    PubMed

    Babu, A Giridhar; Kim, Jong-Dae; Oh, Byung-Taek

    2013-04-15

    Phytoremediation shows potential for remediating mine tailing sites contaminated with heavy metals. Our aim was to isolate, characterize, and assess the potential of endophytic bacteria to enhance growth and metal accumulation by the hyperaccumulator Alnus firma. A bacterial strain isolated from roots of Pinus sylvestris had the capacity to remove heavy metals from mine tailing and was identified as Bacillus thuringiensis GDB-1 based on 16S ribosomal DNA sequencing. GDB-1 exhibited plant growth-promoting traits, including 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase activity, indole acetic acid (IAA) and siderophore production, and P solubilization. The efficiency of GDB-1 to remove heavy metals was influenced by pH and initial metal concentration. Removal capacity (mg/l) was 77% for Pb (100), 64% for Zn (50), 34% for As (50), 9% for Cd (10), 8% for Cu (10), and 8% for Ni (10) during the active growth cycle in heavy metal-amended, mine tailing extract medium. Inoculating soil with GDB-1 significantly increased biomass, chlorophyll content, nodule number, and heavy metal (As, Cu, Pb, Ni, and Zn) accumulation in A. firma seedlings. Results indicate that inoculating the native plant A. firma with B. thuringiensis GDB-1 improves its efficiency for phytoremediation of soil containing mine tailings contaminated with heavy metals.

  20. Is it true that polymerization of vegetable oil occurs through Diels-Alder reaction?

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Diels-Alder reaction mechanism is known to be one of the major reaction mechanisms to produce dimers and polymers during heating process of vegetable oil. However, our NMR study showed no evidence for Diels-Alder products. Soybean oil oxidized at 180 °C for 24 hrs with 1.45 surface area-to-volume ...

  1. Why a Proximity-Induced Diels–Alder Reaction is So Fast

    PubMed Central

    Krenske, Elizabeth H.; Perry, Emma W.; Jerome, Steven V.; Maimone, Thomas J.; Baran, Phil S.; Houk, K. N.

    2012-01-01

    Unlike normal Diels–Alder reactions of acyclic alkadienes with alkenes, the vinylbicyclo[2.2.2]octene employed in the Baran total synthesis of vinigrol undergoes quantitative Diels–Alder reaction with a tethered alkene at room temperature. Density functional theory calculations reveal that this unprecedented reactivity originates from a combination of preorganization, diene strain, and tether stabilization. PMID:22630569

  2. A facile avenue to conductive polymer brushes via cyclopentadiene-maleimide Diels-Alder ligation.

    PubMed

    Yameen, Basit; Rodriguez-Emmenegger, Cesar; Preuss, Corinna M; Pop-Georgievski, Ognen; Verveniotis, Elisseos; Trouillet, Vanessa; Rezek, Bohuslav; Barner-Kowollik, Christopher

    2013-10-07

    Cyclopentadienyl end-capped poly(3-hexylthiophene) was employed to fabricate conductive surface tethered polymer brushes via a facile route based on cyclopentadiene-maleimide Diels-Alder ligation. The efficient nature of the Diels-Alder ligation was further combined with a biomimetic polydopamine-assisted functionalization of surfaces, making it an access route of choice for P3HT surface immobilization.

  3. Phylogeny of Morella rubra and Its Relatives (Myricaceae) and Genetic Resources of Chinese Bayberry Using RAD Sequencing

    PubMed Central

    Liu, Luxian; Jin, Xinjie; Chen, Nan; Li, Xian; Li, Pan; Fu, Chengxin

    2015-01-01

    Phylogenetic relationships among Chinese species of Morella (Myricaceae) are unresolved. Here, we use restriction site-associated DNA sequencing (RAD-seq) to identify candidate loci that will help in determining phylogenetic relationships among Morella rubra, M. adenophora, M. nana and M. esculenta. Three methods for inferring phylogeny, maximum parsimony (MP), maximum likelihood (ML) and Bayesian concordance, were applied to data sets including as many as 4253 RAD loci with 8360 parsimony informative variable sites. All three methods significantly favored the topology of (((M. rubra, M. adenophora), M. nana), M. esculenta). Two species from North America (M. cerifera and M. pensylvanica) were placed as sister to the four Chinese species. According to BEAST analysis, we deduced speciation of M. rubra to be at about the Miocene-Pliocene boundary (5.28 Ma). Intraspecific divergence in M. rubra occurred in the late Pliocene (3.39 Ma). From pooled data, we assembled 29378, 21902 and 23552 de novo contigs with an average length of 229, 234 and 234 bp for M. rubra, M. nana and M. esculenta respectively. The contigs were used to investigate functional classification of RAD tags in a BLASTX search. Additionally, we identified 3808 unlinked SNP sites across the four populations of M. rubra and discovered genes associated with fruit ripening and senescence, fruit quality and disease/defense metabolism based on KEGG database. PMID:26431030

  4. Wood anatomical analysis of Alnus incana and Betula pendula injured by a debris-flow event.

    PubMed

    Arbellay, Estelle; Stoffel, Markus; Bollschweiler, Michelle

    2010-10-01

    Vessel chronologies in ring-porous species have been successfully employed in the past to extract the climate signal from tree rings. Environmental signals recorded in vessels of ring-porous species have also been used in previous studies to reconstruct discrete events of drought, flooding and insect defoliation. However, very little is known about the ability of diffuse-porous species to record environmental signals in their xylem cells. Moreover, time series of wood anatomical features have only rarely been used to reconstruct former geomorphic events. This study was therefore undertaken to characterize the wood anatomical response of diffuse-porous Alnus incana (L.) Moench and Betula pendula Roth to debris-flow-induced wounding. Tree microscopic response to wounding was assessed through the analysis of wood anatomical differences between injured rings formed in the debris-flow event year and uninjured rings formed in the previous year. The two ring types were examined close and opposite to the injury in order to determine whether wound effects on xylem cells decrease with increasing tangential distance from the injury. Image analysis was used to measure vessel parameters as well as fiber and parenchyma cell (FPC) parameters. The results of this study indicate that injured rings are characterized by smaller vessels as compared with uninjured rings. By contrast, FPC parameters were not found to significantly differ between injured and uninjured rings. Vessel and FPC parameters mainly remained constant with increasing tangential distance from the injury, except for a higher proportion of vessel lumen area opposite to the injury within A. incana. This study highlights the existence of anatomical tree-ring signatures-in the form of smaller vessels-related to past debris-flow activity and addresses a new methodological approach to date injuries inflicted on trees by geomorphic processes.

  5. Niche separation in Varecia variegata rubra and Eulemur fulvus albifrons: I. Interspecific patterns.

    PubMed

    Vasey, N

    2000-07-01

    Niche separation was documented in a year-long study of Varecia variegata rubra and Eulemur fulvus albifrons on the Masoala Peninsula, Madagascar. Feeding trees were measured, and diet, forest height, and forest site were recorded at 5-min time points on focal animals. For time point data, multivariate and bivariate analysis of frequencies was employed to examine how niche dimensions vary between species according to sex, season, and reproductive stage. V. v. rubra feeds in larger trees than E. f. albifrons. V. v. rubra has a diet consisting mainly of fruit, whereas E. f. lbifrons has a more varied diet. V. v. ubra ranges mainly above 15 m in tree crowns, whereas E. f. albifrons ranges mainly below 15 m in a wide array of forest sites. Both species are largely frugivorous, but they harvest fruit in different-sized trees, in different quantities, and in different forest strata. Niche partitioning varies in tandem with seasonal shifts in climate and food availability and with reproductive stages. Seasonal shifts in forest site and forest height use are largely attributed to species-specific tactics for behavioral thermoregulation and predator avoidance. The diet of E. f. albifrons is diverse whether examined by season or reproductive stage. However, females of both species diversify their diets with more low-fiber protein than males during gestation, lactation, and the hot seasons. This pattern is most pronounced for V. v. rubra females and may be directly attributed to high energetic investment in reproduction. These results suggest that niche partitioning may be driven more by the energetic requirements of reproductive females than males.

  6. The potential of Festuca rubra and Calamagrostis epigejos for the revegetation of fly ash deposits.

    PubMed

    Mitrović, Miroslava; Pavlović, Pavle; Lakusić, Dmitar; Djurdjević, Lola; Stevanović, Branka; Kostić, Olga; Gajić, Gordana

    2008-12-15

    Two grass species, Festuca rubra (sown) and Calamagrostis epigejos (naturally recolonised), were studied at two fly ash deposit lagoons, weathered 5 (L1) and 13 years (L2). Both species were assessed in terms of their invasive ability, photosynthetic efficiency, trace elements accumulation, and damage symptoms, while the characteristics of the habitat were assessed in terms of trace element content, and the pH and EC of the ash. In the ash weathered for 5 and 13 years, B and Mn concentrations fell within the normal range for soils, while there was an As, Mo and Cu excess, and Se and Zn deficit. There was no difference in the photosynthetic efficiency (ns) of the C. epigejos populations at the different-aged ash lagoons, but differences were found between the populations of F. rubra (P<0.001). F. rubra displayed damage symptoms, in the form of leaf tip chlorosis and necrosis, and wilting seedlings--a result of B accumulation in toxic concentrations and a Cu and Mn deficit. After 13 years the sown F. rubra remained over 9.5% of the ash lagoon's area (L2), while over the same period the naturally recolonised C. epigejos had overgrown 87.5% of the area. The greater colonisation and survival potential of C. epigejos is a result of multiple tolerance to the conditions at ash deposits and of the competitive ability of this species to dominate the colonised habitat. Therefore, characteristics of naturally colonised species can be used for modelling future actions of biological restoration of fly ash deposits aimed at binding the ash with minimal investment (the short-term aim), and for providing conditions for revegetation, and shortening the successive phases in the revegetation of ash deposits after the closure of thermal plants (the long-term aim).

  7. The intriguing complexity of parthenogenesis inheritance in Pilosella rubra (Asteraceae, Lactuceae).

    PubMed

    Rosenbaumová, Radka; Krahulcová, Anna; Krahulec, František

    2012-09-01

    Neither the genetic basis nor the inheritance of apomixis is fully understood in plants. The present study is focused on the inheritance of parthenogenesis, one of the basic elements of apomixis, in Pilosella (Asteraceae). A complex pattern of inheritance was recorded in the segregating F(1) progeny recovered from reciprocal crosses between the facultatively apomictic hexaploid P. rubra and the sexual tetraploid P. officinarum. Although both female and male reduced gametes of P. rubra transmitted parthenogenesis at the same rate in the reciprocal crosses, the resulting segregating F(1) progeny inherited parthenogenesis at different rates. The actual transmission rates of parthenogenesis were significantly correlated with the mode of origin of the respective F(1) progeny class. The inheritance of parthenogenesis was significantly reduced in F(1) n + n hybrid progeny from the cross where parthenogenesis was transmitted by female gametes. In F(1) n + 0 polyhaploid progeny from the same cross, however, the transmission rate of parthenogenesis was high; all fertile polyhaploids were parthenogenetic. It appeared that reduced female gametes transmitting parthenogenesis preferentially developed parthenogenetically and only rarely were fertilized in P. rubra. The fact that the determinant for parthenogenesis acts gametophytically in Pilosella and the precocious embryogenesis in parthenogenesis-transmitting megagametophytes was suggested as the most probable explanations for this observation. Furthermore, we observed the different expression of complete apomixis in the non-segregating F(1) 2n + n hybrids as compared to their apomictic maternal parent P. rubra. We suggest that this difference is a result of unspecified interactions between the parental genomes.

  8. Heavy metal stress in alders: Tolerance and vulnerability of the actinorhizal symbiosis.

    PubMed

    Bélanger, Pier-Anne; Bellenger, Jean-Philippe; Roy, Sébastien

    2015-11-01

    Alders have already demonstrated their potential for the revegetation of both mining and industrial sites. These actinorhizal trees and shrubs and the actinobacteria Frankia associate in a nitrogen-fixing symbiosis which could however be negatively affected by the presence of heavy metals, and accumulate them. In our hydroponic assay with black alders, quantification of the roots and shoots metal concentrations showed that, in the absence of stress, symbiosis increases Mo and Ni root content and simultaneously decreases Mo shoot content. Interestingly, the Mo shoot content also decreases in the presence of Ni, Cu, Pb, Zn and Cd for symbiotic alders. In symbiotic alders, Pb shoot translocation was promoted in presence of Pb. On the other hand, Cd exclusion in symbiotic root tissues was observed with Pb and Cd. In the presence of symbiosis, only Cd and Pb showed translocation into aerial tissues when present in the nutrient solution. Moreover, the translocation of Ni to shoot was prevented by symbiosis in the presence of Cd, Ni and Pb. The hydroponic experiment demonstrated that alders benefit from the symbiosis, producing more biomass (total, root and shoot) than non nodulated alders in control condition, and in the presence of metals (Cu, Ni, Zn, Pb and Cd). Heavy metals did not reduce the nodule numbers (SNN), but the presence of Zn or Cd did reduce nodule allocation. Our study suggests that the Frankia-alder symbiosis is a promising (and a compatible) plant-microorganism association for the revegetation of contaminated sites, with minimal risk of metal dispersion.

  9. Factors affecting suitability of Quercus rubra as hosts for Enaphalodes rufulus (Coleoptera: Cerambycidae).

    PubMed

    Haavik, L J; Fierke, M K; Stephen, F M

    2010-04-01

    Epidemic populations of Enaphalodes rufulus (Haldeman), red oak borer, a native longhorned wood boring beetle, were implicated as a major contributor to a recent widespread oak mortality event in the Ozark National Forest of Arkansas. We assessed potential factors affecting suitability of a primary host Quercus rubra L., northern red oak, which experienced dieback and mortality throughout two successive borer cohorts. We sampled trees with various E. rufulus infestation levels during 2001-2003 when populations were at outbreak levels and 2003-2005 when borer numbers were declining. We measured phloem thickness and calculated a vigor index; the ratio of the past 5-yr basal area increment to sapwood area. We also counted established first year larval feeding galleries and outer-bark adult emergence holes and measured surface area of feeding galleries on a subset of Q. rubra to assess the importance of host susceptibility versus suitability. Phloem thickness did not exhibit any patterns among hosts of varying infestation levels and was therefore not likely an important factor limiting larval success. Less vigorous Q. rubra appeared to be the most suitable hosts, although it is unclear whether reduced vigor was initially caused by stress of E. rufulus infestation or environmental factors. Host suitability seems to be more important than host susceptibility, as numbers of initiated galleries were not consistently different among host infestation classes and between both cohorts, whereas numbers of emerging adults did differ predictably among host infestation classes.

  10. Anti-inflammatory activity of myricetin isolated from Myrica rubra Sieb. et Zucc. leaves.

    PubMed

    Wang, Shu-Jun; Tong, Yan; Lu, Shuang; Yang, Rui; Liao, Xu; Xu, Ying-Feng; Li, Xun

    2010-10-01

    MYRICA RUBRA Sieb. et Zucc. leaves are commonly used in folk medicine to treat inflammatory disorders in China. Present studies on the anti-inflammatory effect of myricetin from MYRICA RUBRA Sieb. et Zucc. leaves was evaluated with various IN VIVO models of both acute and chronic inflammations such as xylene-induced ear edema, acetic acid-induced vascular permeability, carrageenan-induced paw edema, leukocyte migration assay, and cotton pellet granuloma models. Myricetin showed a significant inhibition on ear edema and hind paw edema caused by xylene and carrageenan, respectively. Furthermore, it also inhibited the increase in capillary permeability induced by the production of acetic acid in the human body. Myricetin significantly decreased the serum levels of MDA and, in turn, increased the serum levels of SOD in the carrageenan-induced paw edema model. Concurrently, myricetin also significantly decreased leukocyte count. During chronic inflammation, myricetin inhibited the formation of granuloma tissue. These results, collectively, demonstrate that myricetin possesses a potent anti-inflammatory function on acute and chronic inflammation. Its anti-inflammatory mechanisms are probably associated with the inhibition of antioxidant activity. These results also support the claims of traditional Chinese medicine practitioners about the use of MYRICA RUBRA Sieb. et Zucc. leaves in the treatment of inflammatory diseases.

  11. Late onset pityriasis rubra pilaris type IV treated with low-dose acitretin.

    PubMed

    Mota, Fernando; Carvalho, Sandrina; Sanches, Madalena; Selores, Manuela

    2016-01-01

    Pityriasis rubra pilaris is a chronic inflammatory dermatosis of unknown etiology and great clinical variability. It has been divided into six categories. Types III, IV, and V occur in childhood and are distinguished by their clinical presentation, age of onset, and course. We report a 19-year-old male patient with a 2-week history of pruritic, scaling dermatosis of the hands, feet, elbows, and knees. He had no family history of skin disease. On physical examination, we observed circumscribed, reddish-orange, scaling plaques affecting the elbows and knees and a waxy palmoplantar keratoderma. The skin biopsy showed acanthosis, alternating orthokeratosis, parakeratosis, and follicular plugging suggestive of pityriasis rubra pilaris. The patient started treatment with oral acitretin, 25 mg every other day. The treatment was tolerated well, and after 6 months the lesions had resolved completely. Pityriasis rubra pilaris is a chronic papulosquamous disorder of unknown pathogenesis, characterized by reddish-orange scaly plaques, palmoplantar keratoderma, and keratotic follicular papules. There is still no consensus regarding the treatment, but therapeutic options include systemic retinoids, particularly acitretin in the recommended dose of 0.5 to 0.75 mg/kg/day. In our case, the patient was treated with a low-dose regimen of acitretin, which was effective and well tolerated.

  12. Flavonoid constituents in the leaves of Myrica rubra sieb. et zucc. with anti-inflammatory activity.

    PubMed

    Kim, Han Hyuk; Kim, Dong Hee; Kim, Manh Heun; Oh, Myoeng Hwan; Kim, So Ra; Park, Kwang Jun; Lee, Min Won

    2013-12-01

    The leaves of Myrica rubra sieb. et zucc. have been used in oriental traditional medicine for the treatment of burns, skin diseases, and as an antidiarrheal in China, Japan, and Korea. Activity guided isolation of the leaves of M. rubra has led to the isolation of five flavonoid: myricetin (1), myricitrin (2), myricetin 3-O-(2″-O-galloyl)-α-L-rhamnopyranoside (3), myricetin 3-O-(2″-O-galloyl)-β-D-galactopyranoside (4), and quercetin 3-O-(2″-O-galloyl)-β-D-galactopyranoside (5). All isolates were evaluated for their antioxidant potency against the superoxide anion (O2 (-)), and compounds 3-5 showed potent scavenging activities with 50 % inhibition concentration (IC50) values compared to the positive control, allopurinol. Compounds 1-5 were evaluated as inhibitors of various macrophage functions involved in the inflammatory process. These five compounds significantly and dose dependently inhibited lipopolysaccharide (LPS)-stimulated nitric oxide (NO), pro-inflammatory cytokines, and the protein levels of inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) in LPS-stimulated RAW 264.7 macrophages. Our results suggest that galloyl flavonol glycosides (3-5) isolated from M. rubra might be beneficial for the treatment of inflammation-related diseases.

  13. [Alder forests of Numidia (N.E. Algeria): floristic biodiversity, vulnerability and conservation].

    PubMed

    Belouahem-Abed, Djamila; Belouahem, Foudil; Benslama, Mohamed; de Bélair, Gérard; Muller, Serge D

    2011-01-01

    The phytoecological study of the alder forests of north-east Algeria shows that these habitats with boreal affinities harbour very high species richness (> 400 species) and complex structures, which suggest their ancient origin. They correspond phytosociologically to two syntaxa, the Campanulo alatae-Alnenion glutinosae (riparian alder forests) and the Rusco hypophylli-Alnetum glutinosae (peat-forming alder carrs), respectively. Their degraded state and their regressive dynamics, observed during the 14 years of the study, reveal their precarious situation and their rapid ongoing decline under the influence of human-induced uncontroled disturbances (cutting, burning, draining, dumping…). With regard to their ecological, historical and patrimonial importance, the alder forests of Algerian Numidia should be urgently protected, with the aim of assuring the perennity of their exceptional floristic corteges.

  14. Envisioning an enzymatic Diels-Alder reaction by in situ acid-base catalyzed diene generation.

    PubMed

    Linder, Mats; Johansson, Adam Johannes; Manta, Bianca; Olsson, Philip; Brinck, Tore

    2012-06-07

    We present and evaluate a new and potentially efficient route for enzyme-mediated Diels-Alder reactions, utilizing general acid-base catalysis. The viability of employing the active site of ketosteroid isomerase is demonstrated.

  15. Rheological and chemical analysis of reverse gelation in a covalently crosslinked Diels-Alder polymer network

    PubMed Central

    Adzima, Brian J.; Aguirre, H. Alan; Kloxin, Christopher J.; Scott, Timothy F.; Bowman, Christopher N.

    2009-01-01

    A network polymer, incorporating dynamic and reversible crosslinks, was synthesized using the Diels-Alder reaction. Fourier transform infrared (FTIR) spectroscopy was used to characterize the reaction rate and thermodynamic equilibrium over a broad temperature range. Equilibrium conversion of the furan and maleimide varied from 74% at 85°C to 24% at 155°C, demonstrating significant depolymerization via the retro-Diels-Alder reaction. The gel point temperature, as determined by rheometry using the Winter-Chambon criterion, was 92°C, corresponding to a gel-point conversion of 71%, consistent with the Flory-Stockmayer equation. The scaling exponents for the complex moduli, viscosity, and plateau modulus, in the vicinity of the gel-point, were determined and compared with experimental and theoretical literature values. Further, the material exhibited a low frequency relaxation owing to dynamic rearrangement of crosslinks by the Diels-Alder and retro-Diels-Alder reactions. PMID:20711364

  16. Drought-Induced Xylem Dysfunction in Petioles, Branches, and Roots of Populus balsamifera L. and Alnus glutinosa (L.) Gaertn.

    PubMed Central

    Hacke, U.; Sauter, J. J.

    1996-01-01

    Variation in vulnerability to xylem cavitation was measured within individual organs of Populus balsamifera L. and Alnus glutinosa (L.) Gaertn. Cavitation was quantified by three different techniques: (a) measuring acoustic emissions, (b) measuring loss of hydraulic conductance while air-dehydrating a branch, and (c) measuring loss of hydraulic conductance as a function of positive air pressure injected into the xylem. All of these techniques gave similar results. In Populus, petioles were more resistant than branches, and branches were more resistant than roots. This corresponded to the pattern of vessel width: maximum vessel diameter in 1- to 2-year-old roots was 140 [mu]m, compared to 65 and 45 [mu]m in rapidly growing 1-year-old shoots and petioles, respectively. Cavitation in Populus petioles started at a threshold water potential of -1.1 MPa. The lowest leaf water potential observed was -0.9 MPa. In Alnus, there was no relationship between vessel diameter and the cavitation response of a plant organ. Although conduits were narrower in petioles than in branches, petioles were more vulnerable to cavitation. Cavitation in petioles was detected when water potential fell below -1.2 MPa. This value equaled midday leaf water potential in late June. As in Populus, roots were the most vulnerable organ. The significance of different cavitation thresholds in individual plant organs is discussed. PMID:12226296

  17. Potential for phytoextraction of copper by Sinapis alba and Festuca rubra cv. Merlin grown hydroponically and in vineyard soils.

    PubMed

    Malagoli, Mario; Rossignolo, Virginia; Salvalaggio, Nico; Schiavon, Michela

    2014-03-01

    The extensive use of copper-bearing fungicides in vineyards is responsible for the accumulation of copper (Cu) in soils. Grass species able to accumulate Cu could be cultivated in the vineyard inter-rows for copper phytoextraction. In this study, the capacity of Festuca rubra cv Merlin and Sinapis alba to tolerate and accumulate copper (Cu) was first investigated in a hydroponic system without the interference of soil chemical-physical properties. After the amendment of Cu (5 or 10 mg Cu l-(1)) to nutrient solution, shoot Cu concentration in F. rubra increased up to 108.63 mg Cu kg(-1) DW, more than three times higher than in S. alba (31.56 mg Cu kg(-1) DW). The relationship between Cu concentration in plants and external Cu was dose-dependent and species specific. Results obtained from the hydroponic experiment were confirmed by growing plants in pots containing soil collected from six Italian vineyards. The content of soil organic matter was crucial to enhance Cu tolerance and accumulation in the shoot tissues of both plant species. Although S. alba produced more biomass than F. rubra in most soils, F. rubra accumulated significantly more Cu (up to threefold to fourfold) in the shoots. Given these results, we recommended that F. rubra cv Merlin could be cultivated in the vineyard rows to reduce excess Cu in vineyard soils.

  18. Essential Oil from Myrica rubra Leaves Potentiated Antiproliferative and Prooxidative Effect of Doxorubicin and its Accumulation in Intestinal Cancer Cells.

    PubMed

    Ambrož, Martin; Hanušová, Veronika; Skarka, Adam; Boušová, Iva; Králová, Věra; Langhasová, Lenka; Skálová, Lenka

    2016-01-01

    Essential oil from the leaves of Myrica rubra, a subtropical Asian fruit tree traditionally used in folk medicines, has a significant antiproliferative effect in several intestinal cancer cell lines. Doxorubicin belongs to the most important cytostatics used in cancer therapy. The present study was designed to evaluate the effects of defined essential oil from M. rubra leaves on efficacy, prooxidative effect, and accumulation of doxorubicin in cancer cell lines and in non-cancerous cells. For this purpose, intestinal adenocarcinoma CaCo2 cells were used. Human fibroblasts (periodontal ligament) and a primary culture of rat hepatocytes served as models of non-cancerous cells. The results showed that the sole essential oil from M. rubra has a strong prooxidative effect in cancer cells while it acts as a mild antioxidant in hepatocytes. Combined with doxorubicin, the essential oil enhanced the antiproliferative and prooxidative effects of doxorubicin in cancer cells. At higher concentrations, synergism of doxorubicin and essential oil from M. rubra was proved. In non-cancerous cells, the essential oil did not affect the toxicity of doxorubicin and the doxorubicin-mediated reactive oxygen species formation. The essential oil increased the intracellular concentration of doxorubicin and enhanced selectively the doxorubicin accumulation in nuclei of cancer cells. Taken together, essential oil from M. rubra leaves could be able to improve the doxorubicin efficacy in cancer cells due to an increased reactive oxygen species production, and the doxorubicin accumulation in nuclei of cancer cells.

  19. Mannich-Michael versus formal aza-Diels-Alder approaches to piperidine derivatives.

    PubMed

    Girling, P Ricardo; Kiyoi, Takao; Whiting, Andrew

    2011-05-07

    A review into the aza-Diels-Alder reaction, mainly concentrating on literature examples that form piperidin-4-ones from the reaction of imines and electron rich dienes or enones, either through a Lewis acidic/Brønsted acid approach or through the use of an organocatalyst. This review questions whether the mechanism of the aza-Diels-Alder reaction is step wise as opposed to concerted when using oxygenated dienes.

  20. Looking beyond the endo Rule in a Diels-Alder Discovery Lab

    NASA Astrophysics Data System (ADS)

    Jarret, Ronald M.; New, Jamie; Hurley, Rebecca; Gillooly, Laura

    2001-09-01

    The commonly described reaction of maleic anhydride and cyclopentadiene generates a Diels-Alder product in accord with the endo rule. Replacing the dienophile with maleic acid or fumaric acid (with modified reaction conditions) allows students to discover or verify that the Diels-Alder reaction is stereospecific with respect to the stereochemistry of the alkene. The recording of NMR spectra is a particularly useful means of establishing cis-trans stereochemistry (symmetry) of the products.

  1. Diels–Alder reactions in confined spaces: the influence of catalyst structure and the nature of active sites for the retro-Diels–Alder reaction

    PubMed Central

    Cantín, Ángel

    2016-01-01

    Summary Diels–Alder cycloaddition between cyclopentadiene and p-benzoquinone has been studied in the confined space of a pure silica zeolite Beta and the impact on reaction rate due to the concentration effect within the pore and diffusion limitations are discussed. Introduction of Lewis or Brønsted acid sites on the walls of the zeolite strongly increases the reaction rate. However, contrary to what occurs with mesoporous molecular sieves (MCM-41), Beta zeolite does not catalyse the retro-Diels–Alder reaction, resulting in a highly selective catalyst for the cycloaddition reaction. PMID:27829925

  2. Tree Age Effects on Fine Root Biomass and Morphology over Chronosequences of Fagus sylvatica, Quercus robur and Alnus glutinosa Stands

    PubMed Central

    Jagodzinski, Andrzej M.; Ziółkowski, Jędrzej; Warnkowska, Aleksandra; Prais, Hubert

    2016-01-01

    There are few data on fine root biomass and morphology change in relation to stand age. Based on chronosequences for beech (9–140 years old), oak (11–140 years) and alder (4–76 years old) we aimed to examine how stand age affects fine root biomass and morphology. Soil cores from depths of 0–15 cm and 16–30 cm were used for the study. In contrast to previously published studies that suggested that maximum fine root biomass is reached at the canopy closure stage of stand development, we found almost linear increases of fine root biomass over stand age within the chronosequences. We did not observe any fine root biomass peak in the canopy closure stage. However, we found statistically significant increases of mean fine root biomass for the average individual tree in each chronosequence. Mean fine root biomass (0–30 cm) differed significantly among tree species chronosequences studied and was 4.32 Mg ha-1, 3.71 Mg ha-1 and 1.53 Mg ha-1, for beech, oak and alder stands, respectively. The highest fine root length, surface area, volume and number of fine root tips (0–30 cm soil depth), expressed on a stand area basis, occurred in beech stands, with medium values for oak stands and the lowest for alder stands. In the alder chronosequence all these values increased with stand age, in the beech chronosequence they decreased and in the oak chronosequence they increased until ca. 50 year old stands and then reached steady-state. Our study has proved statistically significant negative relationships between stand age and specific root length (SRL) in 0–30 cm soil depth for beech and oak chronosequences. Mean SRLs for each chronosequence were not significantly different among species for either soil depth studied. The results of this study indicate high fine root plasticity. Although only limited datasets are currently available, these data have provided valuable insight into fine root biomass and morphology of beech, oak and alder stands. PMID:26859755

  3. Tree Age Effects on Fine Root Biomass and Morphology over Chronosequences of Fagus sylvatica, Quercus robur and Alnus glutinosa Stands.

    PubMed

    Jagodzinski, Andrzej M; Ziółkowski, Jędrzej; Warnkowska, Aleksandra; Prais, Hubert

    2016-01-01

    There are few data on fine root biomass and morphology change in relation to stand age. Based on chronosequences for beech (9-140 years old), oak (11-140 years) and alder (4-76 years old) we aimed to examine how stand age affects fine root biomass and morphology. Soil cores from depths of 0-15 cm and 16-30 cm were used for the study. In contrast to previously published studies that suggested that maximum fine root biomass is reached at the canopy closure stage of stand development, we found almost linear increases of fine root biomass over stand age within the chronosequences. We did not observe any fine root biomass peak in the canopy closure stage. However, we found statistically significant increases of mean fine root biomass for the average individual tree in each chronosequence. Mean fine root biomass (0-30 cm) differed significantly among tree species chronosequences studied and was 4.32 Mg ha(-1), 3.71 Mg ha(-1) and 1.53 Mg ha(-1), for beech, oak and alder stands, respectively. The highest fine root length, surface area, volume and number of fine root tips (0-30 cm soil depth), expressed on a stand area basis, occurred in beech stands, with medium values for oak stands and the lowest for alder stands. In the alder chronosequence all these values increased with stand age, in the beech chronosequence they decreased and in the oak chronosequence they increased until ca. 50 year old stands and then reached steady-state. Our study has proved statistically significant negative relationships between stand age and specific root length (SRL) in 0-30 cm soil depth for beech and oak chronosequences. Mean SRLs for each chronosequence were not significantly different among species for either soil depth studied. The results of this study indicate high fine root plasticity. Although only limited datasets are currently available, these data have provided valuable insight into fine root biomass and morphology of beech, oak and alder stands.

  4. Effect of fertiliser application and abandonment on plant species composition of Festuca rubra grassland

    NASA Astrophysics Data System (ADS)

    Pavlů, Vilém; Gaisler, Jan; Pavlů, Lenka; Hejcman, Michal; Ludvíková, Vendula

    2012-11-01

    Little is known about the effects of nitrogen (N), phosphorus (P) and potassium (K) application on soil chemical properties and plant species composition of mountain Festuca rubra grasslands. In this study, we aimed to determine whether fertiliser application affects plant species composition and soil properties during periods of management, and whether residual after-effects of fertiliser application can be detected eight years after its use is abandoned. The experiment with unfertilised control, PK treatment and treatments with low and higher level of NPK application under three (intensive management from 1993 to 1997) and two cut management (moderate management from 1997 to 1999) was established in the Jizera Mts. (Czech Republic) on F. rubra meadow and then the experiment was eight years abandoned. Immediately after the introduction of intensive management, a decrease in species richness and diversification of plant species composition occurred. Plant communities which had diversified in different fertiliser treatments persisted under moderately intensive management. The cover of Alopecurus pratensis increased to >50% while the cover of Agrostis capillaris decreased to <5% in NPK treatments during the period of intensive management. Trifolium repens became the dominant species in the PK treatment. Within eight years, under no management, the differences in plant species composition disappeared, species richness decreased and F. rubra, followed by Hypericum maculatum, became dominant in all treatments. The differences in biomass P concentration and plant available P and K concentrations in the soil were still detectable eight years after the last fertiliser application. As shown in this study, moderate application of NPK and consequent abandonment need not generate irreversible changes in species composition of mountain grassland.

  5. Environmental factors affecting the start of pollen season and concentrations of airborne Alnus pollen in two localities of Galicia (NW Spain).

    PubMed

    Rodriguez-Rajo, Francisco Javier; Dopazo, Angeles; Jato, Victoria

    2004-01-01

    Alnus pollen is an early component of the annual atmospheric aerosol of the north-west regions of Spain, which causes the first occurrence of allergic symptoms. Seasonal and intra-daily variation of Alnus pollination, and the influence that main meteorological parameters exert, was studied in this paper. Monitoring was carried out from 1993-2002, by using two Lanzoni VPPS 2000 volumetric samplers. Once the atmospheric behaviour of this pollen had been identified, the final objective was to elaborate predictive models to determine the onset of the Alnus pollen season and its concentrations during the pollination period in two localities of north-west Spain (Santiago and Ourense). Winter chilling required to overcome the bud-dormancy period was similar in both cities, with around 800 Chilling Hours (C.H.) and 5.5 degrees C threshold temperature. Calculation of heat requirement for bud growth was carried out with maximum temperature, with around 50 Growth Degree Days (G.D.D. degrees C) needed, with 6 degrees C threshold temperature. Data from 2002 were used in order to determine the real validity of the models. This year was not taken into account to establish the aforementioned models. The variation between the predicted start of the pollen season and the observed season was smallest in Ourense. Verifying the proposed models for predicting daily mean concentrations of Alnus pollen during the pollen season shows that the predicted curves fits the observed variations of daily mean concentrations.

  6. Draft Genome sequence of Frankia sp. Strain QA3, a nitrogen-fixing actinobacterium isolated from the root nodule of Alnus nitida

    SciTech Connect

    Sen, Arnab; Beauchemin, Nicholas; Bruce, David; Chain, Patrick S. G.; Chen, Amy; Davenport, Karen W.; Deshpande, Shweta; Detter, J. Chris; Furnholm, Teal; Ghodhbane-Gtari, Faten; Goodwin, Lynne A.; Gtari, Maher; Han, James; Huntemann, Marcel; Ivanova, N; Kyrpides, Nikos C; Land, Miriam L; Markowitz, Victor; Mavromatis, K; Nolan, Matt; Nouioui, Imen; Pagani, Ioanna; Pati, Amrita; Pitluck, Sam; Santos, Catarina; Sur, Saubashya; Szeto, Ernest; Tavares, Fernando; Teshima, Hazuki; Thakur, Subarna; Wall, Luis; Woyke, Tanja; Wishart, Jessie; Tisa, Louis S.

    2013-01-01

    Members of actinomycete genus Frankia form a nitrogen-fixing symbiosis with 8 different families of actinorhizal plants. We report a high-quality draft genome sequence for Frankia sp. stain QA3, a nitrogen-fixing actinobacterium isolated from root nodules of Alnus nitida.

  7. Transcript profiling of the salt-tolerant Festuca rubra ssp. litoralis reveals a regulatory network controlling salt acclimatization.

    PubMed

    Diédhiou, Calliste J; Popova, Olga V; Golldack, Dortje

    2009-05-01

    We report an analysis of salt-stress responses in the monocotyledonous halophyte Festuca rubra ssp. litoralis. Salt-dependent expression of transcripts encoding a PIP2;1 aquaporin, V-ATPase subunit B, and the Na+/H+ antiporter NHX was characterized. Transcription of FrPIP2;1, FrVHA-B, and FrNHX1 was induced in root tissue of F. rubra ssp. litoralis by salt treatment, and during salt-stress F. rubra ssp. litoralis accumulated sodium in leaves and roots. Cell specificity of FrPIP2;1, FrVHA-B, and FrNHX1 transcription was analyzed by in situ PCR in roots of F. rubra ssp. litoralis. Expression of the genes was localized to the root epidermis, cortex cells, endodermis, and the vascular tissue. In plants treated with 500 mM NaCl, transcripts were repressed in the epidermis and the outer cortex cells, whereas endodermis and vasculature showed strong signals. These data demonstrate that transcriptional regulation of the aquaporin PIP2;1, V-ATPase, and the Na+/H+ antiporter NHX is correlated with salt tolerance in F. rubra ssp. litoralis and suggests coordinated control of ion homeostasis and water status at high salinity in plants. Salt-induced transcript accumulation in F. rubra ssp. litoralis was further monitored by cDNA-arrays with expressed sequence tags derived from a cDNA subtraction library. The salt-regulated transcripts included those involved in the control of gene expression and signal transduction elements such as a serine/threonine protein kinase, an SNF1-related protein kinase, and a WRKY-type transcription factor. Other ESTs with salt-dependent regulation included transcripts encoding proteins that function in metabolism, general stress responses, and defense and transport proteins.

  8. Cytotoxic constituents of the bark of Plumeria rubra collected in Indonesia.

    PubMed

    Kardono, L B; Tsauri, S; Padmawinata, K; Pezzuto, J M; Kinghorn, A D

    1990-01-01

    By bioactivity-directed fractionation, six cytotoxic constituents have been characterized from the bark of Plumeria rubra collected in Indonesia. Three iridoids, fulvoplumierin [1], allamcin [2], and allamandin [3], as well as 2,5-dimethoxy-p-benzoquinone [4], were found to be active constituents of the P. rubra petroleum-ether- and CHCl3-soluble extracts. Cytotoxic compounds isolated from the H2O-soluble extract of the bark were the iridoid plumericin [5], and the lignan liriodendrin [6]. Each of these substances was found to demonstrate general cytotoxic activity when evaluated with a panel of cell lines composed of murine lymphocytic leukemia (P-388) and a number of human cancer cell-types (breast, colon, fibrosarcoma, lung, melanoma, KB). Five additional iridoids, 15-demethylplumieride [7], plumieride [8], alpha-allamcidin [9], beta-allamcidin [10], and 13-O-trans-p-coumaroylplumieride [11], were obtained as inactive constituents. Compound 7 was found to be a novel natural product, and its structure was determined by spectroscopic methods and by conversion to plumieride [8]. The configuration of the C-4 stereocenter was unambiguously assigned for compounds 9 and 10, and certain nmr reassignments have been provided for compound 1.

  9. Draft Genome Sequence of Pseudomonas putida Strain GM4FR, an Endophytic Bacterium Isolated from Festuca rubra L.

    PubMed Central

    Hollensteiner, Jacqueline; Granzow, Sandra; Daniel, Rolf; Vidal, Stefan; Wemheuer, Bernd

    2017-01-01

    ABSTRACT Pseudomonas putida GM4FR is an endophytic bacterium isolated from aerial plant tissues of Festuca rubra L. Functional annotation of the draft genome (7.1 Mb) revealed 6,272 predicted protein-encoding genes. The genome provides insights into the biocontrol and plant growth-promoting potential of P. putida GM4FR. PMID:28360162

  10. The major veins of mesomorphic leaves revisited: tests for conductive overload in Acer saccharum (Aceraceae) and Quercus rubra (Fagaceae).

    PubMed

    Sack, Lawren; Cowan, Peter D; Holbrook, N Michele

    2003-01-01

    Many leaves survive the severing of their major veins in apparently excellent health. According to the classical explanation, the leaf minor veins provide "conductive overload," an excess of parallel conductive paths, rendering the major veins hydraulically dispensable. Whether such an excess of conductive paths exists has important implications for vascular design and for leaf response to vascular damage. We subjected leaves of Acer saccharum and Quercus rubra to cutting treatments that disrupted the major vein system and determined leaf survival, stomatal conductance (g), quantum yield of photosystem II (Φ(PSII)), and leaf hydraulic conductance (K(leaf)). For A. saccharum, the cuts led to the death of distal lamina. For Q. rubra, however, the treated leaves typically remained apparently healthy. Despite their appearance, the treated Q. rubra leaves had a strongly reduced K(leaf), relative to control leaves, and g and Φ(PSII) were reduced distal to the cuts, respectively, by 75-97% and 48-76%. Gas exchange proximal to the cuts was unaffected, indicating the independence of lamina regions and their local stomata. Analogous results were obtained with excised Q. rubra leaves. These studies demonstrate an indispensable, vital role of the major veins in conducting water throughout the lamina.

  11. Linking Landscape Characteristics and High Stream Nitrogen in the Oregon Coast Range: Red Alder Complicates Use of Nutrient Criteria

    EPA Science Inventory

    Red alder (a nitrogen-fixing tree) and sea salt inputs can strongly influence stream nitrogen concentrations in western Oregon and Washington. We compiled a database of stream nitrogen and landscape characteristics in the Oregon Coast Range. Basal area of alder, expressed as a ...

  12. Diels-Alder reactions: The effects of catalyst on the addition reaction

    NASA Astrophysics Data System (ADS)

    Yilmaz, Özgür; Kus, Nermin Simsek; Tunç, Tuncay; Sahin, Ertan

    2015-10-01

    The reaction between 2,3-dimethyl-1,3-butadiene and dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate is efficiently achieved with small amounts of catalyst, i.e. phenol, AcOH, nafion, and β-cyclodextrin. Exo-diastereoselective cycloaddition reactions were observed both without catalyst and different catalysts for 48 days. As a result, different products (tricyclicmolecule 5, retro-Diels-Alder product 6, and oxidation product 7) were obtained with different catalysts. In addition, we synthesized Diels-Alders product 8 and tricyclocyclitol 10 via Diels-Alder reaction. The structures of these products were characterized by 1H NMR, 13C NMR, MS and IR spectroscopy.

  13. Activity budgets and activity rhythms in red ruffed lemurs (Varecia rubra) on the Masoala Peninsula, Madagascar: seasonality and reproductive energetics.

    PubMed

    Vasey, Natalie

    2005-05-01

    The activity budgets and daily activity rhythms of Varecia rubra were examined over an annual cycle according to season and reproductive stage. Given the relatively high reproductive costs and patchy food resources of this species, I predicted that V. rubra would 1) travel less and feed more during seasonal resource scarcity in an attempt to maintain energy balance, and 2) show sex differences in activity budgets due to differing reproductive investment. Contrary to the first prediction, V. rubra does not increase feeding time during seasonal food scarcity; rather, females feed for a consistent amount of time in every season, whereas males feed most during the resource-rich, hot dry season. The results are consistent with other predictions: V. rubra travels less in the resource-scarce cold rainy season, and there are some pronounced sex differences, with females feeding more and resting less than males in every season and in every reproductive stage except gestation. However, there are also some provocative similarities between the sexes when activity budgets are examined by reproductive stage. During gestation, female and male activity budgets do not differ and appear geared toward energy accumulation: both sexes feed and rest extensively and travel least during this stage. During lactation, activity budgets are geared toward high energy expenditure: both sexes travel most and in equal measure, and rest least, although it remains the case that females feed more and rest less than males. These similarities between female and male activity budgets appear related to cooperative infant care. The high energetic costs of reproduction in V. rubra females may require that they allot more time to feeding year round, and that their overall activity budget be more directly responsive to seasonal climate change, seasonal food distribution, and reproductive schedules.

  14. Electrostatic catalysis of a Diels-Alder reaction.

    PubMed

    Aragonès, Albert C; Haworth, Naomi L; Darwish, Nadim; Ciampi, Simone; Bloomfield, Nathaniel J; Wallace, Gordon G; Diez-Perez, Ismael; Coote, Michelle L

    2016-03-03

    It is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could affect the outcomes of a range of chemical reactions, regardless of whether a redox system is involved. This possibility arises because many formally covalent species can be stabilized via minor charge-separated resonance contributors. When an applied electric field is aligned in such a way as to electrostatically stabilize one of these minor forms, the degree of resonance increases, resulting in the overall stabilization of the molecule or transition state. This means that it should be possible to manipulate the kinetics and thermodynamics of non-redox processes using an external electric field, as long as the orientation of the approaching reactants with respect to the field stimulus can be controlled. Here, we provide experimental evidence that the formation of carbon-carbon bonds is accelerated by an electric field. We have designed a surface model system to probe the Diels-Alder reaction, and coupled it with a scanning tunnelling microscopy break-junction approach. This technique, performed at the single-molecule level, is perfectly suited to deliver an electric-field stimulus across approaching reactants. We find a fivefold increase in the frequency of formation of single-molecule junctions, resulting from the reaction that occurs when the electric field is present and aligned so as to favour electron flow from the dienophile to the diene. Our results are qualitatively consistent with those predicted by quantum-chemical calculations in a theoretical model of this system, and herald a new approach to chemical catalysis.

  15. Validation of the Alder Hey Triage Pain Score

    PubMed Central

    Stewart, B; Lancaster, G; Lawson, J; Williams, K; Daly, J

    2004-01-01

    Aims: To describe the validation and reliability of a new pain tool (the Alder Hey Triage Pain Score, AHTPS) for children at triage in the accident and emergency (A&E) setting. Methods: A new behavioural observational pain tool was developed because of dissatisfaction with available tools and a lack of confidence in self-assessment scores at triage. The study was conducted in a large paediatric A&E department; 575 children (aged 0–16 years) were included. Inter-rater reliability and various aspects of validity were assessed. In addition this tool was compared to the Wong-Baker self-assessment tool.1 The children were concurrently scored by a research nurse and triage nurses to assess inter-rater reliability. Construct validity was assessed by comparing the research nurse's triage score with the research nurse reassessment score after intervention and/or analgesia. Known group construct validity was assessed by comparing the research nurse's score at triage with the level of pain of the condition as judged by the discharge diagnosis. Predictive validity was assessed by comparing the research nurse's AHTPS with the level of analgesia needed by each patient. The AHTPS was also compared to a self-assessment score. Results: A high level of inter-rater reliability, kappa statistic 0.84 (95% CI 0.80 to 0.88), was shown. Construct validity was well demonstrated; known group construct validity and predictive validity were also demonstrated to a varying degree. Conclusions: Results support the use of this observational pain scoring tool in the triage of children in A&E. PMID:15210492

  16. Symmetry-enthalpy correlations in Diels-Alder reactions.

    PubMed

    Tuvi-Arad, Inbal; Avnir, David

    2012-08-06

    Woodward-Hoffmann (WH) rules provide strict symmetry selection rules: when they are obeyed, a reaction proceeds; when they are not obeyed, there is no reaction. However, the voluminous experimental literature provides ample evidence that strict compliance to symmetry requirements is not an obstacle for a concerted reaction to proceed, and therefore the idea has developed that it is enough to have a certain degree of the required symmetry to have reactivity. Here we provide quantitative evidence of that link, and show that as one deviates from the desired symmetry, the enthalpy of activation increases, that is, we show that concerted reactions slow down the further they are from the ideal symmetry. Specifically, we study the deviation from mirror symmetry (evaluated with the continuous symmetry measure (CSM)) of the [4+2] carbon skeleton of the transition state of a series of twelve Diels-Alder reactions in seven different solvents (and in the gas phase), in which the dienes are butadiene, cyclopentadiene, cyclohexadiene, and cycloheptadiene; the dienophiles are the 1-, 1,1-, and 1,1,2-cyanoethylene derivatives; the solvents were chosen to sample a range of dielectric constants from heptane to ethanol. These components provide twenty-four symmetry-enthalpy DFT-calculated correlation lines (out of which only one case is a relatively mild exception) that show the general trend of increase in enthalpy as symmetry decreases. The various combinations between the dienophiles, cyanoethylenes, and solvents provide all kinds of sources for symmetry deviations; it is therefore remarkable that although the enthalpy of activation is dictated by various parameters, symmetry emerges as a primary parameter. In our analysis we also bisected this overall picture into solvent effects and geometry variation effects to evaluate under which conditions the electronic effects are more dominant than symmetry effects.

  17. [Effects of the decomposition of poplar and alder mixed leaf litters on soil microbial biomass].

    PubMed

    Chen, Qin; Fang, Sheng-Zuo; Tian, Ye

    2012-08-01

    An incubation test was conducted to study the effects of the decomposition of poplar and trabeculate alder leaf litters with different mixed ratios and under different application ways on soil microbial biomass carbon (MBC) and nitrogen (MBN). The mixed ratio of the litters had significant effects on soil MBC and MBN. On the 30th day of incubation, soil MBC and MBN were significantly higher in the treatments with > or = 50% of alder litter than in the treatment with poplar litter only and the control. On the 75th day of incubation, the soil MBC in the treatments with > or = 40% of alder litter and the soil MBN in the treatments with > or = 30% of alder litter were significantly greater than those in the treatment with poplar litter only and the control. After 135 days incubation, soil MBC and MBN were significant higher in the treatments with > or = 20% and > or = 40% of alder litter than in the treatment with poplar litter only and the control, respectively. There was no significant difference in the soil MBC/MBN between the treatments with different mixed ratios of poplar and alder leaf litters and the control. Overall, soil MBC/MBN increased during the early period of incubation and decreased in the later period, suggesting that soil microflora changed during the decomposition of the litters. In the whole incubation period, the application ways of the litters had lesser effects on the soil MBC, MBN, and MBC/MBN, indicating that the addition ways of the litters did not affect soil microflora.

  18. Enantioselective Organocatalytic Diels–Alder Trapping of Photochemically Generated Hydroxy‐o‐Quinodimethanes

    PubMed Central

    Dell'Amico, Luca; Vega‐Peñaloza, Alberto; Cuadros, Sara

    2016-01-01

    Abstract The photoenolization/Diels–Alder strategy offers straightforward access to synthetically valuable benzannulated carbocyclic products. This historical light‐triggered process has never before succumbed to efforts to develop an enantioselective catalytic approach. Herein, we demonstrate how asymmetric organocatalysis provides simple yet effective catalytic tools to intercept photochemically generated hydroxy‐o‐quinodimethanes with high stereoselectivity. We used a chiral organic catalyst, derived from natural cinchona alkaloids, to activate maleimides toward highly stereoselective Diels–Alder reactions. An unconventional mechanism of stereocontrol is operative, wherein the organocatalyst is actively involved in both the photochemical pathway, by leveraging the formation of the reactive photoenol, and the stereoselectivity‐defining event. PMID:26797768

  19. Diels–Alder reactions of myrcene using intensified continuous-flow reactors

    PubMed Central

    Álvarez-Diéguez, Miguel Á; Kohl, Thomas M; Tsanaktsidis, John

    2017-01-01

    This work describes the Diels–Alder reaction of the naturally occurring substituted butadiene, myrcene, with a range of different naturally occurring and synthetic dienophiles. The synthesis of the Diels–Alder adduct from myrcene and acrylic acid, containing surfactant properties, was scaled-up in a plate-type continuous-flow reactor with a volume of 105 mL to a throughput of 2.79 kg of the final product per day. This continuous-flow approach provides a facile alternative scale-up route to conventional batch processing, and it helps to intensify the synthesis protocol by applying higher reaction temperatures and shorter reaction times. PMID:28228853

  20. Seepage study for unnamed tributary to Alder Creek, Stevens County, Washington

    USGS Publications Warehouse

    Carpenter, P.J.; Drost, B.W.

    1979-01-01

    Analysis of seepage measurements in the Alder Creek basin, Stevens County, Wash., shows that approximately 50% of 0.2 cubic foot per second taken from an unnamed tributary and used for the 1978 irrigation season would have reached Alder Creek as surface flow. Differences in discharge and specific conductance are explained by the basin geology, physical characteristics, climate, and water use. Only general conclusions could be made from data collected for five seepage measurements because irrigation activities could not be scheduled to allow the hydrologic system to reach equilibrium. (USGS)

  1. Tandem enyne metathesis-Diels-Alder reaction for construction of natural product frameworks.

    PubMed

    Rosillo, Marta; Domínguez, Gema; Casarrubios, Luis; Amador, Ulises; Pérez-Castells, Javier

    2004-03-19

    Enynes connected through aromatic rings are used as substrates for metathesis reactions. The reactivity of three ruthenium carbene complexes is compared. The resulting 1,3-dienes are suitable precursors of polycyclic structures via a Diels-Alder process. Some domino RCM-Diels-Alder reactions are performed, suggesting a possible beneficial effect of the ruthenium catalyst in the cycloaddition process. Other examples require Lewis acid cocatalyst. When applied to aromatic ynamines or enamines, a new synthesis of vinylindoles is achieved. Monitorization of several metathesis reactions with NMR shows the different behavior for ruthenium catalysts. New carbenic species are detected in some reactions with an important dependence on the solvent used.

  2. Stereoselection in Intramolecular Diels-Alder Reactions of 2-Cyano-1-azadienes: Indolizidine and Quinolizidine Synthesis.

    PubMed

    Tay, Gidget C; Sizemore, Nicholas; Rychnovsky, Scott D

    2016-07-01

    Progress toward understanding the scope and diastereoselectivity of intramolecular Diels-Alder reactions using 2-cyano-1-azadienes is described herein. The resulting cyanoenamine products are underutilized intermediates in organic synthesis. Assembly of the Diels-Alder precursors was achieved using an improved imine condensation/oxidative cyanation protocol. By this method, several highly substituted indolizidine and quinolizidine architectures were constructed. Quantum mechanical DFT calculations at the B3LYP/6-31+G(d) level of theory were performed for these cyclizations and provide insights into the origins of the observed diastereoselectivities.

  3. Dry deposition of sulfate to Quercus rubra and Liriodendron tulipifera foliage

    SciTech Connect

    Vandenberg, J.J.

    1987-01-01

    Estimates were made of the rate of dry deposition to red oak (Quercus rubra) and tulip poplar (Liriodendron tulipifera) foliage. In the laboratory, radioactive ammonium sulfate aerosols were generated in an exposure chamber. These aerosols were dry deposited onto leaves that were sequentially washed to examine the efficacy of washing procedures in removal of surface deposits. Over 90% of dry deposited sulfate was removed after a 30 second wash duration. Laboratory procedures also estimated the magnitude of foliar sulfur that leached into leaf wash solutions. The majority of laboratory leaves demonstrated no leaching of sulfur from the internal pool. However, some leaves showed significant sulfur leaching. It was concluded that leaching of internal sulfur was highly leaf specific. This indicated that each leaf used in field experiments needed to be individually examined for leaching.

  4. Minor secondary metabolic products from the stem bark of Plumeria rubra Linn. displaying antimicrobial activities.

    PubMed

    Kuigoua, Guy Merlin; Kouam, Simeon F; Ngadjui, Bonaventure T; Schulz, Barbara; Green, Ivan R; Choudhary, M Iqbal; Krohn, Karsten

    2010-04-01

    Four new iridoids viz., plumeridoids A, B, and C and epiplumeridoid C were isolated from the stem bark of Plumeria rubra Linn. together with twenty-four known compounds viz., 1-( P-hydroxyphenyl)propan-1-one, isoplumericin, plumericin, dihydroplumericin, allamcin, fulvoplumerin, allamandin, plumieride, P- E-coumaric acid, 2,6-dimethoxy- P-benzoquinone, scopoletin, cycloart-25-en-3 beta,24-diol, 2,4,6-trimethoxyaniline, ajunolic acid, ursolic acid, oleanolic acid, beta-amyrin acetate, betulinic acid, lupeol and its acetate, 2,3-dihydroxypropyl octacosanoate, glucoside of beta-sitosterol, and a mixture of common sterols (stigmasterol and beta-sitosterol). Their structures were determined by means of spectroscopic data including HREIMS, 1H NMR, 13C NMR, 2D NMR (HMQC, HMBC, NOESY) and by comparison with published data. All but one of thirteen tested compounds exhibited antifungal, antialgal, and/or antibacterial activities.

  5. Highly Enantioselective Production of (R)-Halohydrins with Whole Cells of Rhodotorula rubra KCh 82 Culture

    PubMed Central

    Janeczko, Tomasz; Dymarska, Monika; Kostrzewa-Susłow, Edyta

    2014-01-01

    Biotransformation of ten α-haloacetophenones in the growing culture of the strain Rhodotorula rubra KCh 82 has been carried out. Nine of the substrates underwent an effective enantioselective reduction to the respective (R)-alcohols according to Prelog’s rule, with the exception of 2-chloro-1,2-diphenylethan-1-one that was not transformed by this strain. The expected reduction proceeded without dehalogenation, leading to the respective (R)-halohydrins in high yields. The use of this biocatalyst yielded (R)-2-bromo-1-phenyl-ethan-1-ol (enantiomeric excess (ee) = 97%) and its derivatives: 4'-Bromo- (ee = 99%); 4'-Chloro- (ee > 99%); 4'-Methoxy- (ee = 96%); 3'-Methoxy- (ee = 93%); 2'-Methoxy- (ee = 98%). There were also obtained and characterized 2,4'-dichloro-, 2,2',4'-trichloro- and 2-chloro-4'-fluoro-phenyetan-1-ol with >99% of enantiomeric excesses. PMID:25486054

  6. Geographic Variation in Festuca rubra L. Ploidy Levels and Systemic Fungal Endophyte Frequencies.

    PubMed

    Dirihan, Serdar; Helander, Marjo; Väre, Henry; Gundel, Pedro E; Garibaldi, Lucas A; Irisarri, J Gonzalo N; Saloniemi, Irma; Saikkonen, Kari

    2016-01-01

    Polyploidy and symbiotic Epichloë fungal endophytes are common and heritable characteristics that can facilitate environmental range expansion in grasses. Here we examined geographic patterns of polyploidy and the frequency of fungal endophyte colonized plants in 29 Festuca rubra L. populations from eight geographic sites across latitudes from Spain to northernmost Finland and Greenland. Ploidy seemed to be positively and negatively correlated with latitude and productivity, respectively. However, the correlations were nonlinear; 84% of the plants were hexaploids (2n = 6x = 42), and the positive correlation between ploidy level and latitude is the result of only four populations skewing the data. In the southernmost end of the gradient 86% of the plants were tetraploids (2n = 4x = 28), whereas in the northernmost end of the gradient one population had only octoploid plants (2n = 8x = 56). Endophytes were detected in 22 out of the 29 populations. Endophyte frequencies varied among geographic sites, and populations and habitats within geographic sites irrespective of ploidy, latitude or productivity. The highest overall endophyte frequencies were found in the southernmost end of the gradient, Spain, where 69% of plants harbored endophytes. In northern Finland, endophytes were detected in 30% of grasses but endophyte frequencies varied among populations from 0% to 75%, being higher in meadows compared to riverbanks. The endophytes were detected in 36%, 30% and 27% of the plants in Faroe Islands, Iceland and Switzerland, respectively. Practically all examined plants collected from southern Finland and Greenland were endophyte-free, whereas in other geographic sites endophyte frequencies were highly variable among populations. Common to all populations with high endophyte frequencies is heavy vertebrate grazing. We propose that the detected endophyte frequencies and ploidy levels mirror past distribution history of F. rubra after the last glaciation period, and local

  7. Effect of nitrogen supply and defoliation on loss of organic compounds from roots of Festuca rubra.

    PubMed

    Paterson, E; Sim, A

    2000-08-01

    The aim of this study was to determine the effects of N-supply and defoliation on rhizodeposition from Festuca rubra, in the context of whole-plant C- partitioning and root morphology. Plants were grown for 36 d in axenic sand microcosms continuously percolated with nutrient solutions of either high or low N concentration (2 mM or 0.01 mM NH(4)NO(3), respectively). The effects of partial defoliation at weekly intervals were determined at high and low N. At low N, dry matter accumulation in roots and shoots was reduced significantly (P<0.001), with proportionately increased partitioning to roots, in comparison with the high N treatment. Root morphology was also affected by N-treatment; at low N, lower biomass production was offset by increased specific root length (P<0.001), reducing the magnitude of the significant (P=0.002) increase in total root length at high N. Cumulative release of organic C from roots of F: rubra over the experimental period was not altered significantly by N-treatment. However, as a proportion of net C-assimilation, rhizodeposition was significantly (P<0.001) greater at low N than at high N. Defoliation transiently (3-5 d) increased the release of soluble organic compounds from roots at each N-supply rate, and increased significantly (P<0.001) cumulative rhizodeposition over the experimental period. These effects of N-supply and defoliation on rhizodeposition are of importance in understanding interactions between plant and microbial productivity in grazed grasslands, and in interpretation of concurrent effects on microbially driven nutrient cycling processes in these systems.

  8. Geographic Variation in Festuca rubra L. Ploidy Levels and Systemic Fungal Endophyte Frequencies

    PubMed Central

    Dirihan, Serdar; Helander, Marjo; Väre, Henry; Gundel, Pedro E.; Garibaldi, Lucas A.; Irisarri, J. Gonzalo N.; Saloniemi, Irma; Saikkonen, Kari

    2016-01-01

    Polyploidy and symbiotic Epichloë fungal endophytes are common and heritable characteristics that can facilitate environmental range expansion in grasses. Here we examined geographic patterns of polyploidy and the frequency of fungal endophyte colonized plants in 29 Festuca rubra L. populations from eight geographic sites across latitudes from Spain to northernmost Finland and Greenland. Ploidy seemed to be positively and negatively correlated with latitude and productivity, respectively. However, the correlations were nonlinear; 84% of the plants were hexaploids (2n = 6x = 42), and the positive correlation between ploidy level and latitude is the result of only four populations skewing the data. In the southernmost end of the gradient 86% of the plants were tetraploids (2n = 4x = 28), whereas in the northernmost end of the gradient one population had only octoploid plants (2n = 8x = 56). Endophytes were detected in 22 out of the 29 populations. Endophyte frequencies varied among geographic sites, and populations and habitats within geographic sites irrespective of ploidy, latitude or productivity. The highest overall endophyte frequencies were found in the southernmost end of the gradient, Spain, where 69% of plants harbored endophytes. In northern Finland, endophytes were detected in 30% of grasses but endophyte frequencies varied among populations from 0% to 75%, being higher in meadows compared to riverbanks. The endophytes were detected in 36%, 30% and 27% of the plants in Faroe Islands, Iceland and Switzerland, respectively. Practically all examined plants collected from southern Finland and Greenland were endophyte-free, whereas in other geographic sites endophyte frequencies were highly variable among populations. Common to all populations with high endophyte frequencies is heavy vertebrate grazing. We propose that the detected endophyte frequencies and ploidy levels mirror past distribution history of F. rubra after the last glaciation period, and local

  9. The effect of limited availability of N or water on C allocation to fine roots and annual fine root turnover in Alnus incana and Salix viminalis.

    PubMed

    Rytter, Rose-Marie

    2013-09-01

    The effect of limited nitrogen (N) or water availability on fine root growth and turnover was examined in two deciduous species, Alnus incana L. and Salix viminalis L., grown under three different regimes: (i) supply of N and water in amounts which would not hamper growth, (ii) limited N supply and (iii) limited water supply. Plants were grown outdoors during three seasons in covered and buried lysimeters placed in a stand structure and filled with quartz sand. Computer-controlled irrigation and fertilization were supplied through drip tubes. Production and turnover of fine roots were estimated by combining minirhizotron observations and core sampling, or by sequential core sampling. Annual turnover rates of fine roots <1 mm (5-6 year(-1)) and 1-2 mm (0.9-2.8 year(-1)) were not affected by changes in N or water availability. Fine root production (<1 mm) differed between Alnus and Salix, and between treatments in Salix; i.e., absolute length and biomass production increased in the order: water limited < unlimited < N limited. Few treatment effects were detected for fine roots 1-2 mm. Proportionally more C was allocated to fine roots (≤2 mm) in N or water-limited Salix; 2.7 and 2.3 times the allocation to fine roots in the unlimited regime, respectively. Estimated input to soil organic carbon increased by ca. 20% at N limitation in Salix. However, future studies on fine root decomposition under various environmental conditions are required. Fine root growth responses to N or water limitation were less pronounced in Alnus, thus indicating species differences caused by N-fixing capacity and slower initial growth in Alnus, or higher fine root plasticity in Salix. A similar seasonal growth pattern across species and treatments suggested the influence of outer stimuli, such as temperature and light.

  10. What determines Alnus-associated ectomycorrhizal community diversity and specificity? A comparison of host and habitat effects at a regional scale.

    PubMed

    Roy, Mélanie; Rochet, Juliette; Manzi, Sophie; Jargeat, Patricia; Gryta, Hervé; Moreau, Pierre-Arthur; Gardes, Monique

    2013-06-01

    · Global-scale analyses of ectomycorrhizal (ECM) fungi communities emphasize host plant families as the main drivers of diversity. This study aims to test, on Alnus-ECM communities, which fungi are said to be 'host-specific', to what extent host species, habitat and distance explain their alpha and beta diversity variations, and their specificity. · In France, ECM communities associated with two subgenera and five species of Alnus, were sampled on 165 trees from 39 lowland to subalpine sites. In all, 1178 internal transcribed spacer (ITS) sequences of ECM fungi clustered in 86 molecular operational taxonomic units (MOTUs). · The species richness was low but still variable, and the evenness of communities was lower on organic soils and in Corsica. Similarity between communities was influenced both by host, soil parameters, altitude and longitude, but not by climate and distance. A large majority of 'specific' fungi were shared between host species within a subgenus, and showed habitat preferences within the subgenus distribution range. · Our study confirms that Alnus ECM communities are low in diversity, highly conserved at a regional scale, and partly shared between congeneric host species. A large part of alpha and beta diversity variations remained unexplained, and other processes may shape these communities.

  11. Total synthesis of (±)-epithuriferic acid methyl ester via Diels-Alder reaction.

    PubMed

    Koprowski, Marek; Bałczewski, Piotr; Owsianik, Krzysztof; Różycka-Sokołowska, Ewa; Marciniak, Bernard

    2016-02-07

    In this paper, we have described the first total synthesis of (±)-epithuriferic acid methyl ester from non-natural sources, in four steps (20% overall yield). The key step involves the Diels-Alder reaction of isobenzofuran with methyl 3-(dimethoxyphosphoryl)acrylate which is controlled by "ortho" regio- and endo stereoselectivities due to the COOMe group.

  12. Synthesis and Diels-Alder cycloaddition reaction of norbornadiene and benzonorbornadiene dimers.

    PubMed

    Nişanci, Bilal; Dalkiliç, Erdin; Güney, Murat; Daştan, Arif

    2009-08-11

    Dimeric forms of norbornadiene and benzonorbornadiene were synthesized starting with known monobromide derivatives. The Diels-Alder cycloaddition reaction of dimers with TCNE and PTAD was investigated and new norbornenoid polycyclics were obtained. All compounds were characterized properly using NMR spectroscopy.

  13. Concerning the reactivity of PTAD with isomeric dienes: the mechanism of the Diels-Alder cycloaddition.

    PubMed

    Alberti, Mariza N; Orfanopoulos, Michael

    2009-04-02

    Cyclopropyl substituted dienes are employed as mechanistic probes in the triazolinedione Diels-Alder (DA) reaction. In aprotic and protic solvents, apart from the DA adducts that bear an intact cyclopropyl group, complicated and rearranged products are also obtained. These results provide solid evidence for the involvement of an open intermediate with a lifetime greater than 2 x 10(-12) s.

  14. Oxazole as an electron-deficient diene in the Diels-Alder reaction.

    PubMed

    Suárez-Moreno, Galdina Vanessa; González-Zamora, Eduardo; Méndez, Francisco

    2011-12-16

    The Diels-Alder cycloaddition reaction of oxazole with ethylene is facilitated by addition of an alkyl group or Brønsted or Lewis acids to the oxazole nitrogen atom. The efficacy consists of stabilizing the transition state, lowering the activation barrier and the HOMO(dienophile)-LUMO(diene) gap, and increasing the reaction exothermicity.

  15. Biotransformation of a cage-like diels-alder adduct and derivatives by Mucor ramosissimus samutsevitsch

    PubMed Central

    Ito, Felicia Megumi; Mena, Ana Elisa Maciel; Marques, Maria Rita; de Lima, Dênis Pires; Beatriz, Adilson

    2009-01-01

    The present study aimed to evaluate the ability for biotransformation of the Diels-Alder adduct tricyclo[6.2.1.02,7]undeca-4,9-dien-3,6-dione (1) and two synthetic derivatives by the saprobe fungus Mucor ramosissimus Samutsevitsch. Products from oxidation, isomerization and, regioselective and enantioselective reduction were achieved. PMID:24031400

  16. Enantioselective Synthesis of (+)-Estrone Exploiting a Hydrogen Bond-Promoted Diels−Alder Reaction

    PubMed Central

    2010-01-01

    Starting from Dane’s diene and methylcyclopentenedione, (+)-estrone is synthesized along the Quinkert−Dane route in 24% total yield. The key step is an enantioselective Diels−Alder reaction promoted by an amidinium catalyst as efficiently as by a traditional Ti-TADDOLate Lewis acid. PMID:20302330

  17. Scope of the Inverse Electron Demand Diels-Alder Reactions of 1,2,3-Triazine

    PubMed Central

    Anderson, Erin D.; Boger, Dale L.

    2011-01-01

    An examination of the scope of the inverse electron demand Diels–Alder reactions of the parent unsubstituted 1,2,3-triazine is described including the first report of its unique capabilities for participating in previously unexplored [4 + 2] cycloaddition reactions with heterodienophiles. PMID:21488676

  18. High-pressure Diels-Alder approach to natural kainic acid.

    PubMed

    Pandey, Sushil K; Orellana, Arturo; Greene, Andrew E; Poisson, Jean-François

    2006-11-23

    The first Diels-Alder based synthesis of (-)-kainic acid is described. Danishefsky's diene and a vinylogous malonate derived from 4-hydroxyproline combine under high pressure to afford a key bicyclic intermediate with virtually no loss of enantiopurity. This adduct can be converted into the natural product with complete stereocontrol. [reaction: see text].

  19. A Computational Experiment of the Endo versus Exo Preference in a Diels-Alder Reaction

    ERIC Educational Resources Information Center

    Rowley, Christopher N.; Woo, Tom K.

    2009-01-01

    We have developed and tested a computational laboratory that investigates an endo versus exo Diels-Alder cycloaddition. This laboratory employed density functional theory (DFT) calculations to study the cycloaddition of N-phenylmaleimide to furan. The endo and exo stereoisomers of the product were distinguished by building the two isomers in a…

  20. Synthesis of isoquinuclidines from highly substituted dihydropyridines via the Diels-Alder reaction.

    PubMed

    Martin, Rhia M; Bergman, Robert G; Ellman, Jonathan A

    2013-02-01

    A stereo- and regioselective Diels-Alder reaction for the synthesis of highly substituted isoquinuclidines from dihydropyridines and electron-deficient alkenes has been developed. While reactions with activated dienophiles proceed readily under thermal conditions, the use of Lewis acid additives is necessary to facilitate cycloadditions for less reactive alkenes. This procedure affords the target compounds in high yields and diastereoselectivities.

  1. Alnus peptides modify membrane porosity and induce the release of nitrogen-rich metabolites from nitrogen-fixing Frankia

    PubMed Central

    Carro, Lorena; Pujic, Petar; Alloisio, Nicole; Fournier, Pascale; Boubakri, Hasna; Hay, Anne E; Poly, Franck; François, Philippe; Hocher, Valerie; Mergaert, Peter; Balmand, Severine; Rey, Marjolaine; Heddi, Abdelaziz; Normand, Philippe

    2015-01-01

    Actinorhizal plant growth in pioneer ecosystems depends on the symbiosis with the nitrogen-fixing actinobacterium Frankia cells that are housed in special root organs called nodules. Nitrogen fixation occurs in differentiated Frankia cells known as vesicles. Vesicles lack a pathway for assimilating ammonia beyond the glutamine stage and are supposed to transfer reduced nitrogen to the plant host cells. However, a mechanism for the transfer of nitrogen-fixation products to the plant cells remains elusive. Here, new elements for this metabolic exchange are described. We show that Alnus glutinosa nodules express defensin-like peptides, and one of these, Ag5, was found to target Frankia vesicles. In vitro and in vivo analyses showed that Ag5 induces drastic physiological changes in Frankia, including an increased permeability of vesicle membranes. A significant release of nitrogen-containing metabolites, mainly glutamine and glutamate, was found in N2-fixing cultures treated with Ag5. This work demonstrates that the Ag5 peptide is central for Frankia physiology in nodules and uncovers a novel cellular function for this large and widespread defensin peptide family. PMID:25603394

  2. Preparative isolation and purification of antioxidative diarylheptanoid derivatives from Alnus japonica by high-speed counter-current chromatography.

    PubMed

    Lim, Soon Sung; Lee, Min Young; Ahn, Hong Ryul; Choi, Soon Jung; Lee, Jae-Yong; Jung, Sang Hoon

    2011-12-01

    This study employed the online HPLC-2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS)(+) bioassay to rapidly determine the antioxidant compounds occurring in the crude extract of Alnus japonica. The negative peaks of the ABTS(+) radical scavenging detection system, which indicated the presence of antioxidant activity, were monitored by measuring the decrease in absorbance at 734 nm. The ABTS(+)-based antioxidant activity profile showed that three negative peaks exhibited antioxidant activity. High-speed counter-current chromatography (HSCCC) was used for preparative scale separation of the three active peaks from the extract. The purity of the isolated compounds was analyzed by HPLC and their structures were identified by (1)H- and (13)C-nuclear magnetic resonance spectrometry (NMR), heteronuclear multiple bond correlation (HMBC), and heteronuclear single quantum correlation (HSQC). Two solvent systems composed of n-hexane/ethylacetate/methanol/water (4:6:4:6, v/v) and of ethyl acetate/methanol/water (1:0.1:1, v/v) were performed in high-speed counter-current chromatography. Consequently, a total of 527 mg of hirsutanonol 5-O-β-D-glucopyranoside, 80.04 mg of 3-deoxohirsutenonol 5-O-β-D-glucopyranoside, and 91.0 mg of hirsutenone were obtained with purity of 94.7, 90.5, and 98.6%, respectively.

  3. Changes in sediment volume in Alder Lake, Nisqually River Basin, Washington, 1945-2011

    USGS Publications Warehouse

    Czuba, Jonathan A.; Olsen, Theresa D.; Czuba, Christiana R.; Magirl, Christopher S.; Gish, Casey C.

    2012-01-01

    The Nisqually River drains the southwest slopes of Mount Rainier, a glaciated stratovolcano in the Cascade Range of western Washington. The Nisqually River was impounded behind Alder Dam when the dam was completed in 1945 and formed Alder Lake. This report quantifies the volume of sediment deposited by the Nisqually and Little Nisqually Rivers in their respective deltas in Alder Lake since 1945. Four digital elevation surfaces were generated from historical contour maps from 1945, 1956, and 1985, and a bathymetric survey from 2011. These surfaces were used to compute changes in sediment volume since 1945. Estimates of the volume of sediment deposited in Alder Lake between 1945 and 2011 were focused in three areas: (1) the Nisqually River delta, (2) the main body of Alder Lake, along a 40-meter wide corridor of the pre-dam Nisqually River, and (3) the Little Nisqually River delta. In each of these areas the net deposition over the 66-year period was 42,000,000 ± 4,000,000 cubic meters (m3), 2,000,000 ± 600,000 m3, and 310,000 ± 110,000 m3, respectively. These volumes correspond to annual rates of accumulation of 630,000 ± 60,000 m3/yr, 33,000 ± 9,000 m3/yr, and 4,700 ± 1,600 m3/yr, respectively. The annual sediment yield of the Nisqually (1,100 ± 100 cubic meters per year per square kilometer [(m3/yr)/km2]) and Little Nisqually River basins [70 ± 24 (m3/yr)/km2] provides insight into the yield of two basins with different land cover and geomorphic processes. These estimates suggest that a basin draining a glaciated stratovolcano yields approximately 15 times more sediment than a basin draining forested uplands in the Cascade Range. Given the cumulative net change in sediment volume in the Nisqually River delta in Alder Lake, the total capacity of Alder Lake since 1945 decreased about 3 percent by 1956, 8 percent by 1985, and 15 percent by 2011.

  4. Pityriasis rubra pilaris in the setting of HIV infection: clinical behaviour and association with explosive cystic acne.

    PubMed

    Martin, A G; Weaver, C C; Cockerell, C J; Berger, T G

    1992-06-01

    The development of pityriasis rubra pilaris (PRP) in three patients with human immunodeficiency virus (HIV) infection is described. Two of the patients had onset of severe generalized cystic acne concomitant with their development of PRP. PRP and acne conglobata should be added to the group of cutaneous disorders that can present in a more virulent manner in the setting of HIV infection. The association of cystic acne with PRP and their response to treatment are discussed.

  5. Intercolony aggression within and among local populations of the invasive ant, Myrmica rubra (Hymenoptera: Formicidae), in coastal Maine.

    PubMed

    Garnas, Jeffrey R; Drummond, Francis A; Groden, Eleanor

    2007-02-01

    Myrmica rubra L. was introduced into New England in the early 20th century, and at present, has a patchy distribution in parts of northeastern North America, including records from 31 communities in Maine. M. rubra is highly polygynous, and colonies reproduce vegetatively, forming dense local populations where conditions are favorable. Using mobile nests and baited arenas in a series of field aggression bioassays, we tested patterns of internest tolerance within and among local populations on Mt. Desert Island, ME. We found that foragers originating from fragments of the same colony or from neighboring nests retained a high level of intraspecific tolerance over several months, whereas significant intercolony aggression among workers was present between colonies within the same local patch separated by approximately 10 m. Within populations, aggression score values were found to increase linearly with internest distance within a site. Aggression was highest between colonies from spatially different populations on the island and was higher still when nests were assayed against colonies at an off-island site 70 km away in Castine, ME. These data strongly suggest a multicolonial organization within and among local populations of M. rubra in parts of its introduced range. These findings contradict the loss of intraspecific aggression and unicolonial social structure over large geographic areas that have previously been observed in other invasive ant species, particularly Linepithema humile Mayr.

  6. Basella alba rubra spinach pigment-sensitized TiO2 thin film-based solar cells

    NASA Astrophysics Data System (ADS)

    Gokilamani, N.; Muthukumarasamy, N.; Thambidurai, M.; Ranjitha, A.; Velauthapillai, Dhayalan

    2015-03-01

    Nanocrystalline TiO2 thin films have been prepared by sol-gel dip coating method. The X-ray diffraction results showed that TiO2 thin films annealed at 400, 450 and 500 °C are of anatase phase and the peak corresponding to the (101) plane is present in all the samples. The grain size of TiO2 thin films was found to increase with increasing annealing temperature. The grain size is found to be 20, 25 and 33 nm for the films annealed at 400, 450 and 500 °C. The structure of the TiO2 nanocrystalline thin films have been examined by high-resolution transmission electron microscope, Raman spectroscopy and FTIR spectroscopy. TiO2 thin films were sensitized by natural dyes extracted from basella alba rubra spinach. It was found that the absorption peak of basella alba rubra extract is at about 665 nm. The dye-sensitized TiO2-based solar cell sensitized using basella alba rubra exhibited a J sc of 4.35 mA cm-2, V oc of 0.48 V, FF of 0.35 and efficiency of 0.70 %. Natural dyes as sensitizers for dye-sensitized solar cells are promising because of their environmental friendliness, low-cost production and fully biodegradable.

  7. Alder Expansion as a Coastal Warming Signal - Linking Coastal Alaskan Carbon to Vegetation Change with Climate

    NASA Astrophysics Data System (ADS)

    Peteet, D. M.; Nichols, J. E.; Moy, C. M.; McGeachy, A.

    2014-12-01

    Corser Bog (60.5296364oN, 145.453858oW), 21 km east of Cordova, AK is a sphagnum-dominated peatland 42 m asl. adjacent to Sheridan Glacier and the Copper River Delta. Deglaciation at 11.5 ka began with shallow pond deposition, reflecting regional warmth with the pioneers Alnus crispa subsp. sinuata, Salix, and ferns colonizing the fresh, mineral soils on the landscape. Continued early Holocene warming/melting of glaciers led to the foundation species Alnus dominance and peatland formation, surrounded by shrubs such as Rubus spectabilis, Sambucus racemosa, and wetland species such as Myrica gale and Potentilla palustris. As Sphagnum peat accumulated, the highest rates of carbon accumulation for a few centuries are represented at 50 g/m2/a, similar to short-term very high rates in the early Holocene throughout the circumboreal region but varying within the early Holocene due to development of local wet, bryophytic environments. A shift to sedge peat regionally along the South-Central Alaskan coast 7.6 - 3.7 ka is paralleled by a more evaporative, drier climate with Rhododendron groenlandicum presence, lower carbon accumulation (13 g/m2/a), and minimal macrofossil preservation, which is paralleled regionally in coastal muskegs both to the northwest and southeast and by a hiatus in a nearby lake record. A cooler, moister climate is evident in Corser Bog with the shift to Sphagnum peat at 3.7 ka, regional shifts from sedge to Sphagnum peat throughout the entire coastline from Yakutat to Girdwood, AK and the demonstration of glacial advances in the region. Alnus pollen markedly increases to 60% in the uppermost sample, indicative of a major signal for glacial recession in this region.

  8. Effect of Counterion Structure on Rates and Diastereoselectivities in α,β-Unsaturated Iminium-Ion Diels-Alder Reactions

    PubMed Central

    Marcoux, David; Bindschädler, Pascal; Speed, Alexander W. H.; Chiu, Anna; Pero, Joseph E.; Borg, George A.; Evans, David A.

    2012-01-01

    The use of cyclic α,β-unsaturated iminium-ion dienophiles is documented in two highly diastereoselective Diels-Alder (DA) reactions. The dienophilic counterion was found to have a significant effect on reactivity. PMID:21678927

  9. New domino transposition/intramolecular Diels-Alder reaction in monocyclic allenols: a general strategy for tricyclic compounds.

    PubMed

    Alcaide, Benito; Almendros, Pedro; Aragoncillo, Cristina; Redondo, María C

    2002-07-21

    A novel and direct synthetic strategy to prepare fused tricycles has been developed from monocyclic allenols, masked functionalized dienes, which underwent a domino allenol transposition/intramolecular Diels-Alder reaction.

  10. Growth of fullerene fragments using the Diels-Alder cycloaddition reaction: first step towards a C60 synthesis by dimerization.

    PubMed

    Mojica, Martha; Méndez, Francisco; Alonso, Julio A

    2013-02-13

    Density Functional Theory has been used to model the Diels-Alder reactions of the fullerene fragments triindenetriphenilene and pentacyclopentacorannulene with ethylene and 1,3-butadiene. The purpose is to prove the feasibility of using Diels-Alder cycloaddition reactions to grow fullerene fragments step by step, and to dimerize fullerene fragments, as a way to obtain C₆₀. The dienophile character of the fullerene fragments is dominant, and the reaction of butadiene with pentacyclopentacorannulene is favored.

  11. Anti-tumor effect of Radix Paeoniae Rubra extract on mice bladder tumors using intravesical therapy

    PubMed Central

    Lin, Mei-Yi; Chiang, Su-Yin; Li, Yi-Zhen; Chen, Mei-Fang; Chen, Yueh-Sheng; Wu, Jin-Yi; Liu, Yi-Wen

    2016-01-01

    Radix Paeoniae Rubra (RPR) is the dried root of Paeonia lactiflora Pallas and Paeonia veitchii Lynch, and is a herbal medicine that is widely used in traditional Chinese medicine for the treatment of blood-heat and blood-stasis syndrome, similarly to Cortex Moutan. The present study identified the same three components in RPR and Cortex Moutan extracts. In addition, it has been reported that RPR has an anti-cancer effect. Bladder cancer is the seventh most common type of cancer worldwide. Due to the high recurrence rate, identifying novel drugs for bladder cancer therapy is essential. In the present study, RPR extract was evaluated as a bladder cancer therapy in vitro and in vivo. The present results revealed that RPR extract reduced the cell viability of bladder cancer cells with a half maximal inhibitory concentration of 1–3 mg/ml, and had an extremely low cytotoxic effect on normal urothelial cells. Additionally, RPR decreased certain cell cycle populations, predominantly cells in the G1 phase, and caused a clear sub-G increase. In a mouse orthotopic bladder tumor model, intravesical application of RPR extract decreased the bladder tumor size without altering the blood biochemical parameters of the mice. In summary, the present results demonstrate the anti-proliferative properties of RPR extract on bladder cancer cells, and its anti-bladder tumor effect in vivo. Compared to Cortex Moutan extract, RPR extract may provide a more effective alternative therapeutic strategy for the intravesical therapy of superficial bladder cancer. PMID:27446367

  12. [Effects of simulated acid rain on water physiological characteristics of Myrica rubra seedlings].

    PubMed

    Yaho, Zhao-bin; Jiang, Hong; Yu, Shu-quan; Lu, Mei-juan

    2011-08-01

    Taking the seedlings of typical subtropical economic tree species Myrica rubra in Zhejiang Province as test materials, a pot experiment was conducted to study their water physiological characteristics under effects of simulated acid rain (pH 2.5 and pH 4.0), with water (pH 5.6) as the control. Season, year, and acid rain all had significant effects on the photosynthetic rate (Pn). Among the treatments, the Pn had a greater difference in summer than in spring and autumn, and was higher in treatment acid rain (pH 4.0). Season, year, acid rain, and the interactions of season and year and of the three factors had significant effects on the stomata conductance (Gs), and also, the Gs had a greater difference among the treatments in summer than in spring and autumn. Acid rain had inhibitory effect on Gs. Season, year, acid rain, and the interactions of season and year and of season and acid rain affected the transpiration rate (Tr) significantly. Same as Pn and Gs, the Tr had a greater difference among the treatments in summer than in spring and autumn. Acid rain (pH 2.5) had the strongest inhibitory effect on Tr. Acid rain and the interactions of season and year and of season and acid rain had significant effects on the water use efficiency (WUE), and acid rain (pH 2.5) had definitely positive effect on the WUE.

  13. In vitro Anti-Thrombotic Activity of Extracts from Blacklip Abalone (Haliotis rubra) Processing Waste

    PubMed Central

    Suleria, Hafiz Ansar Rasul; Hines, Barney M.; Addepalli, Rama; Chen, Wei; Masci, Paul; Gobe, Glenda; Osborne, Simone A.

    2016-01-01

    Waste generated from the processing of marine organisms for food represents an underutilized resource that has the potential to provide bioactive molecules with pharmaceutical applications. Some of these molecules have known anti-thrombotic and anti-coagulant activities and are being investigated as alternatives to common anti-thrombotic drugs, like heparin and warfarin that have serious side effects. In the current study, extracts prepared from blacklip abalone (Haliotis rubra) processing waste, using food grade enzymes papain and bromelain, were found to contain sulphated polysaccharide with anti-thrombotic activity. Extracts were found to be enriched with sulphated polysaccharides and assessed for anti-thrombotic activity in vitro through heparin cofactor-II (HCII)-mediated inhibition of thrombin. More than 60% thrombin inhibition was observed in response to 100 μg/mL sulphated polysaccharides. Anti-thrombotic potential was further assessed as anti-coagulant activity in plasma and blood, using prothrombin time (PT), activated partial thromboplastin time (aPTT), and thromboelastography (TEG). All abalone extracts had significant activity compared with saline control. Anion exchange chromatography was used to separate extracts into fractions with enhanced anti-thrombotic activity, improving HCII-mediated thrombin inhibition, PT and aPTT almost 2-fold. Overall this study identifies an alternative source of anti-thrombotic molecules that can be easily processed offering alternatives to current anti-thrombotic agents like heparin. PMID:28042854

  14. New-onset vitiligo during long-term, stable infliximab treatment of pityriasis rubra pilaris.

    PubMed

    Mattox, Adam R; Chappell, Jeaneen A; Hurley, M Yadira

    2013-02-01

    Incidents of new-onset vitiligo attributed to infliximab therapy for rheumatoid arthritis and ulcerative colitis have been reported. Reported cases share a common theme in that symptoms manifested in close proximity to the initiation or significant dose increase of the medication. This case describes the presentation of infliximab-induced vitiligo in a patient using it for long-term treatment of stable pityriasis rubra pilaris. The patient was initiated and titrated to a stable dose of infliximab totaling 27 months' duration. He was able to achieve near-complete resolution of symptoms before developing depigmented patches consistent with vitiligo. Infliximab was discontinued. Tacrolimus 0.1% ointment and narrow-band ultraviolet B light successfully repigmented the patches. The association of discontinuing infliximab and resolution of vitiligo suggests infliximab had a role in this case. Though the mechanism of involvement is undetermined, infliximab may have induced an autoimmune process by paradoxically activating lymphocytes. Alternatively, infliximab antibodies may have led to the process by disrupting the normal balance of cytokines.

  15. Effects of Invasive European Fire Ants (Myrmica rubra) on Herring Gull (Larus argentatus) Reproduction

    PubMed Central

    DeFisher, Luke E.; Bonter, David N.

    2013-01-01

    Various invasive ant species have negatively affected reproductive success in birds by disrupting nest site selection, incubation patterns, food supply, and by direct predation on nestlings. Impacts can be particularly severe when non-native ants colonize seabird nesting islands where thousands of birds may nest in high densities on the ground or in burrows or crevices. Here we report on the first documented effects of Myrmica rubra, the European fire ant, on the reproduction of birds in its non-native range. We documented herring gulls (Larus argentatus) on Appledore Island, Maine, engaging in more erratic incubation behaviors at nests infested by the ants. Newly-hatched chicks in some nests were swarmed by ants, leading to rapid chick death. Due to high overall rates of chick mortality, survival probabilities did not vary between nests with and without ant activity, however chick growth rates were slower at nests with ants than at ant-free nests. Ant infestation likely leads to longer-term fitness consequences because slower growth rates early in life may ultimately lead to lower post-fledging survival probabilities. PMID:23691168

  16. Quercus rubra-associated ectomycorrhizal fungal communities of disturbed urban sites and mature forests.

    PubMed

    Karpati, Amy S; Handel, Steven N; Dighton, John; Horton, Thomas R

    2011-08-01

    The presence and quality of the belowground mycorrhizal fungal community could greatly influence plant community structure and host species response. This study tests whether mycorrhizal fungal communities in areas highly impacted by anthropogenic disturbance and urbanization are less species rich or exhibit lower host root colonization rates when compared to those of less disturbed systems. Using a soil bioassay, we sampled the ectomycorrhizal fungal (EMF) communities associating with Quercus rubra (northern red oak) seedlings in soil collected from seven sites: two mature forest reference sites and five urban sites of varying levels of disturbance. Morphological and polymerase chain reaction-restriction fragment length polymorphism analyses of fungi colonizing root tips revealed that colonization rates and fungal species richness were significantly lower on root systems of seedlings grown in disturbed site soils. Analysis of similarity showed that EMF community composition was not significantly different among several urban site soils but did differ significantly between mature forest sites and all but one urban site. We identified a suite of fungal species that occurred across several urban sites. Lack of a diverse community of belowground mutualists could be a constraint on urban plant community development, especially of late-successional woodlands. Analysis of urban EMF communities can add to our understanding of urban plant community structure and should be addressed during ecological assessment before pragmatic decisions to restore habitats are framed.

  17. Purification of peroxidase from red cabbage (Brassica oleracea var. capitata f. rubra) by affinity chromatography.

    PubMed

    Somtürk, Burcu; Kalın, Ramazan; Özdemir, Nalan

    2014-08-01

    Peroxidase was purified in a single step using 4-amino benzohydrazide affinity chromatography from red cabbage (Brassica oleracea var. capitata f. rubra), and some important biochemical characteristics of the purified enzyme were determined. The enzyme, with a specific activity of 3,550 EU/mg protein, was purified 120.6-fold with a yield of 2.9% from the synthesized affinity matrix. The molecular weight of the enzyme was found to be 69.3 kDa by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). The enzyme exhibited maximum activity at pH 7.0 and 30 °C. For guaiacol substrate, the K m and V max values were found as 0.048 mM and 1.46 EU/mL/min, respectively. Additionally, the IC50 and K i values for 4-amino benzohydrazide were calculated to be 1.047 and 0.702±0.05 mM, respectively, and 4-amino benzohydrazide showed noncompetitive inhibition.

  18. Phosphate-limited continuous culture of Rhodotorula rubra: kinetics of transport, leakage, and growth.

    PubMed Central

    Robertson, B R; Button, D K

    1979-01-01

    The phosphate-limited growth kinetics of Rhodotorula rubra, a small yeast of marine origin, were examined by analysis of 32P distributions in continuous cultures. Isotope relaxation procedures were used to identify unidirectional flows of Pi and organic phosphate among compartments modeled during growth. The concentrations of phosphates in these compartments at various growth rates were used, together with attendant flows, to produce a mathematical model of growth. Both Pi and phosphate-containing metabolic intermediates leaked from cells during growth. Total leakage ranged from 4 to 10% of influx and was comprised mostly of Pi. Transport capacity was at least 10 times that required for growth at saturating Pi concentrations, so that influx was linear with concentration during growth. This led to the realization that the curvature of Monod plots (Kmu = 12 nM mumax = 0.18/h, and the threshold At = 2.5 nM) is due to change in yield with growth rate. Growth rate related to Pi by the affinity, aA (= 0.43 liter/mg of cells.h) of cells for Pi and the growth rate-dependent yield. It was also specified by a series of kinetic constants that specified flow among the various compartments and equilibrium compartment concentrations as they were set by extracellular Pi. The importance of leakage by healthy cells to the organic chemistry of aquatic systems is noted. PMID:37231

  19. Familial pityriasis rubra pilaris is caused by mutations in CARD14.

    PubMed

    Fuchs-Telem, Dana; Sarig, Ofer; van Steensel, Maurice A M; Isakov, Ofer; Israeli, Shirli; Nousbeck, Janna; Richard, Katharina; Winnepenninckx, Veronique; Vernooij, Marigje; Shomron, Noam; Uitto, Jouni; Fleckman, Philip; Richard, Gabriele; Sprecher, Eli

    2012-07-13

    Pityriasis rubra pilaris (PRP) is a papulosquamous disorder phenotypically related to psoriasis. The disease has been occasionally shown to be inherited in an autosomal-dominant fashion. To identify the genetic cause of familial PRP, we ascertained four unrelated families affected by autosomal-dominant PRP. We initially mapped PRP to 17q25.3, a region overlapping with psoriasis susceptibility locus 2 (PSORS2 [MIM 602723]). Using a combination of linkage analysis followed by targeted whole-exome sequencing and candidate-gene screening, we identified three different heterozygous mutations in CARD14, which encodes caspase recruitment domain family, member 14. CARD14 was found to be specifically expressed in the skin. CARD14 is a known activator of nuclear factor kappa B signaling, which has been implicated in inflammatory disorders. Accordingly, CARD14 levels were increased, and p65 was found to be activated in the skin of PRP-affected individuals. The present data demonstrate that autosomal-dominant PRP is allelic to familial psoriasis, which was recently shown to also be caused by mutations in CARD14.

  20. Diversity and Specificity of Frankia Strains in Nodules of Sympatric Myrica gale, Alnus incana, and Shepherdia canadensis Determined by rrs Gene Polymorphism

    PubMed Central

    Huguet, Valerie; Batzli, Janet Mccray; Zimpfer, Jeff F.; Normand, Philippe; Dawson, Jeffrey O.; Fernandez, Maria P.

    2001-01-01

    The identity of Frankia strains from nodules of Myrica gale, Alnus incana subsp. rugosa, and Shepherdia canadensis was determined for a natural stand on a lake shore sand dune in Wisconsin, where the three actinorhizal plant species were growing in close proximity, and from two additional stands with M. gale as the sole actinorhizal component. Unisolated strains were compared by their 16S ribosomal DNA (rDNA) restriction patterns using a direct PCR amplification protocol on nodules. Phylogenetic relationships among nodular Frankia strains were analyzed by comparing complete 16S rDNA sequences of study and reference strains. Where the three actinorhizal species occurred together, each host species was nodulated by a different phylogenetic group of Frankia strains. M. gale strains from all three sites belonged to an Alnus-Casuarina group, closely related to Frankia alni representative strains, and were low in diversity for a host genus considered promiscuous with respect to Frankia microsymbiont genotype. Frankia strains from A. incana nodules were also within the Alnus-Casuarina cluster, distinct from Frankia strains of M. gale nodules at the mixed actinorhizal site but not from Frankia strains from two M. gale nodules at a second site in Wisconsin. Frankia strains from nodules of S. canadensis belonged to a divergent subset of a cluster of Elaeagnaceae-infective strains and exhibited a high degree of diversity. The three closely related local Frankia populations in Myrica nodules could be distinguished from one another using our approach. In addition to geographic separation and host selectivity for Frankia microsymbionts, edaphic factors such as soil moisture and organic matter content, which varied among locales, may account for differences in Frankia populations found in Myrica nodules. PMID:11319089

  1. Polar Diels-Alder reactions using electrophilic nitrobenzothiophenes. A combined experimental and DFT study

    NASA Astrophysics Data System (ADS)

    Della Rosa, Claudia D.; Mancini, Pedro M. E.; Kneeteman, Maria N.; Lopez Baena, Anna F.; Suligoy, Melisa A.; Domingo, Luis R.

    2015-01-01

    The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.

  2. Use of wetlands for production of woody plants for fuels and petrochemical substitutes. [Alders, willows, poplars

    SciTech Connect

    Farnham, R.S.; Read, P.

    1981-03-01

    Work performed on this project in the past year has included the evaluations of natural stands productivity for wetland biomass species; propagation studies with alder, willow and poplar species; nursery establishment for production of cultivars and evaluation of wetland soils suitable for production of woody biomass species. Also a biomass research facility has been established in N. Minnesota suitable for long-term research and demonstration. Propagation research has included both micro and macro propagation techniques with native willows, selected willow clones from Sweden, alder seed selection from Finland and hybrid poplar clones from US Forest Service, Rhinelander, Wisconsin. Approximately 100,000 rooted plants will be available for field research by June 1, 1981.

  3. Origins of Stereoselectivity in Diels-Alder Cycloadditions Catalyzed by Chiral Imidazolidinones

    PubMed Central

    Gordillo, Ruth; Houk, K. N.

    2011-01-01

    B3LYP/6-31G(d) density functional theory has been used to study Diels-Alder reactions of cyclopentadiene with α,β-unsaturated aldehydes and ketones organocatalyzed by MacMillan’s chiral imidazolidinones. Preferred conformations of transition structures and reaction intermediates have been located. The dramatically different reactivities and enantioselectivities exhibited by two similar chiral imidazolidinones are rationalized. PMID:16536527

  4. The unexpected product of Diels-Alder reaction between "indanocyclon" and maleimide

    NASA Astrophysics Data System (ADS)

    Dobrowolski, Michał A.; Roszkowski, Piotr; Struga, Marta; Szulczyk, Daniel

    2017-02-01

    A heterocyclic compound commonly known as "indanocyclon" undergoes an unexpected Diels-Alder addition with maleimide. The resulting product has been isolated and characterized in order to get an information about its structure and possible mechanism of the reaction. Extensive comparison of single crystal properties of 3-(2,8-dioxo-1,3-diphenyl-2,8-dihydrocyclopenta[a]inden-8a(1H)-yl)pyrrolidine-2,5-dione and favorable product of the reaction has been also performed.

  5. Control of femtosecond laser driven retro-Diels-Alder-like reaction of dicyclopentadiene

    NASA Astrophysics Data System (ADS)

    Das, Dipak Kumar; Goswami, Tapas; Goswami, Debabrata

    2010-12-01

    Using femtosecond time resolved degenerate pump-probe mass spectrometry coupled with simple linearly chirped frequency modulated pulse, we elucidate that the dynamics of retro-Diels-Alder reaction of diclopentadiene (DCPD) to cyclopentadiene (CPD) in supersonic molecular beam occurs in ultrafast time scale. Negatively chirped pulse enhances the ion yield of CPD, as compared to positively chirped pulse. This indicates that by changing the frequency (chirp) of the laser pulse we can control the ion yield of a chemical reaction.

  6. Intramolecular Diels–Alder Reactions of Cycloalkenones: Stereoselectivity, Lewis Acid Acceleration, and Halogen Substituent Effects

    PubMed Central

    2015-01-01

    The intramolecular Diels–Alder reactions of cycloalkenones and terminal dienes occur with high endo stereoselectivity, both thermally and under Lewis-acidic conditions. Through computations, we show that steric repulsion and tether conformation govern the selectivity of the reaction, and incorporation of either BF3 or α-halogenation increases the rate of cycloaddition. With a longer tether, isomerization from a terminal diene to the more stable internal diene results in a more facile cycloaddition. PMID:24410341

  7. Diels-Alder reactions as an efficient route to high purity cyclic polymers.

    PubMed

    Glassner, Mathias; Blinco, James P; Barner-Kowollik, Christopher

    2011-05-18

    A simple and efficient route for the synthesis of cyclic polymer systems is presented. Linear furan protected α-maleimide-ω-cyclopentadienyl functionalized precursors (poly(methyl methacrylate) and poly(tert-butyl acrylate)) were synthesized via atom transfer radical polymerization (ATRP) and subsequent substitution of the bromine end-group with cyclopentadiene. Upon heating at high dilution, deprotection of the dieneophile occurs followed by an intramolecular Diels-Alder reaction yielding a high purity cyclic product.

  8. Acid-free aza Diels-Alder reaction of Danishefsky's diene with imines.

    PubMed

    Yuan, Yu; Li, Xin; Ding, Kuiling

    2002-09-19

    [reaction: see text] A highly efficient aza Diels-Alder reaction of Danishefsky's diene with imines was found to occur in methanol in the absence of any acids at room temperature to give corresponding 2-substituted dihydro-4-pyridone derivatives in high yields. This reaction can be also carried out in a three-component one-pot reaction manner. The reaction was found to proceed through a Mannich-type condensation mechanism.

  9. Biomass of Speckled Alder on an Air-Polluted Mountain Site and its Response to Fertilization

    NASA Astrophysics Data System (ADS)

    Kuneš, Ivan; Baláš, Martin; Koňasová, Tereza; Špulák, Ondřej; Balcar, Vratislav; Millerová, Kateřina Bednářová; Kacálek, Dušan; Jakl, Michal; Zahradník, Daniel; Vítámvás, Jan; Š´astná, Jaroslava; Jaklová Dytrtová, Jana

    2014-12-01

    The article summarizes outcomes of a biomass study conducted in a young speckled alder plantation on a cold mountain site. At this location, the previously existing old forest was clear felled because of damage from air pollution, and present-day surface humus is in need of restoration. The intention of this study was to quantify the biomass and nutrients accumulated by alders and their components and assess whether the initial fertilization resulted in increased biomass production and nutrient accumulation in the biomass. Besides the control, two fertilized treatments were installed. In the surface treatment (SUT), the amendment was applied as a base dressing in small circles around trees. In the planting-hole treatment (PHT), the amendment was incorporated into soil inside the planting holes. Five growth seasons after planting and fertilization, six alders from each treatment were harvested including roots. Their biomass was quantified and analyzed for macroelements. The greatest pool of dry mass (DM) was branches in the control and stem wood in the fertilized treatments. The greatest pools of macroelements were leaves and branches. The most pronounced effects of fertilization were recorded in the DM and consequently in the absolute quantities of nutrients. The DM of an average tree in the control, SUT, and PHT was 85, 226, and 231 g, respectively. The absolute contents of nutrients per tree in the fertilized treatments showed the following increases, as compared with the control: (N) 2.5-2.6 times; (P) 1.6-2.4 times; (K) 1.8-2.1 times; and (Mg) 1.8-2.0 times, respectively. Speckled alder responded positively to fertilization.

  10. Red waters of Myrionecta rubra are biogeochemical hotspots for the Columbia River estuary with impacts on primary/secondary productions and nutrient cycles

    SciTech Connect

    Herfort, Lydie; Peterson, Tawnya D.; Prahl, Fredrick G.; McCue, Lee Ann; Needoba, Joe A.; Crump, Byron C.; Roegner, G. Curtis; Campbell, Victoria; Zuber, Peter A.

    2012-02-29

    The localized impact of blooms of the mixotrophic ciliate Myrionecta rubra in the Columbia River estuary during 2007-2010 was evaluated with biogeochemical, light microscopy, physiological and molecular data. M. rubra affected surrounding estuarine nutrient cycles, as indicated by high and low concentrations of organic nutrients and inorganic nitrogen, respectively, associated with red waters. M. rubra blooms also altered the energy transfer pattern in patches of the estuarine water that contain the ciliate by creating areas characterized by high primary production and elevated levels of fresh autochthonous particulate organic matter, therefore shifting the trophic status in emergent red water areas of the estuary from net heterotrophy towards autotrophy. The pelagic estuarine bacterial community structure was unaffected by M. rubra abundance, but red waters of the ciliate do offer a possible link between autotrophic and heterotrophic processes since they were associated with elevated dissolved organic matter and enhanced microbial secondary production. Taken together these findings suggest that M. rubra red waters are biogeochemical hotspots of the Columbia River estuary.

  11. Light-induced hetero-Diels-Alder cycloaddition: a facile and selective photoclick reaction.

    PubMed

    Arumugam, Selvanathan; Popik, Vladimir V

    2011-04-13

    2-Napthoquinone-3-methides (oNQMs) generated by efficient photodehydration (Φ=0.2) of 3-(hydroxymethyl)-2-naphthol undergo facile hetero-Diels-Alder addition (k(D-A)∼ 4×10(4) M(-1) s(-1)) to electron-rich polarized olefins in an aqueous solution. The resulting photostable benzo[g]chromans are produced in high to quantitative yield. The unreacted oNQM is rapidly hydrated (k(H2O) ∼145 s(-1)) to regenerate the starting diol. This competition between hydration and cycloaddition makes oNQMs highly selective, since only vinyl ethers and enamines are reactive enough to form the Diels-Alder adduct in an aqueous solution; no cycloaddition was observed with other types of alkenes. To achieve photolabeling or photoligation of two substrates, one is derivatized with a vinyl ether moiety, while 3-(hydroxymethyl)-2-naphthol is attached to the other via an appropriate linker. The light-induced Diels-Alder "click" strategy permits the formation of either a permanent or hydrolytically labile linkage. Rapid kinetics of this photoclick reaction (k=4×10(4) M(-1) s(-1)) is useful for time-resolved applications. The short lifetime (τ ∼7 ms in H(2)O) of the active form of the photoclick reagent prevents its migration from the site of irradiation, thus, allowing for spatial control of the ligation or labeling.

  12. Flash-flood impacts cause changes in wood anatomy of Alnus glutinosa, Fraxinus angustifolia and Quercus pyrenaica.

    PubMed

    Ballesteros, J A; Stoffel, M; Bollschweiler, M; Bodoque, J M; Díez-Herrero, A

    2010-06-01

    Flash floods may influence the development of trees growing on channel bars and floodplains. In this study, we analyze and quantify anatomical reactions to wounding in diffuse-porous (Alnus glutinosa L.) and ring-porous (Fraxinus angustifolia Vahl. and Quercus pyrenaica Willd.) trees in a Mediterranean environment. A total of 54 cross-sections and wedges were collected from trees that had been injured by past flash floods. From each of the samples, micro-sections were prepared at a tangential distance of 1.5 cm from the injury to determine wounding-related changes in radial width, tangential width and lumen of earlywood vessels, and fibers and parenchyma cells (FPC). In diffuse-porous A. glutinosa, the lumen area of vessels shows a significant (non-parametric test, P-value <0.05) decrease by almost 39% after wounding. For ring-porous F. angustifolia and Q. pyrenaica, significant decreases in vessel lumen area are observed as well by 59 and 42%, respectively. Radial width of vessels was generally more sensitive to the decrease than tangential width, but statistically significant values were only observed in F. angustifolia. Changes in the dimensions of earlywood FPC largely differed between species. While in ring-porous F. angustifolia and Q. pyrenaica the lumen of FPC dropped by 22 and 34% after wounding, we observed an increase in FPC lumen area in diffuse-porous A. glutinosa of approximately 35%. Our data clearly show that A. glutinosa represents a valuable species for flash-flood research in vulnerable Mediterranean environments. For this species, it will be possible in the future to gather information on past flash floods with non-destructive sampling based on increment cores. In ring-porous F. angustifolia and Q. pyrenaica, flash floods leave less drastic, yet still recognizable, signatures of flash-flood activity through significant changes in vessel lumen area. In contrast, the use of changes in FPC dimensions appears less feasible for the determination of

  13. Influence of papermill sludge on growth of Medicago sativa, Festuca rubra and Agropyron trachycaulum in gold mine tailings: a greenhouse study.

    PubMed

    Green, Scott; Renault, Sylvie

    2008-02-01

    A greenhouse study was undertaken to determine the suitability of adding papermill sludge to neutral/alkaline gold mine tailings to improve the establishment of Festuca rubra, Agropyron trachycaulum and Medicago sativa. Festuca rubra root and shoot biomass and A. Trachycaulum shoot biomass were increased with papermill sludge amendment. The addition of papermill sludge and fertilizer drastically increased the shoot and root biomass of M. sativa (20-30 times) while A. trachycaulum and F. rubra showed a more moderate increase in growth. Photosynthetic pigment content of the leaves was higher in papermill sludge treatments than in the treatments without papermill sludge. The organic carbon content, macro-aggregate content and field capacity of the gold mine tailings were increased while the bulk density was decreased by the addition of papermill sludge. This study suggests that addition of papermill sludge and adequate fertilization can alleviate some of the adverse conditions of neutral/alkaline gold mine tailings.

  14. Steep Decline and Cessation in Seed Dispersal by Myrmica rubra Ants

    PubMed Central

    2015-01-01

    Myrmecochorous diaspores bear a nutrient-rich appendage, the elaiosome, attractive to ant workers that retrieve them into the nest, detach the elaiosome and reject the seed intact. While this interaction is beneficial for the plant partner by ensuring its seed dispersal, elaiosome consumption has various effects −positive, negative or none − on ants’ demography and survival, depending on both the ant/plant species involved. In this context, the contribution of ants to seed dispersal strongly varies according to the ant/plant pairs considered. In this paper, we investigate whether the dynamics of myrmecochory also vary on a temporal scale, for a given pair of partners: Myrmica rubra ants and Viola odorata seeds. During their first encounter with seeds, ants collect all the diaspores and eat the majority of elaiosomes. Both the harvesting effort and the elaiosome consumption decline when seeds are offered on the next week and completely cease for the following weeks. This is related to a decrease in the number of foragers reaching the food source, as well as to a reduced probability for an ant contacting a seed to retrieve it. Seed retrieval is not reactivated after seven weeks without any encounter with V. odorata seeds. By contrast, naive ant colonies only fed with fruit flies do not show a decline of prey harvesting of which the speed of retrieval even increases over the successive weeks. Myrmecochory may thus be labile at the scale of a fruiting season due to the ability of ants to steeply tune and cease for several months the harvesting of these seemingly poorly rewarding items and to maintain cessation of seed exploitation. The present study emphasizes the importance of a long-lasting follow up of the myrmecochory process, to assess the stability of this ant-plant partnership and to identify mechanisms of adaptive harvesting in ants. PMID:26414161

  15. Dankookia rubra gen. nov., sp. nov., an alphaproteobacterium isolated from sediment of a shallow stream.

    PubMed

    Kim, Wan-Hoe; Kim, Do-Hak; Kang, Keunsoo; Ahn, Tae-Young

    2016-06-01

    WS-10(T)-a Gram-negative, non-motile, and aerobic bacterial strain-was isolated from the sediment of a shallow stream in Korea. The optimum ranges of temperature and pH for growth were 20-40°C (optimum 28°C) and pH 6.0-8.0 (optimum pH 7.0), respectively. The DNA G+C content of strain WS-10(T) was 72.7 mol%. The major fatty acids (>5%) were summed feature 8 (C18:1 ω7c), summed feature 3 (C16:1 ω7c and/or C16:1 ω6c), C16:0, and C18:1 2-OH. The major polar lipids consisted of phosphatidylcholine, phosphatidylglycerol, phosphatidylethanolamine, and unidentified aminolipids. Q-10 was the predominant respiratory quinone. The highest similarities in the 16S rRNA gene sequence were shown with Paracraurococcus ruber (95.3%), Belnapia soli (95.3%), B. moabensis (95.1%), and B. rosea (95.0%). A phylogenetic analysis based on 16S rRNA gene sequence comparisons showed that strain WS-10T formed a distinct line within a clade containing the genera Paracraurococcus, Craurococcus, and Belnapia in the family Acetobacteraceae. On the basis of polyphasic evidence, strain WS-10(T) represents a novel species of a new genus in the family Acetobacteraceae, for which the name Dankookia rubra gen. nov., sp. nov. is proposed. The type strain of the type species is WS-10(T) (= KACC 18533(T) = JCM 30602(T)).

  16. Steep Decline and Cessation in Seed Dispersal by Myrmica rubra Ants.

    PubMed

    Bologna, Audrey; Detrain, Claire

    2015-01-01

    Myrmecochorous diaspores bear a nutrient-rich appendage, the elaiosome, attractive to ant workers that retrieve them into the nest, detach the elaiosome and reject the seed intact. While this interaction is beneficial for the plant partner by ensuring its seed dispersal, elaiosome consumption has various effects -positive, negative or none - on ants' demography and survival, depending on both the ant/plant species involved. In this context, the contribution of ants to seed dispersal strongly varies according to the ant/plant pairs considered. In this paper, we investigate whether the dynamics of myrmecochory also vary on a temporal scale, for a given pair of partners: Myrmica rubra ants and Viola odorata seeds. During their first encounter with seeds, ants collect all the diaspores and eat the majority of elaiosomes. Both the harvesting effort and the elaiosome consumption decline when seeds are offered on the next week and completely cease for the following weeks. This is related to a decrease in the number of foragers reaching the food source, as well as to a reduced probability for an ant contacting a seed to retrieve it. Seed retrieval is not reactivated after seven weeks without any encounter with V. odorata seeds. By contrast, naive ant colonies only fed with fruit flies do not show a decline of prey harvesting of which the speed of retrieval even increases over the successive weeks. Myrmecochory may thus be labile at the scale of a fruiting season due to the ability of ants to steeply tune and cease for several months the harvesting of these seemingly poorly rewarding items and to maintain cessation of seed exploitation. The present study emphasizes the importance of a long-lasting follow up of the myrmecochory process, to assess the stability of this ant-plant partnership and to identify mechanisms of adaptive harvesting in ants.

  17. Physiological Adjustments of Leaf Respiration to Atmospheric Warming in Betula alleghaniensis and Quercus rubra

    SciTech Connect

    Vollmar, A.; Gunderson, C.

    2006-01-01

    Global air temperatures are predicted to rise 1° to 4.5° Celsius by the year 2100. This climatic change is expected to have a great effect on the succession and migration of temperate deciduous forest species. Most physiologically based models of forest response to climatic change focus on the ecosystems as a whole instead of on individual tree species, assuming that the effects of warming on respiration are generally the same for each species, and that processes can not adjust to a changing climate. Experimental data suggest that physiological adjustments are possible, but there is a lack of data in deciduous species. In order to correctly model the effects of climate change on temperate species, species-specific respiration acclimation (adjustment) to rising temperatures is being determined in this experiment. Two temperate deciduous tree species Betula alleghaniensis (BA) and Quercus rubra (QR) were grown over a span of four years in open-top chambers and subjected to two different temperature treatments; ambient and ambient plus 4° Celsius (E4). Between 0530 hours and 1100 hours, respiration was measured over a range of leaf temperatures on several comparable, fully expanded leaves in each treatment. Circular punches were taken from the leaves and dried at 60°C to determine leaf mass per area (LMA). Respiration rates at a common temperature decreased by 15-18% in both species, and the entire resperation versus temperature curve shifted by at least 4°C, indicating a large degree of physiological acclimation. Foliar mass per area decreased with increasing growth temperature for both species. It can be concluded that there is a relationship between leaf respiration and foliar mass as it relates to respiratory acclimation, and that these two species had similar patterns of adjustment to warming.

  18. Cecembia rubra sp. nov., a thermophilic bacterium isolated from a hot spring sediment.

    PubMed

    Duan, Yan-Yan; Ming, Hong; Dong, Lei; Yin, Yi-Rui; Meng, Xiao-Lin; Zhou, En-Min; Zhang, Jian-Xin; Nie, Guo-Xing; Li, Wen-Jun

    2015-07-01

    A Gram-staining negative, rod-shaped bacterium, designated strain YIM 78110(T), was isolated from a sediment sample collected from Hehua hot spring in Tengchong, Yunnan province, south-west China. The taxonomic status of strain YIM 78110(T) was confirmed by a polyphasic approach. 16S rRNA gene sequence analysis indicated that strain YIM 78110(T) belongs to the genus Cecembia, displaying 96.8% and 94.7% sequence similarity with the two most closely related type strains, Cecembia calidifontis RQ-33(T) and Cecembia lonarensis LW9T, respectively. The low value of DNA-DNA hybridization (52.3 ± 2.3%) between strain YIM 78110(T) and its closest neighbour, Cecembia calidifontis RQ-33(T), indicated that this new isolate represented a different genomic species in the genus Cecembia. The temperature for growth ranged from 30 to 50 °C. The pH for growth ranged from pH 4.0 to 10.0, with NaCl tolerance of 0.5-6.0% (w/v). The predominant menaquinone of strain YIM 78110(T) was MK-7 and the major polar lipid was phosphatidylethanolamine. The major fatty acids were iso-C15:0 and C15:0. The DNA G+C content was 47.1 mol%. On the basis of physiological, biochemical and phylogenetic analyses, it is proposed that strain YIM 78110(T) represents a novel species of the genus Cecembia, for which the name Cecembia rubra sp. nov. is proposed. The type strain is YIM 78110(T) ( = CCTCC AB2013287(T) = DSM 28057(T)).

  19. Reproduction and development in Halocaridina rubra Holthuis, 1963 (Crustacea: Atyidae) clarifies larval ecology in the Hawaiian anchialine ecosystem.

    PubMed

    Havird, Justin C; Vaught, Rebecca C; Weese, David A; Santos, Scott R

    2015-10-01

    Larvae in aquatic habitats often develop in environments different from those they inhabit as adults. Shrimp in the Atyidae exemplify this trend, as larvae of many species require salt or brackish water for development, while adults are freshwater-adapted. An exception within the Atyidae family is the "anchialine clade," which are euryhaline as adults and endemic to habitats with subterranean fresh and marine water influences. Although the Hawaiian anchialine atyid Halocaridina rubra is a strong osmoregulator, its larvae have never been observed in nature. Moreover, larval development in anchialine species is poorly studied. Here, reproductive trends in laboratory colonies over a 5-y period are presented from seven genetic lineages and one mixed population of H. rubra; larval survivorship under varying salinities is also discussed. The presence and number of larvae differed significantly among lineages, with the mixed population being the most prolific. Statistical differences in reproduction attributable to seasonality also were identified. Larval survivorship was lowest (12% settlement rate) at a salinity approaching fresh water and significantly higher in brackish and seawater (88% and 72%, respectively). Correlated with this finding, identifiable gills capable of ion transport did not develop until metamorphosis into juveniles. Thus, early life stages of H. rubra are apparently excluded from surface waters, which are characterized by lower and fluctuating salinities. Instead, these stages are restricted to the subterranean (where there is higher and more stable salinity) portion of Hawaii's anchialine habitats due to their inability to tolerate low salinities. Taken together, these data contribute to the understudied area of larval ecology in the anchialine ecosystem.

  20. Changes in the pollen seasons of the early flowering trees Alnus spp. and Corylus spp. in Worcester, United Kingdom, 1996-2005

    NASA Astrophysics Data System (ADS)

    Emberlin, Jean; Smith, Matt; Close, Rebecca; Adams-Groom, Beverley

    2007-01-01

    Previous work on Betula spp. (birch) in the UK and at five sites in Europe has shown that pollen seasons for this taxon have tended to become earlier by about 5-10 days per decade in most regions investigated over the last 30 years. This pattern has been linked to the trend to warmer winters and springs in recent years. However, little work has been done to investigate the changes in the pollen seasons for the early flowering trees. Several of these, such as Alnus spp. and Corylus spp., have allergens, which cross-react with those of Betula spp., and so have a priming effect on allergic people. This paper investigates pollen seasons for Alnus spp. and Corylus spp. for the years 1996-2005 at Worcester, in the West Midlands, United Kingdom. Pollen data for daily average counts were collected using a Burkard volumetric trap sited on the exposed roof of a three-storey building. The climate is western maritime. Meteorological data for daily temperatures (maximum and minimum) and rainfall were obtained from the local monitoring sites. The local area up to approximately 10 km surrounding the site is mostly level terrain with some undulating hills and valleys. The local vegetation is mixed farmland and deciduous woodland. The pollen seasons for the two taxa investigated are typically late December or early January to late March. Various ways of defining the start and end of the pollen seasons were considered for these taxa, but the most useful was the 1% method whereby the season is deemed to have started when 1% of the total catch is achieved and to have ended when 99% is reached. The cumulative catches (in grains/m3) for Alnus spp. varied from 698 (2001) to 3,467 (2004). For Corylus spp., they varied from 65 (2001) to 4,933 (2004). The start dates for Alnus spp. showed 39 days difference in the 10 years (earliest 2000 day 21, latest 1996 day 60). The end dates differed by 26 days and the length of season differed by 15 days. The last 4 years in the set had notably higher

  1. Changes in the pollen seasons of the early flowering trees Alnus spp. and Corylus spp. in Worcester, United Kingdom, 1996-2005.

    PubMed

    Emberlin, Jean; Smith, Matt; Close, Rebecca; Adams-Groom, Beverley

    2007-01-01

    Previous work on Betula spp. (birch) in the UK and at five sites in Europe has shown that pollen seasons for this taxon have tended to become earlier by about 5-10 days per decade in most regions investigated over the last 30 years. This pattern has been linked to the trend to warmer winters and springs in recent years. However, little work has been done to investigate the changes in the pollen seasons for the early flowering trees. Several of these, such as Alnus spp. and Corylus spp., have allergens, which cross-react with those of Betula spp., and so have a priming effect on allergic people. This paper investigates pollen seasons for Alnus spp. and Corylus spp. for the years 1996-2005 at Worcester, in the West Midlands, United Kingdom. Pollen data for daily average counts were collected using a Burkard volumetric trap sited on the exposed roof of a three-story building. The climate is western maritime. Meteorological data for daily temperatures (maximum and minimum) and rainfall were obtained from the local monitoring sites. The local area up to approximately 10 km surrounding the site is mostly level terrain with some undulating hills and valleys. The local vegetation is mixed farmland and deciduous woodland. The pollen seasons for the two taxa investigated are typically late December or early January to late March. Various ways of defining the start and end of the pollen seasons were considered for these taxa, but the most useful was the 1% method whereby the season is deemed to have started when 1% of the total catch is achieved and to have ended when 99% is reached. The cumulative catches (in grains/m(3)) for Alnus spp. varied from 698 (2001) to 3,467 (2004). For Corylus spp., they varied from 65 (2001) to 4,933 (2004). The start dates for Alnus spp. showed 39 days difference in the 10 years (earliest 2000 day 21, latest 1996 day 60). The end dates differed by 26 days and the length of season differed by 15 days. The last 4 years in the set had notably

  2. [Research of the essential oil of Plumeria rubra var. actifolia from Laos by supercritical carbon dioxide extraction].

    PubMed

    Xiao, Xin-Yu; Cui, Long-Hai; Zhou, Xin-Xin; Wu, Yan; Ge, Fa-Huan

    2011-05-01

    The orthogonal test and the supercritical carbon dioxide fluid extraction were used for optimizing the extraction of the essential oil from Plumeria rubra var. actifolia for the first time. Compared with the steam distillation, the optimal operation parameter of extraction was as follows: extraction pressure 25 MPa, extraction temperature 45 degrees C; separator I pressure 12 MPa, separator I temperature 55 degrees C; separator II pressure 6 MPa, separator II temperature 30 degrees C. Under this condition the yield of the essential oil was 5.8927%. The components were separated and identified by GC-MS. 53 components of Plumeria rubra var. actifolia measured by SFE method were identified and determined by normalization method. The main components were 1, 6, 10-dodecatrien-3-ol, 3, 7, 11-trimethyl, benzoic acid, 2-hydroxy-, phenylmethyl ester, 1, 2-benzenedicarboxylic acid, bis(2-methylpropyl) ester,etc.. 1, 2-Benzenedicarboxylic acid, bis (2-methylpropyl) este. took up 66.11% of the total amount, and there was much difference of the results from SD method.

  3. The effect of induced heat waves on Pinus taeda and Quercus rubra seedlings in ambient and elevated CO2 atmospheres.

    PubMed

    Ameye, Maarten; Wertin, Timothy M; Bauweraerts, Ingvar; McGuire, Mary Anne; Teskey, Robert O; Steppe, Kathy

    2012-10-01

    Here, we investigated the effect of different heat-wave intensities applied at two atmospheric CO2 concentrations ([CO2]) on seedlings of two tree species, loblolly pine (Pinus taeda) and northern red oak (Quercus rubra). Seedlings were assigned to treatment combinations of two levels of [CO2] (380 or 700 μmol mol(-1)) and four levels of air temperature (ambient, ambient +3°C, or 7-d heat waves consisting of a biweekly +6°C heat wave, or a monthly +12°C heat wave). Treatments were maintained throughout the growing season, thus receiving equal heat sums. We measured gas exchange and fluorescence parameters before, during and after a mid-summer heat wave. The +12°C heat wave, significantly reduced net photosynthesis (Anet) in both species and [CO2] treatments but this effect was diminished in elevated [CO2]. The decrease in Anet was accompanied by a decrease in Fv'/Fm' in P. taeda and ΦPSII in Q. rubra. Our findings suggest that, if soil moisture is adequate, trees will experience negative effects in photosynthetic performance only with the occurrence of extreme heat waves. As elevated [CO2] diminished these negative effects, the future climate may not be as detrimental to plant communities as previously assumed.

  4. [Distribution of pyrimidine blocks in the DNA of Brevibacterium linens, Arthrobacter globiformis, Nocardia corallina and Nocardia rubra].

    PubMed

    Eroshina, N V; Golovlev, E L; Geĭdarov, T G; Bur'ianov, Ia I

    1975-01-01

    The nucleotide composition and the frequency of pyrimidine blocks were studied in DNA of the following bacteria: Brevibacterium linens (Weignamm, 1910) Breed, 1953; Arthrobacter globiformis (Conn, 1928) Conn et Dimmick, 1947; Nocardia corallina (Bergey et al., 1923) Waksman et Henrici, 1948; Nocardia rubra (Krassilnikov, 1949) Waksman et Henrici, 1948. These organisms are classed by some microbiologists as mycobacteria (the Mycobacteriaceae family) while other authors regard them as representatives of three families belonging to two orders. About 60 percent of all pyrimidines in DNA of these bacteria are found in the sequences pur-pyr-pur and pur-pyr-pyr-pur, the number of dipyrimidines being higher than the amount of monopyrimidine nucleotides. The content of dipyrimidine nucleotides in DNA of Nocardia corallina and Nocardia rubra is higher (16.8 mole %) than the content of dipyrimidine blocks in DNA of Brevibacterium linens and Arthrobacter globiformis, in which the quantity of dipyrimidines is almost the same (13.9 and 14.4 mole %). A new characteristic, the selected mean value, is suggested to evaluate differences in the distribution of pyrimidines in DNA.

  5. Detection of QTL for growth rate in the blacklip abalone (Haliotis rubra Leach) using selective DNA pooling.

    PubMed

    Baranski, M; Rourke, M; Loughnan, S; Hayes, B; Austin, C; Robinson, N

    2008-12-01

    The objective of this study was to identify QTL for growth rate in the blacklip abalone Haliotis rubra using selective DNA pooling. Three full-sibling families of H. rubra derived from crosses of wild broodstock were used. DNA was extracted from the largest and smallest 10% of progeny and combined into two pools for each phenotypic tail. The DNA pools were typed with 139 microsatellites, and markers showing significant differences between the peak height ratios of alleles inherited from the parents were individually genotyped and analysed by interval mapping. A strong correlation (r = 0.94, P < 0.001) was found between the t-values from the analysis of pools and the t-values from the analysis of individual genotypes. Based on the interval mapping analysis, QTL were detected on nine linkage groups at a chromosome-wide P < 0.01 and one linkage group at a chromosome-wide P < 0.05. The study demonstrated that selective DNA pooling is efficient and effective as a first-pass screen for the discovery of QTL in an aquaculture species.

  6. A Diels-Alder super diene breaking benzene into C2H2 and C4H4 units

    NASA Astrophysics Data System (ADS)

    Inagaki, Yusuke; Nakamoto, Masaaki; Sekiguchi, Akira

    2014-01-01

    Cyclic polyene with six carbon atoms (benzene) is very stable, whereas cyclic polyene with four carbon atoms (cyclobutadiene) is extremely unstable. The electron-withdrawing pentafluorophenyl group of a substituted cyclobutadiene lowers the energy of the lowest unoccupied molecular orbital, greatly increasing its reactivity as a diene in Diels-Alder reactions with acetylene, ethylene and even benzene. Here we show that the reaction with benzene occurs cleanly at the relatively low temperature of 120 °C and results in the formal fragmentation of benzene into C2H2 and C4H4 units, via a unique Diels-Alder/retro-Diels-Alder reaction. This is a new example of the rare case where breaking the C-C bond of benzene is possible with no activation by a transition metal.

  7. A Diels–Alder super diene breaking benzene into C2H2 and C4H4 units

    PubMed Central

    Inagaki, Yusuke; Nakamoto, Masaaki; Sekiguchi, Akira

    2014-01-01

    Cyclic polyene with six carbon atoms (benzene) is very stable, whereas cyclic polyene with four carbon atoms (cyclobutadiene) is extremely unstable. The electron-withdrawing pentafluorophenyl group of a substituted cyclobutadiene lowers the energy of the lowest unoccupied molecular orbital, greatly increasing its reactivity as a diene in Diels–Alder reactions with acetylene, ethylene and even benzene. Here we show that the reaction with benzene occurs cleanly at the relatively low temperature of 120 °C and results in the formal fragmentation of benzene into C2H2 and C4H4 units, via a unique Diels–Alder/retro-Diels–Alder reaction. This is a new example of the rare case where breaking the C–C bond of benzene is possible with no activation by a transition metal. PMID:24398593

  8. Total Synthesis of the Galbulimima Alkaloids Himandravine and GB17 Using Biomimetic Diels–Alder Reactions of Double Diene Precursors

    PubMed Central

    Larson, Reed T.; Pemberton, Ryan P.; Franke, Jenna M.; Tantillo, Dean J.; Thomson, Regan J.

    2015-01-01

    The enantioselective total syntheses of himandravine and GB17 were completed through a common biomimetic strategy involving Diels–Alder reactions of unusual double diene containing linear precursors. The double diene precursors, containing or lacking a C12 substituent as required to produce GB17 or himandravine, respectively, were found to undergo Diels–Alder reactions to afford mixtures of regioisomeric cycloadducts that map onto the alternative carbocyclic frameworks of both himandravine and GB17. Computational investigations revealed that these Diels–Alder reactions proceed via transition state structures of similar energy that have a high degree of bispericyclic character and that the low levels of regioselectivity observed in the reactions are a consequence of competing orbital interaction and distortion energies. The combined experimental and computational results provide valuable insights into the biosynthesis of the Galbulimima alkaloids. PMID:26305231

  9. Regiocontrol by remote substituents. An enantioselective total synthesis of frenolicin B via a highly regioselective Diels-Alder reaction

    SciTech Connect

    Kraus, G.A.; Li, J. ); Gordon, M.S.; Jensen, J.H. )

    1993-06-30

    The quinone subunit is contained in a broad range of biologically important natural products such as frenolicin B, which is a member of the pyranonaphthoquinone family. The diverse biological activity of quinones has led to the development of several new synthetic methods for quinones. Among the pathways featuring a cycloaddition reaction, one of the most general methods for the regiospecific synthesis of substituted quinones was pioneered by H.J. Rapoport and others. This method involves the Diels-Alder reaction of a substituted quinone. As part of a program to evaluate the directing effects of functional groups not directly attached to the atoms undergoing Diels-Alder cycloaddition, we now report that remote substituents on a dienophile can confer excellent regioselectivity in Diels-Alder reactions. This work has led to an extremely direct synthesis of the pyranonaphthoquinone framework and to the first synthesis of frenolicin B (1). 19 refs., 1 fig.

  10. Roles of gibberellins and abscisic acid in dormancy and germination of red bayberry (Myrica rubra) seeds.

    PubMed

    Chen, Shun-Ying; Kuo, Shing-Rong; Chien, Ching-Te

    2008-09-01

    Intact seeds from freshly harvested fruits of Myrica rubra (Sieb et Zucc.) were dormant and required 8 weeks of warm stratification followed by 12 weeks of cold stratification for germination. Exogenous application of gibberellic acid (GA(3)) to intact fresh seeds was effective in breaking dormancy, with > 70% of seeds germinating when treated with 5.2 mM GA(3) and incubated at a day/night temperature of 30/20 degrees C for 20 weeks. Removing the hard endocarp or endocarp plus seed coat of fresh seeds promoted germination, and addition of GA(3) to the embryo accelerated germination. The gibberellins GA(1) and GA(4) were more effective than GA(3) in promoting germination of seeds with the endocarp removed. Endogenous contents of GA(1), GA(3), GA(4), GA(7) and GA(20) were quantified by gas chromatography-mass spectrometry-selected ion monitoring in the endocarps, seed coats and embryos of fresh seeds treated with 5.2 mM GA(3). The content of GA(3) decreased in the endocarp during incubation, whereas GA(1) contents increased in the endocarp and seed coat. A high GA(1) content was detected in the endocarps and embryos of newly germinated seeds. We speculate that GA(3) was converted to GA(1) during incubation and that GA(1) is involved in seed germination. Endogenous abscisic acid (ABA) contents were measured in fresh seeds and in warm and cold stratified seeds. The ABA content in fresh seeds was distributed in the order endocarp > seed coat > embryo, with the content in the endocarp being about 132-fold higher than in the seed coat and embryo. Total ABA content of seeds subjected to warm or cold stratification, or both, was 8.7- to 14.0-fold lower than that of fresh seeds. Low contents of endogenous GA(1), GA(3), GA(7) and GA(20), but elevated contents of GA(4), were found in the seed coats and endocarps of warm plus cold stratified seeds and in the seed coats and embryos of newly germinated seeds. These observations, coupled with the finding that GA stimulated

  11. Aqueous catalysis: Methylrhenium trioxide (MTO) as a homogeneous catalyst for the Diels-Alder reaction

    SciTech Connect

    Zhu, Z.; Espenson, J.H.

    1997-04-16

    The title compound proves to be an effective and efficient catalyst for the Diels-Alder reaction when the dienophile is an {alpha},{beta}-unsaturated ketone or aldehyde. It is especially effective in water. Equal amounts of any such dienophile and any of six representative dienes (isoprene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, cyclopentadiene, 1,2,3,4,5,-pentamethylcyclopentadiene, and 1,3-cyclohexadiene) were used, along with 1% MTO. The reactions gave usually > 90% isolated yield of the cycloaddition product except for the larger dienophiles. Nearly exclusively, there was formed one product isomer, the same one that usually predominates. The reactions were often run in chloroform (mostly) and in other organic solvents. A select number were carried out in water, where the reactions gave a greater product yield in a considerably shorter time. Water, itself, is known to enhance the rates of Diels-Alder reactions, but MTO exerts an additional accelerating effect. Kinetics studies were carried out to show that the rate is proportional to the catalyst concentration. The products do not inhibit the reaction. The desirability of MTO as a Diels-Alder catalyst stems from a combination of favorable properties: the inertness to air/oxygen, the tolerance for many substrates, the use of an aqueous medium, and the absence of product inhibition. The initial step appears to be the (weak) coordination of the carbonyl oxygen to the electropositive rhenium center. Steric crowding around rhenium inhibits reactions of the larger dienophiles. 26 refs., 3 figs., 4 tabs.

  12. Insight on mendable resin made by combining Diels-Alder epoxy adducts with DGEBA

    NASA Astrophysics Data System (ADS)

    Dello Iacono, S.; Martone, A.; Filippone, G.; Acierno, D.; Zarrelli, M.; Giordano, M.; Amendola, E.

    2016-05-01

    Formation of micro-cracks is a critical problem in polymers and polymer composites during their service in structural applications. In this context, materials endowed with self-healing features would lead to the next polymers generation. In the present paper, an epoxy system integrating Diels-Alder epoxy adducts is investigated by thermal and spectroscopic analysis. The direct and retro D-A reaction have been studied by FTIR and specific absorption bands have been identified. Finally, mechanical tests have been performed on the system. The polymer is able to heal fracture and micro-cracks recovering its stiffness after a thermal treatment.

  13. Asymmetric Syntheses of the Flavonoid Diels–Alder Natural Products Sanggenons C and O

    PubMed Central

    Qi, Chao; Xiong, Yuan; Eschenbrenner-Lux, Vincent; Cong, Huan

    2016-01-01

    Metal-catalyzed, double Claisen rearrangement of a bis-allyloxyflavone has been utilized to enable a concise synthesis of the hydrobenzofuro[3,2-b]chromenone core structure of the natural products sanggenon A and sanggenol F. In addition, catalytic, enantioselective [4+2] cycloadditions of 2′-hydroxychalcones have been accomplished using B(OPh)3/BINOL complexes. Asymmetric syntheses of the flavonoid Diels–Alder natural products sanggenons C and O have been achieved employing a stereodivergent reaction of a racemic mixture (stereodivergent RRM) involving [4+2] cycloaddition. PMID:26735066

  14. Mechanistic insights into the stepwise Diels-Alder reaction of 4,6-dinitrobenzofuroxan.

    PubMed

    Linder, Mats; Johansson, Adam Johannes; Brinck, Tore

    2012-01-06

    The stepwise Diels-Alder reaction between 1-trimethylsiloxy-1,3-butadiene and 4,6-dinitrobenzofuroxan is explored using state-of-the-art computational methods. The results support a stepwise mechanism via a persistent intermediate, however, not the one previously reported (Lakhdar et al., Chem. Eur. J.2007, 16, 5681) but a heterocyclic adduct. The novel DFT functional M062X and the SCS-MP2 method were essential to reproduce a reasonable potential energy surface for this challenging system.

  15. 1-Azadienes as regio- and chemoselective dienophiles in aminocatalytic asymmetric Diels-Alder reaction.

    PubMed

    Ma, Chao; Gu, Jing; Teng, Bin; Zhou, Qing-Qing; Li, Rui; Chen, Ying-Chun

    2013-12-20

    Electron-deficient 1-aza-1,3-butadienes containing a 1,2-benzoisothiazole-1,1-dioxide or 1,2,3-benzoxathiazine-2,2-dioxide motif act as regio- and chemoselective dienophiles in normal-electron-demand Diels-Alder reactions with HOMO-raised trienamines, rather than typical 4π-participation in inverse-electron-demand versions. The enantioenriched cycloadducts could be efficiently converted to spiro or fused frameworks with high structural and stereogenic complexity by a sequential aza-benzoin reaction or other transformations.

  16. Structural Modification of Sol-Gel Materials through Retro Diels-Alder Reaction

    SciTech Connect

    SHALTOUT,RAAFAT M.; LOY,DOUGLAS A.; MCCLAIN,MARK D.; PRABAKAR,SHESHASAYANA; GREAVES,JOHN; SHEA,KENNETH J.

    1999-12-08

    Hydrolysis and condensation of organically bridged bis-triethoxysilanes, (EtO){sub 3}Si-R-Si(OEt){sub 3}, results in the formation of three dimensional organic/inorganic hybrid networks (Equation 1). Properties of these materials, including porosity, are dependent on the nature of the bridging group, R. Flexible groups (akylene-spacers longer than five carbons in length) polymerize under acidic conditions to give non-porous materials. Rigid groups (such as arylene-, alkynylene-, or alkenylene) form non-porous, microporous, and macroporous gels. In many cases the pore size distributions are quite narrow. One of the motivations for preparing hybrid organic-inorganic materials is to extend the range of properties available with sol-gel systems by incorporating organic groups into the inorganic network. For example, organically modified silica gels arc either prepared by co-polymerizing an organoalkoxysilane with a silica precursor or surface silylating the inorganic gel. This can serve to increase hydrophobicity or to introduce some reactive organic functionality. However, the type and orientation of these organic functionalities is difficult to control. Furthermore, many organoalkoxysilanes can act to inhibitor even prevent gelation, limiting the final density of organic functionalities. We have devised a new route for preparing highly functionalized pores in hybrid materials using bridging groups that are thermally converted into the desired functionalities after the gel has been obtained. In this paper, we present the preparation and characterization of bridged polysilsesquioxanes with Diels-Alder adducts as the bridging groups from the sol-gel polymerization of monomers 2 and 4. The bridging groups are constructed such that the retro Diela-Alder reaction releases the dienes and leaves the dienophiles as integral parts of the network polymers. In the rigid architecture of a xerogel, this loss of organic functionality should liberate sufficient space to modify the

  17. Diels-Alder cycloadditions in water for the straightforward preparation of peptide–oligonucleotide conjugates

    PubMed Central

    Marchán, Vicente; Ortega, Samuel; Pulido, Daniel; Pedroso, Enrique; Grandas, Anna

    2006-01-01

    The Diels-Alder reaction between diene-modified oligonucleotides and maleimide-derivatized peptides afforded peptide–oligonucleotide conjugates with high purity and yield. Synthesis of the reagents was easily accomplished by on-column derivatization of the corresponding peptides and oligonucleotides. The cycloaddition reaction was carried out in mild conditions, in aqueous solution at 37°C. The speed of the reaction was found to vary depending on the size of the reagents, but it can be completed in 8–10 h by reacting the diene-oligonucleotide with a small excess of maleimide-peptide. PMID:16478710

  18. Diels-Alder reactions of five-membered heterocycles containing one heteroatom.

    PubMed

    Ding, Xiaoyuan; Nguyen, Son T; Williams, John D; Peet, Norton P

    2014-12-17

    Diels-Alder reactions of five-membered heterocycles containing one heteroatom with an N-arylmaleimide were studied. Cycloaddition of 2,5-dimethylfuran (4) with 2-(4-methylphenyl)maleimide (3) in toluene at 60 °C gave bicyclic adduct 5. Cycloadditions of 3 with 2,5-dimethylthiophene (11) and 1,2,5-trimethylpyrrole (14) were also studied. Interestingly, the bicyclic compound 5 cleanly rearranged, with loss of water, when treated with p-toluenesulfonic acid in toluene at 80 °C to give 4,7-dimethyl-2-p-tolylisoindoline-1,3-dione (6).

  19. Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

    PubMed Central

    Miller, Marvin J

    2016-01-01

    Summary The hetero-Diels–Alder reaction between a nitroso dienophile and a conjugated diene to give the 3,6-dihydro-2H-1,2-oxazine scaffold is useful for the synthesis of many biologically interesting molecules due to the diverse opportunities created by subsequent transformations of the resulting 1,2-oxazine ring. This review discusses the rationale for the observed regio- and stereoselectivity and the methods developed in recent years used to control and improve the stereo- and regioselectivity for the synthesis of 1,2-oxazine scaffolds. PMID:27829901

  20. Highly enantioselective access to cannabinoid-type tricyles by organocatalytic Diels–Alder reactions

    PubMed Central

    Volz, Nicole; Gläser, Franziska; Nieger, Martin

    2012-01-01

    Summary After prosperous domino reactions towards benzopyrans, the products were used as the starting material in Lewis acid catalyzed and organocatalytic Diels–Alder reactions to build up a tricyclic system. Herein, an asymmetric induction up to 96% enantiomeric excess was obtained by the use of imidazolidinone catalysts. This approach can be utilized to construct the tricyclic system in numerous natural products, in particular the scaffold of tetrahydrocannabinol (THC) being the most representative one. Compared with other published methods, condensation with a preexisting cyclohexane moiety in the precursor is needed to gain the heterogenic tricycle systems, whereas we present a novel strategy towards cannabinoid derivatives based on a flexible modular synthesis. PMID:23019475

  1. Highly enantioselective access to cannabinoid-type tricyles by organocatalytic Diels-Alder reactions.

    PubMed

    Bräse, Stefan; Volz, Nicole; Gläser, Franziska; Nieger, Martin

    2012-01-01

    After prosperous domino reactions towards benzopyrans, the products were used as the starting material in Lewis acid catalyzed and organocatalytic Diels-Alder reactions to build up a tricyclic system. Herein, an asymmetric induction up to 96% enantiomeric excess was obtained by the use of imidazolidinone catalysts. This approach can be utilized to construct the tricyclic system in numerous natural products, in particular the scaffold of tetrahydrocannabinol (THC) being the most representative one. Compared with other published methods, condensation with a preexisting cyclohexane moiety in the precursor is needed to gain the heterogenic tricycle systems, whereas we present a novel strategy towards cannabinoid derivatives based on a flexible modular synthesis.

  2. Thiourea-catalyzed Diels-Alder reaction of a naphthoquinone monoketal dienophile.

    PubMed

    Kramer, Carsten S; Bräse, Stefan

    2013-01-01

    A variety of organocatalysts were screened for the catalysis of the naphthoquinone monoketal Diels-Alder reaction. In this study we found that Schreiner's thiourea catalyst 10 and Jacobson's thiourea catalyst 12 facilitate the cycloaddition of the sterically hindered naphthoquinone monoketal dienophile 3 with diene 4. The use of thiourea catalysis allowed for the first time the highly selective synthesis of the exo-product 2a in up to 63% yield. In this reaction a new quaternary center was built. The so formed cycloaddition product 2a represents the ABC tricycle of beticolin 0 (1) and is also a valuable model substrate for the total synthesis of related natural products.

  3. Draft Genome Sequence of Bacillus pumilus Strain GM3FR, an Endophyte Isolated from Aerial Plant Tissues of Festuca rubra L.

    PubMed Central

    Hollensteiner, Jacqueline; Daniel, Rolf; Liesegang, Heiko; Vidal, Stefan

    2017-01-01

    ABSTRACT Here, we report the draft genome sequence of Bacillus pumilus GM3FR, an endophytic bacterium isolated from aerial plant tissues of Festuca rubra L. The draft genome consists of 3.5 Mb and harbors 3,551 predicted protein-encoding genes. The genome provides insights into the biocontrol potential of B. pumilus GM3FR. PMID:28360161

  4. Osmoregulation in the Hawaiian anchialine shrimp Halocaridina rubra (Crustacea: Atyidae): expression of ion transporters, mitochondria-rich cell proliferation and hemolymph osmolality during salinity transfers.

    PubMed

    Havird, Justin C; Santos, Scott R; Henry, Raymond P

    2014-07-01

    Studies of euryhaline crustaceans have identified conserved osmoregulatory adaptions allowing hyper-osmoregulation in dilute waters. However, previous studies have mainly examined decapod brachyurans with marine ancestries inhabiting estuaries or tidal creeks on a seasonal basis. Here, we describe osmoregulation in the atyid Halocaridina rubra, an endemic Hawaiian shrimp of freshwater ancestry from the islands' anchialine ecosystem (coastal ponds with subsurface freshwater and seawater connections) that encounters near-continuous spatial and temporal salinity changes. Given this, survival and osmoregulatory responses were examined over a wide salinity range. In the laboratory, H. rubra tolerated salinities of ~0-56‰, acting as both a hyper- and hypo-osmoregulator and maintaining a maximum osmotic gradient of ~868 mOsm kg(-1) H2O in freshwater. Furthermore, hemolymph osmolality was more stable during salinity transfers relative to other crustaceans. Silver nitrate and vital mitochondria-rich cell staining suggest all gills are osmoregulatory, with a large proportion of each individual gill functioning in ion transport (including when H. rubra acts as an osmoconformer in seawater). Additionally, expression of ion transporters and supporting enzymes that typically undergo upregulation during salinity transfer in osmoregulatory gills (i.e. Na(+)/K(+)-ATPase, carbonic anhydrase, Na(+)/K(+)/2Cl(-) cotransporter, V-type H(+)-ATPase and arginine kinase) were generally unaltered in H. rubra during similar transfers. These results suggest H. rubra (and possibly other anchialine species) maintains high, constitutive levels of gene expression and ion transport capability in the gills as a means of potentially coping with the fluctuating salinities that are encountered in anchialine habitats. Thus, anchialine taxa represent an interesting avenue for future physiological research.

  5. Use of radiometric indices to evaluate Zn and Pb stress in two grass species (Festuca rubra L. and Vulpia myuros L.).

    PubMed

    Gómez, J; Yunta, F; Esteban, E; Carpena, R O; Zornoza, P

    2016-11-01

    Vegetation indices obtained from radiometric measurements have been used to estimate the stress response of plants grown in contaminated sites. The phytotoxicity of Pb and Zn in Festuca rubra L. and Vulpia myuros L. plants grown under hydroponic conditions was evaluated using vegetation indices obtained from radiometric measurements. The plants were supplied with 3 mM Zn (+Zn), 500 μM Pb (+Pb) and 500 μM Pb with EDTA (+PbEDTA) for 3 months. Significantly higher Zn concentrations in F. rubra shoots compared with V. myuros shoots were detected for Zn and Pb treatments. EDTA increased Pb transport to the shoots for both grasses, while Pb-treated plants retained Pb primarily in the roots. All vegetation indices tested showed the highest differences in F. rubra under +PbEDTA treatment and minor effects under +Zn, whereas the major variations for V. myuros corresponded to +Zn treatment, followed by +PbEDTA. Red edge normalized difference vegetation index, yellowness index and anthocyanin concentration index were the most sensitive indices to report Zn and Pb phytotoxicity in these grasses. According to the results obtained, both metal concentrations and radiometric indices suggested that Pb is more phytotoxic to F. rubra, which tolerates high Zn levels, whereas V. myuros was strongly affected by high Zn levels and markedly tolerant to Pb, even when applied in a mobile form (PbEDTA). Both species could be used in the phytostabilization of Zn- and Pb-contaminated soils. The abilities of F. rubra to accumulate Zn and V. myuros to accumulate Pb in the roots would facilitate a more efficient phytoremediation strategy when used in combination.

  6. Ecology and behaviour of the Alder Flycatcher Empidonax alnorum, Tyrannidae in winter

    USGS Publications Warehouse

    Foster, M.; Adams, N.J.; Slotow, R.H.

    1999-01-01

    The Alder Flycatcher Empidonax alnorum (Tyrannidae) winters from Colombia and Venezuela, south to northern Argentina. We studied the species in Manu National Park, Madre de Dios, Peru. In this area the species occupies riparian zones along lowland meander rivers as well as adjacent transition zone forest in the floodplain. These habitats have a number of age-related longitudinal zones (parallel to the river margin) that are short term (I-2 year) transitory stages in the succession to floodplain forest. The fast growing plant species that make up these habitats are suitable for commercial harvest for paper pulp. We examined habitat use of the species in an attempt to identify the effects of such harvest and resulting habitat loss on these birds. The Alder Flycatcher favours two longitudinal zones where it establishes territories. The territories may be long-term or transitory, and are often occupied and defended by two individuals, generally of different age. One bird tends to be more active in territory defence than the other. Defence involves patrolling, vocal duels, and chases. Birds sally for insects but also eat large quantities of fruit.

  7. Ecology and behaviour of the Alder Flycatcher Empidonax alnorum, Tyrannidae in winter

    USGS Publications Warehouse

    Foster, M.; Adams, N.J.; Slotow, R.H.

    1998-01-01

    The Alder Flycatcher Empidonax alnorum (Tyrannidae) winters from Colombia and Venezuela, south to northern Argentina. We studied the species in Manu National Park, Madre de Dios, Peru. In this area the species occupies riparian zones along lowland meander rivers as well as adjacent transition zone forest in the floodplain. These habitats have a number of age-related longitudinal zones (parallel to the river margin) that are short term (I-2 year) transitory stages in the succession to floodplain forest. The fast growing plant species that make up these habitats are suitable for commercial harvest for paper pulp. We examined habitat use of the species in an attempt to identify the effects of such harvest and resulting habitat loss on these birds. The Alder Flycatcher favours two longitudinal zones where it establishes territories. The territories may be long-term or transitory, and are often occupied and defended by two individuals, generally of different age. One bird tends to be more active in territory defence than the other. Defence involves patrolling, vocal duels, and chases. Birds sally for insects but also eat large quantities of fruit.

  8. New Insights into the Diels-Alder Reaction of Graphene Oxide.

    PubMed

    Brisebois, Patrick P; Kuss, Christian; Schougaard, Steen B; Izquierdo, Ricardo; Siaj, Mohamed

    2016-04-18

    Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies.

  9. Diels-Alder reactions of 4-halo masked o-benzoquinones. Experimental and theoretical investigations.

    PubMed

    Surasani, Seshi Reddy; Parumala, Santosh Kumar Reddy; Peddinti, Rama Krishna

    2014-08-14

    The studies on [4 + 2] cycloaddition of 4-halo derivatives of 6,6-dimethoxycyclohexa-2,4-dienones known as orthoquinone monoketals/masked o-benzoquinones are described. The 4-fluoro, 4-chloro- and 4-iodo-masked o-benzoquinones were stable enough for their isolation and characterization. These conjugated dienones cycloadded with several electron-deficient and electron-rich dienophiles in a highly regio- and stereo-selective manner to afford the corresponding halo bicyclo[2.2.2]octenone derivatives in high to excellent chemical yields. The halo masked o-benzoquinones did not undergo dimerization under the reaction conditions. To evaluate the observed selectivities of these Diels-Alder reactions, we have performed quantum mechanical calculations for the reactions between halo masked o-benzoquinones and methyl vinyl ketone and ethyl vinyl ether at the B3LYP/6-31G** theory level. The differences in HOMO and LUMO energy gaps suggest that these reactions can be classified as inverse electron-demand Diels-Alder reactions. The calculated transition state energies and global electronic indexes supported the experimentally observed selectivities of the reaction in many cases.

  10. Liquid phase thermochemical energy conversion systems - An application of Diels-Alder chemistry

    NASA Astrophysics Data System (ADS)

    Lenz, T. G.; Hegedus, L. S.; Vaughan, J. D.

    1982-12-01

    A method of thermochemical energy conversion, transport, and storage research involving moderate and low temperature liquid phase systems employing Diels-Alder cycloaddition chemistry is described. Proposed as a heat storage system for solar and industrial waste heat, the system involves the meeting, in a reactor, of energy-depleted and energy-rich fluids. The poor fluid gains energy and goes through a chemical, endothermic dissociative change. The use of Diels-Alder reactions provides completely reversible chemical reactions for this application. The heated fluid can be retransported for storage or implementation as a heat source. The return reaction, releasing the stored heat, can be done spontaneously or in the presence of a catalyst such as Lewis acids. Attention is recommended for the Wentworth-Chen temperature of 250-300 C to minimize the system thermal degradation. Research in the synthesis of diene and dienophile candidate chemicals, into sealed tube and reaction kinetic techniques, and into NMR techniques for identifying further reaction candidates are discussed.

  11. Stepwise Diels-Alder: more than just an oddity? A computational mechanistic study.

    PubMed

    Linder, Mats; Brinck, Tore

    2012-08-03

    We have employed hybrid DFT and SCS-MP2 calculations at the SMD-PCM-6-311++G(2d,2p)//6-31+G(d) level to investigate the relationship between three possible channels for forming a Diels-Alder adduct from a highly nucleophilic diene and moderately to highly electrophilic dienophiles. We discuss geometries optimized using the B3LYP and M06-2X functionals with the 6-31+(d) basis set. The transition states and intermediates are characterized on the basis of geometric and electronic properties, and we also address the possibility of predicting detectability of a zwitterionic intermediate based on its relative stability. Our results show that a conventional Diels-Alder transition state conformation yields intermediates in all four investigated cases, but that these are too short-lived to be detected experimentally for the less activated reactants. The stepwise trans pathway, beginning with a conjugate addition-like transition state, becomes increasingly competitive with more activated reactants and is indeed favored for the most electrophilic dienophiles. Addition of a trans diene leads to a dead-end as the trans intermediates have insurmountable rotation barriers that prohibit formation of the second bond, unless another, heterocyclic intermediate is formed. We also show that introduction of a hydrogen bond donating catalyst favors a stepwise pathway even for less activated dienophiles.

  12. Reconfigurable biodegradable shape-memory elastomers via Diels-Alder coupling.

    PubMed

    Ninh, Chi; Bettinger, Christopher J

    2013-07-08

    Synthetic biodegradable elastomers are a class of polymers that have demonstrated far-reaching utility as biomaterials for use in many medical applications. Biodegradable elastomers can be broadly classified into networks prepared by either step-growth or chain-growth polymerization. Each processing strategy affords distinct advantages in terms of capabilities and resulting properties of the network. This work describes the synthesis, processing, and characterization of cross-linked polyester networks based on Diels-Alder coupling reactions. Hyperbranched furan-modified polyester precursors based on poly(glycerol-co-sebacate) are coupled with bifunctional maleimide cross-linking agents. The chemical and thermomechanical properties of the elastomers are characterized at various stages of network formation. Experimental observations of gel formation are compared to theoretical predictions derived from Flory-Stockmayer relationships. This cross-linking strategy confers unique advantages in processing and properties including the ability to fabricate biodegradable reconfigurable covalent networks without additional catalysts or reaction byproducts. Reconfigurable biodegradable networks using Diels-Alder cycloaddition reactions permit the fabrication of shape-memory polymers with complex permanent geometries. Biodegradable elastomers based on polyester networks with molecular reconfigurability achieve vastly expanded properties and processing capabilities for potential applications in medicine and beyond.

  13. Unconventional exo selectivity in thermal normal-electron-demand Diels–Alder reactions

    PubMed Central

    Ho, Guo-Ming; Huang, Ci-Jhang; Li, Elise Yu-Tzu; Hsu, Sheng-Kai; Wu, Ti; Zulueta, Medel Manuel L.; Wu, Kevin Binchia; Hung, Shang-Cheng

    2016-01-01

    The Diels–Alder reaction is a useful tool for generating functionalized chiral molecules through the concerted cycloaddition of dienes and dienophiles leading to six-membered rings. Traditionally, the selective predictions of the products rely heavily on consideration of the secondary orbital interactions that stabilize the endo pathway. However, there remain some basic examples defying this notion and produce the exo-isomer as major product. Here we systematically evaluated of the structural features driving exo selectivity in thermal normal-electron-demand Diels–Alder reactions. Substitution at the Cβ position and the size and electronegativity of the electron-withdrawing group of the dienophile are contributing factors. Experimental and computational studies both point toward the steric and electrostatic forces between the substituents in both the diene and the dienophile that increase the likelihood of the exo pathway. For these substrates, the dominance of the endo pathway is reduced by transition state distortions and poor structural alignments of the reacting partners. We also noted the tilt of the dienophile with respect to the diene causing steric strain on the functionalities at the more advanced bond forming carbon-carbon position of the endo transition state. Insights into such factors may benefit synthetic planning and asserting control over this important named reaction. PMID:27731360

  14. Unconventional exo selectivity in thermal normal-electron-demand Diels–Alder reactions

    NASA Astrophysics Data System (ADS)

    Ho, Guo-Ming; Huang, Ci-Jhang; Li, Elise Yu-Tzu; Hsu, Sheng-Kai; Wu, Ti; Zulueta, Medel Manuel L.; Wu, Kevin Binchia; Hung, Shang-Cheng

    2016-10-01

    The Diels–Alder reaction is a useful tool for generating functionalized chiral molecules through the concerted cycloaddition of dienes and dienophiles leading to six-membered rings. Traditionally, the selective predictions of the products rely heavily on consideration of the secondary orbital interactions that stabilize the endo pathway. However, there remain some basic examples defying this notion and produce the exo-isomer as major product. Here we systematically evaluated of the structural features driving exo selectivity in thermal normal-electron-demand Diels–Alder reactions. Substitution at the Cβ position and the size and electronegativity of the electron-withdrawing group of the dienophile are contributing factors. Experimental and computational studies both point toward the steric and electrostatic forces between the substituents in both the diene and the dienophile that increase the likelihood of the exo pathway. For these substrates, the dominance of the endo pathway is reduced by transition state distortions and poor structural alignments of the reacting partners. We also noted the tilt of the dienophile with respect to the diene causing steric strain on the functionalities at the more advanced bond forming carbon-carbon position of the endo transition state. Insights into such factors may benefit synthetic planning and asserting control over this important named reaction.

  15. Stabilization of metals in acidic mine spoil with amendments and red fescue (Festuca rubra L.) growth.

    PubMed

    Simon, László

    2005-12-01

    Stabilization of metals with amendments and red fescue (Festuca rubra, cv. Keszthelyi 2) growth was studied on an acidic and phytotoxic mine spoil (pH(KCl) 3.20-3.26; Cd 7.1 mg kg(-1), Cu 120 mg kg(-1), Pb 2154 mg kg(-1) and Zn 605 mg kg(-1)) from Gyöngyösoroszi, Hungary in a pot experiment. Raising the pH above 5.0 by lime (CaCO(3)), and supplementing with 40 mg kg(-1)nitrogen (NH(4)NO(3)) made this material suitable for plant growth. All cultures were limed with 0.5% (m/m) CaCO(3) (treatment 1), which was combined with 5% (m/m) municipal sewage sludge compost (treatment 2), 5% (m/m) peat (treatment 3), 7.5% (m/m) natural zeolite (clinoptilolite) (treatment 4), and 0.5 (m/m) KH(2)PO(4) (treatment 5). Treatments 1-5 were combined with each other (treatment 6). After 60 days of red fescue growth, pH of the limed mine spoil decreased in all cultures units. Application of peat caused the highest pH decrease (1.15), while decrease of pH was less than 0.23 in treatments 2, 5 or 6. Application of lime significantly reduced concentrations of metals in the 'plant available' fraction of mine spoil compared to non-limed mine spoil. Amendments added to limed mine spoil changed variously the ratio of Cd, Cu, Pb and Zn in exchangeable or 'plant available' fractions, differently influencing the phytoavailability of these metals. Most of the metals were captured in the roots of test plants. Treatment 2 caused the appearance of less Cd in shoots (<0.1 microg g(-1)) or roots (3.11 microg g(-1)), while treatment 5 resulted in the highest Cd concentration (2.13 microg g(-1)) in shoots. Treatments did not influence significantly the Cu accumulation in shoots. The Pb accumulation of roots (44.7 microg g(-1)) was most effectively inhibited by combined treatment, while the highest value (136 microg g(-1)) was found in the culture treated with potassium phosphate. Pb concentration in shoots was below the detection limit, except for treatments 5 and 6. Peat application resulted in higher

  16. Isospora cardellinae n. sp. (Apicomplexa: Eimeriidae) from the red warbler Cardellina rubra (Swainson) (Passeriformes: Parulidae) in Mexico.

    PubMed

    Salgado-Miranda, Celene; Medina, Juan Pablo; Zepeda-Velázquez, Andrea Paloma; García-Conejo, Michele; Galindo-Sánchez, Karla Patricia; Janczur, Mariusz Krzysztof; Soriano-Vargas, Edgardo

    2016-10-01

    A new coccidian species (Protozoa: Apicomplexa: Eimeriidae) collected from the red warbler Cardellina rubra (Swainson) is reported from the Nevado de Toluca National Park, Mexico. Isospora cardellinae n. sp. has subspherical oöcysts, measuring on average 26.6 × 25.4 μm, with smooth, bi-layered wall, c.1.3 μm thick. Micropyle, oöcyst residuum, and polar granule are absent. Sporocysts are ovoidal, measuring on average 19.0 × 12.0 µm, with a knob-like Stieda body, a trapezoidal sub-Stieda body and sporocyst residuum composed of scattered spherules of different sizes. Sporozoites are vermiform with one refractile body and a nucleus. This is the fourth description of an isosporoid coccidian infecting a New World warbler.

  17. Evaluation of an onion extract, Centella asiatica, and hyaluronic acid cream in the appearance of striae rubra.

    PubMed

    Draelos, Zoe Diana; Gold, Michael H; Kaur, Mandeep; Olayinka, Babajide; Grundy, Starr L; Pappert, Eric J; Hardas, Bhushan

    2010-01-01

    This study evaluated the effect of an onion extract cream with Centella asiatica and hyaluronic acid in improving the appearance of striae rubra (SR). Women participants with bilateral, outer aspect of the thigh SR were randomized to apply a quarter-sized amount of the onion extract cream twice daily for 12 weeks to the randomized left or right, outer aspect of the thigh. No treatment was administered to the contralateral side. Participants were evaluated at weeks 2, 4, 8, and 12. Primary efficacy endpoints included color, texture, softness, and overall appearance of SR by the participant and investigator at week 12. The treated thigh demonstrated a statistically significant difference in the mean change in participant and investigator evaluations in overall appearance, texture, color, and softness compared with the untreated thigh at week 12. No adverse events occurred during the study. The onion extract cream was well tolerated and significantly improved the appearance of SR in women.

  18. Microwave-Enhanced Organic Syntheses for the Undergraduate Laboratory: Diels-Alder Cycloaddition, Wittig Reaction, and Williamson Ether Synthesis

    ERIC Educational Resources Information Center

    Baar, Marsha R.; Falcone, Danielle; Gordon, Christopher

    2010-01-01

    Microwave heating enhanced the rate of three reactions typically performed in our undergraduate organic chemistry laboratory: a Diels-Alder cycloaddition, a Wittig salt formation, and a Williamson ether synthesis. Ninety-minute refluxes were shortened to 10 min using a laboratory-grade microwave oven. In addition, yields improved for the Wittig…

  19. Investigation of the possibility of functionalization of C20 fullerene by benzene via Diels-Alder reaction

    NASA Astrophysics Data System (ADS)

    Siadati, Seyyed Amir; Nami, Navabeh

    2016-10-01

    C20 fullerene, this novel species with all its pentagonal faces has displayed some unique operations in making fast pericyclic reactions. As an example, the high dienophile character of the C20 fullerene and the ability of this species in making an ultra-fast Diels-Alder reaction with 1,3-butadiene, has been recently reported. Moreover, new experimental reports claim that the C60 fullerene, one of the fullerene family, could make a Diels-Alder reaction with the central ring of anthracene and make the ring non-aromatic. These reports may encourage researchers to do more studies on the properties of this small carbon cage. To address this question, the present research has discussed all the reaction channels of the Diels-Alder cycloaddition of benzene molecule as a 1,3-diene with the C20 fullerene in order to answer this question: "Is C20fullerene able to make a Diels-Alder reaction with this molecule?".

  20. Sorocenols G and H, Anti-MRSA Oxygen Heterocyclic Diels-Alder-type Adducts from Sorocea muriculata Roots

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bioassay-guided fractionation of a root extract of Sorocea muriculata led to the isolation and identification of two new oxygen heterocyclic Diels-Alder-type adducts, sorocenols G (1) and H (2), along with lupeol-3-(3'R-hydroxytetradecanoate) and oxyresveratrol. The structures of 1 and 2 were eluci...

  1. Organocatalytic sequential hetero-Diels-Alder and Friedel-Crafts reaction: constructions of fused heterocycles with scaffold diversity.

    PubMed

    Zhou, Si-Li; Li, Jun-Long; Dong, Lin; Chen, Ying-Chun

    2011-11-04

    A highly enantioselective aza-Diels-Alder and Friedel-Crafts reaction sequence of N-sulfonyl-1-aza-1,3-butadienes and aliphatic aldehydes tethered to an arene motif has been developed, affording the fused chiral piperidine frameworks with a versatile scaffold diversity. A similar strategy has been applied for the construction of complex chiral tetrahydroquinoxaline structures.

  2. A Counterion‐Directed Approach to the Diels–Alder Paradigm: Cascade Synthesis of Tricyclic Fused Cyclopropanes

    PubMed Central

    Kiss, Emily; Campbell, Craig D.; Driver, Russell W.; Jolliffe, John D.; Lang, Rosemary; Sergeieva, Tetiana; Okovytyy, Sergiy

    2016-01-01

    Abstract An approach to the intramolecular Diels–Alder reaction has led to a cascade synthesis of complex carbocycles composed of three fused rings and up to five stereocenters with complete stereocontrol. Computational analysis reveals that the reaction proceeds by a Michael/Michael/cyclopropanation/epimerization cascade in which size and coordination of the counterion is key. PMID:27714921

  3. A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction.

    PubMed

    McGee, Philippe; Bétournay, Geneviève; Barabé, Francis; Barriault, Louis

    2017-01-12

    We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this Au(I) -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine.

  4. Biosynthesis inspired Diels-Alder route to pyridines: synthesis of the 2,3-dithiazolylpyridine core of the thiopeptide antibiotics.

    PubMed

    Moody, Christopher J; Hughes, Rachael A; Thompson, Stewart P; Alcaraz, Lilian

    2002-08-21

    Reaction of serine derived 1-alkoxy-2-azadienes with dehydroalanine derived dienophiles results in Diels-Alder reaction and aromatisation to give 2,3,6-trisubstituted pyridines, thereby establishing the viability of the proposed biosynthetic route to the pyridine ring of the thiopeptide antibiotics originally proposed by Bycroft and Gowland.

  5. Silver-Catalyzed Formal Inverse Electron-Demand Diels-Alder Reaction of 1,2-Diazines and Siloxy Alkynes

    PubMed Central

    Türkmen, Yunus E.; Montavon, Timothy J.; Kozmin, Sergey A.; Rawal, Viresh H.

    2012-01-01

    A highly effective silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes has been developed. The reactions provide ready access to a wide range of siloxy naphthalenes and anthracenes, which are formed in good to high yields, under mild reaction conditions, using low catalyst loadings. PMID:22607029

  6. Highly enantioselective aza-Diels-Alder reaction of 1-azadienes with enecarbamates catalyzed by chiral phosphoric acids.

    PubMed

    He, Long; Laurent, Gregory; Retailleau, Pascal; Folléas, Benoît; Brayer, Jean-Louis; Masson, Géraldine

    2013-10-11

    On demand: A highly enantio- and diastereoselective synthesis of 6-amino- trisubstituted tetrahydropyridine compounds has been developed through the inverse-electron-demand aza-Diels-Alder reaction of N-aryl α,β-unsaturated ketimines with enecarbamates (E)-1. Chiral phosphoric acid catalysts achieve simultaneous activation of both the 1-azadiene and dienophile partners.

  7. Strong counteranion effects on the catalytic activity of cationic silicon Lewis acids in Mukaiyama aldol and Diels-Alder reactions.

    PubMed

    Hara, Kenji; Akiyama, Ryuto; Sawamura, Masaya

    2005-12-08

    [chemical reaction: see text]. A toluene-coordinated silyl borate, [Et3Si(toluene)]B(C6F5)4, demonstrated catalytic activities significantly higher than those of Me3SiOTf and Me3SiNTf2 in Mukaiyama aldol and Diels-Alder reactions.

  8. Fungal Endophyte (Epichloë festucae) Alters the Nutrient Content of Festuca rubra Regardless of Water Availability

    PubMed Central

    Vázquez-de-Aldana, Beatriz R.; García-Ciudad, Antonia; García-Criado, Balbino; Vicente-Tavera, Santiago; Zabalgogeazcoa, Iñigo

    2013-01-01

    Festuca rubra plants maintain associations with the vertically transmitted fungal endophyte Epichloë festucae. A high prevalence of infected host plants in semiarid grasslands suggests that this association could be mutualistic. We investigated if the Epichloë-endophyte affects the growth and nutrient content of F. rubra plants subjected to drought. Endophyte-infected (E+) and non-infected (E−) plants of two half-sib lines (PEN and RAB) were subjected to three water availability treatments. Shoot and root biomass, nutrient content, proline, phenolic compounds and fungal alkaloids were measured after the treatments. The effect of the endophyte on shoot and root biomass and dead leaves depended on the plant line. In the PEN line, E+ plants had a greater S:R ratio than E-, but the opposite occurred in RAB. In both plant lines and all water treatments, endophyte-infected plants had greater concentrations of N, P and Zn in shoots and Ca, Mg and Zn in roots than E- plants. On average, E+ plants contained in their shoots more P (62%), Zn (58%) and N (19%) than E- plants. While the proline in shoots increased in response to water stress, the endophyte did not affect this response. A multivariate analysis showed that endophyte status and plant line impose stronger differences in the performance of the plants than the water stress treatments. Furthermore, differences between PEN and RAB lines seemed to be greater in E- than in E+ plants, suggesting that E+ plants of both lines are more similar than those of their non-infected version. This is probably due to the endophyte producing a similar effect in both plant lines, such as the increase in N, P and Zn in shoots. The remarkable effect of the endophyte in the nutrient balance of the plants could help to explain the high prevalence of infected plants in natural grasslands. PMID:24367672

  9. Fungal endophyte (Epichloë festucae) alters the nutrient content of Festuca rubra regardless of water availability.

    PubMed

    Vázquez-de-Aldana, Beatriz R; García-Ciudad, Antonia; García-Criado, Balbino; Vicente-Tavera, Santiago; Zabalgogeazcoa, Iñigo

    2013-01-01

    Festuca rubra plants maintain associations with the vertically transmitted fungal endophyte Epichloë festucae. A high prevalence of infected host plants in semiarid grasslands suggests that this association could be mutualistic. We investigated if the Epichloë-endophyte affects the growth and nutrient content of F. rubra plants subjected to drought. Endophyte-infected (E+) and non-infected (E-) plants of two half-sib lines (PEN and RAB) were subjected to three water availability treatments. Shoot and root biomass, nutrient content, proline, phenolic compounds and fungal alkaloids were measured after the treatments. The effect of the endophyte on shoot and root biomass and dead leaves depended on the plant line. In the PEN line, E+ plants had a greater S:R ratio than E-, but the opposite occurred in RAB. In both plant lines and all water treatments, endophyte-infected plants had greater concentrations of N, P and Zn in shoots and Ca, Mg and Zn in roots than E- plants. On average, E+ plants contained in their shoots more P (62%), Zn (58%) and N (19%) than E- plants. While the proline in shoots increased in response to water stress, the endophyte did not affect this response. A multivariate analysis showed that endophyte status and plant line impose stronger differences in the performance of the plants than the water stress treatments. Furthermore, differences between PEN and RAB lines seemed to be greater in E- than in E+ plants, suggesting that E+ plants of both lines are more similar than those of their non-infected version. This is probably due to the endophyte producing a similar effect in both plant lines, such as the increase in N, P and Zn in shoots. The remarkable effect of the endophyte in the nutrient balance of the plants could help to explain the high prevalence of infected plants in natural grasslands.

  10. Larvicidal activity of silver nanoparticles synthesized using Plumeria rubra plant latex against Aedes aegypti and Anopheles stephensi.

    PubMed

    Patil, Chandrashekhar D; Patil, Satish V; Borase, Hemant P; Salunke, Bipinchandra K; Salunkhe, Rahul B

    2012-05-01

    In the present study activity of silver nanoparticles (AgNPs) synthesized using Plumeria rubra plant latex against second and fourth larval instar of Aedes aegypti and Anopheles stephensi was determined. Range of concentrations of synthesized AgNps (10, 5, 2.5, 1.25, 0.625, 0.3125 ppm) and aqueous crude latex (1,000, 500, 250, 125, 62.50, 31.25 ppm) were tested against larvae of A. aegypti and A. Stephensi. The synthesized AgNps from P. rubra latex were highly toxic than crude latex extract in both mosquito species. The LC(50) values for second and fourth larval instars after 24 h of crude latex exposure were 1.49, 1.82 ppm against A. aegypti and 1.10, 1.74 ppm against A. stephensi respectively. These figures were 181.67, 287.49 ppm against A. aegypti and 143.69, 170.58 ppm against A. stephensi respectively for crude latex extract. The mortality rates were positively correlated with the concentration of AgNPs. The characterization studies of synthesized AgNPs by UV-Vis spectrophotometry, transmission electron microscopy (TEM), Particle size analysis (PSA) and zeta potential confirmed the spherical shape and size (32-200 nm) of silver nanoparticles along with stability. Toxicity studies carried out against non-target fish species Poecilia reticulata, the most common organism in the habitats of A. aegypti and A. stephensi showed no toxicity at LC(50) and LC(90) doses of the AgNPs. This is the first report on mosquito larvicidal activity of latex synthesized nanoparticles.

  11. Nymphaea rubra ameliorates TNF-α-induced insulin resistance via suppression of c-Jun NH2-terminal kinase and nuclear factor-κB in the rat skeletal muscle cells.

    PubMed

    Gautam, Sudeep; Rahuja, Neha; Ishrat, Nayab; Asthana, R K; Mishra, D K; Maurya, Rakesh; Jain, Swatantra Kumar; Srivastava, Arvind Kumar

    2014-12-01

    In this work, we demonstrated insulin signaling and the anti-inflammatory effects by the chloroform fraction of ethanolic extract of Nymphaea rubra flowers in TNF-α-induced insulin resistance in the rat skeletal muscle cell line (L6 myotubes) to dissect out its anti-hyperglycemic mechanism. N. rubra enhances the GLUT4-mediated glucose transport in a dose dependent manner and also increases the tyrosine phosphorylation of both IR-β and IRS-1, and the IRS-1 associated PI-3 kinase activity in TNF-α-treated L6 myotubes. Moreover, N. rubra decreases Ser(307) phosphorylation of IRS-1 by the suppression of JNK and NF-κB activation. In conclusion, N. rubra reverses the insulin resistance by the inhibition of c-Jun NH2-Terminal Kinase and Nuclear-κB.

  12. Diversity-Oriented Approaches to Polycyclics and Bioinspired Molecules via the Diels-Alder Strategy: Green Chemistry, Synthetic Economy, and Beyond.

    PubMed

    Kotha, Sambasivarao; Chavan, Arjun S; Goyal, Deepti

    2015-05-11

    We describe diverse approaches to various dienes and their utilization in the Diels-Alder reaction to produce a variety of polycycles. The dienes covered here are prepared by simple alkylation reaction or via the Claisen rearrangement or by enyne metathesis of alkyne or enyne building blocks. Here, we have also included the Diels-Alder chemistry of dendralenes, a higher analog of cross-conjugated dienes. The present article is inclusive of o-xylylene derivatives that are generated in situ starting with benzosultine or benzosulfone derivatives. The Diels-Alder reaction of these dienes with various dienophiles gave diverse polycyclic systems and biologically important targets.

  13. Synthesis of tetrasubstituted 1-silyloxy-3-aminobutadienes and chemistry beyond Diels–Alder reactions

    PubMed Central

    Li, Xijian; Peng, Siyu; Li, Li; Huang, Yong

    2015-01-01

    Electron-rich dienes have revolutionized the synthesis of complex compounds since the discovery of the legendary Diels–Alder cycloaddition reaction. This highly efficient bond-forming process has served as a fundamental strategy to assemble many structurally formidable molecules. Amino silyloxy butadienes are arguably the most reactive diene species that are isolable and bottleable. Since the pioneering discovery by Rawal, 1-amino-3-silyloxybutadienes have been found to undergo cycloaddition reactions with unparalleled mildness, leading to significant advances in both asymmetric catalysis and total synthesis of biologically active natural products. In sharp contrast, this class of highly electron-rich conjugated olefins has not been studied in non-cycloaddition reactions. Here we report a simple synthesis of tetrasubstituted 1-silyloxy-3-aminobutadienes, a complementarily substituted Rawal's diene. This family of molecules is found to undergo a series of intriguing chemical transformations orthogonal to cycloaddition reactions. Structurally diverse polysubstituted ring architectures are established in one step from these dienes. PMID:25898310

  14. Click and Patterned Functionalization of Graphene by Diels-Alder Reaction.

    PubMed

    Li, Jing; Li, Meng; Zhou, Li-Li; Lang, Shuang-Yan; Lu, Hai-Yan; Wang, Dong; Chen, Chuan-Feng; Wan, Li-Jun

    2016-06-22

    Chemical functionalization is a promising approach to controllably manipulate the characteristics of graphene. Here, we designed cis-dienes, featuring two dihydronaphthalene backbones, to decorate a graphene surface via Diels-Alder (DA) click reaction. The installation of a diene moiety into a nonplanar molecular structure to form cis-conformation enables a rapid (∼5 min) DA reaction between graphene and diene groups. Patterned graphene of sub-micrometer resolution can be obtained by easily soaking poly(methyl methacrylate)-masked graphene in solution of hydroxyl-substituted cis-diene at room temperature. The functionalization degree can be further controlled by carrying out the reaction at higher temperature. The present result gives important insight into the effect of molecular conformation on the graphene functionalization process, and provides an effective and facile method for graphene functionalization.

  15. (18)F-Based Pretargeted PET Imaging Based on Bioorthogonal Diels-Alder Click Chemistry.

    PubMed

    Meyer, Jan-Philip; Houghton, Jacob L; Kozlowski, Paul; Abdel-Atti, Dalya; Reiner, Thomas; Pillarsetty, Naga Vara Kishore; Scholz, Wolfgang W; Zeglis, Brian M; Lewis, Jason S

    2016-02-17

    A first-of-its-kind (18)F pretargeted PET imaging approach based on the bioorthogonal inverse electron demand Diels-Alder (IEDDA) reaction between tetrazine (Tz) and trans-cyclooctene (TCO) is presented. As proof-of-principle, a TCO-bearing immunoconjugate of the anti-CA19.9 antibody 5B1 and an Al[(18)F]NOTA-labeled tetrazine radioligand were harnessed for the visualization of CA19.9-expressing BxPC3 pancreatic cancer xenografts. Biodistribution and (18)F-PET imaging data clearly demonstrate that this methodology effectively delineates tumor mass with activity concentrations up to 6.4 %ID/g at 4 h after injection of the radioligand.

  16. Impact of Lewis acids on Diels-Alder reaction reactivity: a conceptual density functional theory study.

    PubMed

    Xia, Yue; Yin, Dulin; Rong, Chunying; Xu, Qiong; Yin, Donghong; Liu, Shubin

    2008-10-09

    Density functional theory (DFT) and conceptual/chemical DFT studies are carried out in this work for the normal electron demand Diels-Alder reaction between isoprene and acrolein to compare chemical reactivity and regioselectivity of the reactants in the absence and presence of Lewis acid (LA) catalysts. A cyclic coplanar structure of acrolein-LA complex has been observed and the natural bond orbital analysis has been employed to interpret the interaction between acrolein and LAs. Reactivity indices from frontier molecular orbital energies are proved to be adequate and efficient to evaluate the catalytic property of LAs. Linear relationships have been discovered among the bond order, bond length, catalytic activation, and chemical reactivity for the systems concerned. The validity and applicability of maximum hardness principle, minimum polarizability principle, and minimum electrophilicity principle are examined and discussed in the prediction of the major regioselective isomer and the preferred reaction pathway for the reactions in the present study.

  17. Bio‐orthogonal Fluorescent Labelling of Biopolymers through Inverse‐Electron‐Demand Diels–Alder Reactions

    PubMed Central

    Kozma, Eszter; Demeter, Orsolya

    2017-01-01

    Abstract Bio‐orthogonal labelling schemes based on inverse‐electron‐demand Diels–Alder (IEDDA) cycloaddition have attracted much attention in chemical biology recently. The appealing features of this reaction, such as the fast reaction kinetics, fully bio‐orthogonal nature and high selectivity, have helped chemical biologists gain deeper understanding of biochemical processes at the molecular level. Listing the components and discussing the possibilities and limitations of these reagents, we provide a recent snapshot of the field of IEDDA‐based biomolecular manipulation with special focus on fluorescent modulation approaches through the use of bio‐orthogonalized building blocks. At the end, we discuss challenges that need to be addressed for further developments in order to overcome recent limitations and to enable researchers to answer biomolecular questions in more detail. PMID:28070925

  18. Characterization of vanadium ion uptake in sulfonated diels alder poly(phenylene) membranes

    DOE PAGES

    Lawton, Jamie; Jones, Amanda; Tang, Zhijiang; ...

    2015-11-28

    Sulfonated diels alder poly(phenylene) (SDAPP), alternative aromatic hydrocarbon membranes for vanadium redox flow batteries (VRFBs) are characterized using electron paramagnetic resonance (EPR). Membranes soaked in sulfuric acid and vanadyl sulfate are analyzed to determine the membrane environment in which the vanadyl ion (VO2+) diffuses in the membranes. These results are compared to Nafion 117 membranes. In contrast to Nafion, the VO2+ in SDAPP membranes exists in two different environments. The results of analysis of rotational diffusion determined from fits the EPR spectral lineshapes in comparison with previously reported permeation studies and measurements of partitioning functions reported here suggest that themore » diffusion pathways in SDAPP are very different than in Nafion.« less

  19. Carbocations as Lewis acid catalysts in Diels-Alder and Michael addition reactions.

    PubMed

    Bah, Juho; Franzén, Johan

    2014-01-20

    In general, Lewis acid catalysts are metal-based compounds that owe their reactivity to a low-lying empty orbital. However, one potential Lewis acid that has received negligible attention as a catalyst is the carbocation. We have demonstrated the potential of the carbocation as a highly powerful Lewis acid catalyst for organic reactions. The stable and easily available triphenylmethyl (trityl) cation was found to be a highly efficient catalyst for the Diels-Alder reaction for a range of substrates. Catalyst loadings as low as 500 ppm, excellent yields, and good endo/exo selectivities were achieved. Furthermore, by changing the electronic properties of the substituents on the tritylium ion, the Lewis acidity of the catalyst could be tuned to control the outcome of the reaction. The ability of this carbocation as a Lewis acid catalyst was also further extended to the Michael reaction.

  20. Effect of Diels-Alder Reaction in C60-Tetracene Photovoltaic Devices.

    PubMed

    Proudian, Andrew P; Jaskot, Matthew B; Lyiza, Christelle; Diercks, David R; Gorman, Brian P; Zimmerman, Jeramy D

    2016-10-12

    Developing organic photovoltaic materials systems requires a detailed understanding of the heterojunction interface, as it is the foundation for photovoltaic device performance. The bilayer fullerene/acene system is one of the most studied models for testing our understanding of this interface. We demonstrate that the fullerene and acene molecules chemically react at the heterojunction interface, creating a partial monolayer of a Diels-Alder cycloadduct species. Furthermore, we show that the reaction occurs during standard deposition conditions and that thermal annealing increases the concentration of the cycloadduct. The cycloaddition reaction reduces the number of sites available at the interface for charge transfer exciton recombination and decreases the charge transfer state reorganization energy, increasing the open circuit voltage. The submonolayer quantity of the cycloadduct renders it difficult to identify with conventional characterization techniques; we use atom probe tomography to overcome this limitation while also measuring the spatial distribution of each chemical species.

  1. Poly /Diels-Alder/ matrix resins. [high temperature resistant graphite reinforced composites

    NASA Technical Reports Server (NTRS)

    Jones, R. J.; Orell, M. K.; Sheppard, C. H.; Vaughan, R. W.

    1977-01-01

    A poly (Diels-Alder) (PDA) resin approach was investigated as a means to achieve autoclavability of high-temperature resistant resin/fiber composites under mild fabrication conditions. The results of the study were highly promising and program objectives were achieved. Low-void content Type A-S graphite reinforced composites were autoclave fabricated from a PDA resin/fiber prepreg prepared from an acetone:methanol:dioxane varnish. Autoclave conditions were 400 F and 100 psi for up to two hours duration. After postcure at temperatures up to 600 F, the composites demonstrated high initial mechanical properties at temperatures up to 550 F. The results from isothermal aging studies in air for 1000 hours indicated potential for long-term (over 1000 hours) use at 500 F and shorter-term use at 550 F.

  2. Total synthesis of (+)-gelsemine via an organocatalytic Diels–Alder approach

    PubMed Central

    Chen, Xiaoming; Duan, Shengguo; Tao, Cheng; Zhai, Hongbin; Qiu, Fayang G.

    2015-01-01

    The structurally complex alkaloid gelsemine was previously thought to have no significant biological activities, but a recent study has shown that it has potent and specific antinociception in chronic pain. While this molecule has attracted significant interests from the synthetic community, an efficient synthetic strategy is still the goal of many synthetic chemists. Here we report the asymmetric total synthesis of (+)-gelsemine, including a highly diastereoselective and enantioselective organocatalytic Diels–Alder reaction, an efficient intramolecular trans-annular aldol condensation furnishing the prolidine ring and establishing the configuration of the C20 quaternary carbon stereochemical centre. The entire gelsemine skeleton was constructed through a late-stage intramolecular SN2 substitution. The enantiomeric excess of this total synthesis is over 99%, and the overall yield is around 5%. PMID:25995149

  3. Dynamics of methane production, sulfate reduction, and denitrification in a permanently waterlogged alder swamp

    SciTech Connect

    Westermann, P.; Ahring, B.K.

    1987-10-01

    The dynamics of sulfate reduction, methane production, and denitrification were investigated in a permanently waterlogged alder swamp. Molybdate, an inhibitor of sulfate reduction, stimulated methane production in soil slurries, thus suggesting competition for common substrates between sulfate-reducing and methane-producing bacteria. Acetate, hydrogen, and methanol were found to stimulate both sulfate reduction and methane production, while trimethylamine mainly stimulated methane production. Nitrate addition reduced both methane production and sulfate reduction, either as a consequence of competition of poisoning of the bacteria. Sulfate-reducing bacteria were only slightly limited by the availability of electron acceptors, while denitrifying bacteria were seriously limited by low nitrate concentrations. Arrhenius plots of the three processes revealed different responses to temperature changes in the slurries. Methane production was most sensitive to temperature changes, followed by denitrification and sulfate reduction. No significant differences between slope patterns were observed when comparing summer and winter measurements, indicating similar populations regarding temperature responses.

  4. Characterization of vanadium ion uptake in sulfonated diels alder poly(phenylene) membranes

    SciTech Connect

    Lawton, Jamie; Jones, Amanda; Tang, Zhijiang; Lindsey, Melanie; Zawodzinski, Thomas A

    2015-11-28

    Sulfonated diels alder poly(phenylene) (SDAPP), alternative aromatic hydrocarbon membranes for vanadium redox flow batteries (VRFBs) are characterized using electron paramagnetic resonance (EPR). Membranes soaked in sulfuric acid and vanadyl sulfate are analyzed to determine the membrane environment in which the vanadyl ion (VO2+) diffuses in the membranes. These results are compared to Nafion 117 membranes. In contrast to Nafion, the VO2+ in SDAPP membranes exists in two different environments. The results of analysis of rotational diffusion determined from fits the EPR spectral lineshapes in comparison with previously reported permeation studies and measurements of partitioning functions reported here suggest that the diffusion pathways in SDAPP are very different than in Nafion.

  5. Thiourea-catalyzed Diels–Alder reaction of a naphthoquinone monoketal dienophile

    PubMed Central

    Kramer, Carsten S

    2013-01-01

    Summary A variety of organocatalysts were screened for the catalysis of the naphthoquinone monoketal Diels–Alder reaction. In this study we found that Schreiner's thiourea catalyst 10 and Jacobson's thiourea catalyst 12 facilitate the cycloaddition of the sterically hindered naphthoquinone monoketal dienophile 3 with diene 4. The use of thiourea catalysis allowed for the first time the highly selective synthesis of the exo-product 2a in up to 63% yield. In this reaction a new quaternary center was built. The so formed cycloaddition product 2a represents the ABC tricycle of beticolin 0 (1) and is also a valuable model substrate for the total synthesis of related natural products. PMID:23946836

  6. The inverse electron demand Diels-Alder click reaction in radiochemistry.

    PubMed

    Reiner, Thomas; Zeglis, Brian M

    2014-04-01

    The inverse electron-demand Diels-Alder (IEDDA) cycloaddition between 1,2,4,5-tetrazines and strained alkene dienophiles is an emergent variety of catalyst-free 'click' chemistry that has the potential to have a transformational impact on the synthesis and development of radiopharmaceuticals. The ligation is selective, rapid, high-yielding, clean, and bioorthogonal and, since its advent in 2008, has been employed in a wide variety of chemical settings. In radiochemistry, the reaction has proven particularly useful with (18)  F and has already been utilized to create a number of (18)  F-labeled agents, including the PARP1-targeting small molecule (18)  F-AZD2281, the αv β3 integrin-targeting peptide (18)  F-RGD, and the GLP-1-targeting peptide (18)  F-exendin. The inherent flexibility of the ligation has also been applied to the construction of radiometal-based probes, specifically the development of a modular strategy for the synthesis of radioimmunoconjugates that effectively eliminates variability in the construction of these agents. Further, the exceptional speed and biorthogonality of the reaction have made it especially promising in the realm of in vivo pretargeted imaging and therapy, and pretargeted imaging strategies based on the isotopes (111) In, (18)  F, and (64) Cu have already proven capable of producing images with high tumor contrast and low levels of uptake in background, nontarget organs. Ultimately, the characteristics of inverse electron-demand Diels-Alder click chemistry make it almost uniquely well-suited for radiochemistry, and although the field is young, this ligation has the potential to make a tremendous impact on the synthesis, development, and study of novel radiopharmaceuticals.

  7. Development and applications of Diels-Alder cycloadditions of 2'-hydroxychalcones

    NASA Astrophysics Data System (ADS)

    Cong, Huan

    Single electron transfer (SET)-initiated formal [4+2] cycloadditions of 2'-hydroxychalcones have been achieved employing a combination of Lewis acid and electron donor as catalyst. Mechanistic studies using cyclic voltammetry (CV) and deuterium labeling experiments suggested a radical anion-mediated stepwise mechanism. The utility of this methodology was established in the first total synthesis of natural product nicolaioidesin C. A novel silica-supported silver nanoparticle (AgNP) catalyst has been developed as a highly active, reusable, and user-friendly catalyst for Diels-Alder cycloadditions of 2'-hydroxychalcones, as showcased by the first total synthesis of natural product panduratin A. Our work demonstrates results from an interdisciplinary research project involving synthetic methodology development, nanometric material preparation, heterogeneous catalysis, natural product synthesis, and mechanistic studies using various instrumental techniques. Biomimetic, dehydrogenative cycloadditions of 2'-hydroxychalcones have been achieved using a mixture of platinum on activated carbon (Pt/C) and silica-supported silver nanoparticles (AgNP's) catalysts. This heterogeneous multicatalytic protocol converts a prenyl subunit in situ to diene which subsequently reacts with a 2'-hyroxychalcone dienophile to provide Diels-Alder cycloadducts in a single step. Using this methodology, a concise synthesis of the core structure of the natural product brosimone B has been accomplished. Enantioselective cycloadditions of 2'-hydroxychalcones have been established with excellent yields and enantioselectivity. Two optimized catalytic conditions have been developed: the first method utilizes a catalyst system comprised of chiral rare earth metal complex and electron donor; the second approach involves a chiral borate catalyst. The asymmetric total synthesis of natural product (+)-sorocenol B has been pursued.

  8. Tyrosine-lipid peroxide adducts from radical termination: para coupling and intramolecular Diels-Alder cyclization.

    PubMed

    Shchepin, Roman; Möller, Matias N; Kim, Hye-young H; Hatch, Duane M; Bartesaghi, Silvina; Kalyanaraman, Balaraman; Radi, Rafael; Porter, Ned A

    2010-12-15

    Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogues of tyrosine gave rise to lipid peroxide-tyrosine (phenol) adducts in both aqueous micellar and organic solutions. The novel adducts were isolated and characterized by 1D and 2D NMR spectroscopy as well as by mass spectrometry (MS). The spectral data suggest that the polyunsaturated lipid peroxyl radicals give stable peroxide coupling products exclusively at the para position of the tyrosyl (phenoxy) radicals. These adducts have characteristic (13)C chemical shifts at 185 ppm due to the cross-conjugated carbonyl of the phenol-derived cyclohexadienone. The primary peroxide adducts subsequently undergo intramolecular Diels-Alder (IMDA) cyclization, affording a number of diastereomeric tricyclic adducts that have characteristic carbonyl (13)C chemical shifts at ~198 ppm. All of the NMR HMBC and HSQC correlations support the structure assignments of the primary and Diels-Alder adducts, as does MS collision-induced dissociation data. Kinetic rate constants and activation parameters for the IMDA reaction were determined, and the primary adducts were reduced with cuprous ion to give a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found in either the primary or cuprous reduction product mixtures. These studies provide a framework for understanding the nature of lipid-protein adducts formed by peroxyl-tyrosyl radical-radical termination processes. Coupling of lipid peroxyl radicals with tyrosyl radicals leads to cyclohexenone and cyclohexadienone adducts, which are of interest in and of themselves since, as electrophiles, they are likely targets for protein nucleophiles. One consequence of lipid peroxyl reactions with tyrosyls may therefore be protein-protein cross-links via interprotein Michael adducts.

  9. Screening the wetland plant species Alisma plantago-aquatica, Carex rostrata and Phalaris arundinacea for innate tolerance to zinc and comparison with Eriophorum angustifolium and Festuca rubra Merlin.

    PubMed

    Matthews, David J; Moran, Bridget M; Otte, Marinus L

    2005-03-01

    Several wetland plant species appear to have constitutive metal tolerance. In previous studies, populations from contaminated and non-contaminated sites of the wetland plants Typha latifolia, Phragmites australis, Glyceria fluitans and Eriophorum angustifolium were found to be tolerant to high concentrations of metals. This study screened three other species of wetland plants: Alisma plantago-aquatica, Carex rostrata and Phalaris arundinacea for innate tolerance to zinc. The degree of tolerance was compared to known zinc-tolerant E. angustifolium and Festuca rubra Merlin. It was found that A. plantago-aquatica and P. arundinacea did not posses innate tolerance to zinc, but that C. rostrata was able to tolerate elevated levels of zinc, at levels comparable to those tolerated by E. angustifolium and F. rubra Merlin. The findings support the theory that some wetland angiosperm species tend to be tolerant to exposure to high levels of metals, regardless of their origin.

  10. Bisoxazoline-Lewis acid-catalyzed direct-electron demand oxo-hetero-Diels-Alder reactions of N-oxy-pyridine aldehyde and ketone derivatives.

    PubMed

    Landa, Aitor; Richter, Bo; Johansen, Rasmus Lyng; Minkkilä, Anna; Jørgensen, Karl Anker

    2007-01-05

    A general catalytic oxo-hetero-Diels-Alder reaction for pro-chiral aldehyde and ketone N-oxy-pyridines is presented. The catalytic and asymmetric oxo-hetero-Diels-Alder reaction of electron-rich dienes with N-oxy-pyridine-2-carbaldehyde and ketone derivatives, catalyzed by chiral copper(II)-bisoxazoline complexes, gives optically active six-membered oxygen heterocycles in moderate to good yields and with excellent enantioselectivities.

  11. Synthesis of Isochromene-Type Scaffolds via Single-Flask Diels–Alder-[4 + 2]-Annulation Sequence of a Silyl-Substituted Diene with Menadione

    PubMed Central

    2015-01-01

    A sequential Diels–Alder reaction/silicon-directed [4 + 2]-annulation was developed to assemble hydroisochromene-type ring systems from menadione 2. In the first step, a Diels–Alder of the 1-silyl-substituted butadiene 1 with 2 furnished an intermediate cyclic allylsilane. Subsequently, TMSOTf promoted a [4 + 2]-annulation through trapping of an oxonium, generated by condensation between an aldehyde and the TBS protected alcohol resulted in the formation of a cis-fused hydroisochromene 13. PMID:24918110

  12. Synthesis of isochromene-type scaffolds via single-flask Diels-Alder-[4 + 2]-annulation sequence of a silyl-substituted diene with menadione.

    PubMed

    Lee, Jihoon; Panek, James S

    2014-06-20

    A sequential Diels-Alder reaction/silicon-directed [4 + 2]-annulation was developed to assemble hydroisochromene-type ring systems from menadione 2. In the first step, a Diels-Alder of the 1-silyl-substituted butadiene 1 with 2 furnished an intermediate cyclic allylsilane. Subsequently, TMSOTf promoted a [4 + 2]-annulation through trapping of an oxonium, generated by condensation between an aldehyde and the TBS protected alcohol resulted in the formation of a cis-fused hydroisochromene 13.

  13. Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

    PubMed

    Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

    2015-09-23

    Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

  14. Susceptibilities of Different Test Systems from Maize (Zea mays), Poa annua, and Festuca rubra to Herbicides That Inhibit the Enzyme Acetyl-Coenzyme A Carboxylase

    PubMed

    Herbert; Cole; Pallett; Harwood

    1996-06-01

    The susceptibilities of maize (Zea mays cv. Champ) and two graminicide-resistant grass species, Poa annua (annual meadow grass) and Festuca rubra (red fescue), to two aryloxyphenoxypropionates (quizalofop and fluazifop) and a cyclohexanedione (sethoxydim) graminicide were evaluated in leaf blades and isolated chloroplasts, and by assaying acetyl-coenzyme A carboxylase (ACCase) in desalted leaf homogenates. The graminicide resistance of P. annua and F. rubra appeared to be at the level of ACCase. Festuca rubra ACCase was highly insensitive and P. annua ACCase was partially insensitive to the graminicides that were tested. Fatty acid synthesis in isolated maize chloroplasts was more susceptible to inhibition than was ACCase activity from whole leaves. There was a smaller difference in graminicide sensitivity between these two test systems in P. annua. The developmental pattern of ACCase specific activity and its inhibition by quizalofop was measured in maize and P. annua leaf blades. There was an age-dependent increase in the sensitivity of maize leaf ACCase activity to inhibition by quizalofop. Together with the greater susceptibility of chloroplasts compared with leaf homogenates this could imply that a graminicide-insensitive (extrachloroplastic) ACCase isoform is less highly expressed in older leaves. Poa annua ACCase did not significantly alter in sensitivity as leaves aged, consistent with the smaller difference in the level of inhibition between chloroplasts and leaf homogenates in this species. A small pyruvate carboxylase activity was detected in maize leaves after 9 days. By 38 days, when leaves were senescing, pyruvate carboxylase activity predominated over ACCase.

  15. Phylogenetic utility, and variability in structure and content, of complete mitochondrial genomes among genetic lineages of the Hawaiian anchialine shrimp Halocaridina rubra Holthuis 1963 (Atyidae:Decapoda).

    PubMed

    Justice, Joshua L; Weese, David A; Santos, Scott Ross

    2016-07-01

    The Atyidae are caridean shrimp possessing hair-like setae on their claws and are important contributors to ecological services in tropical and temperate fresh and brackish water ecosystems. Complete mitochondrial genomes have only been reported from five of the 449 species in the family, thus limiting understanding of mitochondrial genome evolution and the phylogenetic utility of complete mitochondrial sequences in the Atyidae. Here, comparative analyses of complete mitochondrial genomes from eight genetic lineages of Halocaridina rubra, an atyid endemic to the anchialine ecosystem of the Hawaiian Archipelago, are presented. Although gene number, order, and orientation were syntenic among genomes, three regions were identified and further quantified where conservation was substantially lower: (1) high length and sequence variability in the tRNA-Lys and tRNA-Asp intergenic region; (2) a 317-bp insertion between the NAD6 and CytB genes confined to a single lineage and representing a partial duplication of CytB; and (3) the putative control region. Phylogenetic analyses utilizing complete mitochondrial sequences provided new insights into relationships among the H. rubra genetic lineages, with the topology of one clade correlating to the geologic sequence of the islands. However, deeper nodes in the phylogeny lacked bootstrap support. Overall, our results from H. rubra suggest intra-specific mitochondrial genomic diversity could be underestimated across the Metazoa since the vast majority of complete genomes are from just a single individual of a species.

  16. Frugivory and seed dispersal patterns of the red-ruffed lemur, Varecia rubra, at a forest restoration site in Masoala National Park, Madagascar.

    PubMed

    Martinez, Barbara T; Razafindratsima, Onja H

    2014-01-01

    Frugivorous primates can play a critical role in the regeneration of degraded habitats by dispersing seeds of their food plants. We studied the diet and seed dispersal patterns of 3 groups of habituated red-ruffed lemurs (Varecia rubra) in a rain forest restoration site in Masoala National Park, Madagascar, to assess the species' seed dispersal effectiveness. Fruits accounted for 61% of the diet, with an average foraging time of 10 min per fruit patch per day. Seeds from 75% of the consumed fruit species were recovered in the collected V. rubra feces. We traced the potential parent plants of 20 dispersed-seed species to calculate a gut passage range (63-423 min; mean = 225, n = 35). The median seed dispersal distance from the potential parent plant was 48 m (mean = 83 m, range 0-568 m, n = 194). The home ranges of 2 of the 3 groups overlapped with the regenerating forest parcels. Although 92% of fecal samples with seeds were dispersed into the undisturbed forest, V. rubra fed on the fruits of the non-native pioneer shrub Clidemia hirta, while also dispersing native and non-native seed species into the regenerating forest parcels.

  17. Initial and continued effects of a release spray in a coastal Oregon douglas-fir plantation. Forest Service research paper

    SciTech Connect

    Miller, R.E.; Obermeyer, E.L.

    1996-03-01

    Portions of a 4-year-old Douglas-fir (Pseudotsuga menziesii var. menziesii (Mirb.) Franco) plantation were sprayed with herbicide. Five years after spraying the authors established 18 plots and used several means to determine retrospectively that six plots probably received full spray treatment and six others received no spray. Various portions of the remaining six plots were sprayed. Herbicide reduced number and size of red alder (Alnus rubra Bong.), increased number and size of planted Douglas-fir, damaged terminal shoots of Douglas-fir resulting in more abnormal boles and branching, and increased number of volunteer conifers. Fifteen of the eighteen plots were thinned, in the subsequent 6 years, thinned plots that had received full release at age 4 averaged 9 percent more volume growth (all species) than plots not released.

  18. Diels-Alder Trapping of Photochemically Generated Dienes with Acrylic Esters: A Novel Approach to Photocured Polymer Film Development

    NASA Technical Reports Server (NTRS)

    Ilhan, Faysal; Tyson, Daniel S.; Smith, Deedee; Meador, Mary Ann; Meador, Michael A.

    2004-01-01

    Diels-Alder cycloadditions have often been utilized in polymer synthesis as an alternative to condensation reactions. In our earlier efforts, we developed a new method for the preparation of linear aromatic polyimides, which employs o-quionodimethanes (o-QDMs), generated by a well-known photochemical reaction: the photoenolization of o-methylphenyl ketones. Photolysis of o-methylbenzophenone 1 produces hydroxy-o-quino- diemthane 2, which can be trapped with dienophiles, such as dimethyl acetylenedicarboxylate, to efficiently yield the corresponding cycloadduct (Scheme 1). Here we extend this approach to a novel photocuring process for development of polymer films. We synthesized a series of molecules with multi o-mehtylphenyl ketone functionalities. We further investigated these molecules as photoreactive monomers to obtain polyester films through Diels-Alder cycloadditions.

  19. Expanding the scope of cyclopropene reporters for the detection of metabolically engineered glycoproteins by Diels–Alder reactions

    PubMed Central

    Späte, Anne-Katrin; Schart, Verena F; Häfner, Julia; Niederwieser, Andrea; Mayer, Thomas U

    2014-01-01

    Summary Monitoring glycoconjugates has been tremendously facilitated by the development of metabolic oligosaccharide engineering. Recently, the inverse-electron-demand Diels–Alder reaction between methylcyclopropene tags and tetrazines has become a popular ligation reaction due to the small size and high reactivity of cyclopropene tags. Attaching the cyclopropene tag to mannosamine via a carbamate linkage has made the reaction even more efficient. Here, we expand the application of cyclopropene tags to N-acylgalactosamine and N-acylglucosamine derivatives enabling the visualization of mucin-type O-glycoproteins and O-GlcNAcylated proteins through Diels–Alder chemistry. Whereas the previously reported cyclopropene-labeled N-acylmannosamine derivative leads to significantly higher fluorescence staining of cell-surface glycoconjugates, the glucosamine derivative gave higher labeling efficiency with protein preparations containing also intracellular proteins. PMID:25298790

  20. Quantitative structure-activation barrier relationship modeling for Diels-Alder ligations utilizing quantum chemical structural descriptors

    PubMed Central

    2013-01-01

    Background In the present study, we show the correlation of quantum chemical structural descriptors with the activation barriers of the Diels-Alder ligations. A set of 72 non-catalysed Diels-Alder reactions were subjected to quantitative structure-activation barrier relationship (QSABR) under the framework of theoretical quantum chemical descriptors calculated solely from the structures of diene and dienophile reactants. Experimental activation barrier data were obtained from literature. Descriptors were computed using Hartree-Fock theory using 6-31G(d) basis set as implemented in Gaussian 09 software. Results Variable selection and model development were carried out by stepwise multiple linear regression methodology. Predictive performance of the quantitative structure-activation barrier relationship (QSABR) model was assessed by training and test set concept and by calculating leave-one-out cross-validated Q2 and predictive R2 values. The QSABR model can explain and predict 86.5% and 80% of the variances, respectively, in the activation energy barrier training data. Alternatively, a neural network model based on back propagation of errors was developed to assess the nonlinearity of the sought correlations between theoretical descriptors and experimental reaction barriers. Conclusions A reasonable predictability for the activation barrier of the test set reactions was obtained, which enabled an exploration and interpretation of the significant variables responsible for Diels-Alder interaction between dienes and dienophiles. Thus, studies in the direction of QSABR modelling that provide efficient and fast prediction of activation barriers of the Diels-Alder reactions turn out to be a meaningful alternative to transition state theory based computation. PMID:24171724

  1. Synthesis of polysubstituted 3-hydroxypyridines via the revisited hetero-Diels-Alder reaction of 5-alkoxyoxazoles with dienophiles.

    PubMed

    Sabot, Cyrille; Oueis, Emilia; Brune, Xavier; Renard, Pierre-Yves

    2012-01-18

    A general and single-step access to polysubstituted 3-hydroxypyridine scaffolds via hetero-Diels-Alder (HDA) reactions between readily prepared 5-ethoxyoxazoles and dienophiles is reported. The HDA reaction, run in the presence of Nd(OTf)(3) at room temperature, was successfully applied to various 5-ethoxyoxazoles showing good functional group tolerance, and led to a straightforward process to obtain useful building-blocks.

  2. Controlled spacing of 60-carbon spheres with 1,4-cyclohexadienyl ladders by pairwise Diels-Alder cycloaddition to buckminsterfullerene

    SciTech Connect

    Paquette, L.A.; Graham, R.J.

    1995-05-19

    This article focuses on the synthesis of Buckminsterfullerenes using a pair of Diels-Alder reactions involving C{sub 60} and the multiply unsaturated bisdienes 1 - 3. The achievement of a dumbbell-like structure may not be desirable for solubility, but controlled spacing of the spheres using 1,4-cyclohexadienyl in this manner will lead to other structure-function insights. 20 refs., 2 figs.

  3. Chiral GAP catalysts of phosphonylated imidazolidinones and their applications in asymmetric Diels-Alder and Friedel-Crafts reactions.

    PubMed

    Qiao, Shuo; Mo, Junming; Wilcox, Cody B; Jiang, Bo; Li, Guigen

    2017-02-21

    The design and synthesis of recyclable imidazolidinone catalysts using GAP chemistry/technique was described. Their applications in asymmetric Diels-Alder and Friedel-Crafts reactions with α,β-unsaturated aldehydes resulted in excellent yields and higher enantioselectivities than previous processes. As recyclable small molecular catalysts, phosphonylated imidazolidinones can be recovered and reused for up to three runs without costing significant decrease in catalytic activity.

  4. Enantioselective Diels-Alder reaction of 1,2-dihydropyridines with aldehydes using β-amino alcohol organocatalyst.

    PubMed

    Kohari, Yoshihito; Okuyama, Yuko; Kwon, Eunsang; Furuyama, Taniyuki; Kobayashi, Nagao; Otuki, Teppei; Kumagai, Jun; Seki, Chigusa; Uwai, Koji; Dai, Gang; Iwasa, Tatsuo; Nakano, Hiroto

    2014-10-17

    The enantioselective Diels-Alder reaction of 1,2-dihydropyridines with aldehydes using an easily prepared optically active β-amino alcohol catalyst was found to provide optically active isoquinuclidines, an efficient synthetic intermediate of pharmaceutically important compounds such as oseltamivir phosphate, with a satisfactory chemical yield and enantioselectivity (up to 96%, up to 98% ee). In addition, the obtained highly optically pure isoquinuclidine was easily converted to an optically active piperidine having four successive carbon centers.

  5. A new approach to the synthesis of monomers and polymers incorporating furan/maleimide Diels-Alder adducts

    NASA Astrophysics Data System (ADS)

    Banella, Maria Barbara; Gioia, Claudio; Vannini, Micaela; Colonna, Martino; Celli, Annamaria; Gandini, Alessandro

    2016-05-01

    The Diels-Alder reaction between furan and maleimide moieties is a well-known and widely used strategy to build bio-based macromolecular structures with peculiar properties. The furan-maleimide adducts are thermally reversible because they can be broken above about 120°C and recombined at lower temperatures. At the moment only the monomers exhibiting the furan or the maleimide moieties on their extremity are used in order to get linear or cross-linked polymeric structures. The innovative idea described here consists in using a monomer bearing two carboxylic acidic groups on its extremities and a furan-maleimide Diels-Alder adduct within its structure. This monomer can give rise to classical polycondensation reactions leading to polymers. These polymers (which are polyesters in the present case) can be broken at high temperatures in correspondence of the furane-maleimide Diels-Alder adduct leading to segments exhibiting furan or maleimide moieties at their extremities, which at lower temperature recombine leading to random or block copolymers.

  6. Design Paradigm Utilizing Reversible Diels-Alder Reactions to Enhance the Mechanical Properties of 3D Printed Materials.

    PubMed

    Davidson, Joshua R; Appuhamillage, Gayan A; Thompson, Christina M; Voit, Walter; Smaldone, Ronald A

    2016-07-06

    A design paradigm is demonstrated that enables new functional 3D printed materials made by fused filament fabrication (FFF) utilizing a thermally reversible dynamic covalent Diels-Alder reaction to dramatically improve both strength and toughness via self-healing mechanisms. To achieve this, we used as a mending agent a partially cross-linked terpolymer consisting of furan-maleimide Diels-Alder (fmDA) adducts that exhibit reversibility at temperatures typically used for FFF printing. When this mending agent is blended with commercially available polylactic acid (PLA) and printed, the resulting materials demonstrate an increase in the interfilament adhesion strength along the z-axis of up to 130%, with ultimate tensile strength increasing from 10 MPa in neat PLA to 24 MPa in fmDA-enhanced PLA. Toughness in the z-axis aligned prints increases by up to 460% from 0.05 MJ/m(3) for unmodified PLA to 0.28 MJ/m(3) for the remendable PLA. Importantly, it is demonstrated that a thermally reversible cross-linking paradigm based on the furan-maleimide Diels-Alder (fmDA) reaction can be more broadly applied to engineer property enhancements and remending abilities to a host of other 3D printable materials with superior mechanical properties.

  7. Purification of a lectin from M. rubra leaves using immobilized metal ion affinity chromatography and its characterization.

    PubMed

    Sureshkumar, Thavamani; Priya, Sulochana

    2012-12-01

    Lectins represent a heterogeneous group of proteins/glycoproteins with unique carbohydrate specificity, with wide range of biomedical applications. The multi-step purification protocols generally used for purification of lectin result in a significant reduction in the final yield and activity. In the present study, Morus rubra lectin (MRL) was purified to homogeneity from the leaves using a single-step immobilized metal ion affinity chromatography (IMAC) procedure. The approximate molecular weight of purified MRL resolved as a single band on SDS-PAGE was 52 kDa. Final percentage yield of purified lectin by IMAC was calculated as 74.7 %. Purified MRL was specific to three sugars, galactose, D-galactosamine and N-acetyl-D-galactosamine, and rendered haemagglutination (HA) activity towards different human blood group RBCs. MRL showed stability over a wide range of temperature (up to 80 °C) and pH (4-11). Chelation of the lectin with EDTA did not alter HA which indicates that metal ion is not required for activity. In the presence of Fe(2+), Ca(2+), Zn(2+), Ni(2+), Mn(2+), Na(+) and K(+), HA activity was reduced to 50 %, whereas the presence of trivalent metal ions (Fe3(+) and Al(3+)) and Cu(2+) did not affect the activity. In the presence of Mg(2+) and Hg(2+), only 25 % of HA activity remained.

  8. Intensity and importance of competition for a grass (Festuca rubra) and a legume (Trifolium pratense) vary with environmental changes.

    PubMed

    Zhang, Junyan; Cheng, Genwei; Yu, Feihai; Kräuchi, Norbert; Li, Mai-He

    2008-12-01

    How plant competition varies across environmental gradients has been a long debate among ecologists. We conducted a growth chamber experiment to determine the intensity and importance of competition for plants grown in changed environmental conditions. Festuca rubra and Trifolium pratense were grown in monoculture and in two- and/or three-species mixtures under three environmental treatments. The measured competitive variations in terms of growth (height and biomass) were species-dependent. Competition intensity for Festuca increased with decreased productivity, whilst competition importance displayed a humpback response. However, significant response was detected in neither competition intensity nor importance for Trifolium. Intensity and importance of competition followed different response patterns, suggesting that they may not be correlated along an environmental gradient. The biological and physiological variables of plants play an important role to determine the interspecific competition associated with competition intensity and importance. However, the competitive feature can be modified by multiple environmental changes which may increase or hinder how competitive a plant is.

  9. Expression and function analysis of the metallothionein-like (MT-like) gene from Festuca rubra in Chlamydomonas reinhardtii chloroplast.

    PubMed

    Han, SiHai; Hu, ZhangLi; Lei, AnPing

    2008-12-01

    The cDNA of the metallothionein-like (MT-like) gene from Festuca rubra cv. Merlin was optimized with bias codon of Chlamydomonas reinhardtii chloroplast genome. The optimized MT-like gene was delivered into C. reinhardtii chloroplast and the transgenic strains expressing MT-like gene was obtained. PCR-Southern blot and RT-PCR-Southern blot analysis demonstrated that the MT-like gene was integrated into chloroplast genome of C. reinhardtii and expressed at the transcriptional level. The cadmium binding capacity of the transgenic C. reinhardtii was determined by hydride generation-atomic fluorescence spectrometry (HG-AFS) and the binding properties were analyzed. Results showed that the transgenic C. reinhardtii expressing the MT-like gene exhibited remarkably higher Cd(2+) binding capacity and grew to higher densities at toxic Cd(2+) concentrations (40-100 micromol/L) than the wild type strain, and that the IC(50) of Cd(2+) (3-d treating) to algal cell growth of transgenic strain was 55.43% higher than that of the wild type strain, indicating that the Cd(2+) binding capacity and Cd(2+) tolerance of C. reinhardtii was enhanced through the expression of the foreign MT-like gene in chloroplast.

  10. Restoration of regeneration potential of long-term cultures of red fescue (Festuca rubra L.) by elevated sucrose levels.

    PubMed

    Zaghmout, O M; Torello, W A

    1992-04-01

    A tissue culture protocol for restoring embryogenic ability and increasing green plant regeneration from long-term callus (5-year old) and suspension cultures of "Dawson" red fescue (Festuca rubra var trichyoplylla Gaud) was developed. Pretreatment with elevated levels of sucrose over the standard level (60 mM) enhanced regeneration capacity and decreased the number of albino plants. The highest degree of embryogenesis and green shoot number occurred when calli were pre-treated on MS basal medium supplemented with 120 mM sucrose. Mannitol caused callus discoloration and death if added to pre-treatment media at 60, 90, 120, 150 or 180 mM. Cell suspension growth was greatest when 135 mM sucrose was added to the pre-treatment growth media. High concentrations of sucrose (135 and 180 mM) were necessary for plant regeneration from suspension aggregates pretreated with 135 or 180 mM sucrose and then plated on a growth regulator-free regeneration medium composed of half-strength MS salts and B5 vitamins.

  11. Pseudorhabdosynochus regius n. sp. (Monogenea, Diplectanidae) from the mottled grouper Mycteroperca rubra (Teleostei) in the Mediterranean Sea and Eastern Atlantic

    PubMed Central

    Chaabane, Amira; Neifar, Lassad; Justine, Jean-Lou

    2015-01-01

    Pseudorhabdosynochus regius n. sp. is described from the gills of the mottled grouper Mycteroperca rubra caught off Senegal, Tunisia and Libya (type-locality: off Dakar, Senegal). The species is distinguished from its congeners by the structure of its sclerotised vagina (length 26–35 μm), which exhibits a trumpet in continuity with the primary canal, a straight primary canal, and primary and secondary chambers included in a common sclerotised mass along the primary canal. The species is also characterised by small squamodiscs (length 20–40 μm) with 10–11 rows of rodlets. Its closest relatives (based on the structure of the sclerotised vagina) are species mostly found in the Mediterranean Sea and parasites on species of Mycteroperca. A second species of Pseudorhabdosynochus Yamaguti, 1958 is reported from the same host and localities but not described. A list of diplectanids from groupers in the Mediterranean Sea is provided. We point out that a recent article was not compliant with the new Article 8.5.3 of the International Code of Zoological Nomenclature; for this reason, three species, P. nhatrangensis Dang, Bristow, Schander & Berland, 2013, P. vietnamensis Dang et al., 2013 and P. brunei Dang et al., 2013, are invalid. PMID:25674913

  12. Reduced translocation of current photosynthate precedes changes in gas exchange for Quercus rubra seedlings under flooding stress.

    PubMed

    Sloan, Joshua L; Islam, M Anisul; Jacobs, Douglass F

    2016-01-01

    Northern red oak (Quercus rubra L.) seedlings are frequently planted on suboptimal sites in their native range in North America, subjecting them to environmental stresses, such as flooding, for which they may not be well adapted. Members of the genus Quercus exhibit a wide range of responses to flooding, and responses of northern red oak to flooding remain inadequately described. To better understand the physiological effects of root system inundation in post-transplant northern red oak seedlings and the effects of flooding on endogenous patterns of resource allocation within the plant, we observed the effects of short-term flooding initiated at the linear shoot growth stage on net photosynthetic rates, dark respiration, chlorophyll fluorescence (Fv/Fm) and translocation of (13)C-labeled current photosynthate. Downward translocation of current photosynthate declined after 4 days of flooding and was the first measured physiological response to flooding; net photosynthetic rates decreased and dark respiration rates increased after 7 days of flooding. Short-term flooding did not affect maximal potential efficiency of photosystem II (Fv/Fm). The finding that decreased downward translocation of (13)C-labeled current photosynthate preceded reduced net photosynthesis and increased dark respiration during flooding suggests the occurrence of sink-limited photosynthesis under these conditions.

  13. Nocardia rubra cell-wall skeleton promotes CD4(+) T cell activation and drives Th1 immune response.

    PubMed

    Wang, Guangchuan; Wu, Jie; Miao, Miao; Dou, Heng; Nan, Ning; Shi, Mingsheng; Yu, Guang; Shan, Fengping

    2017-03-15

    Several lines of evidences have shown that Nocardia rubra cell wall skeleton (Nr-CWS) has immunoregulatory and anti-tumor activities. However, there is no information about the effect of Nr-CWS on CD4(+) T cells. The aim of this study was to explore the effect of Nr-CWS on the phenotype and function of CD4(+) T cells. Our results of in vitro experiments showed that Nr-CWS could significantly up-regulate the expression of CD69 and CD25 on CD4(+) T cells, promote the proliferation of CD4(+) T cells, increase the production of IFN-γ, TNF-α and IL-2 in the supernatants, but has no significant effect on the apoptosis and death of CD4(+) T cells. Results of in vivo experiments showed that Nr-CWS could promote the proliferation of CD4(+) T cells, and increase the production of IL-2, IFN-γ and TNF-α (Th1 type cytokines). These data suggest that Nr-CWS can enhance the activation of CD4(+) T cells, promote the proliferation of CD4(+) T cells and the differentiation of CD4(+) T cells to Th1 cells.

  14. Silylium ion-catalyzed challenging Diels-Alder reactions: the danger of hidden proton catalysis with strong Lewis acids.

    PubMed

    Schmidt, Ruth K; Müther, Kristine; Mück-Lichtenfeld, Christian; Grimme, Stefan; Oestreich, Martin

    2012-03-07

    The pronounced Lewis acidity of tricoordinate silicon cations brings about unusual reactivity in Lewis acid catalysis. The downside of catalysis with strong Lewis acids is, though, that these do have the potential to mediate the formation of protons by various mechanisms, and the thus released Brønsted acid might even outcompete the Lewis acid as the true catalyst. That is an often ignored point. One way of eliminating a hidden proton-catalyzed pathway is to add a proton scavenger. The low-temperature Diels-Alder reactions catalyzed by our ferrocene-stabilized silicon cation are such a case where the possibility of proton catalysis must be meticulously examined. Addition of the common hindered base 2,6-di-tert-butylpyridine resulted, however, in slow decomposition along with formation of the corresponding pyridinium ion. Quantitative deprotonation of the silicon cation was observed with more basic (Mes)(3)P to yield the phosphonium ion. A deuterium-labeling experiment verified that the proton is abstracted from the ferrocene backbone. A reasonable mechanism of the proton formation is proposed on the basis of quantum-chemical calculations. This is, admittedly, a particular case but suggests that the use of proton scavengers must be carefully scrutinized, as proton formation might be provoked rather than prevented. Proton-catalyzed Diels-Alder reactions are not well-documented in the literature, and a representative survey employing TfOH is included here. The outcome of these catalyses is compared with our silylium ion-catalyzed Diels-Alder reactions, thereby clearly corroborating that hidden Brønsted acid catalysis is not operating with our Lewis acid. Several simple-looking but challenging Diels-Alder reactions with exceptionally rare dienophile/enophile combinations are reported. Another indication is obtained from the chemoselectivity of the catalyses. The silylium ion-catalyzed Diels-Alder reaction is general with regard to the oxidation level of the

  15. Diels Alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

    DOE PAGES

    Small, Leo J.; Pratt, III, Harry D.; Fujimoto, Cy H.; ...

    2015-10-23

    Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3–10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediatemore » ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. As a result, improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.« less

  16. Diels Alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

    SciTech Connect

    Small, Leo J.; Pratt, III, Harry D.; Fujimoto, Cy H.; Anderson, Travis M.

    2015-10-23

    Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3–10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediate ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. As a result, improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.

  17. On the method-dependence of transition state asynchronicity in Diels-Alder reactions.

    PubMed

    Linder, Mats; Brinck, Tore

    2013-04-14

    This work discusses the dependence of transition state geometries on the choice of quantum chemical optimization method for the extensively studied Diels-Alder reaction. Rather significant differences are observed between post-Hartree-Fock methods and (hybrid) density functional theory, where the latter predicts larger asynchronicities. The results show that the low MP2 asynchronicity observed is likely artificial. Still, there are significant discrepancies between hybrid and pure density functionals. The role of the exchange functional seems to be most prominent in less activated reacting systems, while the importance of the correlation functional seems to increase as they become more activated by, e.g., an electron-donating group on the diene. To correct the dubious MP2 geometries, we employed the SCS-MP2 protocol for transition state optimization, which leads to significantly better results with respect to CCSD/6-31+G(d) level calculations. We conclude that in order for hybrid functionals to give descriptions consistent with the sample post-Hartree-Fock methods, a balanced combination of both Hartree-Fock exchange (with a couple of exceptions) and a well-behaved correlation functional is required. Given that the benchmark CCSD/6-31+G(d) geometries are sufficient representations, the best geometries were obtained using ωB97X(D), B2PLYP(D) and M06-2X.

  18. Vanadium redox flow battery efficiency and durability studies of sulfonated Diels Alder poly(phenylene)s

    SciTech Connect

    Fujimoto, Cy H.; Kim, Soowhan; Stains, Ronald; Wei, Xiaoliang; Li, Liyu; Yang, Zhenguo

    2012-07-01

    Sulfonated Diels Alder poly(phenylene) (SDAPP) was examined for vanadium redox flow battery (VRFB) use. The ion exchange capacity (IEC) was varied from 1.4, 1.6 and 2.0 meq/g in order to tune the proton conductivity and vanadium permeability. Coulombic efficiencies between 92 to 99% were observed, depending on IEC (lower IEC, higher coulombic efficiencies). In all cases the SDAPP displayed comparable energy efficiencies (88 - 90%) to Nafion 117 (88%) at 50mA/cm2. Membrane durability also was dependent on IEC; SDAPP with the highest IEC lasted slightly over 50 cycles while SDAPP with the lowest IEC lasted over 400 cycles and testing was discontinued only due to time constraints. Accelerated vanadium lifetime studies were initialed with SDAPP, by soaking films in a 0.1 M V5+ and 5.0 M total SO4-2 solution. The rate of degradation was also proportional with IEC; the 2 meq/g sample dissolved within 376 hours, the 1.6 meq/g sample dissolved after 860 hours, while the 1.4 meq/g sample broke apart after 1527 hours.

  19. A Single Molecular Diels-Alder Crosslinker for Achieving Recyclable Cross-Linked Polymers.

    PubMed

    Chen, Shengli; Wang, Fenfen; Peng, Yongjin; Chen, Tiehong; Wu, Qiang; Sun, Pingchuan

    2015-09-01

    A triol-functional crosslinker combining the thermoreversible properties of Diels-Alder (DA) adducts in one molecule is designed, synthesized, and used as an ideal substitute of a traditional crosslinker to prepare thermal recyclable cross-linked polyurethanes with excellent mechanical properties and recyclability in a very simple and efficient way. The recycle property of these materials achieved by the DA/retro-DA reaction at a suitable temperature is verified by differential scanning calorimetry and in situ variable temperature solid-state NMR experiments during the cyclic heating and cooling processes. The thermal recyclability and remending ability of the bulk polyurethanes is demonstrated by three polymer processing methods, including hot-press molding, injection molding, and solution casting. It is notable that all the recycled cross-linked polymers display nearly invariable elongation/stress at break compared to the as-synthesized samples. Further end-group functionalization of this single molecular DA crosslinker provides the potential in preparing a wide range of recyclable cross-linked polymers.

  20. Combinatorial Synthesis of Linearly Condensed Polycyclic Compounds, Including Anthracyclinones, Through Tandem Diels-Alder Additions

    NASA Astrophysics Data System (ADS)

    Vogel, Pierre

    Double exocyclic 1,3-dienes such as 2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane and its 1-substituted derivatives undergo two successive Diels-Alder additions with large reactivity difference between the addition of the first equivalent (k 1) and the second equivalent (k 2) of dienophile. This allows one to prepare, through parallel synthesis, a large number of linearly condensed polycyclic systems containing three annulated six-membered rings, including naphthacenyl systems and anthracyclinones. The large k 1/k 2 rate constant ratio is a consequence of the Dimroth principle, the first cycloaddition being significantly more exothermic then the second one. Control of regio- and stereoselectivity of the two successive cycloadditions is possible by 1-substitution of the 2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane, for instance by a 1-(dimethoxymethyl) group, or by stereoselective disubstitution of the double diene by arenesulfenyl substituents. Enantiomerically pure anthracyclinones and analogues are obtained using enantiomerically pure dienophiles such as 3-oxo-but-2-en-2-yl esters. The chemistry so-developed has allowed the preparation of enantiomerically pure 6-((aminoalkoxy)oxy)methyl-6,7-dideoxyidarubicinones that are DNA intercalators and inhibitors of topoisomerase II-induced DNA strained religation.

  1. Liquid-Crystalline Ionic Liquids as Ordered Reaction Media for the Diels-Alder Reaction.

    PubMed

    Bruce, Duncan W; Gao, Yanan; Canongia Lopes, José Nuno; Shimizu, Karina; Slattery, John M

    2016-11-02

    Liquid-crystalline ionic liquids (LCILs) are ordered materials that have untapped potential to be used as reaction media for synthetic chemistry. This paper investigates the potential for the ordered structures of LCILs to influence the stereochemical outcome of the Diels-Alder reaction between cyclopentadiene and methyl acrylate. The ratio of endo- to exo-product from this reaction was monitored for a range of ionic liquids (ILs) and LCILs. Comparison of the endo:exo ratios in these reactions as a function of cation, anion and liquid crystallinity of the reaction media, allowed for the effects of liquid crystallinity to be distinguished from anion effects or cation alkyl chain length effects. These data strongly suggest that the proportion of exo-product increases as the reaction media is changed from an isotropic IL to a LCIL. A detailed molecular dynamics (MD) study suggests that this effect is related to different hydrogen bonding interactions between the reaction media and the exo- and endo-transition states in solvents with layered, smectic ordering compared to those that are isotropic.

  2. Returning to the Alder Hey report and its reporting: addressing confusions and improving inquiries.

    PubMed

    Dewar, S; Boddington, P

    2004-10-01

    The Royal Liverpool Children's Inquiry investigated the circumstances leading to the removal, retention, and disposal of human tissue, including children's organs, at the Royal Liverpool Children's NHS Trust (the Alder Hey Hospital). It recommended changes to procedures for obtaining consent for postmortems and retaining organs and tissues for research or education. However, the report contains five areas of confusion. Firstly, it allowed the cultural and historical traditions of horror over the use and misuse of body parts to suffuse the logical analysis of past wrongs and future rights. Secondly, it makes an inappropriate conflation between seeking redress for past wrongs and shaping future policy. Thirdly, the report takes a muddled stance over the value of bodily integrity at burial. Fourthly, the report is inconsistent over the justification for future organ and tissue collections. Fifthly, the notion of "respect" is used with troublesome looseness. The extent to which subsequent policy work has furthered the search for greater ethical clarity over these difficult issues is discussed, together with reflection on three particular improvements that could be made to the process of such an inquiry.

  3. Quantitative rate determination by dynamic nuclear polarization enhanced NMR of a Diels-Alder reaction.

    PubMed

    Zeng, Haifeng; Lee, Youngbok; Hilty, Christian

    2010-11-01

    Emerging techniques for hyperpolarization of nuclear spins, foremost dynamic nuclear polarization (DNP), lend unprecedented sensitivity to nuclear magnetic resonance spectroscopy. Sufficient signal can be obtained from a single scan, and reactions even far from equilibrium can be studied in real-time. When following the progress of a reaction by nuclear magnetic resonance, however, spin relaxation occurs concomitantly with the reaction to alter resonance line intensities. Here, we present a model for accounting for spin-relaxation in such reactions studied by hyperpolarized NMR. The model takes into account auto- and cross-relaxation in dipole-dipole coupled spin systems and is therefore applicable to NMR of hyperpolarized protons, the most abundant NMR-active nuclei. Applied to the Diels-Alder reaction of 1,4-dipheneylbutadiene (DPBD) with 4-phenyl-1,2,4-triazole-3,5-dione (PTD), reaction rates could be obtained accurately and reproducibly. Additional parameters available from the same experiment include relaxation rates of the reaction product, which may yield further information about the molecular properties of the product. The method presented is also compatible with an experiment where a single spin in the reactant is labeled in its spin-state by a selective radio frequency pulse for subsequent tracking through the reaction, allowing the unambiguous identification of its position in the product molecule. In this case, the chemical shift specificity of high-resolution NMR can allow for the simultaneous determination of reaction rates and mechanistic information in one experiment.

  4. The Preventive Effect on Ethanol-Induced Gastric Lesions of the Medicinal Plant Plumeria rubra: Involvement of the Latex Proteins in the NO/cGMP/K ATP Signaling Pathway.

    PubMed

    de Alencar, Nylane Maria Nunes; Pinheiro, Rachel Sindeaux Paiva; de Figueiredo, Ingrid Samantha Tavares; Luz, Patrícia Bastos; Freitas, Lyara Barbosa Nogueira; de Souza, Tamiris de Fátima Goebel; do Carmo, Luana David; Marques, Larisse Mota; Ramos, Marcio Viana

    2015-01-01

    Plumeria rubra (Apocynaceae) is frequently used in folk medicine for the treatment of gastrointestinal disorders, hepatitis, and tracheitis, among other infirmities. The aim of this study was to investigate the gastroprotective potential of a protein fraction isolated from the latex of Plumeria rubra (PrLP) against ethanol-induced gastric lesions and describe the underlying mechanisms. In a dose-dependent manner, the pretreatment with PrLP prevented ethanol-induced gastric lesions in mice after single intravenous administration. The gastroprotective mechanism of PrLP was associated with the involvement of prostaglandins and balance of oxidant/antioxidant factors. Secondarily, the NO/cGMP/KATP pathway and activation of capsaicin-sensitive primary afferents were also demonstrated as part of the mechanism. This study shows that proteins extracted from the latex of P. rubra prevent gastric lesions induced in experimental animals. Also, the results support the use of the plant in folk medicine.

  5. The Preventive Effect on Ethanol-Induced Gastric Lesions of the Medicinal Plant Plumeria rubra: Involvement of the Latex Proteins in the NO/cGMP/KATP Signaling Pathway

    PubMed Central

    de Alencar, Nylane Maria Nunes; Pinheiro, Rachel Sindeaux Paiva; de Figueiredo, Ingrid Samantha Tavares; Luz, Patrícia Bastos; Freitas, Lyara Barbosa Nogueira; de Souza, Tamiris de Fátima Goebel; do Carmo, Luana David; Marques, Larisse Mota; Ramos, Marcio Viana

    2015-01-01

    Plumeria rubra (Apocynaceae) is frequently used in folk medicine for the treatment of gastrointestinal disorders, hepatitis, and tracheitis, among other infirmities. The aim of this study was to investigate the gastroprotective potential of a protein fraction isolated from the latex of Plumeria rubra (PrLP) against ethanol-induced gastric lesions and describe the underlying mechanisms. In a dose-dependent manner, the pretreatment with PrLP prevented ethanol-induced gastric lesions in mice after single intravenous administration. The gastroprotective mechanism of PrLP was associated with the involvement of prostaglandins and balance of oxidant/antioxidant factors. Secondarily, the NO/cGMP/KATP pathway and activation of capsaicin-sensitive primary afferents were also demonstrated as part of the mechanism. This study shows that proteins extracted from the latex of P. rubra prevent gastric lesions induced in experimental animals. Also, the results support the use of the plant in folk medicine. PMID:26788111

  6. The effect of red beet (Beta vulgaris var. rubra) fiber on alimentary hypercholesterolemia and chemically induced colon carcinogenesis in rats.

    PubMed

    Bobek, P; Galbavý, S; Mariássyová, M

    2000-06-01

    The effect of diet supplemented with 5% and 15% cellulose or with 15% fiber isolated from red beet (Beta vulgaris var. rubra) on the development of alimentary hypercholesterolemia and chemically induced colon carcinoma was studied in male Wistar rats. Hypercholesterolemia was induced by a diet containing 0.3% of cholesterol and colon carcinoma was induced by treatment with dimethylhydrazine (20 mg/kg, 12 doses applied s.c. in one-week intervals). Fibrous matter isolated from red beet contained 89% fiber, of which 9% was in water soluble form. Animals were killed 14 weeks after the application of dimethylhydrazine (i.e. 26 weeks after starting on the diets). Red beet fiber diet (and not the increased cellulose intake) caused a reduction of serum cholesterol and triacylglycerol levels (by 30 and 40%, respectively) and a significant increase in the fraction of cholesterol carried in HDL. This diet induced also a significant decrease (almost by 30%) of cholesterol content in aorta. Higher cellulose content in the diet and even more so the administration of red beet fiber caused a significant reduction of conjugated dienes content in plasma, erythrocytes and in liver. Also observed were increases in the activities of superoxide dismutase and catalase in erythrocytes and in colon and activities of glutathione peroxidase and glutathione-S-transferase in liver. The presence of both higher cellulose content and red beet fiber in the diet significantly reduced the incidence of precancerous lesions--aberrant crypt foci--in the colon. The diet containing red beet fiber did not affect significantly the incidence of colon tumours although the number of animals bearing tumours was reduced by 30%.

  7. Phytochemical Characterization of Chinese Bayberry (Myrica rubra Sieb. et Zucc.) of 17 Cultivars and Their Antioxidant Properties

    PubMed Central

    Zhang, Xianan; Huang, Huizhong; Zhang, Qiaoli; Fan, Fangjuan; Xu, Changjie; Sun, Chongde; Li, Xian; Chen, Kunsong

    2015-01-01

    In order to fully understand the variations of fruit quality-related phytochemical composition in Chinese bayberry (Myrica rubra Sieb. et Zucc.), mature fruit of 17 cultivars from Zhejiang and Jiangsu provinces was used for the investigation of fruit quality attributes, including fruit color, soluble sugars, organic acids, total phenolics, flavonoids, antioxidant capacity, etc. Sucrose was the main soluble sugar, while citric acid was the main organic acid in bayberry fruit. The content of total phenolics and total flavonoids were positively correlated with 2,2-diphenyl-1-picrylhydrazyl (DPPH), ferric reducing antioxidant power (FRAP) antioxidant activity and 2,2ʹ-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radical scavenging activity. Five anthocyanidins, i.e., delphinidin–hexoside (Dp–Hex), cyanidin-3–O-galactoside (C-3–Gal), cyanidin-3–O-glucoside (C-3–Glu), pelargonidin-3–O-glucoside (Pg-3–Glu) and peonidin-3-O-glucoside (Pn-3–Glu), and seven flavonols compounds, i.e., myricetin-3-O-rhamnoside (M-3–Rha), myricetin deoxyhexoside–gallate (M-DH–G), quercetin-3-O-galactoside (Q-3–Gal), quercetin-3–O-glucoside (Q-3–Glu), quercetin-3–O-rhamnoside (Q-3–Rha), kaempferol-3–O-galactoside (K-3–Gal) and kaempferol-3–O-glucoside (K-3–Glu), were identified and characterized among the cultivars. The significant differences in phytochemical compositions among cultivars reflect the diversity in bayberry germplasm, and cultivars of good flavor and/or rich in various health-promoting phytochemicals are good candidates for future genetic breeding of bayberry fruit of high quality. In conclusion, our results may provide important information for further breeding or industrial utilization of different bayberry resources. PMID:26042467

  8. Phytochemical Characterization of Chinese Bayberry (Myrica rubra Sieb. et Zucc.) of 17 Cultivars and Their Antioxidant Properties.

    PubMed

    Zhang, Xianan; Huang, Huizhong; Zhang, Qiaoli; Fan, Fangjuan; Xu, Changjie; Sun, Chongde; Li, Xian; Chen, Kunsong

    2015-06-02

    In order to fully understand the variations of fruit quality-related phytochemical composition in Chinese bayberry (Myrica rubra Sieb. et Zucc.), mature fruit of 17 cultivars from Zhejiang and Jiangsu provinces was used for the investigation of fruit quality attributes, including fruit color, soluble sugars, organic acids, total phenolics, flavonoids, antioxidant capacity, etc. Sucrose was the main soluble sugar, while citric acid was the main organic acid in bayberry fruit. The content of total phenolics and total flavonoids were positively correlated with 2,2-diphenyl-1-picrylhydrazyl (DPPH), ferric reducing antioxidant power (FRAP) antioxidant activity and 2,2'-azino-bis(3-ethylbenzothiazoline- 6-sulphonic acid) (ABTS) radical scavenging activity. Five anthocyanidins, i.e., delphinidin-hexoside (Dp-Hex), cyanidin-3-O-galactoside (C-3-Gal), cyanidin-3-O-glucoside (C-3-Glu), pelargonidin-3-O-glucoside (Pg-3-Glu) and peonidin-3-O-glucoside (Pn-3-Glu), and seven flavonols compounds, i.e., myricetin-3-O-rhamnoside (M-3-Rha), myricetin deoxyhexoside-gallate (M-DH-G), quercetin-3-O-galactoside (Q-3-Gal), quercetin-3- O-glucoside (Q-3-Glu), quercetin-3-O-rhamnoside (Q-3-Rha), kaempferol-3-O-galactoside (K-3-Gal) and kaempferol-3-O-glucoside (K-3-Glu), were identified and characterized among the cultivars. The significant differences in phytochemical compositions among cultivars reflect the diversity in bayberry germplasm, and cultivars of good flavor and/or rich in various health-promoting phytochemicals are good candidates for future genetic breeding of bayberry fruit of high quality. In conclusion, our results may provide important information for further breeding or industrial utilization of different bayberry resources.

  9. Characterization of major betalain pigments -gomphrenin, betanin and isobetanin from Basella rubra L. fruit and evaluation of efficacy as a natural colourant in product (ice cream) development.

    PubMed

    Kumar, S Sravan; Manoj, P; Shetty, N P; Prakash, Maya; Giridhar, P

    2015-08-01

    Basella rubra L. (Basellaceae) commonly known as Malabar spinach is a leafy vegetable which accumulates pigments in its fruits. To find out the feasibility of utilizing pigment rich extracts of its fruit as natural food colourant, fruits at different stages were analysed for pigment profiling, carbohydrate content, physical dimensions and weight. Total betalains content increased rapidly from early (green) through intermediate (half-done red-violet) to matured stage (red-violet). Maximum pigment content was observed in ripened fruits (143.76 mg/100 g fresh weight). The major betalain pigment characterized was gomphrenin I in ripened fruits (26.06 mg), followed by intermediate fruits (2.15 mg) and least in early fruits (0.23 mg) in 100 g of fresh deseeded fruits. Total carbohydrates content and the chroma values (redness) were also increased during ontogeny of B. rubra fruits. The textural characters of developing fruits showed the smoothness of green fruits with lower rupture force (0.16 N/s) than ripe ones (0.38 N/s). The pigment-rich fruit extract was used as natural colourant in ice-cream, to evaluate its effect on physicochemical properties and acceptability of the product. After six months of storage at -20 °C, 86.63 % colour was retained in ice-cream. The ice-cream had good overall sensorial quality and was liked by consumers indicating that addition of B. rubra fruit extract did not alter the sensory quality of the product. The colour values also indicate that there was no significant decrease of this pigment-rich extracts of fruits for its incorporation in food products.

  10. Comparison of sensitivity of grasses (Lolium perenne L. and Festuca rubra L.) and lettuce (Lactuca sativa L.) exposed to water contaminated with microcystins.

    PubMed

    Pereira, Silvia; Saker, Martin L; Vale, Micaela; Vasconcelos, Vitor M

    2009-07-01

    The effects of aqueous extracts from Microcysts aeruginosa strains (both microcystin-producers and non-microcystin producers) on germination and root growth were investigated for three economically important plant species: Festuca rubra L., Lolium perenne L., and Lactuca sativa L. There was a clear inhibition of root growth for L. sativa exposed to strains containing microcystins (5.9-56.4 microg L(-1)). The strain that produced the most pronounced effects contained the lowest concentration of microcystin suggesting that other cellular compounds may also affect growth.

  11. Effects of elevated ultraviolet radiation and endophytic fungi on plant growth and insect feeding in Lolium perenne, Festuca rubra, F. arundinacea and F. pratensis.

    PubMed

    McLeod, A R; Rey, A; Newsham, K K; Lewis, G C; Wolferstam, P

    2001-09-01

    Plants of perennial ryegrass (Lolium perenne L.), red fescue (Festuca rubra L.), tall fescue (F. arundinacea Schreb.) and meadow fescue (F. pratensis Huds) were exposed at an outdoor facility located in Edinburgh, UK to modulated levels of UV-B radiation (280-315 nm) using banks of cellulose diacetate filtered UV-B fluorescent lamps that also produce UV-A radiation (315-400 nm). The plants were derived from a single clone of each species and were grown both with and without colonization by naturally-occurring fungal endophytes. The UV-B treatment was a 30% elevation above the ambient erythemally-weighted level of UV-B during July to October. Growth of treated plants was compared with plants grown under elevated UV-A radiation alone produced by banks of polyester filtered lamps and with plants grown at ambient levels of solar radiation under banks of unenergized lamps. At the end of the treatment period, sample leaves were collected for feeding trials with the desert locust Schistocerca gregaria (Forsk). The UV-B treatment produced no effects on the aboveground biomass of any of the four grasses. The UV-B treatment and the UV-A control exposure both increased plant height and the number of daughter plants formed by rhizome growth in F. rubra. There were significant effects of endophyte presence on the total fresh and dry weights of F. arundinacea and F. rubra, on fresh weight only in F. pratensis, and on the fresh and dry weights of inflorescence in F. arundinacea and L. perenne. There were no effects of UV treatments on the absolute amounts of leaf consumed or on the feeding preferences of locusts for leaves with or without endophyte in three species: F. rubra, F. arundinacea and L. perenne. In F. pratensis there was no effect of UV treatment on the weight of leaves consumed but a significant UV x endophyte interaction caused by a marked change in feeding preference between leaves with and without endophyte that differed between the UV-B treatment and UV-A control

  12. Diastereoselective Diels–Alder Reactions of N-Sulfonyl-1-aza-1,3-butadienes With Optically Active Enol Ethers: An Asymmetric Variant of the 1-Azadiene Diels–Alder Reaction

    PubMed Central

    Clark, Ryan C.; Pfeiffer, Steven S.

    2008-01-01

    The first detailed study of a room temperature asymmetric Diels–Alder reaction of N-sulfonyl-1-aza-1,3-butadienes enlisting a series of nineteen enol ethers bearing chiral auxilaries is reported with many providing highly diastereoselective (endo and facial diastereoselection) reactions largely the result of an exquisitely organized [4 + 2] cycloaddition transition state. Three new, readily accessible, and previously unexplored auxilaries (18a, 19a and 37a) rationally emerged from the studies and provide remarkable selectivities (for 19a and 37a: 49:1 endo:exo and 48:1 facial selectivity) that promise to be useful in systems beyond those detailed. PMID:16492042

  13. Synthesis of novel dendritic 2,2'-bipyridine ligands and their application to Lewis acid-catalyzed diels-alder and three-component condensation reactions.

    PubMed

    Muraki, Takahito; Fujita, Ken-ichi; Kujime, Masato

    2007-10-12

    A series of dendritic ligands with a 2,2'-bipyridine core was synthesized through the coupling of 4,4'-dihydroxy-2,2'-bipyridine with poly(aryl ether) dendrons. The corresponding dendritic Cu(OTf)2 catalysts were used for Diels-Alder and three-component condensation reactions. The dendritic Cu(OTf)2-catalyzed Diels-Alder reaction proceeded smoothly, and these dendritic catalysts could be recycled without deactivation by reprecipitation. Three-component condensation reactions such as Mannich-type reactions also proceeded not only in dichloromethane but also in water. Furthermore, a positive dendritic effect on chemical yields was observed in both Diels-Alder reactions and aqueous-media three-component condensation reactions.

  14. Winter behavior and ecology of the Alder Flycatcher (Empidonax alnorum) in Peru

    USGS Publications Warehouse

    Foster, M.S.

    2007-01-01

    The winter ecology and behavior of Alder Flycatchers (Empidonax alnorum) were studied along the Manu, a white-water meander river in Manu National Park, Madre de Dios, Peru during October and November, 1993 to 1997. The birds occupied territories in primary-succession habitats on growing point bars. They were most common in mixed stands of Tessaria integrifolia (Asteraceae) and Gynerium sagittatum (Gramineaceae) interspersed with bare sand areas. The uneven height of the Tessaria canopy, which resulted in openings in the vegetation large enough for the birds to flycatch, was an important habitat feature. Birds obtained insects, which formed about 96% of the diet, by aerial hawking (91%), perch gleaning (6%), and hover gleaning (3%). They also fed on fruit. Territory sizes ranged from 0.04 to 0.25 ha. Of nine territories that we observed closely, six were occupied by two birds each, two by one bird each, and one by three birds. Every territory had one dominant individual who was primarily responsible for territory defense; the other birds were associates. Vocalizations given included the fee-bee-o song, a two-syllable song, and the pit note, which are also given on the breeding grounds. A series of pits given increasingly rapidly signaled a territorial interaction. In aggressive encounters, the birds (1) interacted vocally, remaining on their territories and counter calling or exchanging agitated calls; (2) moved toward a common territorial boundary and engaged in a vocal duel; or (3) the dominant chased intruders out of the territory. Chases were most common when a wave of new birds entered the area. Dominant birds, which sang the full song, were probably adult males. Immature males do not sing a full song, and females are not known to sing in nature. Associate individuals were likely females or young males.

  15. Winter behavior and ecology of the Alder Flycatcher (Empidonax alnorum) in Peru

    USGS Publications Warehouse

    Foster, M.S.

    2007-01-01

    The winter ecology and behavior of Alder Flycatchers (Empidonax alnorum) were studied along the Manu, a white-water meander river in Manu National Park, Madre de Dios, Peru?? during October and November, 1993 to 1997. The birds occupied territories in primary-succession habitats on growing point bars. They were most common in mixed stands of Tessaria integrifolia (Asteraceae) and Gynerium sagittatum (Gramineaceae) interspersed with bare sand areas. The uneven height of the Tessaria canopy, which resulted in openings in the vegetation large enough for the birds to flycatch, was an important habitat feature. Birds obtained insects, which formed about 96% of the diet, by aerial hawking (91%), perch gleaning (6%), and hover gleaning (3%). They also fed on fruit. Territory sizes ranged from 0.04 to 0.25 ha. Of nine territories that we observed closely, six were occupied by two birds each, two by one bird each, and one by three birds. Every territory had one dominant individual who was primarily responsible for territory defense; the other birds were associates. Vocalizations given included the fee-bee-o song, a two-syllable song, nd the pit note, which are also given on the breeding grounds. A series of pits given increasingly rapidly signaled a territorial interaction. In aggressive encounters, the birds (1) interacted vocally, remaining on their territories and counter calling or exchanging agitated calls; (2) moved toward a common territorial boundary and engaged in a vocal duel; or (3) the dominant chased intruders out of the territory. Chases were most common when a wave of new birds entered the area. Dominant birds, which sang the full song, were probably adult males. Immature males do not sing a full song, and females are not known to sing in nature. Associate individuals were likely females or young males. ?? The Neotropical Ornithological Society.

  16. Novel Diels-Alder based self-healing epoxies for aerospace composites

    NASA Astrophysics Data System (ADS)

    Coope, T. S.; Turkenburg, D. H.; Fischer, H. R.; Luterbacher, R.; van Bracht, H.; Bond, I. P.

    2016-08-01

    Epoxy resins containing Diels-Alder (DA) furan and maleimide moieties are presented with the capability to self-heal after exposure to an external heat source. A conventional epoxy amine system has been combined with furfuryl and maleimide functional groups in a two-step process, to avoid major side-reactions, and the concentration of a thermo-reversibly binding cross-linker was considered to balance thermoset and thermoplastic behaviours, and the subsequent self-healing performance. In the context of self-repair technologies an inbuilt ‘intrinsic’ self-healing system is deemed favourable as the healing agent can be placed in known ‘hot spot’ regions (i.e. skin-stringer run outs, ply drops and around drilled holes) where operational damage predominately occurs in load bearing aerospace structures. In this study, the mechanical and self-healing performance of furan functionalised epoxy resins containing varying amounts (10, 20, 30 or 40 pph) of bismaleimide were investigated using a bulk epoxy polymer tapered double cantilever beam test specimen geometry. Two forms, a thin film and a bulk material, were evaluated to account for future integration methods into fibre reinforced polymer (FRP) composites. The highest healing efficiency, with respect to the obtained initial load value, was observed from the 20 pph bulk material derivative. The polymers were successful in achieving consistent multiple (three) healing cycles when heated at 150 °C for 5 min. This novel investigated DA material exhibits favourable processing characteristics for FRP composites as preliminary studies have shown successful coextrution with reinforcing fibres to form free standing films and dry fibre impregnation.

  17. Computational design of a lipase for catalysis of the Diels-Alder reaction.

    PubMed

    Linder, Mats; Hermansson, Anders; Liebeschuetz, John; Brinck, Tore

    2011-04-01

    Combined molecular docking, molecular dynamics (MD) and density functional theory (DFT) studies have been employed to study catalysis of the Diels-Alder reaction by a modified lipase. Six variants of the versatile enzyme Candida Antarctica lipase B (CALB) have been rationally engineered in silico based on the specific characteristics of the pericyclic addition. A kinetic analysis reveals that hydrogen bond stabilization of the transition state and substrate binding are key components of the catalytic process. In the case of substrate binding, which has the greater potential for optimization, both binding strength and positioning of the substrates are important for catalytic efficiency. The binding strength is determined by hydrophobic interactions and can be tuned by careful selection of solvent and substrates. The MD simulations show that substrate positioning is sensitive to cavity shape and size, and can be controlled by a few rational mutations. The well-documented S105A mutation is essential to enable sufficient space in the vicinity of the oxyanion hole. Moreover, bulky residues on the edge of the active site hinders the formation of a sandwich-like nearattack conformer (NAC), and the I189A mutation is needed to obtain enough space above the face of the α,β-double bond on the dienophile. The double mutant S105A/I189A performs quite well for two of three dienophiles. Based on binding constants and NAC energies obtained from MD simulations combined with activation energies from DFT computations, relative catalytic rates (v(cat)/v(uncat)) of up to 103 are predicted.

  18. Harnessing the bioorthogonal inverse electron demand Diels-Alder cycloaddition for pretargeted PET imaging.

    PubMed

    Reiner, Thomas; Lewis, Jason S; Zeglis, Brian M

    2015-02-03

    Due to their exquisite affinity and specificity, antibodies have become extremely promising vectors for the delivery of radioisotopes to cancer cells for PET imaging. However, the necessity of labeling antibodies with radionuclides with long physical half-lives often results in high background radiation dose rates to non-target tissues. In order to circumvent this issue, we have employed a pretargeted PET imaging strategy based on the inverse electron demand Diels-Alder cycloaddition reaction. The methodology decouples the antibody from the radioactivity and thus exploits the positive characteristics of antibodies, while eschewing their pharmacokinetic drawbacks. The system is composed of four steps: (1) the injection of a mAb-trans-cyclooctene (TCO) conjugate; (2) a localization time period during which the antibody accumulates in the tumor and clears from the blood; (3) the injection of the radiolabeled tetrazine; and (4) the in vivo click ligation of the components followed by the clearance of excess radioligand. In the example presented in the work at hand, a (64)Cu-NOTA-labeled tetrazine radioligand and a trans-cyclooctene-conjugated humanized antibody (huA33) were successfully used to delineate SW1222 colorectal cancer tumors with high tumor-to-background contrast. Further, the pretargeting methodology produces high quality images at only a fraction of the radiation dose to non-target tissue created by radioimmunoconjugates directly labeled with (64)Cu or (89)Zr. Ultimately, the modularity of this protocol is one of its greatest assets, as the trans-cyclooctene moiety can be appended to any non-internalizing antibody, and the tetrazine can be attached to a wide variety of radioisotopes.

  19. Actinorhizal Alder Phytostabilization Alters Microbial Community Dynamics in Gold Mine Waste Rock from Northern Quebec: A Greenhouse Study

    PubMed Central

    Callender, Katrina L.; Roy, Sébastien; Khasa, Damase P.; Whyte, Lyle G.; Greer, Charles W.

    2016-01-01

    Phytotechnologies are rapidly replacing conventional ex-situ remediation techniques as they have the added benefit of restoring aesthetic value, important in the reclamation of mine sites. Alders are pioneer species that can tolerate and proliferate in nutrient-poor, contaminated environments, largely due to symbiotic root associations with the N2-fixing bacteria, Frankia and ectomycorrhizal (ECM) fungi. In this study, we investigated the growth of two Frankia-inoculated (actinorhizal) alder species, A. crispa and A. glutinosa, in gold mine waste rock from northern Quebec. Alder species had similar survival rates and positively impacted soil quality and physico-chemical properties in similar ways, restoring soil pH to neutrality and reducing extractable metals up to two-fold, while not hyperaccumulating them into above-ground plant biomass. A. glutinosa outperformed A. crispa in terms of growth, as estimated by the seedling volume index (SVI), and root length. Pyrosequencing of the bacterial 16S rRNA gene for bacteria and the ribosomal internal transcribed spacer (ITS) region for fungi provided a comprehensive, direct characterization of microbial communities in gold mine waste rock and fine tailings. Plant- and treatment-specific shifts in soil microbial community compositions were observed in planted mine residues. Shannon diversity and the abundance of microbes involved in key ecosystem processes such as contaminant degradation (Sphingomonas, Sphingobium and Pseudomonas), metal sequestration (Brevundimonas and Caulobacter) and N2-fixation (Azotobacter, Mesorhizobium, Rhizobium and Pseudomonas) increased over time, i.e., as plants established in mine waste rock. Acetate mineralization and most probable number (MPN) assays showed that revegetation positively stimulated both bulk and rhizosphere communities, increasing microbial density (biomass increase of 2 orders of magnitude) and mineralization (five-fold). Genomic techniques proved useful in investigating

  20. Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural.

    PubMed

    Pacheco, Joshua J; Davis, Mark E

    2014-06-10

    Terephthalic acid (PTA), a monomer in the synthesis of polyethylene terephthalate (PET), is obtained by the oxidation of petroleum-derived p-xylene. There is significant interest in the synthesis of renewable, biomass-derived PTA. Here, routes to PTA starting from oxidized products of 5-hydroxymethylfurfural (HMF) that can be produced from biomass are reported. These routes involve Diels-Alder reactions with ethylene and avoid the hydrogenation of HMF to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with high pressure ethylene over a pure-silica molecular sieve containing framework tin (Sn-Beta) to produce the Diels-Alder dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with 31% selectivity at 61% HMFA conversion after 6 h at 190 °C. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of Sn-Beta for 2 h to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with 46% selectivity at 28% MMFC conversion or in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) for 6 h to produce MMBC with 81% selectivity at 26% MMFC conversion. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder dehydration product is observed.

  1. Nitroso Diels-Alder (NDA) Reaction as an Efficient Tool for the Functionalization of Diene-Containing Natural Products

    PubMed Central

    Carosso, Serena; Miller, Marvin J.

    2014-01-01

    This review describes the use of nitroso Diels-Alder reactions for the functionalization of complex diene-containing natural products in order to generate libraries of compounds with potential biological activity. The application of this methodology to the structural modification of a series of natural products (thebaine, steroidal dienes, rapamycin, leucomycin, colchicine, isocolchicine and piperine) is discussed using relevant examples from the literature from 1973 onwards. The biological activity of the resulting compounds is also discussed. Additional comments are provided that evaluate the methodology as a useful tool in organic, bioorganic and medicinal chemistry. PMID:25119424

  2. A Minimal, Unstrained S‐Allyl Handle for Pre‐Targeting Diels–Alder Bioorthogonal Labeling in Live Cells

    PubMed Central

    Oliveira, Bruno L.; Guo, Zijian; Boutureira, Omar; Guerreiro, Ana; Jiménez‐Osés, Gonzalo

    2016-01-01

    Abstract The unstrained S‐allyl cysteine amino acid was site‐specifically installed on apoptosis protein biomarkers and was further used as a chemical handle and ligation partner for 1,2,4,5‐tetrazines by means of an inverse‐electron‐demand Diels–Alder reaction. We demonstrate the utility of this minimal handle for the efficient labeling of apoptotic cells using a fluorogenic tetrazine dye in a pre‐targeting approach. The small size, easy chemical installation, and selective reactivity of the S‐allyl handle towards tetrazines should be readily extendable to other proteins and biomolecules, which could facilitate their labeling within live cells. PMID:27763724

  3. Diels-Alder Reactions of α-Amido Acrylates with N-Cbz-1,2-dihydropyridine and Cyclopentadiene.

    PubMed

    Abas, Hossay; Frampton, Christopher S; Spivey, Alan C

    2016-10-21

    Thermal Diels-Alder reactions of α-amido acrylates with N-Cbz-1,2-dihydropyridine and cyclopentadiene have been explored to investigate the factors influencing the endo/exo selectivity. For the dihydropyridine, steric factors allowed the diastereoselectivity to be modulated to favor either endo- or exo-ester adducts. For cyclopentadiene, the endo-ester adducts were favored regardless of steric perturbation, although catalysis by bulky Lewis acids increased the proportion of exo-ester adducts in some cases. These Lewis acids were incompatible with the dihydropyridine diene as they induced its decomposition.

  4. Elucidation of Diels-Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst

    SciTech Connect

    Do, Phuong T. M.; McAtee, Jesse R.; Watson, Donald A.; Lobo, Raul F.

    2012-12-12

    The reaction of 2,5-dimethylfuran and ethylene to produce p-xylene represents a potentially important route for the conversion of biomass to high-value organic chemicals. Current preparation methods suffer from low selectivity and produce a number of byproducts. Using modern separation and analytical techniques, the structures of many of the byproducts produced in this reaction when HY zeolite is employed as a catalyst have been identified. From these data, a detailed reaction network is proposed, demonstrating that hydrolysis and electrophilic alkylation reactions compete with the desired Diels–Alder/dehydration sequence. This information will allow the rational identification of more selective catalysts and more selective reaction conditions.

  5. Bidentate Lewis Acid Catalyzed Domino Diels-Alder Reaction of Phthalazine for the Synthesis of Bridged Oligocyclic Tetrahydronaphthalenes.

    PubMed

    Schweighauser, Luca; Bodoky, Ina; Kessler, Simon N; Häussinger, Daniel; Donsbach, Carsten; Wegner, Hermann A

    2016-03-18

    A domino process consisting of an inverse and a normal electron-demand Diels-Alder reaction is presented for the formation of bridged tri- and tetracyclic 1,2,3,4-tetrahydronaphthalenes catalyzed by a bidentate Lewis acid. The products were synthesized in a one-pot reaction from commercially available starting materials and contain up to six stereogenic centers. The tetrahydronaphthalenes were isolated as single diastereomers and are derivatives of phenylethylamine, which is well-known as a scaffold of amphetamine or dopamine.

  6. Tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds

    PubMed Central

    Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando

    2015-01-01

    Summary A new tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM–IMDAR protocols. PMID:26425205

  7. Hybrid metal/organo relay catalysis enables enynes to be latent dienes for asymmetric Diels-Alder reaction.

    PubMed

    Han, Zhi-Yong; Chen, Dian-Feng; Wang, Ya-Yi; Guo, Rui; Wang, Pu-Sheng; Wang, Chao; Gong, Liu-Zhu

    2012-04-18

    The hybrid Au(I)/Brønsted acid binary catalyst system enables enynes to serve as latent 1,3-silyloxydienes capable of participating in the first cascade hydrosiloxylation of an enynyl silanol/asymmetric Diels-Alder reaction. A variety of polycyclic compounds bearing multistereogenic centers were obtained in high yields and excellent enantioselectivities from the relay catalytic cascade reaction between (2-(but-3-en-1-ynyl)phenyl) silanols and quinones catalyzed by the combined achiral gold complex and chiral N-triflyl phosphoramide.

  8. One-pot cross-enyne metathesis (CEYM)-Diels-Alder reaction of gem-difluoropropargylic alkynes.

    PubMed

    Fustero, Santos; Bello, Paula; Miró, Javier; Sánchez-Roselló, María; Haufe, Günter; Del Pozo, Carlos

    2013-01-01

    Propargylic difluorides 1 were used as starting substrates in a combination of cross-enyne metathesis and Diels-Alder reactions. Thus, the reaction of 1 with ethylene in the presence of 2(nd) generation Hoveyda-Grubbs catalyst generates a diene moiety which in situ reacts with a wide variety of dienophiles giving rise to a small family of new fluorinated carbo- and heterocyclic derivatives in moderate to good yields. This is a complementary protocol to the one previously described by our research group, which involved the use of 1,7-octadiene as an internal source of ethylene.

  9. Beta-carotene-rich carotenoid-protein preparation and exopolysaccharide production by Rhodotorula rubra GED8 grown with a yogurt starter culture.

    PubMed

    Frengova, Ginka I; Simova, Emilina D; Beshkova, Dora M

    2006-01-01

    The underlying method for obtaining a beta-carotene-rich carotenoid-protein preparation and exopolysaccharides is the associated cultivation of the carotenoid-synthesizing lactose-negative yeast strain Rhodotorula rubra GED8 with the yogurt starter culture (Lactobacillus bulgaricus 2-11 + Streptococcus thermophilus 15HA) in whey ultrafiltrate (45 g lactose/l) with a maximum carotenoid yield of 13.37 mg/l culture fluid on the 4.5th day. The chemical composition of the carotenoid-protein preparation has been identified. The respective carotenoid and protein content is 497.4 microg/g dry cells and 50.3% per dry weight, respectively. An important characteristic of the carotenoid composition is the high percentage (51.1%) of beta-carotene (a carotenoid pigment with the highest provitamin A activity) as compared to 12.9% and 33.7%, respectively, for the other two individual pigments--torulene and torularhodin. Exopolysaccharides (12.8 g/l) synthesized by the yeast and lactic acid cultures, identified as acid biopolymers containing 7.2% glucuronic acid, were isolated in the cell-free supernatant. Mannose, produced exclusively by the yeast, predominated in the neutral carbohydrate biopolymer component (76%). The mixed cultivation of R. rubra GED8 with the yogurt starter (L. bulgaricus 2-11 + S. thermophilus 15HA) in ultrafiltrate under conditions of intracellular production of maximum amount of carotenoids and exopolysaccharides synthesis enables combined utilization of the culture fluid from the fermentation process.

  10. Quartz Crystal Microbalance Analysis of Diels-Alder Reactions of Alkene Gases to Functional Ionic Liquids on Chips.

    PubMed

    Hsu, Tzu-Hsuan; Chiang, Shu-Jen; Chu, Yen-Ho

    2016-11-15

    We demonstrated here a successful development of the use of functional ionic liquids FIL 1 and FIL 3 for chemoselective detection of alkene gases measured by quartz crystal microbalance. This detection of gaseous alkenes was achieved by the Diels-Alder [4 + 2] cycloadditions with FIL 1 and FIL 3 thin-coated on quartz chips. Our functional ionic liquids could be prepared by straightforward synthetic chemistry in short steps and are superior in alkene gas detection. The QCM platform developed in this work is chemoselective with fast gas diffusion into ionic liquids, readily applicable to low molecular weight alkene gases and insensitive to moisture. To the best of our knowledge, this is the first report based upon the Diels-Alder reactions demonstrating sensitive alkene gas detection in ionic liquids on a QCM. This work is a proof-of-concept inspection of the promising use of a QCM-based sensor method for reaction-directed detection of gas samples, which is part of an ongoing program aimed at studying diseases.

  11. Synergistic activation of the Diels-Alder reaction by an organic catalyst and substituents: a computational study.

    PubMed

    Linder, Mats; Brinck, Tore

    2009-04-07

    Density functional theory (DFT), using the hybrid functionals B3LYP and B2PLYP, has been employed to investigate the activation of the acrolein-butadiene Diels-Alder reaction, mediated by a thiourea catalyst. Effects due to electron-donating groups (EDGs) on the diene, as well as electron-withdrawing groups (EWGs) on the dienophile, have also been studied. Organic catalysts such as thioureas are known to lower the activation energy through hydrogen-bonding to the carbonyl oxygen, in a way that mimics the oxyanion holes of hydrolytic enzymes. EDGs and EWGs were found to further activate the reaction, and the catalyst showed a synergistic behavior towards the EDGs. Polar solvents were found to reduce the overall activation energy, but also the relative catalytic effect of the thiourea, in accordance with experimental studies. The substituent-mediated reactions displayed more asynchronous transition structures with lower activation energy, which led us to investigate the possibility of an alternative two-step, Michael-type route, similar to what has been found in macrophomate synthase. Although the concerted Diels-Alder route was found to be favored over the Michael route, the calculated activation energy difference is less than 1 kcal mol(-1), which suggests that the two mechanisms compete, and could be responsible for the particular stereochemical outcome of an experiment.

  12. Magnetic hyaluronic acid nanospheres via aqueous Diels-Alder chemistry to deliver dexamethasone for adipose tissue engineering.

    PubMed

    Jia, Yang; Fan, Ming; Chen, Huinan; Miao, Yuting; Xing, Lian; Jiang, Bohong; Cheng, Qifan; Liu, Dongwei; Bao, Weikang; Qian, Bin; Wang, Jionglu; Xing, Xiaodong; Tan, Huaping; Ling, Zhonghua; Chen, Yong

    2015-11-15

    Biopolymer-based nanospheres have great potential in the field of drug delivery and tissue regenerative medicine. In this work, we present a flexible way to conjugate a magnetic hyaluronic acid (HA) nanosphere system that are capable of vectoring delivery of adipogenic factor, e.g. dexamethasone, for adipose tissue engineering. Conjugation of nanospheres was established by aqueous Diels-Alder chemistry between furan and maleimide of HA derivatives. Simultaneously, a furan functionalized dexamethasone peptide, GQPGK, was synthesized and covalently immobilized into the nanospheres. The magnetic HA nanospheres were fabricated by encapsulating super-paramagnetic iron oxide nanoparticles, which exhibited quick magnetic sensitivity. The aqueous Diels-Alder chemistry made nanospheres high binding efficiency of dexamethasone, and the vectoring delivery of dexamethasone could be easily controlled by a external magnetic field. The potential application of the magnetic HA nanospheres on vectoring delivery of adipogenic factor was confirmed by co-culture of human adipose-derived stem cells (ASCs). In vitro cytotoxicity tests demonstrated that incorporation of dexamethasone into magnetic HA nanospheres showed high efficiency to promote ASCs viabilities, in particular under a magnetic field, which suggested a promising future for adipose regeneration applications.

  13. Employing Arynes in Diels-Alder Reactions and Transition-Metal-Free Multicomponent Coupling and Arylation Reactions.

    PubMed

    Bhojgude, Sachin Suresh; Bhunia, Anup; Biju, Akkattu T

    2016-09-20

    Arynes are highly reactive intermediates having several applications in organic synthesis for the construction of various ortho-disubstituted arenes. Traditionally, arynes are generated in solution from haloarenes under strongly basic conditions. However, the scopes of many of the aryne reactions are limited because of the harsh conditions used for their generation. The renaissance of interest in aryne chemistry is mainly due to the mild conditions for their generation by the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates. This Account is focused on the Diels-Alder reaction of arynes and their transition-metal-free application in multicomponent couplings as well as arylation reactions. The Diels-Alder reaction of arynes is a powerful tool for constructing benzo-fused carbocycles and heterocycles. In 2012, we developed an efficient, broad-scope, and scalable Diels-Alder reaction of pentafulvenes with arynes affording benzonorbornadiene derivatives. Subsequently, we accomplished the Diels-Alder reaction of arynes with dienes such as 1,2-benzoquinones and tropones. Moreover, we uncovered a transition-metal-free protocol for the synthesis of 9,10-dihydrophenanthrenes by the reaction of arynes with styrenes that proceeds via a Diels-Alder/ene-reaction cascade. In addition, we demonstrated the reaction of arynes with indene/benzofurans, which proceeds via a tandem [4 + 2]/[2 + 2] sequence. Multicomponent coupling (MCC) involving arynes mainly comprises the initial addition of a nucleophile to the aryne followed by interception of the aryl anion intermediate with an electrophile (provided the nucleophilic and electrophilic moieties do not belong to the same molecule). We have disclosed aryne MCCs initiated by N-heterocycles such as (iso)quinoline, pyridine, and aziridines. When (iso)quinoline is used as the nucleophilic trigger and N-substituted isatin as the third component, the reaction affords spirooxazino(iso)quinolines via 1,4-dipolar

  14. Diels-Alder Cycloadditions: A MORE Experiment in the Organic Laboratory Including a Diene Identification Exercise Involving NMR Spectroscopy and Molecular Modeling

    ERIC Educational Resources Information Center

    Shaw, Roosevelt; Severin, Ashika; Balfour, Miguel; Nettles, Columbus

    2005-01-01

    Two Diels-Alder reactions are described that are suitable for a MORE (microwave-induced organic reaction enhanced) experiment in the organic chemistry laboratory course. A second experiment in which the splitting patterns of the vinyl protons in the nuclear magnetic resonance (NMR) spectra of two MORE adducts are used in conjunction with molecular…

  15. Illustrating the Utility of X-Ray Crystallography for Structure Elucidation through a Tandem Aldol Condensation/Diels-Alder Reaction Sequence

    ERIC Educational Resources Information Center

    Hoang, Giang T.; Kubo, Tomohiro; Young, Victor G., Jr.; Kautzky, Jacob A.; Wissinger, Jane E.

    2015-01-01

    Two introductory organic chemistry laboratory experiments are described based on the Diels-Alder reaction of 2,3,4,5-tetraphenylcyclopentadienone, which is synthesized prior to or in a one-pot reaction, with styrene. Students are presented with three possible products, the "endo" and "exo" diastereomers and the decarbonylated…

  16. Fast Hetero-Diels-Alder Reactions Using 4-Phenyl-1,2,4-Triazoline-3,5-Dione (PTAD) as the Dienophile

    ERIC Educational Resources Information Center

    Celius, Tevye C.

    2010-01-01

    A hetero-Diels-Alder reaction that proceeds rapidly and only requires a simple filtration to purify the product is presented. The dienophile, 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), is prepared by the heterogeneous oxidation of 4-phenylurazole by the bromenium ion, Br[superscript +], generated in situ by the oxidation of potassium bromide by…

  17. Synthesis of a Self-Healing Polymer Based on Reversible Diels-Alder Reaction: An Advanced Undergraduate Laboratory at the Interface of Organic Chemistry and Materials Science

    ERIC Educational Resources Information Center

    Weizman, Haim; Nielsen, Christian; Weizman, Or S.; Nemat-Nasser, Sia

    2011-01-01

    This laboratory experiment exposes students to the chemistry of self-healing polymers based on a Diels-Alder reaction. Students accomplish a multistep synthesis of a monomer building block and then polymerize it to form a cross-linked polymer. The healing capability of the polymer is verified by differential scanning calorimetry (DSC) experiments.…

  18. Integration of Computational and Preparative Techniques to Demonstrate Physical Organic Concepts in Synthetic Organic Chemistry: An Example Using Diels-Alder Reaction

    ERIC Educational Resources Information Center

    Palmer, David R. J.

    2004-01-01

    The Diels-Alder reaction is used as an example for showing the integration of computational and preparative techniques, which help in demonstrating the physical organic concepts in synthetic organic chemistry. These experiments show that the students should not accept the computational results without questioning them and in many Diels-Alder…

  19. The Synthesis of "N"-Benzyl-2-Azanorbornene via Aqueous Hetero Diels-Alder Reaction: An Undergraduate Project in Organic Synthesis and Structural Analysis

    ERIC Educational Resources Information Center

    Sauvage, Xavier; Delaude, Lionel

    2008-01-01

    The synthesis of "N"-benzyl-2-azanorbornene via aqueous hetero Diels-Alder reaction of cyclopentadiene and benzyliminium chloride formed in situ from benzylamine hydrochloride and formaldehyde is described. Characterization of the product was achieved by IR and NMR spectroscopies. The spectral data acquired are thoroughly discussed. Numerous…

  20. Transformation of D-(-)-ribose into a natural product-like scaffold via a Lewis acid catalyzed intramolecular hetero-Diels-Alder reaction.

    PubMed

    Messer, Roland; Fuhrer, Cyril A; Häner, Robert

    2007-01-01

    Starting from D-(-)-ribose, a tricyclic natural product-like scaffold suitable for combinatorial derivatization was synthesized via an intramolecular hetero-Diels-Alder reaction. Lithium perchlorate was found to enhance the reaction rate and, at the same time, had a pronounced influence on the chemoselectivity of the reaction. The stereochemical course of the reaction, however, was not influenced by the Lewis acid.

  1. Diels-Alder Synthesis of endo-cis-N-phenylbicyclo[2.2.2]oct-5-en-2,3-dicarboximide

    ERIC Educational Resources Information Center

    Baar, Marsha R.; Wustholz, Kristin

    2005-01-01

    A study investigated the Diels-Alder synthesis of endo-cis-N-phenylbicyclo [2.2.2]oct-5-en-2,3-dicarboximide. The amount of time taken by a reaction between the 1,3-cyclohexadiene and N-phenylmaleimide at room temperature and also whether the desired cycloadduct would precipitate directly from the reaction mixture was examined.

  2. Combination of inverse electron-demand Diels-Alder reaction with highly efficient oxime ligation expands the toolbox of site-selective peptide conjugations.

    PubMed

    Hörner, S; Uth, C; Avrutina, O; Frauendorf, H; Wiessler, M; Kolmar, H

    2015-07-14

    A modular approach combining inverse electron-demand Diels-Alder coupling (DARinv) and oxime ligation expands the toolbox of bioorthogonal peptide chemistry. Applicability of versatile site-specific bifunctional building blocks is demonstrated by generation of defined conjugates comprising linear, cystine-bridged and multi-disulfide functional peptides as well as their conjugation with hybrid silsesquioxane nanoparticles.

  3. First kinetic evidence for the CH/π and π/π solute-solvent interaction of C60 in the Diels-Alder reaction with cyclohexadiene.

    PubMed

    Oshima, Takumi; Mikie, Tsubasa; Ikuma, Naohiko; Yakuma, Hajime

    2012-03-07

    The first CH/π solute-solvent interaction of C(60) was evidenced by the kinetic solvent effects in the Diels-Alder reaction with 1,3-cyclohexadiene based on the evaluation of linear free energy relationship of log k(2) with empirical solvent polarity and basicity parameters, E(T)(30) and D(π), respectively.

  4. A π-electronic covalent organic framework catalyst: π-walls as catalytic beds for Diels-Alder reactions under ambient conditions.

    PubMed

    Wu, Yang; Xu, Hong; Chen, Xiong; Gao, Jia; Jiang, Donglin

    2015-06-25

    We report a strategy for developing π-electronic covalent organic frameworks as heterogeneous catalysts that enable the use of columnar π-walls as catalytic beds to facilitate organic transformations in their one-dimensional open channels. The π-frameworks exhibit outstanding catalytic activity, promote Diels-Alder reactions under ambient conditions and are robust for cycle use.

  5. Formal Alder-ene reaction of a bicyclo[1.1.0]butane in the synthesis of the tricyclic quaternary ammonium core of daphniglaucins

    PubMed Central

    Ueda, Masafumi; Walczak, Maciej A. A.; Wipf, Peter

    2008-01-01

    A tricyclic substructure of the tetracyclic nitrogen core of the daphniglaucins was formed by an oxidative activation of the allyl side chain of a bicyclo[1.1.0]butylmethylamine, a spontaneous intramolecular formal Alder-ene reaction, and a selective cyclization of a triol intermediate. PMID:19129907

  6. Reactivity of N-Phenyl-1-Aza-2-Cyano-1,3-Butadienes in the Diels-Alder Reaction.

    PubMed

    Sisti, Nicholas J.; Motorina, Irina A.; Tran Huu Dau, Marie-Elise; Riche, Claude; Fowler, Frank W.; Grierson, David S.

    1996-05-31

    It is found that N-phenyl-2-cyano-1-azadiene 4, prepared via a two-step, one-pot, sequence from acrylanilide, undergoes efficient [4 + 2] cycloaddition with a complete range of electron rich, electron poor, and neutral dienophiles under remarkably mild thermal conditions (90-120 degrees C for 20-48 h). Regiospecific formation of the alpha-cycloadduct wherein the dienophile substituent is alpha to nitrogen is observed for vinyl ethers and styrene, whereas the Diels-Alder reactions with methyl acrylate and methyl vinyl ketone (MVK) produce alpha/beta mixtures in which the alpha-cycloadduct is the major regioisomer (approximately 4-5:1). An essentially identical reaction pattern was observed in the Diels-Alder reaction of N-(p-methoxyphenyl)-2-cyano-1-azadiene 18 and the 4-methyl-substituted azadiene 27. For compound 19 derived from cycloaddition of 18 with ethyl vinyl ether, facile conversion to the dihydropyridine 21 through loss of EtOH on brief acid treatment was also noted. The 2,4-cis-disubstitution pattern confirmed by X-ray diffraction for the major cycloadduct 29 isolated from the reaction of 27 with styrene provides evidence for the endo mode of cycloaddition in the Diels-Alder reaction of N-phenyl(aryl)-2-cyano-1-azadienes. Calculation of the frontier orbital energies and coefficients, as well as the transition state geometries for the [4 + 2] cycloaddition of N-phenyl-2-cyano-1-azadiene 4 with methyl vinyl ether, styrene, and MVK were carried out at the RHF AM1 level (MOPAC, Version 5.0). The FMO treatment indicates that the reaction of 4 with methyl vinyl ether occurs under LUMO(diene) control, whereas in contrast, the corresponding cycloaddition with MVK occurs preferably under HOMO(diene) control. A high degree of asynchronicity is observed in the calculated transition states for reaction of 4 with the three representative dienophiles. In all cases the transition states leading to the alpha-cycloadducts are lower in energy than those giving the beta

  7. Growth and gas exchange in field-grown and greenhouse-grown Quercus rubra following three years of exposure to enhanced UV-B radiation.

    PubMed

    Bassman, John H; Robberecht, Ronald

    2006-09-01

    Long-term effects of enhanced UV-B radiation were evaluated in field-grown and greenhouse-grown Quercus rubra L. (northern red oak), a species with a multiple flushing shoot growth habit. Seeds were germinated and grown in ambient, twice ambient (2x) or three times ambient (3x) biologically effective UV-B radiation from square-wave (greenhouse) or modulated (field) lamp systems for three growing seasons. Greenhouse plants in the 2x treatment had greater heights and diameters during the later part of the first year and into the second year, but by the third year there were no differences among treatments. There were no significant differences in growth among treatments for field plants. Enhanced UV-B radiation did not significantly reduce total biomass or distribution of biomass in either field or greenhouse plants. Net photosynthesis (3x), leaf conductance (2x and 3x) and water-use efficiency (3x) of greenhouse plants were greater in the enhanced UV-B radiation treatments in the second year but unaffected by the treatments in other years. None of the treatments affected these parameters in field plants. Dark respiration was increased by the 3x treatment in the first and third years in greenhouse plants, and by the 2x treatment during the second year in field plants. Enhanced UV-B had variable effects on apparent quantum yield and light compensation points. Chlorophylls were unaffected by enhanced UV-B radiation in both greenhouse and field conditions. Bulk methanol-extractable UV-absorbing compounds were increased only by the 3x treatment in greenhouse plants during the third year and by the 2x treatment in field plants during the second year. Overall, Q. rubra appears relatively resistant to potentially damaging enhanced UV-B radiation and is unlikely to be negatively impacted even in the predicted worst-case scenarios.

  8. Asymmetric Lewis acid organocatalysis of the Diels-Alder reaction by a silylated C-H acid.

    PubMed

    Gatzenmeier, Tim; van Gemmeren, Manuel; Xie, Youwei; Höfler, Denis; Leutzsch, Markus; List, Benjamin

    2016-02-26

    Silylium ion equivalents have shown promise as Lewis acid catalysts for a range of important C-C bond-forming reactions. Here we describe chiral C-H acids that upon in situ silylation, generate silylium-carbanion pairs, which are extremely active Lewis acid catalysts for enantioselective Diels-Alder reactions of cinnamates with cyclopentadiene. Enantiomeric ratios of up to 97:3 and diastereomeric ratios of more than 20:1 are observed across a diverse set of substitution patterns with 1 mole percent (mol %) of C-H acid catalyst and 10 mol % of a silylating reagent. The results show promise for broad applications of such C-H acid-derived silylium ion equivalents in asymmetric Lewis acid catalysis.

  9. Three biscembranoids and their monomeric counterpart cembranoid, a biogenetic Diels-Alder precursor, from the soft coral Sarcophyton elegans.

    PubMed

    Bishara, Ashgan; Rudi, Amira; Benayahu, Yehuda; Kashman, Yoel

    2007-12-01

    Two new cembranoids, methyl tetrahydrosarcoate ( 1) and methyl tetrahydroisosarcoate ( 2), were isolated from the soft coral Sarcophyton elegans, collected at Kitangambwe Kenya, together with four biscembranoids, the known nyalolide ( 3) and the unprecedented desacetylnyalolide ( 4), diepoxynyalolide ( 5), and dioxanyalolide ( 6). The structures and relative stereochemistry of the compounds were elucidated by interpretation of MS, 1D NMR, COSY, HSQC, HMBC, and NOESY experiments. Compound 1 is most likely the dienophile affording, by a Diels-Alder reaction, the four biscembranoids. Dioxanyalolide ( 6) possesses antibacterial activity against Escherichia coli at a concentration of 1.25 microg/mL. Methyl tetrahydrosarcoate ( 1) and diepoxynyalolide ( 5) exhibited LC 50 values of 1.5 microM in a brine shrimp bioassay, while desacetylnyalolide ( 4) was only mildly active.

  10. The hetero-Diels-Alder addition of sulfur dioxide: the pseudo-chair conformation of a 4,5-dialkylsultine.

    PubMed

    Markovic, Dean; Roversi, Elena; Scoppelliti, Rosario; Vogel, Pierre; Meana, Rubén; Sordo, José A

    2003-10-17

    Even unsubstituted butadiene adds to sulfur dioxide in the hetero-Diels-Alder mode more rapidly than in the chelotropic mode. The sultine can be observed in equilibrium with the diene and the sulfur dioxide only at low temperature and in the presence of CF(3)COOH. Crystals of 4,5-dialkyl-sultine resulting from the SO(2) addition to 1,2-dimethylidenecyclohexane have been obtained at -100 degrees C and analyzed by X-ray diffraction. Quantum chemical calculations have shown that hyperconjugative interactions within the sulfinyl moiety are responsible for the anomeric effects observed in sultines that prefer pseudo-chair conformations with pseudo-axial Sdbond;O bonds.

  11. Discovery of TNF inhibitors from a DNA-encoded chemical library based on diels-alder cycloaddition.

    PubMed

    Buller, Fabian; Zhang, Yixin; Scheuermann, Jörg; Schäfer, Juliane; Bühlmann, Peter; Neri, Dario

    2009-10-30

    DNA-encoded chemical libraries are promising tools for the discovery of ligands toward protein targets of pharmaceutical relevance. DNA-encoded small molecules can be enriched in affinity-based selections and their unique DNA "barcode" allows the amplification and identification by high-throughput sequencing. We describe selection experiments using a DNA-encoded 4000-compound library generated by Diels-Alder cycloadditions. High-throughput sequencing enabled the identification and relative quantification of library members before and after selection. Sequence enrichment profiles corresponding to the "bar-coded" library members were validated by affinity measurements of single compounds. We were able to affinity mature trypsin inhibitors and identify a series of albumin binders for the conjugation of pharmaceuticals. Furthermore, we discovered a ligand for the antiapoptotic Bcl-xL protein and a class of tumor necrosis factor (TNF) binders that completely inhibited TNF-mediated killing of L-M fibroblasts in vitro.

  12. Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

    NASA Technical Reports Server (NTRS)

    Tyson, Daniel S.; Ilhan, Faysal; Meador, Mary Ann B.; Smith, Dee Dee; Scheiman, Daniel A.; Meador, Michael A.

    2004-01-01

    Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

  13. Dextran-based self-healing hydrogels formed by reversible diels-alder reaction under physiological conditions.

    PubMed

    Wei, Zhao; Yang, Jian Hai; Du, Xiao Jing; Xu, Feng; Zrinyi, Miklos; Osada, Yoshihito; Li, Fei; Chen, Yong Mei

    2013-09-01

    A dextran-based self-healing hydrogel is prepared by reversible Diels-Alder reaction under physiological conditions. Cytocompatible fulvene-modified dextran as main polymer chains and dichloromaleic-acid-modified poly(ethylene glycol) as cross-linkers are used. Both macro- and microscopic observation as well as the rheological recovery test confirm the self-healing property of the dextran-l-poly(ethylene glycol) hydrogels ("l" means "linked-by"). In addition, scanning electrochemical microscopy is used to qualitatively and quantitatively in situ track the self-healing process of the hydrogel for the first time. It is found that the longitudinal depth of scratch on hydrogel surface almost completely healed at 37 °C after 7 h. This work represents a facile approach for fabrication of polysaccharide self-healing hydrogel, which can be potentially used in several biomedical fields.

  14. Enantioselective Diels-Alder approach to C-3-oxygenated angucyclinones from (SS)-2-(p-tolysulfinyl)-1,4-naphthoquinone.

    PubMed

    Carreño, M C; Urbano, A; Di Vitta, C

    2000-03-03

    Chiral racemic vinylcyclohexenes 2, bearing oxygenated substituents and/or a methyl group at the C-5 position of the cyclohexene ring, were submitted to Diels-Alder reactions with enantiomerically pure (SS)-(2-p-tolylsulfinyl)-1,4-naphthoquinone [(+)-1]. The domino cycloaddition/pyrolytic sulfoxide elimination process led to the formation of enantiomerically enriched angularly tetracyclic quinones anti-6 and syn-7, which were obtained from the kinetic resolution of the racemic diene. In all cases, (SS)-(2-p-tolylsulfinyl)-1,4-naphthoquinone reacted from the less hindered face of the more reactive s-cis conformation, to form products in good enantiomeric excesses. Steric effects and torsional interactions in the corresponding approaches account for the observed pi-facial diastereoselectivities at both partners. The usefulness of this methodology is illustrated with the four-step totally asymmetric synthesis of the C-3-oxygenated angucyclinone derivative (-)-8-deoxytetrangomycin 10 in 26% overall yield and with 50% enantiomeric purity.

  15. Catalytic Effects of Oxide Surfaces on Diels-Alder Cycloaddition between Furan and Methyl Acrylate: A DFT Study

    NASA Astrophysics Data System (ADS)

    Salavati-Fard, Taha; Jenness, Glen; Caratzoulas, Stavros; Doren, Douglas

    Using density functional theory with periodic boundary conditions, we study the catalytic effects of oxide surfaces such as ZrO_2 and HfO_2 on Diels-Alder reaction between furan and methyl acrylate. The cycloadduct can be dehydrated later to produce methyl benzoic which is an important step toward benzoic acid production. The gas-phase and on-surface reaction mechanisms are studied in detail. The surface hydration effects on the reaction mechanism and energy profile are studied as well. Our calculations show that the oxide surfaces catalyze the reaction significantly through the interaction of metal sites with methyl acrylate. The calculations are interpreted by making use of electronic density of states and band structure of the catalyst.

  16. Theoretical study of the regioselectivity of successive 1,3-butadiene Diels-Alder cycloadditions to C{sub 60}

    SciTech Connect

    Sola, M.; Duran, M.; Mestres, J.

    1996-09-18

    The possibility of successive Diels-Alder cycloadditions of 1,3-butadiene to C{sub 60} has been studied theoretically by means of the AM1 semiempirical method. The nine unique possible reaction pathways leading to the experimentally observed T{sub h}-symmetric hexakisadduct have been described, and the most thermodynamically favored has been analyzed in more detail. The enthalpy barrier for the cycloaddition changes from 16.2 kcal/mol in the formation of the monoadduct to 17.8 kcal/mol for the hexakisadduct, increasing slightly with successive attacks. However, once the hexakisadduct is reached, addition of a new 1,3-butadiene has an enthalpy barrier as high as 35.5 kcal/mol, in agreement with the fact that experimentally the heptakisadduct has not yet been observed. 26 refs., 2 figs., 2 tabs.

  17. Diels-Alder functionalized carbon nanotubes for bone tissue engineering: in vitro/in vivo biocompatibility and biodegradability

    NASA Astrophysics Data System (ADS)

    Mata, D.; Amaral, M.; Fernandes, A. J. S.; Colaço, B.; Gama, A.; Paiva, M. C.; Gomes, P. S.; Silva, R. F.; Fernandes, M. H.

    2015-05-01

    The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT membranes (p,f-CNTs). The in vivo subcutaneously implanted materials showed a higher biological reactivity, thus inducing a slighter intense inflammatory response compared to non-functionalized CNT membranes (p-CNTs), but still showing a reduced cytotoxicity profile. Moreover, the in vivo biodegradation of CNTs was superior for p,f-CNT membranes, likely mediated by the oxidation-induced myeloperoxidase (MPO) in neutrophil and macrophage inflammatory milieus. This proves the biodegradability faculty of functionalized CNTs, which potentially avoids long-term tissue accumulation and triggering of acute toxicity. On the whole, the proposed Diels-Alder functionalization accounts for the improved CNT biological response in terms of the biocompatibility and biodegradability profiles. Therefore, CNTs can be considered for use in bone tissue engineering without notable toxicological threats.The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT

  18. Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

    SciTech Connect

    Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; Mench, Matthew M.; Zawodzinski, Thomas A.; Tang, Z. J.

    2015-11-14

    In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not play a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm2.

  19. Regioselective Synthesis of C-3-Functionalized Quinolines via Hetero-Diels-Alder Cycloaddition of Azadienes with Terminal Alkynes.

    PubMed

    Saunthwal, Rakesh K; Patel, Monika; Verma, Akhilesh K

    2016-08-05

    A highly efficient metal and protection-free approach for the regioselective synthesis of C-3-functionalized quinolines from azadienes (in situ generated from 2-aminobenzyl alcohol) and terminal alkynes through [4 + 2] cycloaddition has been developed. An unprecedented reaction of 2-aminobenzyl alcohol with 1,3- and 1,4-diethynylbenzene provided the C-3 tolylquinolines via [4 + 2] HDA and oxidative decarboxylation. The -NH2 group directed mechanistic approach was well supported by the control experiments and deuterium-labeling studies and by isolating the azadiene intermediate. The reactivity and selectivity of unprotected azadiene in metal-free base-assisted hetero-Diels-Alder reaction is exploited to quickly assemble an important class of C-3-functionalized quinolines, which are difficult to access.

  20. Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

    DOE PAGES

    Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; ...

    2015-11-14

    In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm2.« less

  1. Solid lipid nanoparticles affect microbial colonization and enzymatic activity throughout the decomposition of alder leaves in freshwater microcosms.

    PubMed

    Sampaio, A C; Mendes, R J; Castro, P G; Silva, A M

    2017-01-01

    Solid lipid nanoparticles (SLNs) are used as carriers for drug delivery, and are high biocompatible and designed to endure in the host organism. Despite its current industrial production is low, many of these substances are available on the market, and much more are in the production pipeline. As a result, many of them will end in aquatic systems raising the question whether they can pose a risk to aquatic biota and the associated ecological processes. Microbial decomposers of plant litter, play a key role in forested streams being responsible for the energy flow between terrestrial and aquatic environments. Here, we investigated the effects of SLNs on alder leaf litter decomposition by aquatic microbes. Alder leaves were immersed in a stream of Northeast Portugal to allow microbial colonization before being exposed in microcosms of two types of SLNs at two concentrations for 42 days. Results showed that rates of leaf decomposition decreased with exposure to SLNs. Bacterial biomass was not inhibited by SLNs, and cultivable fungi densities remained constant (SLN-A) or increased (SLN-C) compared with control microcosms. The type and concentration of SLNs influenced differently the leaf colonization by fungi as well as fungal sporulation rate. These effects were accompanied by changes in the community extraenzymatic profile: the activities of alkaline phosphatase, acidic phosphatase, Naphthol-AS-BI-phosphohydrolase (P cycle) and lipases increased in the SLNs microcosms. This study provided the first evidence of the adverse effects of the release of SLNs to streams on leaf litter decomposition. Those effects seem to depend on the composition and concentration of SLNs, as well on the microbial target group, or enzyme. Thus, prior to massive industrial production of these nanomaterials, some measures should be taken to avoid environmental impact affecting the microbial communities responsible for detritus decomposition.

  2. B(C6F5)3: A New Class of Strong and Bulky Lewis Acid for Exo-Selective Intermolecular Diels-Alder Reactions of Unreactive Acyclic Dienes with α,β-Enals.

    PubMed

    Zhou, Jia-Hui; Jiang, Bing; Meng, Fei-Fan; Xu, Yun-He; Loh, Teck-Peng

    2015-09-18

    Lewis acid B(C6F5)3 catalyzed the Diels-Alder reactions of multisubstituted open-chain dienes and α,β-enals to afford the desired products with high exo-selectivities are reported. The substituent effect of the dienes and dienophiles on the product's stereoselectivity was thoroughly investigated, and it was found that most of the desired exo-Diels-Alder products could be obtained in good yields and with high exo-stereoselectivities.

  3. Ammonium nitrate, urea, and biuret fertilizers increase volume growth of 57-year-old douglas-fir trees within a gradient of nitrogen deficiency. Forest Service research paper

    SciTech Connect

    Miller, R.E.; Reukema, D.L.; Hazard, J.W.

    1996-03-01

    In a nitrogen-deficient plantation in southwest Washington, the authors (1) compared effects of 224 kg N/ha as ammonium nitrate, urea, and biuret on volume growth of dominant and codominant Douglas-fir (Pseudotsuga menziesii var. menziesii (Mirb.) Franco); (2) determined how 8-year response of these trees to fertilization was related to their distance from a strip of the plantation interplanted with nitrogen-fixing red alder (alnus rubra Bong.); and (3) observed effects of biuret on understory vegetation. On both sides of the strip centerline, the authors grouped subject trees into 30 plots of 4 trees each, based on slope position and distance from alder. The authors randomly assigned three fertilizers and a control within each plot. They analyzed separately data from east and west of the mixed stand certerline. Initial volume differed greatly among the 120 trees on each side, so they used covariance analysis to adjust observed treatment means. Adjusted mean volume growth was increased (p equal to or less than 0.10) by 22 to 28 percent on the east side and by 11 to 14 percent on the west side, with no significant difference in response to the three fertilizers.

  4. Monitoring vegetation water uptake in a semiarid riparian corridor

    NASA Astrophysics Data System (ADS)

    Robinson, J.; Ochoa, C. G.; Leonard, J.

    2015-12-01

    With a changing global climate and growing demand for water throughout the world, responsible and sustainable land and water resource management practices are becoming increasingly important. Accounting for the amount of water used by riparian vegetation is a critical element for better managing water resources in arid and semiarid environments. The objective of this study was to determine water uptake by selected riparian vegetative species in a semiarid riparian corridor in North-Central Oregon. Exo-skin sap flow sensors (Dynamax, Houston, TX, U.S.A.) were used to measure sap flux in red alder (Alnus rubra) trees, the dominant overstory vegetation at the field site. Xylem sap flow data was collected from selected trees at the field site and in a greenhouse setting. Transpiration rates were determined based on an energy balance method, which makes it possible to estimate the mass flow of sap by measuring the velocity of electrical heat pulses through the plant stem. Preliminary field results indicate that red alder tree branches of about 1 inch diameter transpire between 2 and 6 kg of water/day. Higher transpiration rates of up to 7.3 kg of water/day were observed under greenhouse conditions. Streamflow and stream water temperature, vegetation characteristics, and meteorological data were analyzed in conjunction with transpiration data. Results of this study provide insight on riparian vegetation water consumption in water scarce ecosystems. This study is part of an overarching project focused on climate-vegetation interactions and ecohydrologic processes in arid and semiarid landscapes.

  5. First description of the gravid female of Philometra rubra (Leidy, 1856) (Nematoda: Philometridae), a parasite of the abdominal cavity of temperate basses Morone Spp. (Moronidae: Perciformes) in North America.

    PubMed

    Moravec, František; de Buron, Isaure; Measures, Lena

    2013-06-01

    Gravid females of the little-known nematode species Philometra rubra ( Leidy, 1856 ) (Philometridae) are described from specimens from the abdominal cavity of the striped bass, Morone saxatilis (Walbaum), in South Carolina and Canada. The specimens were studied with the use of light and scanning electron microscopy. This species is mainly characterized by the distribution and different sizes of cephalic papillae from the external circle, which is a unique feature compared to other philometrids. Other characteristic features are the shape of the posterior end of body, size and location of caudal projections, and the presence of a well-developed anterior esophageal inflation. The morphology of the male of P. rubra and the life cycle of this nematode are still unknown.

  6. 40Ar/39Ar ages from the rhyolite of Alder Creek, California: Age of the Cobb Mountain Normal-Polarity Subchron revisited

    NASA Astrophysics Data System (ADS)

    Turrin, Brent D.; Donnelly-Nolan, Julie M.; Carter Hearn, B., Jr.

    1994-03-01

    New 40Ar/39Ar age determinations on sanidine from the rhyolite of Alder Creek, California, indicate a 1.186 ±0.006 Ma age for the Cobb Mountain Normal-Polarity Subchron. The new age is statistically older (α = 0.05) than the previously reported K-Ar age (1.12 ±0.02 Ma) and agrees with the age suggested by the astronomical polarity time scale. Incomplete extraction of radiogenic 40Ar (40Ar*) from the sanidine is the most likely reason for the disparity between the 40Ar/39Ar and K-Ar ages. Because the Cobb Mountain subchron is a worldwide, short-duration event, and because no widely used interlaboratory 40Ar/39Ar standard younger than 27 Ma exists, we propose that sanidine from the rhyolite of Alder Creek be considered for use as a new Quaternary 40Ar/39Ar mineral standard.

  7. Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

    PubMed Central

    Flores-Conde, Maria Ines; Reyes, Leonor; Herrera, Rafael; Rios, Hulme; Vazquez, Miguel A.; Miranda, Rene; Tamariz, Joaquin; Delgado, Francisco

    2012-01-01

    Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17), under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO) calculations. PMID:22489113

  8. 40Ar/39Ar ages from the rhyolite of Alder Creek, California: age of the Cobb Mountain normal-polarity subchron revisited

    USGS Publications Warehouse

    Turrin, B.D.; Donnelly-Nolan, J. M.; Hearn, B.C.

    1994-01-01

    New 40Ar/39Ar age determinations on sanidine from the rhyolite of Alder Creek, California, indicate a 1.186 ?? 0.006 Ma age for the Cobb Mountain Normal-Polarity Subchron. The hew age is statistically older (?? = 0.05) than the previously reported K-Ar age (1.12 ?? 0.02 Ma) and agrees with the age suggested by the astronomical polarity time scale. Incomplete extraction of radiogenic 40Ar (40Ar*) from the sanidine is the most likely reason for the disparity between the 40Ar/39Ar and K-Ar ages. Because the Cobb Mountain subchron is a worldwide, short-duration event, and because no widely used interlaboratory 40Ar/39Ar standard younger than 27 Ma exists, it is proposed that sanidine from the rhyolite of Alder Creek be considered for use as a new Quaternary 40Ar/39Ar mineral standard. -Authors

  9. Origins of the Unfavorable Activation and Reaction Energies of 1-Azadiene Heterocycles Compared to 2-Azadiene Heterocycles in Diels-Alder Reactions.

    PubMed

    Fell, Jason S; Martin, Blanton N; Houk, K N

    2017-02-17

    The reactivities of butadiene, cyclopentadiene, furan, thiophene, pyrrole, and their 1-aza- and 2-aza-derivatives in Diels-Alder reactions with ethylene and fumaronitrile were investigated with density functional theory (M06-2X/6-311G(d,p)). The activation free energies for the Diels-Alder reactions of cyclic 1-azadienes are 10-14 kcal mol(-1) higher than those of cyclic 2-azadienes, and the reaction free energies are 17-20 kcal mol(-1) more endergonic. The distortion/interaction model shows that the increased activation energies of cyclic 1-azadienes originate from increased transition state distortion energies and unfavorable interaction energies, arising from addition to the nitrogen terminus of the C═N bond.

  10. Synthesis of Complex Hexacyclic Compounds via a Tandem Rh(II)-Catalyzed Double-Cyclopropanation/Cope Rearrangement/Diels–Alder Reaction

    PubMed Central

    2015-01-01

    Treatment of (E)-1-(methoxymethylene)-1,2,3,4-tetrahydronaphthalene with styryl diazoacetates in the presence of catalytic amounts of the dirhodium complex Rh2(S-DOSP)4 provides a highly enantioenriched hexacyclic product with 10 new stereogenic centers. The transformation proceeds by a cascade sequence starting with a double cyclopropanation of a benzene ring, followed by a Cope rearrangement of a divinylcyclopropane and then an intramolecular Diels–Alder cycloaddition. PMID:25208337

  11. Remarkably high asymmetric amplification in the chiral lanthanide complex-catalyzed hetero-Diels-Alder reaction: first example of the nonlinear effect in ML3 system

    PubMed

    Furuno; Hanamoto; Sugimoto; Inanaga

    2000-01-01

    [reaction: see text] A remarkably high asymmetric amplification was realized in the Yb[(R)-BNP]3-catalyzed hetero-Diels-Alder reaction as the first example in the metal/chiral ligand 1:3 system. The mechanism may be explained by the autogenetic formation of the enantiopure complex as the most active catalyst. The enantiomer-discriminative formation of homochiral ML3 complexes is quite general within the lanthanide metal ions with similar ionic radii to that of the ytterbium ion.

  12. Synthesis of aza polycyclic compounds derived from pyrrolidine, indolizidine, and indole via intramolecular Diels-Alder cycloadditions of neutral 2-azadienes.

    PubMed

    Palacios, Francisco; Alonso, Concepción; Amezua, Patricia; Rubiales, Gloria

    2002-03-22

    A method for the preparation of novel oxaza and diaza polycyclic 9-oxa-4-azaphenanthrene, 5H-pyrido[2,3-a]pyrrolizine, 5H,6H-pyrido[3,2-g]indolizine, and 5H,6H-indeno[2,1-a]indole is described, based on tandem reactions: aza-Wittig reaction of N-vinylic phosphazenes with functionalized aldehydes and an intramolecular aza-Diels-Alder reaction.

  13. An enantioselective Diels-Alder reaction of 1,2-dihydropyridines with α-acyloxyacroleins catalyzed by a chiral primary ammonium salt.

    PubMed

    Ishihara, Kazuaki; Yamada, Hiroki; Akakura, Matsujiro

    2014-06-18

    The first enantioselective Diels-Alder reaction of 1,2-dihydropyridines with α-acyloxyacroleins catalyzed by a chiral primary ammonium salt has been developed and it offers more efficient routes to key synthetic intermediates of alkaloids, for which the direct preparations were unavailable before. The asymmetric induction can be understood through the optimized geometry of an iminium salt aqua complex derived from the catalyst and the dienophile.

  14. Simultaneous analysis of 70 pesticides using HPlc/MS/MS: a comparison of the multiresidue method of Klein and Alder and the QuEChERS method.

    PubMed

    Riedel, Melanie; Speer, Karl; Stuke, Sven; Schmeer, Karl

    2010-01-01

    Since 2003, two new multipesticide residue methods for screening crops for a large number of pesticides, developed by Klein and Alder and Anastassiades et al. (Quick, Easy, Cheap, Effective, Rugged, and Safe; QuEChERS), have been published. Our intention was to compare these two important methods on the basis of their extraction efficiency, reproducibility, ruggedness, ease of use, and speed. In total, 70 pesticides belonging to numerous different substance classes were analyzed at two concentration levels by applying both methods, using five different representative matrixes. In the case of the QuEChERS method, the results of the three sample preparation steps (crude extract, extract after SPE, and extract after SPE and acidification) were compared with each other and with the results obtained with the Klein and Alder method. The extraction efficiencies of the QuEChERS method were far higher, and the sample preparation was much quicker when the last two steps were omitted. In most cases, the extraction efficiencies after the first step were approximately 100%. With extraction efficiencies of mostly less than 70%, the Klein and Alder method did not compare favorably. Some analytes caused problems during evaluation, mostly due to matrix influences.

  15. Frictional Properties of Sand Collected from the 1906 Rupture Zone of the San Andreas Fault at Alder Creek, CA}

    NASA Astrophysics Data System (ADS)

    Crawford, R. D.; Cashman, S.; Marone, C.; Carpenter, B.; Baldwin, J.

    2006-12-01

    For the purpose of determining fault frictional properties of unconsolidated late Holocene fluvial sediments, samples were collected from trenches excavated across the 1906 rupture trace of the San Andreas Fault (SAF) at Alder Creek, CA. Two fault perpendicular ~2.5m deep trenches cut into late Holocene fluvial sand and gravel exposed a narrow (<1m) steeply dipping, branching, and anastomosing fault zone. Fault strands are defined by abrupt contacts and 0.5-2.0cm wide deformation bands. Samples of sand were collected several meters from the fault zone and enclosed in airtight bags to retain their original moisture content. We sheared layers of the sand in a servocontrolled, double direct shear testing machine at room temperature. A leveling jig prepared 5 mm thick layers of sand that were sheared between rough forcing blocks (5cm x 5cm nominal contact). Normal stress was constant during shear and varied over the suite of experiments from 75KPa to 900KPa, to a corresponding burial of ~3-40 meters. Shear loading was accomplished via a displacement rate boundary condition, which was set initially at 20μm/s and then subject to step changes to 200 and 2000μm/s for a cumulative total shear displacement of 25mm. Velocity stepping procedures are used to measure the velocity dependence of friction where the friction rate parameter, a-b, is the change in steady state sliding friction normalized by the log of velocity. In fault gouge it has been demonstrated that stable frictional behavior (a-b>0) is associated with pervasive shearing and velocity strengthening, while unstable velocity weakening frictional behavior (a-b<0) has been correlated with localized shear. The a-b values for the Alder Creek sands decrease steadily from 0.11 at 75KPa normal stress to less than 0.005 at 900KPa normal stress. If this rate can be extrapolated, it would imply a transition to velocity weakening at ~1Mpa normal stress or a burial of ~45m. The average measured and calculated steady

  16. Self-healable interfaces based on thermo-reversible Diels-Alder reactions in carbon fiber reinforced composites.

    PubMed

    Zhang, W; Duchet, J; Gérard, J F

    2014-09-15

    Thermo-reversible Diels-Alder (DA) bonds formed between maleimide and furan groups have been used to generate an interphase between carbon fiber surface and an epoxy matrix leading to the ability of interfacial self-healing in carbon:epoxy composite materials. The maleimide groups were grafted on an untreated T700 carbon fiber from a three step surface treatment: (i) nitric acid oxidization, (ii) tetraethylenepentamine amination, and (iii) bismaleimide grafting. The furan groups were introduced in the reactive epoxy system from furfuryl glycidyl ether. The interface between untreated carbon fiber and epoxy matrix was considered as a reference. The interfacial shear strength (IFSS) was evaluated by single fiber micro-debonding test. The debonding force was shown to have a linear dependence with embedded length. The highest healing efficiency calculated from the debonding force was found to be about 82% more compared to the value for the reference interface. All the interphases designed with reversible DA bonds have a repeatable self-healing ability. As after the fourth healing, they can recover a relatively high healing efficiency (58% for the interphase formed by T700-BMI which is oxidized for 60 min during the first treatment step).

  17. Diels-Alder derivatization for sensitive detection and characterization of conjugated linoleic acids using LC/ESI-MS/MS.

    PubMed

    Higashi, Tatsuya; Takekawa, Mioko; Min, Jun Zhe; Toyo'oka, Toshimasa

    2012-04-01

    The utility of Diels-Alder derivatization with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) for liquid chromatography/electrospray ionization tandem mass spectrometry of conjugated linoleic acids (CLAs) was examined. PTAD rapidly reacted with the CLAs, and the resulting derivatives were highly responsive in electrospray ionization mass spectrometry operating in the positive-ion mode. The derivatives produced characteristic product ions during tandem mass spectrometry, which enabled the sensitive detection [limit of detection 18 fmol (signal-to-noise ratio of 5)] and the identification of the conjugated diene position. The PTAD derivatization also significantly increased the reversed-phase liquid chromatography separation selectivity for the most biologically active CLA isomers: cis-9,trans-11-CLA and trans-10,cis-12-CLA. The PTAD derivatization was applied to analyses of food and biological samples; the major CLAs in milk and beef fat samples were successfully identified, and trace amounts of CLAs in human saliva were detected with a simple pretreatment and short analysis time.

  18. Spiroketals of Pestalotiopsis fici provide evidence for a biosynthetic hypothesis involving diversified Diels-Alder reaction cascades.

    PubMed

    Liu, Ling; Li, Yan; Li, Li; Cao, Ya; Guo, Liangdong; Liu, Gang; Che, Yongsheng

    2013-04-05

    Chloropestolides B-G (1-6), six new metabolites featuring the chlorinated spiro[benzo[d][1,3]dioxine-2,7'-bicyclo[2.2.2]octane]-4,8'-dione (1-3) and spiro[benzo[d][1,3]dioxine-2,1'-naphthalene]-2',4-dione (4-6) skeletons, and their putative biosynthetic precursor dechloromaldoxin (7) were isolated from the scale-up fermentation cultures of the plant endophytic fungus Pestalotiopsis fici . The structures of 1-7 were determined mainly by NMR experiments. The absolute configurations of 1-3 were deduced by analogy to the previously isolated metabolites from the same fungus (9 and 13-18), whereas those of 4, 5, and 7 were assigned by electronic circular dichroism (ECD) calculations. Structurally, the spiroketal skeletons found in 1-3 and 4-6 could be derived from 2,6-dihydroxy-4-methylbenzoic acid with chlorinated bicyclo[2.2.2]oct-2-en-5-one and 4a,5,8,8a-tetrahydronaphthalen-2(1H)-one, respectively. Biogenetically, compounds 1-6 were derived from the same Diels-Alder precursors as the previously isolated 9 and 12-18. In addition, compounds 2 and 3 were proposed as the biosynthetic intermediates of 17 and 16, respectively. Compound 1 was cytotoxic to three human tumor cell lines.

  19. Face-selective Diels-Alder reactions between unsymmetrical cyclohexadienes and symmetric trans-dienophile: an experimental and computational investigation.

    PubMed

    Lahiri, Saswati; Yadav, Somnath; Banerjee, Srirupa; Patil, Mahendra P; Sunoj, Raghavan B

    2008-01-18

    A combined experimental and theoretical study of the Diels-Alder reactions between 2-trimethylsiloxy-1,3-cyclohexadienes (2-11) and (E)-1,4-diphenylbut-2-ene-1,4-dione (1) is reported. Two diastereomeric products, 5-endo-6-exo- (nx) and 5-exo-6-endo- (xn) dibenzoyl derivatives, are possible with symmetric trans-dienophile (1). While in many cases 5-endo-6-exo product is preferred over the corresponding 5-exo-6-endo product, the product ratio nx:xn is found to vary with the position of substituents on the diene. The density functional theory studies with the mPW1PW91/6-31G* as well as the B3LYP/6-31G* levels reveal that the electrostatic repulsion between the oxygen lone pairs on the diene and the dienophile is critical to the observed product selectivities. The optimized transition state geometries though appeared to involve secondary orbital interactions, careful examination of the frontier Kohn-Sham orbitals as well as calculations with the natural bond orbital (NBO) analyses confirm the absence of SOI in these transition states. In the case of methyl-substituted dienes, a cumulative effect of steric and electrostatic interactions between the diene and the dienophile is found to be the controlling element toward the observed selectivity.

  20. Surface patterning with natural and synthetic polymers via an inverse electron demand Diels-Alder reaction employing microcontact chemistry.

    PubMed

    Roling, Oliver; Mardyukov, Artur; Lamping, Sebastian; Vonhören, Benjamin; Rinnen, Stefan; Arlinghaus, Heinrich F; Studer, Armido; Ravoo, Bart Jan

    2014-10-21

    Bioorthogonal ligation methods are the focus of current research due to their versatile applications in biotechnology and materials science for post-functionalization and immobilization of biomolecules. Recently, inverse electron demand Diels-Alder (iEDDA) reactions employing 1,2,4,5-tetrazines as electron deficient dienes emerged as powerful tools in this field. We adapted iEDDA in microcontact chemistry (μCC) in order to create enhanced surface functions. μCC is a straightforward soft-lithography technique which enables fast and large area patterning with high pattern resolutions. In this work, tetrazine functionalized surfaces were reacted with carbohydrates conjugated with norbornene or cyclooctyne acting as strained electron rich dienophiles employing μCC. It was possible to create monofunctional as well as bifunctional substrates which were specifically addressable by proteins. Furthermore we structured glass supported alkene terminated self-assembled monolayers with a tetrazine conjugated atom transfer radical polymerization (ATRP) initiator enabling surface grafted polymerizations of poly(methylacrylate) brushes. The success of the surface initiated iEDDA via μCC as well as the functionalization with natural and synthetic polymers was verified via fluorescence and optical microscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), atomic force microscopy (AFM) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR).

  1. N-(furfural) chitosan hydrogels based on Diels-Alder cycloadditions and application as microspheres for controlled drug release.

    PubMed

    Montiel-Herrera, Marcelino; Gandini, Alessandro; Goycoolea, Francisco M; Jacobsen, Neil E; Lizardi-Mendoza, Jaime; Recillas-Mota, Maricarmen; Argüelles-Monal, Waldo M

    2015-09-05

    In this study, chitosan was chemically modified by reductive amination in a two-step process. The synthesis of N-(furfural) chitosan (FC) was confirmed by FT-IR and (1)H NMR analysis, and the degrees of substitution were estimated as 8.3 and 23.8%. The cross-linkable system of bismaleimide (BM) and FC shows that FC shared properties of furan-maleimide chemistry. This system produced non-reversible hydrogel networks by Diels-Alder cycloadditions at 85 °C. The system composed of BM and FC (23.8% substitution) generated stronger hydrogel networks than those of FC with an 8.3% degree of substitution. Moreover, the FC-BM system was able to produce hydrogel microspheres. Environmental scanning electron microscopy revealed the surface of the microspheres to be non-porous with small protuberances. In water, the microspheres swelled, increasing their volume by 30%. Finally, microspheres loaded with methylene blue were able to release the dye gradually, obeying second-order kinetics for times less than 600 min. This behavior suggests that diffusion is governed by the relaxation of polymer chains in the swelled state, thus facilitating drug release outside the microspheres.

  2. The Influence of Sesquiterpenes from Myrica rubra on the Antiproliferative and Pro-Oxidative Effects of Doxorubicin and Its Accumulation in Cancer Cells.

    PubMed

    Ambrož, Martin; Boušová, Iva; Skarka, Adam; Hanušová, Veronika; Králová, Věra; Matoušková, Petra; Szotáková, Barbora; Skálová, Lenka

    2015-08-21

    The sesquiterpenes β-caryophyllene, β-caryophyllene oxide (CAO), α-humulene (HUM), trans-nerolidol (NER), and valencene (VAL) are substantial components of the essential oil from Myrica rubra leaves which has exhibited significant antiproliferative effects in several intestinal cancer cell lines, with CaCo-2 cells being the most sensitive. The present study was designed to evaluate the effects of these sesquiterpenes on the efficacy and toxicity of the anticancer drug doxorubicin (DOX) in CaCo-2 cancer cells and in primary culture of rat hepatocytes. Our results showed that HUM, NER, VAL and CAO inhibited proliferation of CaCo-2 cancer cells but they did not affect the viability of hepatocytes. CAO, NER and VAL synergistically potentiated the efficacy of DOX in cancer cells killing. All sesquiterpenes exhibited the ability to selectively increase DOX accumulation in cancer cells and did not affect DOX concentration in hepatocytes. Additionally, CAO and VAL were able to increase the pro-oxidative effect of DOX in CaCo-2 cells. Moreover, CAO mildly ameliorated DOX toxicity in hepatocytes. Based on all results, CAO seems to be the most promising compound for further testing.

  3. Discrimination and chemical characterization of different Paeonia lactifloras (Radix Paeoniae Alba and Radix Paeoniae Rubra) by infrared macro-fingerprint analysis-through-separation

    NASA Astrophysics Data System (ADS)

    Wang, Yang; Wang, Ping; Xu, Changhua; Sun, Suqin; Zhou, Qun; Shi, Zhe; Li, Jin; Chen, Tao; Li, Zheng; Cui, Weili

    2015-11-01

    Paeonia lactiflora, a commonly used herbal medicine (HM) in Traditional Chinese Medicine (TCM), mainly has two species, Radix Paeoniae Alba (RPA) and Radix Paeoniae Rubra (RPR), for different clinical applications in TCM. For expounding the chemical profile of RPA and RPR and ensuring the clinical efficacy and safety, an infrared macro-fingerprint analysis-through-separation method integrated with statistical pattern recognition was developed to analyze and discriminate the two Paeonia lactifloras. In IR spectra, the major difference between the two was in the range of 1200-900 cm-1: the strongest peak of RPA was at 1024 cm-1, while that of RPR was 1049 cm-1. The difference was magnified in second derivative spectra. The findings were further verified by investigating the separation process of total glucosides, stepwisely monitored by both of IR and UPLC-MS/MS. Simultaneously, the aqueous extracts of RPA and RPR had been separated continuously to acquire the comprehensively hierarchical chemical characteristics for undoubtedly identification and subsequently discrimination of the two herbs. Moreover, 60 batches of the two HMs (30 for each) were objectively classified by principal component regression (PCR) model based on IR macro-fingerprints.

  4. Inter-sectional hybrids obtained from reciprocal crosses between Begonia semperflorens (section Begonia) and B. 'Orange Rubra' (section Gaerdita × section Pritzelia).

    PubMed

    Chen, Yen-Ming; Mii, Masahiro

    2012-06-01

    Inter-sectional hybrids were successfully obtained by the reciprocal crosses between 11 cultivars (including 6 diploids and 5 tetraploids) of Begonia semperflorens (SS & SSSS genomes) and B. 'Orange Rubra' (RR genome) with the aid of in vitro culture of mature or immature seeds on MS medium containing 0.1 mg l(-1) α-naphthylacetic acid, 0.1 mg l(-1) 6-benzyladenine, 10 mg l(-1) gibberellic acid, 30 g l(-1) sucrose and 2.5 g l(-1) gellan gum. Embryo rescue as ovary culture with immature seeds 12(th)-16(th) day after pollination (DAP) generally gave higher efficiency of plantlet formation, but in some cross combinations, culture of mature seeds (30 DAP) resulted in higher yield of plantlets. Flow cytometric analysis revealed that they were consisted of the plants with various genomic combinations (RS, RR, RSS, RRS, RRSS and RRRRSS) as estimated by the DNA contents of both parents. Hybridity of these plants with various genomic combinations including RR was confirmed by random amplified polymorphic DNA analysis. These results suggested that unreduced gamete formation and spontaneous chromosome doubling were involved in the hybrid formation of various ploidy levels and genomic combinations. These hybrids showed various levels of intermediate traits between both parents according to the genomic compositions, and some of them had desirable characters of both parents.

  5. Growth response of four species of Eastern hardwood tree seedlings exposed to ozone, acidic precipitation, and sulfur dioxide. [Prunus serotina, Acer rubrum, Quercus rubra, Liriodendron tulipifera

    SciTech Connect

    Davis, D.D. Skelly, J.M. )

    1992-03-01

    In 1987 a study was conducted in controlled environment chambers to determine the foliar sensitivity of tree seedlings of eight species to ozone and acidic precipitation, and to determine the influence of leaf position on symptom severity. Jensen and Dochinger conducted concurrent similar studies in Continuously Stirred Tank Reactor (CSTR) chambers with ten species of forest trees. Based on the results of these initial studies, four species representing a range in foliar sensitivity to ozone were chosen: black cherry (Prunus serotina Ehrh.), red maple (Acer rubrum L.), northern red oak (Quercus rubra L.) and yellow-poplar (Liriodendron tulipifera L.). These species were also chosen because of their ecological and/or commercial importance in Pennsylvania. Seedlings were exposed in growth chambers simulated acid rain. In addition acute exposures to sulfur dioxide were conducted in a regime based on unpublished monitoring data collected near coal-fired power plants. The objective of this study was to determine if the pollutant treatments influenced the growth and productivity of seedlings of these four species. This information will help researchers and foresters understand the role of air pollution in productivity of eastern forests.

  6. Comparison of metal tolerant and non-tolerant varieties of Festuca rubra for use in the direct hydraulic seeding of metalliferous fluorspar mine tailings

    SciTech Connect

    Morrey, D.R.; Johnson, M.S.; Cooke, J.A.

    1984-09-01

    The germination and growth of metal tolerant and non-tolerant cultivars of Festuca rubra were compared on metalliferous fluorspar tailings in laboratory and field conditions. The effects of wood pulp mulch and alginate stabilizer on germination and establishment were also assessed in the field experiments. Both cultivars germinated satisfactorily, although the laboratory experiment suggested restricted root development in the non-tolerant cultivar. Both experiments, however, showed that the overall shoot growth and cover of the non-tolerant cultivar were not affected. In fact, in the field experiment, contrary to expectation, the non-tolerant cultivar performed better than the metal tolerant cultivar and showed no pathological symptoms of metal toxicity after 12 months. The advantages of using wood pulp as a mulch were clearly demonstrated. However, the application of an alginate stabilizer had no benefit under these particular experimental conditions. The results suggest that the use of carefully selected non-tolerant cultivars in the revegetation of such calcareous metalliferous wastes is possible, even where the zinc content is as high as 1%.

  7. The effects of zinc on cell viability and on mitochondrial structure in contrasting cultivars of Festuca rubra L. - a rapid test for zinc tolerance.

    PubMed

    Davies, K L; Davies, M S; Francis, D

    1995-01-01

    A 20-min exposure to 5.0 microg Zn cm(-3) reduced the percentage of viable root meristematic cells in three cultivars of Festuca rubra L.: Merlin (Zn-tolerant), Hawk (salt-tolerant but with a degree of Zn tolerance) and S59 (Zn-sensitive). The Zn-induced cell mortality in S59 was approximately twice that of the tolerant cultivars. The mean area of mitochondrial profiles in root meristematic cells of Zn-untreated roots was similar in S59 and Merlin but that of Hawk was smaller. A 4-day exposure to 0.2 microg Zn cm(-3) resulted in mitochondrial swelling in the Zn-sensitive cultivar; there was a 25% increase in the mean area of mitochondrial profiles in this cultivar, but no significant increase occurred in Hawk or Merlin. Zn treatment caused a collapse of the cristae and a localized condensation of the mitochondrial matrix in S59, but not in Hawk or Merlin. The marked increase in cell mortality after only a 20-min Zn exposure and the relative simplicity of the technique, indicates that this procedure could be used as a rapid and independent measure of Zn tolerance.

  8. Centrifugal partition extraction, a new method for direct metabolites recovery from culture broth: case study of torularhodin recovery from Rhodotorula rubra.

    PubMed

    Ungureanu, Camelia; Marchal, Luc; Chirvase, Ana Aurelia; Foucault, Alain

    2013-03-01

    Centrifugal partition extraction (CPE), close to centrifugal partition chromatography, put in contact in a continuous way two immiscible liquid phases. This work presents early experiments on CPE use for solid-liquid-liquid extraction. It was applied to the direct treatment of culture broth for metabolites recovery. Torularhodin is one of the carotenoid pigments produced by the yeast Rhodotorula sp., with a terminal carboxylic group considered nowadays as a powerful antioxidant to be included in food and drugs formulations. Torularhodin was extracted from Rhodotorula rubra ICCF 209 cells by CPE. The recovery of torularhodin reaches 74 μg/g of biomass i.e. 294 μg/L of culture medium. The efficiency of the extraction step increased with the operating flow rate. The extraction yield could reach 91% with a contact time lower than 2 min. A 300 mL apparatus allowed a feed at 90 mL/min. The technique is proposed for extraction or sample preparation before analysis.

  9. Evaluation of the In Vivo Therapeutic Effects of Radix Paeoniae Rubra Ethanol Extract with the Hypoglycemic Activities Measured from Multiple Cell-Based Assays

    PubMed Central

    Chang, Chia-Chuan; Yuan, Wei; Lin, Yun-Lian; Liu, Ren-Shyan; Juan, Yi-Chen; Sun, Wan-Hua; Tsay, Huey Jen; Lee, Yu-Ching

    2016-01-01

    Background. Radix Paeoniae Rubra (Chi Shao) contains several phytochemicals with hypoglycemic actions. Current research aims to explore potential insulinotropic effects and long-term therapeutic efficacy of such herb against type 2 diabetes. Methods. Composition analysis for the ethanol extract (PRExt) was executed by high performance liquid chromatography. Polyphenol-enriched fraction was characterized by high pressure size exclusion chromatography. Multiple cell platforms were employed to evaluate hypoglycemic bioactivities. In animal experiments, blood glucose, the homeostasis model assessment (HOMA)-index assessment, glucose tolerance test, and in vivo glucose uptake were all measured. Additional effects of PRExt on obesity and hepatic steatosis were evaluated by serum and histological analysis. Results. PRExt provides multiple hypoglycemic effects including the enhancement of glucose-mediated insulin secretion. Pentagalloylglucose and polyphenol-enriched fraction are two insulinotropic constituents. Moreover, PRExt intraperitoneal injection causes acute hypoglycemic effects on fasted db/db mice. Oral administration of PRExt (200 mg/kg b.w.) gradually reduces blood glucose in db/db mice to the level similar to that in C57J/B6 mice after 30 days. The improvement of glucose intolerance, HOMA-index, and in vivo glucose uptake is evident in addition to the weight loss effect and attenuation of hepatic steatosis. Conclusion. PRExt is an effective antidiabetic herbal extract with multiple hypoglycemic bioactivities. PMID:28018473

  10. Contrasting patterns of population connectivity between regions in a commercially important mollusc Haliotis rubra: integrating population genetics, genomics and marine LiDAR data.

    PubMed

    Miller, A D; van Rooyen, A; Rašić, G; Ierodiaconou, D A; Gorfine, H K; Day, R; Wong, C; Hoffmann, A A; Weeks, A R

    2016-08-01

    Estimating contemporary genetic structure and population connectivity in marine species is challenging, often compromised by genetic markers that lack adequate sensitivity, and unstructured sampling regimes. We show how these limitations can be overcome via the integration of modern genotyping methods and sampling designs guided by LiDAR and SONAR data sets. Here we explore patterns of gene flow and local genetic structure in a commercially harvested abalone species (Haliotis rubra) from southeastern Australia, where the viability of fishing stocks is believed to be dictated by recruitment from local sources. Using a panel of microsatellite and genomewide SNP markers, we compare allele frequencies across a replicated hierarchical sampling area guided by bathymetric LiDAR imagery. Results indicate high levels of gene flow and no significant genetic structure within or between benthic reef habitats across 1400 km of coastline. These findings differ to those reported for other regions of the fishery indicating that larval supply is likely to be spatially variable, with implications for management and long-term recovery from stock depletion. The study highlights the utility of suitably designed genetic markers and spatially informed sampling strategies for gaining insights into recruitment patterns in benthic marine species, assisting in conservation planning and sustainable management of fisheries.

  11. Occurrence of Encephalitozoon intestinalis in the Red ruffed lemur (Varecia rubra) and the Ring-tailed lemur (Lemur catta) housed in the Poznan Zoological Garden, Poland.

    PubMed

    Słodkowicz-Kowalska, Anna; Majewska, Anna C; Trzesowska, Ewa; Skrzypczak, Łukasz

    2012-01-01

    Encephalitozoon intestinalis is one of the most common microsporidial species found in humans worldwide but it has rarely been identified in animals. The presence of this pathogen has been detected in a few species of domestic, captive and wild mammals as well as in three species of birds. The aim of the present study was to examine fecal samples obtained from mammals housed in the Poznan Zoological Garden, Poland, for the presence of potentially human-infectious microsporidia. A total of 339 fresh fecal samples collected from 75 species of mammals belonging to 27 families and 8 orders were examined for the presence of microsporidian spores. Microsporidian spores were identified in 3 out of 339 (0.9%) examined fecal samples. All samples identified as positive by chromotrope 2R and calcofluor white M2R were also positive by the FISH assay. Using multiplex FISH in all 3 fecal samples, only spores of E. intestinalis were identified in 2 out of 14 Ring-tailed lemurs (Lemur catta) and in one out of 17 Red ruffed lemurs (Varecia variegata rubra). To our knowledge this is the first diagnosis of E. intestinalis in Ring-tailed and Red ruffed lemurs. It should be mentioned that both lemur species are listed by the IUCN Red List of Threatened Species. Although the lemurs were asymptomatically infected, the possibility of widespread infection or death of these animals remains in the event of an elevated stress or a decrease in their immunological functions.

  12. Chemical and Cellular Assays Combined with In Vitro Digestion to Determine the Antioxidant Activity of Flavonoids from Chinese Bayberry (Myrica rubra Sieb. et Zucc.) Leaves

    PubMed Central

    Zhang, Yu; Chen, Shiguo; Wei, Chaoyang; Gong, Hui; Li, Lanqi; Ye, Xingqian

    2016-01-01

    Oxidative stress is highly associated with the development of cardiovascular diseases and cancer and has drawn great attention. Natural products suggest a potential role in prevention of these disorders. The aim of this study was to investigate the antioxidant and anti-cancer properties of Chinese bayberry leaves (Myrica rubra Sieb. et Zucc.) flavonoids (BLF) comprehensively through the combination of in vitro digestion, chemical and cellular antioxidant assays. Based on the LC/MS data, the major flavonoids of BLF were myricitrin and quercetin 3-rhamnoside. BLF owned strong chemical and cellular antioxidant activity (CAA) with its CAA value at 4253.884 ± 435.366 μmol of QE/100 g DW. After the in vitro digestion, the total flavonoids content, myricitrin and quercetin 3-rhamnoside decreased significantly (P < 0.05). Lower levels of the total flavonoid content and cellular uptake of myricitrin and quercetin 3-rhamnoside might contribute to the lower CAA value of digested BLF (DBLF). However, DBLF still owns considerable chemical antioxidant activities and CAA compared with many plants. Furthermore, both BLF and DBLF exhibited dose-dependent relationship against HepG2 proliferation. Taken together, BLF has a great potential to be developed as a natural antioxidant for promoting public health. PMID:27911932

  13. Diversity of Riparian Plants among and within Species Shapes River Communities

    PubMed Central

    Jackrel, Sara L.; Wootton, J. Timothy

    2015-01-01

    Organismal diversity among and within species may affect ecosystem function with effects transmitting across ecosystem boundaries. Whether recipient communities adjust their composition, in turn, to maximize their function in response to changes in donor composition at these two scales of diversity is unknown. We use small stream communities that rely on riparian subsidies as a model system. We used leaf pack experiments to ask how variation in plants growing beside streams in the Olympic Peninsula of Washington State, USA affects stream communities via leaf subsidies. Leaves from red alder (Alnus rubra), vine maple (Acer cinereus), bigleaf maple (Acer macrophyllum) and western hemlock (Tsuga heterophylla) were assembled in leaf packs to contrast low versus high diversity, and deployed in streams to compare local versus non-local leaf sources at the among and within species scales. Leaves from individuals within species decomposed at varying rates; most notably thin leaves decomposed rapidly. Among deciduous species, vine maple decomposed most rapidly, harbored the least algal abundance, and supported the greatest diversity of aquatic invertebrates, while bigleaf maple was at the opposite extreme for these three metrics. Recipient communities decomposed leaves from local species rapidly: leaves from early successional plants decomposed rapidly in stream reaches surrounded by early successional forest and leaves from later successional plants decomposed rapidly adjacent to later successional forest. The species diversity of leaves inconsistently affected decomposition, algal abundance and invertebrate metrics. Intraspecific diversity of leaf packs also did not affect decomposition or invertebrate diversity. However, locally sourced alder leaves decomposed more rapidly and harbored greater levels of algae than leaves sourced from conspecifics growing in other areas on the Olympic Peninsula, but did not harbor greater aquatic invertebrate diversity. In contrast to

  14. Diversity of Riparian Plants among and within Species Shapes River Communities.

    PubMed

    Jackrel, Sara L; Wootton, J Timothy

    2015-01-01

    Organismal diversity among and within species may affect ecosystem function with effects transmitting across ecosystem boundaries. Whether recipient communities adjust their composition, in turn, to maximize their function in response to changes in donor composition at these two scales of diversity is unknown. We use small stream communities that rely on riparian subsidies as a model system. We used leaf pack experiments to ask how variation in plants growing beside streams in the Olympic Peninsula of Washington State, USA affects stream communities via leaf subsidies. Leaves from red alder (Alnus rubra), vine maple (Acer cinereus), bigleaf maple (Acer macrophyllum) and western hemlock (Tsuga heterophylla) were assembled in leaf packs to contrast low versus high diversity, and deployed in streams to compare local versus non-local leaf sources at the among and within species scales. Leaves from individuals within species decomposed at varying rates; most notably thin leaves decomposed rapidly. Among deciduous species, vine maple decomposed most rapidly, harbored the least algal abundance, and supported the greatest diversity of aquatic invertebrates, while bigleaf maple was at the opposite extreme for these three metrics. Recipient communities decomposed leaves from local species rapidly: leaves from early successional plants decomposed rapidly in stream reaches surrounded by early successional forest and leaves from later successional plants decomposed rapidly adjacent to later successional forest. The species diversity of leaves inconsistently affected decomposition, algal abundance and invertebrate metrics. Intraspecific diversity of leaf packs also did not affect decomposition or invertebrate diversity. However, locally sourced alder leaves decomposed more rapidly and harbored greater levels of algae than leaves sourced from conspecifics growing in other areas on the Olympic Peninsula, but did not harbor greater aquatic invertebrate diversity. In contrast to

  15. A new insight on the gas phase retro-Diels-Alder reaction of bicyclic compounds: density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Mora, Jose R.; Lezama, Jesús; Córdova-Sintjago, Tania C.; Chuchani, Gabriel

    2015-11-01

    The mechanisms of the gas-phase thermal decomposition of bicyclo[2.2.1]heptadiene and 3,7,7-trimethylbicyclo[2.2.1]hept-2-ene were examined by density functional theory calculations with the hybrid functionals: B3LYP, CAM-B3LYP, MPW1PW91, and PBEPBE. Reasonable agreements were found between theoretical and experimental values with the B3LYP hybrid functional. Three molecular concerted pathways for bicyclo[2.2.1]heptadiene decomposition are proposed. The retro-Diels-Alder (retro-DA) pathway yields cyclopentadiene and acetylene through a nearly synchronous transition state structure (Sy = 0.97). The other two reaction channels are stepwise with a common step with the formation of the intermediate bicyclo[4.1.0] heptadiene. This reaction is dominated by C-C bond breaking leading to the methylene migration by an early transition state in the reaction coordinate (Sy = 0.91). The rearrangements of the latter intermediate producing toluene were also studied. The retro-DA elimination of 3,7,7-trimethylbicyclo[2.2.1]hept-2-ene gives 1,5,5-trimethyl-cyclopenta-1,3-diene in a less synchronous process (Sy = 0.77). This fact may be due to the electronic effects of the methyl substituent. The latter product is unstable and undergoes methyl migrations to give a more stable isomer 1,2,3-trimethylcyclopenta-1,3-diene. The stepwise mechanism for the retro-DA reaction through a biradical intermediate appears to be unfavourable because the barrier is bigger than that for the concerted reaction.

  16. A new biopesticide from a local Bacillus thuringiensis var. tenebrionis (Xd3) against alder leaf beetle (Coleoptera: Chrysomelidae).

    PubMed

    Eski, Ardahan; Demir, İsmail; Sezen, Kazım; Demirbağ, Zihni

    2017-05-01

    Use of chemical pesticides in agriculture harms humans, non-target organisms and environments, and causes increase resistance against chemicals. In order to develop an effective bio-pesticide against coleopterans, particularly against Agelastica alni (Coleoptera: Chrysomelidae) which is one of the serious pests of alder leaf and hazelnut, we tested the insecticidal effect of 21 Bacillus isolates against the larvae and adults of the pest. Bacillus thuringiensis var. tenebrionis-Xd3 (Btt-Xd3) showed the highest insecticidal effect based on screening tests. For toxin protein production and high sporulation of Xd3, the most suitable medium, pH and temperature conditions were determined as nutrient broth medium enriched with salts, pH 7 and 30 °C, respectively. Sporulated Btt-Xd3 in nutrient broth medium enriched with salts transferred to fermentation medium containing soybean flour, glucose and salts. After fermentation, the mixture was dried in a spray dryer, and spore count of the powder product was determined as 1.6 × 10(10) c.f.u. g(-1). Moisture content, suspensibility and wettability of the formulation were determined as 8.3, 86% and 21 s, respectively. Lethal concentrations (LC50) of formulated Btt-Xd3 were determined as 0.15 × 10(5) c.f.u. ml(-1) for larvae at laboratory conditions. LC50 values were also determined as 0.45 × 10(6) c.f.u. ml(-1) at the field condition on larval stage. Our results showed that a new bio-pesticide developed from B. thuringiensis tenebrionis (Xd3) (Btt-Xd3) may be valuable as a biological control agent for coleopteran pests.

  17. Copper(I)-Catalyzed Asymmetric Desymmetrization through Inverse-Electron-Demand aza-Diels-Alder Reaction: Efficient Access to Tetrahydropyridazines Bearing a Unique α-Chiral Silane Moiety.

    PubMed

    Wei, Liang; Zhou, Yu; Song, Zhi-Min; Tao, Hai-Yan; Lin, Zhenyang; Wang, Chun-Jiang

    2017-04-11

    An unprecedented copper(I)-catalyzed asymmetric desymmetrization of 5-silylcyclopentadienes with in situ formed azoalkene was realized through an inverse-electron-demand aza-Diels-Alder reaction (IEDDA) pathway, in which 5-silylcyclopentadienes served as efficient enophiles. This new protocol provides a facile access to the biologically important heterocyclic tetrahydropyridazines containing a unique α-chiral silane motif and three adjoining stereogenic centers in generally good yield (up to 92 %) with exclusive regioselectivity, high diastereoselectivity (>20:1 diastereomeric ratio), and excellent enantioselectivity (up to 98 % enantiomeric excess). DFT calculations and control experiments further confirmed the proposed reaction mechanism.

  18. Bisadducts from the Diels-Alder Trapping of Bis(o-Xylenols) Photochemically Generated from 2,5-Dibenzoyl-p-xylene

    NASA Technical Reports Server (NTRS)

    Meador, Michael A.; Kinder, James D.; Kirby, James P.

    2003-01-01

    Photolysis of 2,5-dibenzoyl-p-xylene produces two discrete o-xylenols which undergo Diels-Alder cycloadditions with standard dienophiles, such as methyl acrylate, to produce 1,5-dihydroxy-1,5-diphenyl-l,2,3,4,5,6,7,8-octahydroanthracenes, 2a, in good yield (greater than 80%). The anti bisadduct crystallizes into hydrogen bonded stacks. Conversion of both syn- and anti-bisadducts to the corresponding anthracenes was achieved through the use of standard dehydration and aromatization chemistry.

  19. Ultra-high precision 40Ar/39Ar ages for Fish Canyon Tuff and Alder Creek Rhyolite sanidine: New dating standards required?

    NASA Astrophysics Data System (ADS)

    Phillips, D.; Matchan, E. L.

    2013-11-01

    The 40Ar/39Ar dating technique is a high precision (<0.1%) method with wide application to geological samples. However, the method is predicated on the availability of natural mineral standards of known age. Widely used 40Ar/39Ar standards include sanidine from the (ca. 28 Ma) Fish Canyon Tuff (FCT) and the (ca. 1.2 Ma) Alder Creek Rhyolite (ACR). Despite common usage, the ages of FCT and ACR sanidine have proven contentious, with reported values varying by >2%; well outside the ±0.1% aspiration of EARTHTIME (http://www.earth-time.org).

  20. Enantioselective synthesis of allenylenol silyl ethers via chiral lithium amide mediated reduction of ynenoyl silanes and their Diels-Alder reactions.

    PubMed

    Sasaki, Michiko; Kondo, Yasuhiro; Moto-ishi, Ta-ichi; Kawahata, Masatoshi; Yamaguchi, Kentaro; Takeda, Kei

    2015-03-06

    An enantioselective Meerwein-Ponndorf-Verley-type reduction of ynenoylsilanes by a chiral lithium amide followed by a Brook rearrangement and anti-mode protonation across conjugated 1,3-enynes provides allene derivatives bearing a 2-siloxyvinyl moiety in high enantioselectivity. The E/Z geometry of enol silyl ethers is controlled by the geometry of the starting enyne moiety. Thus, (E)- and (Z)-enol silyl ethers are obtained from (Z)- and (E)-ynenoylsilans, respectively. The 2-siloxyvinylallene products can participate in Diels-Alder reactions with reactive dienophiles such as PTAD, which can be achieved in a one-pot operation from ynenoylsilanes.

  1. The acyl nitroso Diels-Alder (ANDA) reaction of sorbate derivatives: an X-ray and 15N NMR study with an application to amino-acid synthesis.

    PubMed

    Bollans, Lee; Bacsa, John; Iggo, Jonathan A; Morris, Gareth A; Stachulski, Andrew V

    2009-11-07

    We present a study of the acyl nitroso Diels-Alder (ANDA) reaction of sorbate esters and sorbic alcohol derivatives, using alkoxycarbonyl nitroso dienophiles. An optimisation of the reaction conditions for ethyl sorbate is first presented, and the product is used in an efficient synthesis of 5-methylornithine. Structure-reactivity trends in sorbic alcohol (E,E-2,4-hexadien-1-ol) and its acylated analogues are then discussed. We present single-crystal X-ray structural proof for key adducts in both series and present in detail a novel HMBC/HSQC ((1)H-(15)N) criterion for ready distinction of regioisomers arising from such ANDA reactions.

  2. Lanthanide (III)-catalyzed enantioselective Diels-Alder reactions. Stereoselective synthesis of both enantiomers by using a single chiral source and a choice of achiral ligands

    SciTech Connect

    Kobayashi, Shu; Ishitani, Haruro )

    1994-05-04

    In this paper, we disclose a conceptually different approach to obtaining both enantiomers; choice of enatiofacial selectivity by use of the enatiomerically same chiral source and different achiral ligands. Both enantiomers of the Diels-Alder adducts between e-acyl-1,3-oxazolidin-2-ones and cyclopentadiene were prepared by chiral lanthanides(III)-catalyzed reactions using the same chiral source, (R)-(+)-binaphthol. It is noted that the chiral catalysts with reverse enantiofacial selectivities could be prepared by using the same chiral source and a choice of achiral ligands. 14 refs., 3 tabs.

  3. From enantiopure hydroxyaldehydes to complex heterocyclic scaffolds: development of domino Petasis/Diels-Alder and cross-metathesis/Michael addition reactions.

    PubMed

    Cannillo, Alexandre; Norsikian, Stéphanie; Tran Huu Dau, Marie-Elise; Retailleau, Pascal; Iorga, Bogdan I; Beau, Jean-Marie

    2014-09-15

    One-step assembly of hexahydroisoindole scaffolds by a sequence that combines the Petasis (borono-Mannich) and Diels-Alder reactions is described. The unique selectivity observed experimentally was confirmed by quantum calculations. The current method is applicable to a broad range of substrates, including free sugars, and holds significant potential to efficiently and stereoselectively build new heterocyclic structures. This easy and fast entry to functionalized polycyclic compounds can be pursued by further transformations, for example, additional ring closure by a cross-metathesis/Michael addition domino sequence.

  4. Tandem one-pot synthesis of flavans by recyclable silica-HClO4 catalyzed Knoevenagel condensation and [4 + 2]-Diels-Alder cycloaddition.

    PubMed

    Bharate, Sandip B; Mudududdla, Ramesh; Bharate, Jaideep B; Battini, Narsaiah; Battula, Satyanarayana; Yadav, Rammohan R; Singh, Baldev; Vishwakarma, Ram A

    2012-07-14

    An efficient one-pot multi-component synthesis of flavans using perchloric acid supported on silica as a recyclable heterogeneous catalyst has been described. This is the first report of direct one-step construction of a flavan skeleton from a phenolic precursor. The method involves a Knoevenagel-type condensation leading to in situ formation of transient O-quinone methide which further undergoes [4 + 2]-Diels-Alder cycloaddition with styrene to yield a flavan skeleton. The method provides easy access to a wide range of bio-active natural products viz. flavonoids, anthocyanins and catechins.

  5. Liquid-crystalline and electron-deficient coronene oligocarboxylic esters and imides by twofold benzogenic Diels-Alder reactions on perylenes.

    PubMed

    Alibert-Fouet, Sonia; Seguy, Isabelle; Bobo, Jean-François; Destruel, Pierre; Bock, Harald

    2007-01-01

    Alkyl esters, imides and imido-esters of coronene-tri-, -tetra- and -octacarboxylic acids are accessible by a twofold oxidative benzogenic Diels-Alder reaction. Alkyl acrylates add to perylene, and maleic alkyl imides react twice with perylene as well as with perylene-tetracarboxylic tetraesters. Coronenes substituted with a greatly variable number of electron-withdrawing substituents are thus accessible, and di- and tetraimide derivatives are shown to be very pronounced electron-acceptor materials. The tri- and tetraalkyl esters and imidoesters self-assemble into columnar liquid-crystalline phases.

  6. Antioxidant and inhibitory effect of red ginger (Zingiber officinale var. Rubra) and white ginger (Zingiber officinale Roscoe) on Fe(2+) induced lipid peroxidation in rat brain in vitro.

    PubMed

    Oboh, Ganiyu; Akinyemi, Ayodele J; Ademiluyi, Adedayo O

    2012-01-01

    Neurodegerative diseases have been linked to oxidative stress arising from peroxidation of membrane biomolecules and high levels of Fe have been reported to play an important role in neurodegenerative diseases and other brain disorder. Malondialdehyde (MDA) is the end-product of lipid peroxidation and the production of this aldehyde is used as a biomarker to measure the level of oxidative stress in an organism. The present study compares the protective properties of two varieties of ginger [red ginger (Zingiber officinale var. Rubra) and white ginger (Zingiber officinale Roscoe)] on Fe(2+) induced lipid peroxidation in rat brain in vitro. Incubation of the brain tissue homogenate in the presence of Fe caused a significant increase in the malondialdehyde (MDA) contents of the brain. However, the aqueous extract from both varieties of ginger caused a significant decrease in the MDA contents of the brain in a dose-dependent manner. However, the aqueous extract of red ginger had a significantly higher inhibitory effect on both Fe(2+)-induced lipid peroxidation in the rat brain homogenates than that of white ginger. This higher inhibitory effect of red ginger could be attributed to its significantly higher phytochemical content, Fe(2+) chelating ability, OH scavenging ability and reducing power. However, part of the mechanisms through which the extractable phytochemicals in ginger (red and white) protect the brain may be through their antioxidant activity, Fe(2+) chelating and OH scavenging ability. Therefore, oxidative stress in the brain could be potentially managed/prevented by dietary intake of ginger varieties (red ginger and white ginger rhizomes).

  7. Influence of overstory density on ecophysiology of red oak (Quercus rubra) and sugar maple (Acer saccharum) seedlings in central Ontario shelterwoods.

    PubMed

    Parker, William C; Dey, Daniel C

    2008-05-01

    A field experiment was established in a second-growth hardwood forest dominated by red oak (Quercus rubra L.) to examine the effects of shelterwood overstory density on leaf gas exchange and seedling water status of planted red oak, naturally regenerated red oak and sugar maple (Acer saccharum Marsh.) seedlings during the first growing season following harvest. Canopy cover of uncut control stands and moderate and light shelterwoods averaged 97, 80 and 49%, respectively. Understory light and vapor pressure deficit (VPD) strongly influenced gas exchange responses to overstory reduction. Increased irradiance beneath the shelterwoods significantly increased net photosynthesis (P(n)) and leaf conductance to water vapor (G(wv)) of red oak and maple seedlings; however, P(n) and G(wv) of planted and naturally regenerated red oak seedlings were two to three times higher than those of sugar maple seedlings in both partial harvest treatments, due in large part to decreased stomatal limitation of gas exchange in red oak as a result of increased VPD in the shelterwoods. In both species, seedling water status was higher in the partial harvest treatments, as reflected by the higher predawn leaf water potential and seedling water-use efficiency in seedlings in shelterwoods than in uncut stands. Within a treatment, planted and natural red oak seedlings exhibited similar leaf gas exchange rates and water status, indicating little adverse physiological effect of transplanting. We conclude that the use of shelterwoods favors photosynthetic potential of red oak over sugar maple, and should improve red oak regeneration in Ontario.

  8. Aqueous seed extract of Cola nitida rubra reduces serum reproductive hormone concentrations and sperm count in adult male albino Wistar rats

    PubMed Central

    Umoh, I. O.; Emmanuel, O. A.; Nna, V. U.

    2014-01-01

    Background: Following the high rate of consumption of Cola nitida (cola nut) among the male population in Nigeria, this study seeks to determine the effects of consumption of Cola nitida on serum reproductive hormones and sperm count, which are major determinants of male fertility. Materials and Methods: Thirty-two male albino wistar rats weighing 180-220 g were used for this study and were divided into 4 groups of eight animals each. Group 1 served as control, group 2 received 2 mg/kg Cola nitida extract (Test 1), group 3 received 6 mg/kg Cola nitida extract (Test 2) and group 4 received 10 mg/kg Cola nitida extract (Test 3). After 6 weeks of treatment, reproductive hormonal assay was carried out using the rat serum. Epididymal spermatozoa were collected and sperm count determined. Results: Serum concentrations of luteinizing hormone (LH) and testosterone were significantly (P < 0.05) reduced in test 2 and 3, compared with control. Sperm count was significantly lower in test group 1 (P < 0.05), 2 (P < 0.001) and 3 (P < 0.001) compared with control, with test 3 significantly (P < 0.05) lower compared with test 1. There was no significant difference in testicular and epididymis weight in the different experimental groups studied. Conclusion: Aqueous seed extract of Cola nitida rubra resulted in reduced serum reproductive hormone concentrations and sperm count in male wistar rats, and may therefore be detrimental to reproductive health, hence the need for regulation of its consumption. PMID:25538361

  9. Anti-proliferative and Apoptotic Effects of Basella rubra (L.) Against 1, 2-Dimethyl Hydrazine-induced Colon Carcinogenesis in Rats.

    PubMed

    Kilari, Bhanu Priya; Kotakadi, Venkata Subbaiah; Penchalaneni, Josthna

    2016-01-01

    Colorectal cancer is a very prevalent diagnosed cancer. The current study was performed in order to examine the role of BRAE (Basella rubra aqueous extract) in regulating aberrant crypt foci (ACF) formation, cell proliferation and inhibition of apoptosis in a colon carcinogenesis model in male Wistar rats. Rats were randomly allocated into six groups. Group I served as control, and group II acted as a drug control administered BRAE (250mg/kg b.w.) orally for 30 weeks. Rats in group III-VI were given subcutaneous injections of DMH (25mg/kg b.w. weekly) for 15 weeks to initiate colon carcinogenesis. Those in group IV and VI were administered BRAE along with DMH injections. Rats in group V were administered with BRAE after cessation of DMH injection. After 30 weeks of experimental period colons were obtained from experimental groups and analyzed for ACF incidence, argyrophilic nucleolar organizing region- associated proteins (AgNOR) count, histopathological and immunohistochemical changes. Only in DMH exposed groups were ACF and AgNOR numbers increased. Administration of BRAE appreciably decreased the numbers of ACF and AgNOR in BRAE treated groups. Histopathological findings revealed a high level of dysplastic changes with decreased number of goblet cells found only in only DMH injected rats. Administration of BRAE in treated group rats reversed these changes. Expression markers for cell proliferation (PCNA and Ki67) were elevated in DMH treated rats, but reduced with BRAE treatement. This expression was reversed with apoptosis markers (p53 and Caspase-3). Thus the results results of the present study were found to be significant and confirmed the potential efficacy of BRAE against colon carcinogenesis.

  10. A comparative study of physiological and morphological seedling traits associated with shade tolerance in introduced red oak (Quercus rubra) and native hardwood tree species in southwestern Germany.

    PubMed

    Kuehne, Christian; Nosko, Peter; Horwath, Tobias; Bauhus, Jürgen

    2014-02-01

    Northern red oak (Quercus rubra L.), a moderately shade-tolerant tree species, is failing to regenerate throughout its native North American range, while successful recruitment in Central Europe has been observed since its introduction. To examine whether comparative photosynthetic performance could explain the regeneration success of this non-native species in Central Europe, we compared the physiological and morphological seedling traits of red oak with three co-occurring tree species under three canopy types in southwestern Germany. Native species included a moderately shade-tolerant native oak (Quercus robur L.) and two shade-tolerant species (Acer pseudoplatanus L. and Carpinus betulus L.). The photosynthetic traits of non-native red oak seedlings were similar to those reported for this species in the native range, where shade-tolerant competitors readily outperform red oak under low light conditions. However, compared with native shade-tolerant species in Europe, red oak seedlings photosynthesized efficiently, especially under closed canopies and in small canopy gaps, exhibiting high photosynthetic capacity, low leaf dark respiration and leaf-level light compensation points that were similar to the more shade-tolerant species. The superior net carbon gain of red oak seedlings at low and moderate light levels was likely facilitated by high leaf areas and reflected by seedling dry masses that were greater than the observed native European species. A competitive advantage for red oak was not evident because relative height growth was inferior to seedlings of co-occurring species. In North America, the inability of seedlings to compete with shade-tolerant tree species in deeply shaded understories is central to the problem of poor oak recruitment. Our study suggests that the ability of non-native red oak to perform equally well to native shade-tolerant species under a variety of light conditions could contribute to the consistent success of red oak regeneration

  11. Molecular Design of a Chiral Brønsted Acid with Two Different Acidic Sites: Regio-, Diastereo-, and Enantioselective Hetero-Diels-Alder Reaction of Azopyridinecarboxylate with Amidodienes Catalyzed by Chiral Carboxylic Acid-Monophosphoric Acid.

    PubMed

    Momiyama, Norie; Tabuse, Hideaki; Noda, Hirofumi; Yamanaka, Masahiro; Fujinami, Takeshi; Yamanishi, Katsunori; Izumiseki, Atsuto; Funayama, Kosuke; Egawa, Fuyuki; Okada, Shino; Adachi, Hiroaki; Terada, Masahiro

    2016-09-07

    A chiral Brønsted acid containing two different acidic sites, chiral carboxylic acid-monophosphoric acid 1a, was designed to be a new and effective concept in catalytic asymmetric hetero-Diels-Alder reactions of azopyridinecarboxylate with amidodienes. The multipoint hydrogen-bonding interactions among the carboxylic acid, monophosphoric acid, azopyridinecarboxylate, and amidodiene achieved high catalytic and chiral efficiency, producing substituted 1,2,3,6-tetrahydropyridazines with excellent stereocontrol in a single step. This constitutes the first example of regio-, diastereo-, and enantioselective azo-hetero-Diels-Alder reactions by chiral Brønsted acid catalysis.

  12. Reactivity of Single-Walled Carbon Nanotubes in the Diels-Alder Cycloaddition Reaction: Distortion-Interaction Analysis along the Reaction Pathway.

    PubMed

    Li, Yingzi; Osuna, Sílvia; Garcia-Borràs, Marc; Qi, Xiaotian; Liu, Song; Houk, Kendall N; Lan, Yu

    2016-08-26

    Diels-Alder cycloaddition is one of the most powerful tools for the functionalization of single-walled carbon nanotubes (SWCNTs). Density functional theory at the B3-LYP level of theory has been used to investigate the reactivity of different-diameter SWCNTs (4-9,5) in Diels-Alder reactions with 1,3-butadiene; the reactivity was found to decrease with increasing SWCNT diameter. Distortion/interaction analysis along the whole reaction pathway was found to be a better way to explore the reactivity of this type of reaction. The difference in interaction energy along the reaction pathway is larger than that of the corresponding distortion energy. However, the distortion energy plots for these reactions show the same trend. Therefore, the formation of the transition state can be determined from the interaction energy. A lower interaction energy leads to an earlier transition state, which indicates a lower activation energy. The computational results also indicate that the original distortion of the SWCNTs leads to an increase in the reactivity of the SWCNTs.

  13. Inverse Electron Demand Diels–Alder Reactions of 1,2,3-Triazines: Pronounced Substituent Effects on Reactivity and Cycloaddition Scope

    PubMed Central

    Anderson, Erin D.; Boger, Dale L.

    2011-01-01

    A systematic study of the inverse electron demand Diels–Alder reactions of 1,2,3-triazines is disclosed, including an examination of the impact of a C5 substituent. Such substituents were found to exhibit a remarkable impact on the cycloaddition reactivity of the 1,2,3-triazine without altering, and perhaps even enhancing, the intrinsic cycloaddition regioselectivity. The study revealed that not only may the reactivity be predictably modulated by a C5 substituent (R = CO2Me > Ph > H), but that the impact is of a magnitude to convert 1,2,3-triazine (1) and its modest cycloaddition scope into a heterocyclic azadiene system with a reaction scope that portends extensive synthetic utility, expanding the range of participating dienophiles. Significantly, the studies define a now powerful additional heterocyclic azadiene, complementary to the isomeric 1,2,4-triazines and 1,3,5-triazines, capable of dependable participation in inverse electron demand Diels–Alder reactions, extending the number of complementary heterocyclic ring systems accessible with implementation of the methodology. PMID:21736324

  14. A Diels-Alder modulated approach to control and sustain the release of dexamethasone and induce osteogenic differentiation of human mesenchymal stem cells.

    PubMed

    Koehler, Kenneth C; Alge, Daniel L; Anseth, Kristi S; Bowman, Christopher N

    2013-05-01

    We report a new approach to controlled drug release based upon exploiting the dynamic equilibrium that exists between Diels-Alder reactants and products, demonstrating the release of a furan containing dexamethasone peptide (dex-KGPQG-furan) from a maleimide containing hydrogel. Using a reaction-diffusion model, the release kinetics were tuned to achieve sustained concentrations conducive to osteogenic differentiation of human mesenchymal stem cells (hMSCs). Efficacy was first demonstrated in a 2D culture model, in which dexamethasone release induced significant increases in alkaline phosphatase (ALP) activity and mineral deposition in hMSCs compared to a dexamethasone-free treatment. The results were similar to that observed with a soluble dexamethasone treatment. More dramatic differences were observed in 3D culture, where co-encapsulation of a dexamethasone releasing hydrogel depot within an hMSC-laden extracellular matrix mimetic poly(ethylene glycol) hydrogel resulted in a local and robust osteogenic differentiation. ALP activity reached levels that were up to six times higher than the dexamethasone free treatment. Interestingly, at 5 and 10 day time points, the ALP activity exceeded the dexamethasone positive control, suggesting a potential benefit of sustained release in 3D culture. After 21 days, substantial mineralization comparable to the positive control was also observed in the hydrogels. Collectively, these results demonstrate Diels-Alder modulated release as an effective and versatile new platform for controlled drug delivery that may prove especially beneficial for sustaining the release of low molecular weight molecules in hydrogel systems.

  15. Regioselective Inverse Electron Demand Diels-Alder Reactions of N-Acyl 6-Amino-3-(methylthio)-1,2,4,5-tetrazines.

    PubMed

    Boger, Dale L.; Schaum, Robert P.; Garbaccio, Robert M.

    1998-09-04

    The regioselective inverse electron demand Diels-Alder reactions of 6-[(tert-butyloxycarbonyl)amino]-3-(methylthio)-1,2,4,5-tetrazine (2), 6-(acetylamino)-3-(methylthio)-1,2,4,5-tetrazine (3), and 6-(benzyloxycarbonyl)amino-3-(methylthio)-1,2,4,5-tetrazine (4) are disclosed. All three underwent regioselective [4 + 2] cycloaddition with electron-rich dienophiles to form the corresponding functionalized 1,2-diazines in excellent yields. An order of reactivity with electron-rich dienophiles was observed with both 2 and 3 being more reactive than 3,6-bis(methylthio)-1,2,4,5-tetrazine (1, i.e. 3 > 2 > 1), and both 3 and 4 were shown to be more robust than 2 at the higher temperatures necessary for [4 + 2] cycloaddition with less reactive dienophiles. The cycloaddition regioselectivity is consistent with the polarization of the diene and the ability of the methylthio group to stabilize a partial negative charge at C-3, and the N-acylamino group to stabilize a partial positive charge at C-6. While intermolecular reactions of unactivated alkynes either did not proceed or required high temperatures and long reaction times, intramolecular Diels-Alder reactions utilizing tethered unactivated acetylenes led to five- and six-membered bicyclic 1,2-diazines under mild conditions.

  16. QM/MM Modeling Finds Diels-Alder Reactions are Accelerated Less On the Surface of Water than In Water

    PubMed Central

    Thomas, Laura L.; Tirado-Rives, Julian; Jorgensen, William L.

    2010-01-01

    Quantum and molecular mechanics (QM/MM) calculations for the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the vacuum-water interface and in the gas phase. In conjunction with previous studies of these cycloadditions in dilute solution, a more complete picture of aqueous environmental effects emerges with implications for the origin of observed rate accelerations using heterogeneous aqueous suspensions, “on water” conditions. The pure TIP4P water slab maintains bulk density and hydrogen bonding properties in central water layers. The bulk region merges to vacuum over a ca. 5-Å band with progressive diminution of density and hydrogen bonding. The relative free energies of activation and transition structures for the reactions at the interface are found to be intermediate between those calculated in the gas phase and in bulk water, i.e., for the reaction with 1,4-naphthoquinone, the ΔΔG ‡’s relative to the gas phase are −3.6 and −7.3 kcal/mol at the interface and in bulk water, respectively. Thus, the results do not support the notion that a water surface is more effective than bulk water for catalysis of such pericyclic reactions. The trend is in qualitative agreement with expectations based on density considerations and estimates of experimental rate constants for the gas phase, a heterogeneous aqueous suspension, and dilute aqueous solution for the reaction of cyclopentadiene with methyl vinyl ketone. Computed energy pair distributions reveal a uniform loss of 0.5 – 1.0 hydrogen bond for the reactants and transition states in progressing from bulk water to the vacuum-water interface. Orientational effects are apparent at the surface, e.g., the carbonyl group in the methyl vinyl ketone transition structure is preferentially oriented into the surface. Also, the transition structure for the 1,4-naphthoquinone case is buried more in the surface, and the free energy of

  17. An efficient Ugi-3CR/aza Diels-Alder/Pomeranz-Fritsch protocol towards novel aza-analogues of (±)-nuevamine, (±)-lennoxamine and magallanesine: a diversity oriented synthesis approach.

    PubMed

    Vázquez-Vera, Óscar; Sánchez-Badillo, Jorge S; Islas-Jácome, Alejandro; Rentería-Gómez, Manuel A; Pharande, Shrikant G; Cortes-García, Carlos J; Rincón-Guevara, Mónica A; Ibarra, Ilich A; Gámez-Montaño, Rocío; González-Zamora, Eduardo

    2017-03-15

    A rapid and efficient synthesis of a series of (±)-nuevamine, (±)-lennoxamine and magallanesine aza analogues is described. The synthetic strategy involves Ugi-3CR and two further condensation processes, aza-Diels-Alder cycloaddition and the Pomeranz-Fritsch reaction. The variation of the chain-size in aldehyde moieties provided structural diversity in only two operational reaction steps.

  18. Astragalus and Paeoniae Radix Rubra extract (APE) inhibits hepatic stellate cell activation by modulating transforming growth factor-β/smad pathway

    PubMed Central

    HUANG, WEIJUAN; LI, LIN; TIAN, XIAOPENG; YAN, JINJIN; YANG, XINZHENG; WANG, XINLONG; LIAO, GUOZHEN; QIU, GENQUAN

    2015-01-01

    Previous studies have shown that Astragalus and Paeoniae Radix Rubra extract (APE) is capable of protecting against liver fibrosis in rats. The hypothesis of the present study was that APE exerts its anti-fibrotic effect by mediating the transforming growth factor β (TGF-β)/Smad signaling pathway. In order to investigate this hypothesis, a series of assays were designed to detect the effects of APE on cell proliferation, cell invasion and the activation of hepatic stellate cells (HSCs). In addition, the effects of APE on the TGF-β/Smad signaling pathway were explored, with the aim of elucidating the underlying mechanisms. HSCs were initially isolated from normal rat liver. A number of assays were then employed in order to evaluate the effects of APE on the function of these cells. Cell proliferation was investigated using an MTT assay and cell invasion was observed with the use of transwell invasion chambers. Collagen synthesis was measured with a 3H-proline incorporation assay and expression of α-smooth muscle actin was used to determine the extent of HSC activation. Protein expression induced by TGF-β1 in HSCs was investigated by western blot and immunofluorescence analyses. Plasminogen activator inhibitor type1 (PAI-1) and urokinase-type plasminogen activator (uPA) transcriptional activity was measured using reverse transcription polymerase chain reaction. The results demonstrated that APE (5–80 μg/ml) significantly inhibited fetal bovine serum-induced cell proliferation in a dose-dependent manner. Cell invasion and activation of HSCs induced by TGF-β1 were disrupted by treatment with APE in a dose-dependent manner. TGF-β1 was observed to increase the phosphorylation of Smad2/3, while APE administered at higher doses produced inhibitory effects on Smad2/3 phosphorylation. In addition, administration of APE abrogated the TGF-β1-induced reduction in Smad-7 expression in a dose-dependent manner. The results further indicated that APE treatment not only

  19. Supplement Analysis for the Transmission System Vegetation Management Program FEIS (DOE/EIS-0285/SA 105 Elbe Tap to Alder-LaGrande No. 1

    SciTech Connect

    Martin, Mark A.

    2002-08-22

    Vegetation Management along the Elbe Tap to Alder-LaGrande No.1 and 115kV transmission line from structure 1/1 through structure 7/17. Corridor width varies. The project area is located within Whatcom County, Washington. BPA proposes to remove unwanted vegetation along the right-of-way, access roads and around tower structures along the subject transmission line corridor. The right-of-way will be treated using selective and non-selective methods that include hand cutting, mowing and herbicide treatments. Approximately 30 miles of access roads will be cleared using selective and non-selective methods that include hand cutting, mowing and herbicide treatments. Tower sites will be treated using selective and non-selective methods that include hand cutting, mowing and herbicide treatments. Vegetation management is required for unimpeded operation and maintenance of the subject transmission line. See Section 1 of the attached checklist for a complete description of the proposal.

  20. Novel N-allyl/propargyl tetrahydroquinolines: Synthesis via Three-component Cationic Imino Diels-Alder Reaction, Binding Prediction, and Evaluation as Cholinesterase Inhibitors.

    PubMed

    Rodríguez, Yeray A; Gutiérrez, Margarita; Ramírez, David; Alzate-Morales, Jans; Bernal, Cristian C; Güiza, Fausto M; Romero Bohórquez, Arnold R

    2016-10-01

    New N-allyl/propargyl 4-substituted 1,2,3,4-tetrahydroquinolines derivatives were efficiently synthesized using acid-catalyzed three components cationic imino Diels-Alder reaction (70-95%). All compounds were tested in vitro as dual acetylcholinesterase and butyryl-cholinesterase inhibitors and their potential binding modes, and affinity, were predicted by molecular docking and binding free energy calculations (∆G) respectively. The compound 4af (IC50 = 72 μm) presented the most effective inhibition against acetylcholinesterase despite its poor selectivity (SI = 2), while the best inhibitory activity on butyryl-cholinesterase was exhibited by compound 4ae (IC50 = 25.58 μm) with considerable selectivity (SI = 0.15). Molecular docking studies indicated that the most active compounds fit in the reported acetylcholinesterase and butyryl-cholinesterase active sites. Moreover, our computational data indicated a high correlation between the calculated ∆G and the experimental activity values in both targets.

  1. Manifestations of the Alder-Rickert reaction in the structures of bicyclo[2.2.2]octadiene and bicyclo[2.2.2]octene derivatives.

    PubMed

    Goh, Yit Wooi; Danczak, Stephen M; Lim, Tang Kuan; White, Jonathan M

    2007-04-13

    The Alder-Rickert ethylene extrusion reaction manifests in the ground state structures of compounds 9-12 which contain the bicyclo[2.2.2]octadiene moiety and compounds 13, 14, and 17-20 which contain the bicyclo[2.2.2]octene moiety. A significant decrease of the 13C-13C one-bond coupling constants for the C-C bonds, which break in this fragmentation reaction, suggests lengthening, and hence weakening of these bonds. In the unsymmetrical systems these effects are also shown to be associated with strengthening of the CH2-CH2 bond, which is ultimately lost from the molecule as ethylene. Low-temperature crystal structures of compounds 9-12 and 16 provide evidence for similar crystal packing requirements of the CH2-CH2 and CH=CH moieties.

  2. The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents.

    PubMed

    Mojica, Martha; Méndez, Francisco; Alonso, Julio A

    2016-02-12

    The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH₂, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF₃, CHO, CN, NO₂). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO₂ substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

  3. Multifunctional Hydrogel with Good Structure Integrity, Self-Healing, and Tissue-Adhesive Property Formed by Combining Diels-Alder Click Reaction and Acylhydrazone Bond.

    PubMed

    Yu, Feng; Cao, Xiaodong; Du, Jie; Wang, Gang; Chen, Xiaofeng

    2015-11-04

    Hydrogel, as a good cartilage tissue-engineered scaffold, not only has to possess robust mechanical property but also has to have an intrinsic self-healing property to integrate itself or the surrounding host cartilage. In this work a double cross-linked network (DN) was designed and prepared by combining Diels-Alder click reaction and acylhydrazone bond. The DA reaction maintained the hydrogel's structural integrity and mechanical strength in physiological environment, while the dynamic covalent acylhydrazone bond resulted in hydrogel's self-healing property and controlled the on-off switch of network cross-link density. At the same time, the aldehyde groups contained in hydrogel further promote good integration of the hydrogel to surrounding tissue based on aldehyde-amine Schiff-base reaction. This kind of hydrogel has good structural integrity, autonomous self-healing, and tissue-adhesive property and simultaneously will have a good application in tissue engineering and tissue repair field.

  4. Influence of diene substitution on Diels-Alder reactions between vinyl dihydronaphthalenes and (SS)-2-(p-tolylsulfinyl)-1,4-benzoquinone.

    PubMed

    Carreño, M Carmen; García-Cerrada, Susana; Sanz-Cuesta, M Jesús; Urbano, Antonio

    2003-05-30

    The asymmetric Diels-Alder reaction between 2-(E-2-acetoxyvinyl)-8-tert-butyl-3,4-dihydronaphthalene (8) and enantiopure (SS)-2-(p-tolylsulfinyl)-1,4-benzoquinone (1) takes place exclusively on the unsubstituted C(5)-C(6) double bond of (SS)-1 with a very high control of the chemo-, regio-, and diastereoselectivity of the process affording tetracyclic sulfinyl derivative 13a possessing five stereogenic centers. The analogue diene 9, lacking the tert-butyl group, gave a less chemoselective reaction (C(2)-C(3)/C(5)-C(6): 60/40) in favor of reaction through the sulfoxide-substituted double bond C(2)-C(3) of 1. Steric effects of the remote tert-butyl group and electronic factors due to the OAc substituent are controlling the process.

  5. Enantioselective aza-Diels-Alder reaction of aldimines with "Danishefsky-type diene" catalyzed by chiral scandium(III)-N,N'-dioxide complexes.

    PubMed

    Shang, Deju; Xin, Junguo; Liu, Yanling; Zhou, Xin; Liu, Xiaohua; Feng, Xiaoming

    2008-01-18

    A new kind of complex prepared from scandium(III) triflate and l-proline-derived N,N'-dioxides has been developed to catalyze the enantioselective aza-Diels-Alder reaction between 1,3-butadiene (diene 1) and aldimines 2, affording the corresponding 2,5-disubstituted dihydropyridinones in moderate to high yields (up to 92%) with good enantioselectivities (up to 90% ee) at room temperature. A variety of aldimines including aromatic, heteroaromatic, conjugated, and aliphatic imines were found to be suitable substrates. Enantiopure samples (up to 99% ee) were obtained for some products by a single recrystallization. The absolute configuration of the products was determined by X-ray diffraction and CD analysis. On the basis of the investigation of 1H NMR spectra and the positive nonlinear effect, the catalyst structure was carefully discussed.

  6. Two Novel 1,2,4,5-Tetrazines that Participate in Inverse Electron Demand Diels–Alder Reactions with an Unexpected Regioselectivity

    PubMed Central

    Hamasaki, Akiyuki; Ducray, Richard

    2008-01-01

    Two new unsymmetrical 1,2,4,5-tetrazines, 3-methylsulfinyl-6-methylthio-1,2,4,5-tetrazine (4) and 3-(benzyloxycarbonyl)amino-6-methylsulfinyl-1,2,4,5-tetrazine (5), were prepared and scope of their participation in intermolecular inverse electron demand Diels–Alder reactions defined. As anticipated, sulfoxides 4 and 5 (4 > 5) display a reactivity that is substantially greater than that of their corresponding sulfides (2 and 3) being derived from their enhanced electron-deficient character and resulting in a wider range of potential dienophile choices or the use of milder reaction conditions. The cycloaddition reactions were expectedly regioselective typically producing a single cycloadduct ensuring their synthetic utility, but both were found to proceed with a regioselectivity opposite what would be anticipated and complementary to that observed with 2 and 3. PMID:16388634

  7. Solvent effects in acid-catalyzed dehydration of the Diels-Alder cycloadduct between 2,5-dimethylfuran and maleic anhydride

    NASA Astrophysics Data System (ADS)

    Salavati-fard, Taha; Caratzoulas, Stavros; Doren, Douglas J.

    2017-03-01

    Dehydration of the cycloadduct produced from the Diels-Alder reaction between 2,5-dimethylfuran and maleic anhydride to 3,6-dimethylphthalic anhydride exemplifies an important step in producing platform chemicals from biomass. The mechanisms of dehydration and catalytic effects of Lewis and Brønsted acids are investigated with density functional theory. The uncatalyzed reaction has a very high activation barrier (68.7 kcal/mol) in the gas phase and it is not significantly affected by solvation. With a Lewis acid catalyst, modeled as an alkali ion, the activation barriers are reduced, but intermediates are also stabilized. The net effect in vacuum is that the energetic span, or apparent activation energy of the catalytic cycle, is 77.9 kcal/mol, even higher than the barrier in the uncatalyzed case. In solution, however, the energetic span is reduced by as much as 20 kcal/mol, due to differences in the solvation energy of the transition states and intermediates. In the case of a Brønsted acid catalyst, modeled as a proton, the gas phase transition state energies are reduced even more than in the Lewis acid case, and there is no strong stabilization of the intermediates. The energetic span in vacuum is only 13.8 kcal/mol and is reduced even further in solution. Brønsted acid catalysis appears to be the preferred mechanism for dehydration of this cycloadduct. Since the Diels-Alder reaction that produced the molecule has previously been shown to be catalyzed by Brønsted acids, this suggests that a single catalyst could be used to accelerate both steps.

  8. The relationship between productivities of salmonids and forest stands in northern California watersheds

    USGS Publications Warehouse

    Frazey, S.L.; Wilzbach, M.A.

    2007-01-01

    Productivities of resident salmonids and upland and riporian forests in 22 small watersheds of coastal northern California were estimated and compared to determine whether: 1) upland site productivity predicted riparian site productivity; 2) either upland or riparian site productivity predicted salmonid productivity; and 3) other parameters explained more of the variance in salmonid productivity. Upland and riparian site productivities were estimated using Site Index values for redwood (Sequoia sempervirens) and red alder (Alnus rubra), respectively. Salmonid productivity was indexed by back-calculated length at age 1 of the largest individuals sampled and by total biomass. Upland and riparian site indices were correlated, but neither factor contributed to the best approximating models of salmonid productivity. Total salmonid biomass was best described by a positive relationship with drainage area. Length of dominant fish was best described by a positive relationship with percentage of hardwoods within riparian areas, which may result from nutrient and/or litter subsidies provided by red older. The inability of forest productivity to predict salmon productivity may reflect insufficient variation in independent variables, limitations of the indices, and the operation of other factors affecting salmonid production. The lack of an apparent relationship between upland conifer and salmonid productivity suggests that management of land for timber productivity and component streams for salmonid production in these sites will require separate, albeit integrated, management strategies.

  9. Cascading effects of induced terrestrial plant defences on aquatic and terrestrial ecosystem function.

    PubMed

    Jackrel, Sara L; Wootton, J Timothy

    2015-04-22

    Herbivores induce plants to undergo diverse processes that minimize costs to the plant, such as producing defences to deter herbivory or reallocating limited resources to inaccessible portions of the plant. Yet most plant tissue is consumed by decomposers, not herbivores, and these defensive processes aimed to deter herbivores may alter plant tissue even after detachment from the plant. All consumers value nutrients, but plants also require these nutrients for primary functions and defensive processes. We experimentally simulated herbivory with and without nutrient additions on red alder (Alnus rubra), which supplies the majority of leaf litter for many rivers in western North America. Simulated herbivory induced a defence response with cascading effects: terrestrial herbivores and aquatic decomposers fed less on leaves from stressed trees. This effect was context dependent: leaves from fertilized-only trees decomposed most rapidly while leaves from fertilized trees receiving the herbivory treatment decomposed least, suggesting plants funnelled a nutritionally valuable resource into enhanced defence. One component of the defence response was a decrease in leaf nitrogen leading to elevated carbon : nitrogen. Aquatic decomposers prefer leaves naturally low in C : N and this altered nutrient profile largely explains the lower rate of aquatic decomposition. Furthermore, terrestrial soil decomposers were unaffected by either treatment but did show a preference for local and nitrogen-rich leaves. Our study illustrates the ecological implications of terrestrial herbivory and these findings demonstrate that the effects of selection caused by terrestrial herbivory in one ecosystem can indirectly shape the structure of other ecosystems through ecological fluxes across boundaries.

  10. Tent caterpillars are robust to variation in leaf phenology and quality in two thermal environments.

    PubMed

    Sarfraz, Rana M; Kharouba, Heather M; Myers, Judith H

    2013-10-01

    The synchrony between emergence of spring-active, insect herbivores and the budburst of their host plants could be affected by warming temperatures with influences on the availability and quality of foliage as it undergoes physical and chemical changes. This can affect the growth and survival of insects. Here, we used sun-exposed and shaded trees to determine whether the synchrony between egg hatch of western tent caterpillar, Malacosoma californicum pluviale Dyar (Lepidoptera:Lasiocampidae) and budburst of its host red alder, Alnus rubra Bongard (Betulaceae)changes with different thermal environments (temperature and light together). To explore the potential outcome of a shift in phenological synchrony, we used laboratory assays of larval growth and survival to determine the effect of variation in young, youthful and mature leaves from sun-exposed and shaded trees. While the average higher temperature of sun-exposed trees advanced the timing of budburst and egg hatch, synchrony was not disrupted. Leaf quality had no significant influence on growth or survival in the laboratory for early instars reared as family groups. Later instar larvae, however, performed best on mature leaves from sun-exposed trees. The robust relationship between leaf and larval development of western tent caterpillars suggests that warming climates may not have a strong negative impact on their success through shifts in phenological synchrony, but might influence other aspects of leaf quality and larval condition.

  11. Rathayibacter caricis sp. nov. and Rathayibacter festucae sp. nov., isolated from the phyllosphere of Carex sp. and the leaf gall induced by the nematode Anguina graminis on Festuca rubra L., respectively.

    PubMed

    Dorofeeva, Lubov V; Evtushenko, Lyudmila I; Krausova, Valentina I; Karpov, Alexander V; Subbotin, Sergey A; Tiedje, James M

    2002-11-01

    Two novel species, Rathayibacter caricis sp. nov. (type strain VKM Ac-1799T = UCM Ac-618T) and Rathayibacter festucae sp. nov. (type strain VKM Ac-1390T UCM Ac-619T), are proposed for two coryneform actinomycetes found in the phyllosphere of Carex sp. and in the leaf gall induced by the plant-parasitic nematode Anguina graminis on Festuca rubra L., respectively. The strains of the novel species are typical of the genus Rathayibacter in their chemotaxonomic characteristics and fall into the Rathayibacter 16S rDNA phylogenetic cluster. They belong to two separate genomic species and differ markedly from current validly described species of Rathayibacter at the phenotypic level. The most striking feature differentiating Rathayibacter caricis sp. nov. from other species of the genus is the presence of fucose in its cell wall and Rathayibacter festucae sp. nov. can be easily recognized among other yellow-pigmented rathayibacters because of its rose-orange-coloured colonies.

  12. Theoretical study of Diels-Alder cycloadditions of butadiene to C{sub 70}. An insight into the chemical reactivity of C{sub 70} as compared to C{sub 60}

    SciTech Connect

    Mestres, J.; Duran, M.; Sola, M.

    1996-05-02

    The eight unique Diels-Alder cycloadditions of butadiene to C{sub 70} are analyzed theoretically and compared with the well-established, two possible Diels-Alder cycloadditions of butadiene to C{sub 60}. Full geometry optimizations of reactants, adducts, and transition states are performed using the AMI semiempirical method followed by single-point ab initio energy calculations. The results show that the cycloaddition of butadiene to the C{sub 70} fullerene in the gas phase is slightly more reactive than that to C{sub 60}. However, in toluene solution calculations yield that the different solvent effects on C{sub 60} and C{sub 70} cause a significant decrease of the energy barrier in the C{sub 60} cycloaddition, thus predicting a larger reactivity for C{sub 60} as compared to the C{sub 70} fullerene. 36 refs., 2 figs., 3 tabs.

  13. Effects of a natural dam-break flood on geomorphology and vegetation on the Elwha River, Washington, U.S.A.

    USGS Publications Warehouse

    Acker, S.A.; Beechie, T.J.; Shafroth, P.B.

    2008-01-01

    Ephemeral dams caused by landslides have been observed around the world, yet little is known about the effects of their failure on landforms and vegetation. In 1967, a landslide-dam-break flood in a pristine reach of the Elwha River valley filled the former channel and diverted the river. The reach is a reference site for restoration following the planned removal of dams on the river. We identified five surfaces on the 25 ha debris fan deposited by the flood. Based on tree ages and historic air photos, three of the surfaces formed in 1967, while two formed later. The surfaces varied in substrate (silt and sand, to boulders), and height above the river channel. Tree mortality resulted from tree removal and burial by sediment, the latter leaving snags and some surviving trees. Tree species composition was generally consistent within each surface. Dominant species included red alder (Alnus rubra) and Sitka willow (Salix sitchensis), alone or in combination, a combination of Douglas-fir (Pseudotsuga menziesii) and black cottonwood (Populus balsamifera ssp. trichocarpa), or a combination of alder and Cottonwood. There were significant differences between surfaces in stem density, basal area, and rate of basal area growth. The large degree of heterogeneity in forest structure, composition, and productivity within a relatively small floodplain feature is in part due to spatial variability in the intensity of a single disturbance event, and in part due to the occurrence of subsequent, smaller events. To recreate natural diversity of riparian forests may require mimicking the variety of physical and biotic habitats that a single, complex disturbance event may create.

  14. The effects of experimental warming on the timing of a plant-insect herbivore interaction.

    PubMed

    Kharouba, Heather M; Vellend, Mark; Sarfraz, Rana M; Myers, Judith H

    2015-05-01

    The phenology of many species is shifting in response to climatic changes, and these shifts are occurring at varying rates across species. This can potentially affect species' interactions and individual fitness. However, few studies have experimentally tested the influence of warming on the timing of species interactions. This is an important gap in the literature given the potential for different direct and indirect effects of temperature via phenological change. Our aim was to test the effects of warming on the western tent caterpillar (Malacosoma californicum pluviale). In addition to the direct effects of warming, we considered the two primary indirect effects mediated by warming-driven changes in its host plant, red alder (Alnus rubra): changes in resource availability due to phenological mismatch (i.e. changes in the relative timing of the interaction), and changes in resource quality associated with leaf maturation. We experimentally warmed egg masses and larvae of the western tent caterpillar placed on branches of red alder in the field. Warming advanced the timing of larval but not leaf emergence. This led to varying degrees of phenological mismatch, with larvae emerging as much as 25 days before to 10 days after the emergence of leaves. Even the earliest-emerging larvae, however, had high survival in the absence of leaves for up to 3 weeks, and they were surprisingly resistant to starvation. In addition, although warming created phenological mismatch that initially slowed the development of larvae that emerged before leaf emergence, it accelerated larval development once leaves were available. Therefore, warming had no net effect on our measures of insect performance. Our results demonstrate that the indirect effects of warming, in creating phenological mismatch, are as important to consider as the direct effects on insect performance. Although future climatic warming might influence plants and insects in different ways, some insects may be well adapted

  15. Useful dual Diels-Alder behavior of 2-azetidinone-tethered aryl imines as azadienophiles or azadienes: a beta-lactam-based stereocontrolled access to optically pure highly functionalized indolizidine systems.

    PubMed

    Alcaide, Benito; Almendros, Pedro; Alonso, Jose M; Aly, Moustafa F

    2003-07-21

    Imines derived from 4-oxoazetidine-2-carbaldehydes have been found to be versatile Diels-Alder reagents in that they exhibit two reactivity patterns. 2-Azetidinone-tethered imines undergo diastereoselective reaction with Danishefsky's diene in the presence of different Lewis acids. The effect of the amount of catalyst on the conversion rate as well as on the product ratio has been studied. Under standard reaction conditions, indium(III) chloride and zinc(II) iodide provided the best yields, and indium(III) triflate the highest diastereoselectivity in the Lewis acid promoted aza-Diels-Alder cycloaddition. Treatment of the aforementioned imines with cyclopentadiene, 2,3-dimethyl-1,3-butadiene or 3,4-dihydro-2 H-pyran led to cycloadducts arising from inverse electron-demand condensation involving the beta-lactam-tethered aryl imine as the heterodiene component. In addition, the first methodology for preparing indolizidines from beta-lactams has been developed. This process involves amide bond cleavage of the beta-lactam ring in the aza-Diels-Alder cycloadducts with concomitant cyclization. Full chirality transfer occurs when the reaction is performed with an enantiomerically pure substrate.

  16. The Diels-Alder-Reaction with inverse-Electron-Demand, a very efficient versatile Click-Reaction Concept for proper Ligation of variable molecular Partners

    PubMed Central

    Wiessler, Manfred; Waldeck, Waldemar; Kliem, Christian; Pipkorn, Ruediger; Braun, Klaus

    2010-01-01

    The ligation of active pharmaceutical ingredients (API) for working with image processing systems in diagnostics (MRT) attracts increasing notice and scientific interest. The Diels-Alder ligation Reaction with inverse electron demand (DARinv) turns out to be an appropriate candidate. The DARinv is characterized by a specific distribution of electrons of the diene and the corresponding dienophile counterpart. Whereas the reactants in the classical Diels-Alder Reaction feature electron-rich diene and electron-poor dienophile compounds, the DARinv exhibits exactly the opposite distribution of electrons. Substituents with pushing electrones increase and, with pulling electrons reduce the electron density of the dienes as used in the DARinv. We report here that the DARinv is an efficient route for coupling of multifunctional molecules like active peptides, re-formulated drugs or small molecules like the alkyalting agent temozolomide (TMZ). This is an example of our contribution to the "Click chemistry" technology. In this case TMZ is ligated by DARinv as a cargo to transporter molecules facilitating the passage across the cell membranes into cells and subsequently into subcellular components like the cell nucleus by using address molecules. With such constructs we achieved high local concentrations at the desired target site of pharmacological action. The DARinv ligation was carried out using the combination of several technologies, namely: the organic chemistry and the solid phase peptide synthesis which can produce 'tailored' solutions for questions not solely restricted to the medical diagnostics or therapy, but also result in functionalizations of various surfaces qualified amongst others also for array development. We like to acquaint you with the DARinv and we like to exemplify that all ligation products were generated after a rapid and complete reaction in organic solutions at room temperature, in high purity, but also, hurdles and difficulties on the way to the

  17. Metabolic profiling of major vitamin D metabolites using Diels-Alder derivatization and ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Aronov, Pavel A; Hall, Laura M; Dettmer, Katja; Stephensen, Charles B; Hammock, Bruce D

    2008-07-01

    Biologically active forms of vitamin D are important analytical targets in both research and clinical practice. The current technology is such that each of the vitamin D metabolites is usually analyzed by individual assay. However, current LC-MS technologies allow the simultaneous metabolic profiling of entire biochemical pathways. The impediment to the metabolic profiling of vitamin D metabolites is the low level of 1alpha,25-dihydroxyvitamin D(3) in human serum (15-60 pg/mL). Here, we demonstrate that liquid-liquid or solid-phase extraction of vitamin D metabolites in combination with Diels-Alder derivatization with the commercially available reagent 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) followed by ultra-performance liquid chromatography (UPLC)-electrospray/tandem mass spectrometry analysis provides rapid and simultaneous quantification of 1alpha,25-dihydroxyvitamin D(3), 1alpha,25-dihydroxyvitamin D(2), 24R,25-dihydroxyvitamin D(3), 25-hydroxyvitamin D(3) and 25-hydroxyvitamin D(2) in 0.5 mL human serum at a lower limit of quantification of 25 pg/mL. Precision ranged from 1.6-4.8 % and 5-16 % for 25-hydroxyvitamin D(3) and 1alpha,25-dihydroxyvitamin D(3), respectively, using solid-phase extraction.

  18. Polar hetero-Diels-Alder reactions of 4-alkenylthiazoles with 1,2,4-triazoline-3,5-diones: an experimental and computational study.

    PubMed

    Alajarín, Mateo; Cabrera, José; Pastor, Aurelia; Sanchez-Andrada, Pilar; Bautista, Delia

    2008-02-01

    The hetero-Diels-Alder reactions of 4-alkenylthiazoles with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) lead to new heteropolycyclic systems in excellent yields and high levels of stereocontrol through an exclusively suprafacial approach. 4-Alkenylthiazoles with a stereogenic center placed at the alkenylic substituent react with PTAD giving the corresponding chiral cycloadducts in moderate diastereomeric excesses. The stereochemical course is dominated by the steric interactions at the two diastereomeric transition states. A computational study of these processes with structurally simpler reagents has been carried out. A concerted pathway via a highly asynchronous transition state is preferred for 2-unsubstituted 4-vinyl and 4-styrylthiazoles. However, two alternative and equally likely pathways, concerted and stepwise, have been found to be followed by 2-methyl- or 2-phenyl-substituted 4-styrylthiazoles. The concerted pathway features a highly asynchronous transition state. For the stepwise pathway, the rate-determining step is the first one, as the energy barrier for the second step is virtually nonexistent.

  19. The Diels-Alder reaction of 4,6-dinitrobenzofuroxan with 1-trimethylsilyloxybuta-1,3-diene: a case example of a stepwise cycloaddition.

    PubMed

    Lakhdar, Sami; Terrier, François; Vichard, Dominique; Berionni, Guillaume; El Guesmi, Nizar; Goumont, Régis; Boubaker, Taoufik

    2010-05-17

    The reaction of 4,6-dinitrobenzofuroxan (DNBF) with 1-trimethylsilyloxybuta-1,3-diene (8) is shown to afford a mixture of [2+4] diastereomeric cycloadducts (10, 11) through stepwise addition-cyclization pathways. Zwitterionic intermediate sigma-adduct 9, which is involved in the processes, has been successfully characterized by (1)H and (13)C NMR spectroscopy and UV/visible spectrophotometry in acetonitrile. A kinetic study has been carried out in this solvent that revealed that the rate of formation of 9 nicely fits the three-parameter equation log k=s(E+N) developed by Mayr to describe the feasibility of nucleophile-electrophile combinations. This significantly adds to the NMR spectroscopic evidence that the overall cycloadditions take place through a stepwise mechanism. The reaction has also been studied in dichloromethane and toluene. In these less polar solvents, the stability of 9 is not sufficient to allow direct characterization by spectroscopic methods, but a kinetic investigation supports the view that stepwise processes are still operating. An informative comparison of our reaction with previous interactions firmly identified as prototype stepwise cycloadditions is made on the basis of the global electrophilicity index, omega, defined by Parr within the density functional theory, and highlighted by Domingo et al. as a powerful tool for understanding Diels-Alder reactions.

  20. Electronic fluxes during Diels-Alder reactions involving 1,2-benzoquinones: mechanistic insights from the analysis of electron localization function and catastrophe theory.

    PubMed

    González-Navarrete, Patricio; Domingo, Luis R; Andrés, Juan; Berski, Slawomir; Silvi, Bernard

    2012-11-15

    By means of the joint use of electron localization function (ELF) and Thom's catastrophe theory, a theoretical analysis of the energy profile for the hetero-Diels-Alder reaction of 4-methoxy-1,2-benzoquinone 1 and methoxyethylene 2 has been carried out. The 12 different structural stability domains obtained by the bonding evolution theory have been identified as well as the bifurcation catastrophes (fold and cusp) responsible for the changes in the topology of the system. This analysis permits finding a relationship between the ELF topology and the evolution of the bond breaking/forming processes and electron pair rearrangements through the reaction progress in terms of the different ways of pairing up the electrons. The reaction mechanism corresponds to an asynchronous electronic flux; first, the O1-C5 bond is formed by the nucleophilic attack of the C5 carbon of the electron rich ethylene 2 on the most electrophilically activated carbonyl O1 oxygen of 1, and once the σ bond has been completed, the formation process of the second O4C6 bond takes place. In addition, the values of the local electrophilicity and local nucleophilcity indices in the framework of conceptual density functional theory accounts for the asychronicity of the process as well as for the observed regioselectivity.

  1. Activation-strain analysis reveals unexpected origin of fast reactivity in heteroaromatic azadiene inverse-electron-demand diels-alder cycloadditions.

    PubMed

    Talbot, Austin; Devarajan, Deepa; Gustafson, Samantha J; Fernández, Israel; Bickelhaupt, F Matthias; Ess, Daniel H

    2015-01-02

    Heteroaromatic azadienes, especially 1,2,4,5-tetrazines, are extremely reactive partners with alkenes in inverse-electron-demand Diels-Alder reactions. Azadiene cycloaddition reactions are used to construct heterocycles in synthesis and are popular as bioorthogonal reactions. The origin of fast azadiene cycloaddition reactivity is classically attributed to the inverse frontier molecular orbital (FMO) interaction between the azadiene LUMO and alkene HOMO. Here, we use a combination of ab initio, density functional theory, and activation-strain model calculations to analyze physical interactions in heteroaromatic azadiene-alkene cycloaddition transition states. We find that FMO interactions do not control reactivity because, while the inverse FMO interaction becomes more stabilizing, there is a decrease in the forward FMO interaction that is offsetting. Rather, fast cycloadditions are due to a decrease in closed-shell Pauli repulsion between cycloaddition partners. The kinetic-thermodynamic relationship found for these inverse-electron-demand cycloadditions is also due to the trend in closed-shell repulsion in the cycloadducts. Cycloaddition regioselectivity, however, is the result of differences in occupied-unoccupied orbital interactions due to orbital overlap. These results provide a new predictive model and correct physical basis for heteroaromatic azadiene reactivity and regioselectivity with alkene dieneophiles.

  2. Synthesis and Properties of a Novel Pyridineoxazoline Containing Optically Active Helical Polymer as a Catalyst Ligand for Asymmetric Diels-Alder Reaction.

    PubMed

    Wang, Heng; Li, Na; Zhang, Jie; Wan, Xinhua

    2015-08-01

    A novel pyridineoxazoline (PyOx) containing helical polymer, poly{(-)-(S)-4-tert-butyl-2-[5-(4-tert-butylphenyl)-3-vinylpyridin-2-yl]-oxazoline} (PA), was designed and synthesized to approach the effect of chain conformation on the catalytic property. Its complex with Cu(OTf)(2) , i.e., Cu(II)-PA, was employed to catalyze the homogeneous Diels-Alder (D-A) reaction of alkenoyl pyridine N-oxides with cyclopentadiene in tetrahydrofuran. Compared with the previously reported copper complex, Cu(II)-P1 (RSC Advances, 2015, 5, 2882), which was derived from a nonhelical poly[(-)-(S)-4-tert-butyl-2-(3-vinylpyridin-2-yl)-oxazoline], Cu(II)-PA exhibited a remarkably enhanced enantioselectivity and reaction rate. However, its enantioselectivity was lower than the Cu(II) complex of (-)-(S)-4-tert-butyl-2-[5-(4-tert-butylphenyl)-3-vinylpyridin-2-yl]-oxazoline (Cu(II)-A), a low molar mass model compound.

  3. Healable capacitive touch screen sensors based on transparent composite electrodes comprising silver nanowires and a furan/maleimide diels-alder cycloaddition polymer.

    PubMed

    Li, Junpeng; Liang, Jiajie; Li, Lu; Ren, Fengbo; Hu, Wei; Li, Juan; Qi, Shuhua; Pei, Qibing

    2014-12-23

    A healable transparent capacitive touch screen sensor has been fabricated based on a healable silver nanowire-polymer composite electrode. The composite electrode features a layer of silver nanowire percolation network embedded into the surface layer of a polymer substrate comprising an ultrathin soldering polymer layer to confine the nanowires to the surface of a healable Diels-Alder cycloaddition copolymer and to attain low contact resistance between the nanowires. The composite electrode has a figure-of-merit sheet resistance of 18 Ω/sq with 80% transmittance at 550 nm. A surface crack cut on the conductive surface with 18 Ω is healed by heating at 100 °C, and the sheet resistance recovers to 21 Ω in 6 min. A healable touch screen sensor with an array of 8×8 capacitive sensing points is prepared by stacking two composite films patterned with 8 rows and 8 columns of coupling electrodes at 90° angle. After deliberate damage, the coupling electrodes recover touch sensing function upon heating at 80 °C for 30 s. A capacitive touch screen based on Arduino is demonstrated capable of performing quick recovery from malfunction caused by a razor blade cutting. After four cycles of cutting and healing, the sensor array remains functional.

  4. [The role of motivation in the performance of a conditioned switching-over of the maze habit in ants Myrmica rubra after a change in the quality of the food reinforcement].

    PubMed

    Udalova, G P; Karas', A Ia

    2005-01-01

    Active foragers Myrmica rubra were trained in a maze under conditions of different levels of colony need in food with carbohydrate (sugar syrup) or protein (ants Lasius niger pupae) reinforcement. Acquisition of the maze habit was better under conditions of reinforcement with pupae, especially by its time indices. Ants were able to modify the acquired habit when the reinforcement quality was changed. It was shown that learning was possible only when the colony and after a change pupae for the syrup was "hungry". Under these conditions, after a change of the syrup for pupae or visa versa the previously acquired optimum habit was transferred. Several hours later, with satiation of the colony, food reactions learned with protein reinforcement switched-over to "stochastic" non-optimized behavior with the dominance of exploratory reactions. Thus, it was shown that higher social insects ants were capable for conditioned switching-over. Different forms of this phenomenon depended on the level of the colony need in food and, consequently, on the level of the social food motivation of foragers ants.

  5. Screening North American plant extracts in vitro against Trypanosoma brucei, the causative agent for Human African Trypanosomiasis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Natural products extracts from 522 plants collected from different parts of the North America were screened in vitro against trypamastigote forms of Trypanosoma brucei. The active extracts(150)with >90% inhibition at 20ug/mL concentrations from the plants namely, Alnus rubra, Hoita macrostachya, S...

  6. Pi-face-selective Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide and 1-imide and formation of 1,2-thiazetidines.

    PubMed

    Otani, Takashi; Takayama, Jun; Sugihara, Yoshiaki; Ishii, Akihiko; Nakayama, Juzo

    2003-07-09

    3,4-Di-tert-butylthiophene 1-oxide (1a) reacted with a series of electron-deficient alkenic dienophiles at its syn-pi-face relating to the S=O bond to give [4+2] adducts in excellent yields. The 1-oxide 1a also reacted even with angle-strained dienophiles acenaphthylene and norbornene at its syn-pi-face to afford [4+2] adducts; in the latter case, norbornene reacted exclusively at its exo-pi-face. The oxide 1a reacted with dimethyl acetylenedicarboxylate to produce dimethyl 4,5-di-tert-butylphthalate in high yield with spontaneous extrusion of SO from the initial adduct even at room temperature. Similarly, 3,4-di-tert-butylthiophene 1-(p-toluenesulfonyl)imide (3a) reacted with alkenic dienophiles at its syn-pi-face relating to the S=N bond to give [4+2] adducts in good yields. The reaction of 3a with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) afforded a 1,2-thiazetidine 12a, the first example of S-unoxidized 1,2-thiazetidine, in good yield, through rearrangement of the initial [4+2] adduct. The molecular structure of 12a is discussed on the basis of the X-ray crystallographic analysis. Comparison of the foregoing reactions leads to the conclusion that the 1-oxide 1a is more reactive as a diene than the 1-imide 3a, which is more reactive than 3,4-di-tert-butylthiophene 1,1-dioxide. The origin of the syn-pi-face selectivities of 1a and 3a in Diels-Alder reactions is discussed in terms of the orbital mixing rule and steric effect and also based on B3LYP/6-31G(d) calculations.

  7. Dependence of the rate of an interfacial Diels-Alder reaction on the steric environment of the immobilized dienophile: an example of enthalpy-entropy compensation.

    PubMed

    Kwon, Youngeun; Mrksich, Milan

    2002-02-06

    This paper describes a physical organic study of the relationship between the rate for an interfacial Diels-Alder reaction and the steric environment around the reacting molecules. The study used as a model reaction the cycloaddition of cyclopentadiene with a self-assembled monolayer (SAM) presenting benzoquinone groups surrounded by hydroxyl-terminated alkanethiolates. The accessibility of the quinone was varied by preparing monolayers from hydroquinone-terminated alkanethiols of different lengths [HS(CH(2))(n)-HQ, n = 6-14] and a hydroxyl-terminated alkanethiol [HS(CH(2))(11)-OH] of constant length. Cyclic voltammetry was used to measure the rate of the reaction by monitoring the decay of the redox-active quinone. The second-order rate constant showed a modest change as the position of quinone was varied relative to the hydroxyl groups of the monolayer. For monolayers wherein the quinone groups were extended from the interface, the rate constants oscillated near 0.20 M(-1) s(-1) with an even-odd dependence on the length of the alkanethiol. For monolayers that positioned the quinone groups below the surrounding hydroxyl groups, the rate constants decreased by approximately 8-fold. Examination of the activation parameters revealed that the quinone groups that were positioned below the interface (and in a crowded environment) reacted with an enthalpy of activation that was 4 kcal/mol greater than did the quinones that were accessible at the interface. The reaction of the buried quinone, however, proceeded with an entropy of activation that was more favorable by 13 eu, and therefore with a similar free energy of activation. The combination of SAMs for preparing model interfaces and cyclic voltammetry for measuring rates provides a new opportunity for physical organic studies of interfacial reactions.

  8. A complete guide on the influence of metal clusters in the Diels-Alder regioselectivity of I(h)-C80 endohedral metallofullerenes.

    PubMed

    Garcia-Borràs, Marc; Osuna, Sílvia; Luis, Josep M; Swart, Marcel; Solà, Miquel

    2013-10-25

    The chemical functionalization of endohedral metallofullerenes (EMFs) has aroused considerable interest due to the possibility of synthesizing new species with potential applications in materials science and medicine. Experimental and theoretical studies on the reactivity of endohedral metallofullerenes are scarce. To improve our understanding of the endohedral metallofullerene reactivity, we have systematically studied with DFT methods the Diels-Alder cycloaddition between s-cis-1,3-butadiene and practically all X@I(h)-C80 EMFs synthesized to date: X=Sc3N, Lu3N, Y3N, La2, Y3, Sc3C2, Sc4C2, Sc3CH, Sc3NC, Sc4O2 and Sc4O3. We have studied both the thermodynamic and kinetic regioselectivity, taking into account the free rotation of the metallic cluster inside the fullerene. This systematic study has been made possible through the use of the frozen cage model (FCM), a computationally cheap approach to accurately predicting the exohedral regioselectivity of cycloaddition reactions in EMFs. Our results show that the EMFs are less reactive than the hollow I(h)-C80 cage. Except for the Y3 cluster, the additions occur predominantly at the [5,6] bond. In many cases, however, a mixture of the two possible regioisomers is predicted. In general, [6,6] addition is favored in EMFs that have a larger charge transfer from the metal cluster to the cage or a voluminous metal cluster inside. The present guide represents the first complete and exhaustive investigation of the reactivity of I(h)-C80-based EMFs.

  9. An unexpected double Diels-Alder reaction of (E)-2-bromo-4-aryl-1,3-pentadiene involving [1,5]-hydrogen migration and HBr elimination: synthesis of bicyclo[2.2.2]octene derivatives.

    PubMed

    Huang, Pingping; Liu, Lingyan; Chang, Weixing; Li, Jing

    2015-03-01

    An unexpected double Diels-Alder (DDA) reaction of (E)-2-bromo-4-aryl-1,3-pentadiene was developed and resulted in a series of "butterfly-like" bicyclo[2.2.2]octene derivatives in moderate to good yields without the need for a metal catalyst. The proposed mechanism involves a [1,5]-sigmatropic hydrogen migration and HBr elimination. Through this decisive [1,5]-hydrogen shift step, the electronic properties and steric hindrance of the conjugated diene substrate are completely altered and the DDA reaction of this potential diene synthon is successfully achieved.

  10. Domino 6pi-electrocyclization/Diels-Alder reactions on 1,6-disubstituted (E,Z,E)-1,3,5-hexatrienes: versatile access to highly substituted tri- and tetracyclic systems.

    PubMed

    von Essen, Regina; Frank, Daniel; Sünnemann, Hans Wolf; Vidović, Denis; Magull, Jörg; de Meijere, Armin

    2005-11-04

    The (E,Z,E)-1,3,5-hexatrienes 1a, 2a,b and 3b undergo 6pi-electrocyclization within 15-30 min upon heating to 200-215 degrees C. While the cyclohexene-annelated products 8a,b were stable, the analogous cyclopentene- and cycloheptene-annelated derivatives 7a and 9b easily underwent dehydrogenation to the corresponding aromatic compounds 10a and 12b during the work-up. The cyclohexadiene derivatives 8a,b were employed in thermal Diels-Alder reactions with 4-phenyl-3H-1,2,4-triazoline-3,5-dione (PTAD) and tetracyanoethylene (TCNE) to give the expected [4+2] cycloadducts 13a and 14a in good yields (60 and 78%). The initially formed cycloadduct of 8a and dimethyl acetylenedicarboxylate (DMAD) underwent a subsequent retro-Diels-Alder reaction to give the tetrahydronaphthalene 11b (47%). Under high pressure (10 kbar), the cycloadduct 15a was formed at room temperature and could be isolated in 44% yield. TCNE and N-phenylmaleimide with 8a under high pressure also led to the [4+2] cycloadducts 14a and 16a in good yields (60 and 77%). The 6pi-electrocyclization and subsequent Diels-Alder reaction, when performed as a one-pot domino process, provided direct access to Diels-Alder products of intermediately formed 6pi-electrocyclization products, for example from the 1,3,5-hexatrienes 1a,b, 2a,b, 3b and TCNE to the corresponding tricyclic products 17a,b, 14a,b, 18b in moderate to good yields (27-80%) depending on the nature of the alkoxycarbonyl group. Such sequential reactions with N-phenylmaleimide, maleic anhydride, dimethyl maleate and fumarodinitrile, the latter two under high pressure (10 kbar), worked as well to yield 16b (70%), 19a,b (19, 32%) and 20b (39%) and 21b (76%), respectively. With PTAD, however, the hexatrienes 2a,b reacted at ambient temperature without 6pi-electrocyclization to give the formal [4+2] cycloadducts 27a,b (48 and 46%), most probably via zwitterionic intermediates 23a,b and 25a,b.

  11. The [2 + 2] Cycloaddition-Retroelectrocyclization and [4 + 2] Hetero-Diels-Alder Reactions of 2-(Dicyanomethylene)indan-1,3-dione with Electron-Rich Alkynes: Influence of Lewis Acids on Reactivity.

    PubMed

    Donckele, Etienne J; Finke, Aaron D; Ruhlmann, Laurent; Boudon, Corinne; Trapp, Nils; Diederich, François

    2015-07-17

    The reaction of electrophilic 2-(dicyanomethylene)indan-1,3-dione (DCID) with substituted, electron-rich alkynes provides two classes of push-pull chromophores with interesting optoelectronic properties. The formal [2 + 2] cycloaddition-retroelectrocyclization reaction at the exocyclic double bond of DCID gives cyanobuta-1,3-dienes, and the formal [4 + 2] hetero-Diels-Alder (HDA) reaction at an enone moiety of DCID generates fused 4H-pyran heterocycles. Both products can be obtained in good yield and excellent selectivity by carefully tuning the reaction conditions; in particular, the use of Lewis acids dramatically enhances formation of the HDA adduct.

  12. Insights into the Diels-Alder Reaction between 3-Vinylindoles and Methyleneindolinone without and with the Assistance of Hydrogen-Bonding Catalyst Bisthiourea: Mechanism, Origin of Stereoselectivity, and Role of Catalyst.

    PubMed

    Yan, Chao-Xian; Yang, Fan; Yang, Xing; Zhou, Da-Gang; Zhou, Pan-Pan

    2017-03-17

    The Diels-Alder reaction between 3-vinylindoles and methyleneindolinone can proceed both under catalyst-free conditions and with bisthiourea as the catalyst. The reaction with bisthiourea is much faster and results in higher stereoselectivity of the product. The reaction mechanism, origin of stereoselectivity, and role of the catalyst were elaborated based on quantum mechanical calculations and theoretical methods of reactivity indices, NCI, QTAIM, and distortion/interaction models. In the uncatalyzed reaction, the two C-C bonds that are formed undergo conversion from noncovalent to covalent bonding via a concerted asynchronous mechanism. The weak intermolecular interactions formed in the transition state play important roles. The difference between the interaction and distortion energies is responsible for the stereoselectivity. In the catalyzed reaction, bisthiourea induces both the diene and dienophile to approach it via weak intermolecular interactions, which greatly lowers the energy barrier of the reaction and leads to the product with excellent stereoselectivity. The possible pathways of this reaction were explored, which suggested that the formation of the two C-C bonds goes through either a stepwise or concerted asynchronous mechanism. These results detail the reaction mechanism and shed light on both the significant role of the bisthiourea catalyst and the origin of stereoselectivity for this type of Diels-Alder reaction and related ones.

  13. Approach to the study of C-glycosyl flavones acylated with aliphatic and aromatic acids from Spergularia rubra by high-performance liquid chromatography-photodiode array detection/electrospray ionization multi-stage mass spectrometry.

    PubMed

    Ferreres, Federico; Gil-Izquierdo, Angel; Vinholes, Juliana; Grosso, Clara; Valentão, Patrícia; Andrade, Paula B

    2011-03-30

    The use of mass spectrometry (MS) coupled to liquid chromatography (LC) as working tool for the study of the C-glycosyl flavones acylated with aliphatic and aromatic acids has allowed the tentative characterization of these compounds in Spergularia rubra and the establishment of the position of the acylation on the sugar moiety of the C-glycosylation by use of MS data. The combination of retention time (Rt), ultraviolet (UV) and MS(n) data of the compounds revealed their C-glycosyl flavone nature, being luteolin, apigenin and chrysoeriol derivatives. Ten non-acylated flavones were identified, from which six are described for the first time (one 7-O-glycosyl-6,8-diC-glycosyl flavone, four 6,8-diC-glycosyl flavones and one 2"-O-glycosyl-6-C-glycosyl flavone). Twenty-six acylated derivatives were also found for the first time. These compounds are grouped in three classes, namely, C-glycosyl flavones acylated with aliphatic acids, with aromatic acids or with a mixed acylation. The first group is characterized by the presence of one 6,8-diC-(acetyl)glycosyl flavone, four 6,8-diC-(malonyl)glycosyl flavones and two 7-O-glycosyl-6,8-diC-(malonyl)glycosyl flavones, while in the second one twelve 6,8-diC-(acyl)glycosyl flavones and two 7-O-glycosyl-6,8-diC-(acyl)glycosyl flavones are described. The last class contained five 6,8-diC-(malonyl,acyl)glycosyl flavones. No previous work has described the presence of C-glycosyl flavones acylated with aliphatic acids in this genus.

  14. Tandem Intramolecular Diels-Alder/1,3-Dipolar Cycloaddition Cascade of 1,3,4-Oxadiazoles: Initial Scope and Applications.

    PubMed

    Sears, Justin E; Boger, Dale L

    2016-02-16

    impressive range of additional natural products illustrate the power of the methodology. Alternative tethering strategies for the cascade cycloaddition reaction, combined intramolecular and intermolecular variants of either the initiating Diels-Alder reaction or the subsequent carbonyl ylide 1,3-dipolar cycloaddition, an expanded examination of the tethered dipolarophile scope, and applications to additional natural product classes represent attractive areas for future work.

  15. Linear-dendritic supramolecular complexes as nanoscale reaction vessels for "green" chemistry. Diels-Alder reactions between fullerene C60 and polycyclic aromatic hydrocarbons in aqueous medium.

    PubMed

    Simonyan, Arsen; Gitsov, Ivan

    2008-10-21

    This study describes the first Diels-Alder (DA) reaction performed in aqueous medium with highly hydrophobic compounds-fullerene (C 60) as the dienophile and anthracene (An) or tetracene (Tet) as the dienes, respectively. The reactions are performed in nanocontainers, constructed by self-assembly of linear-dendritic amphiphilic copolymers with poly(ethylene glycol), PEG or poly(ethylene oxide), PEO as the hydrophilic blocks and poly(benzyl ether) monodendrons as the hydrophobic fragments: G3PEO13k, dG3 and dG2. Comparative studies under identical conditions are carried out with an amphiphilic linear-linear copolymer, poly(styrene)1800- block-PEO2100, PSt-PEO, and the nonionic surfactant Igepal CO-720, IP720. The binding affinity of supermolecules built of these amphiphiles toward the DA reagents decreases in the following order: G3PEO13k > dG3 > PSt-PEO > dG2 > IP720. The kinetic constant of binding is evaluated for tetracene and decreases in a similar fashion: 5 x 10 (-7) M/min (G3PEO13k), through 4 x 10 (-7) M/min (PSt-PEO) down to 1.5 x 10 (-7) M/min for IP720. The mobility of substrates encapsulated in the micellar core, estimated by pyrene fluorescence decay, is 95-121 ns for the micelles of the linear-dendritic copolymers and notably higher for PSt-PEO (152 ns), revealing the much denser interior of the linear analogue. The apparent kinetic constant for the DA reaction of C 60 and Tet within the G3PEO13k supermolecule in aqueous medium is markedly higher than in organic solvent (toluene), 208 vs 1.82 M /min. With G3PEO13k the conversions reach 49% for the DA reaction between C 60 and An, and 55% for C 60 and Tet. Besides the monoadduct (26.5% yield) the reaction with An produces exclusively increasing amounts of D 2 h -symmetric antipodal bis-adduct, whose yield reaches up to 22.5% after 48 h. In addition to the environmentally friendly conditions notable advantages of the synthetic strategy described are the extended stability of the linear

  16. Tandem Intramolecular Diels–Alder/1,3-Dipolar Cycloaddition Cascade of 1,3,4-Oxadiazoles: Initial Scope and Applications

    PubMed Central

    Sears, Justin E.

    2016-01-01

    total synthesis of an impressive range of additional natural products illustrate the power of the methodology. Alternative tethering strategies for the cascade cycloaddition reaction, combined intramolecular and intermolecular variants of either the initiating Diels–Alder reaction or the subsequent carbonyl ylide 1,3-dipolar cycloaddition, an expanded examination of the tethered dipolarophile scope, and applications to additional natural product classes represent attractive areas for future work. PMID:26813287

  17. Direct and Indirect Determinations of Elementary Rate Constants H + O2: Chain Branching; the Dehydration of tertiary-Butanol; the Retro Diels-Alder Reaction of Cyclohexene; the Dehydration of Isopropanol

    NASA Astrophysics Data System (ADS)

    Heyne, Joshua S.

    Due to growing environmental concern over the continued use of fossil fuels, methods to limit emissions and partially replace fossil fuel use with renewable biofuels are of considerable interest. Developing chemical kinetic models for the chemistry that affects combustion properties is important to understanding how new fuels affect combustion energy conversion processes in transportation devices. This thesis reports the experimental study of several important reactions (the H + O2 branching reaction, the key decomposition reactions of tertiary-butanol, the dehydration reaction of isopropanol, and the retro Diels-Alder reaction of cyclohexene) and develops robust analysis methods to estimate the absolute uncertainties of specific elementary rate constants derived from the experimental data. In the study of the above reactions, both a direct and indirect rate constant determination technique with associated uncertainty estimation methodologies are developed. In the study of the decomposition reactions, a direct determination technique is applied to experimental data gathered in preparation of this thesis. In the case of the dehydration reaction of tertiary-butanol and the retro Diels-Alder reaction of cyclohexene, both of which are used as internal standards for relative rate studies (Herzler et al. 1997) and chemical thermometry (Rosado-Reyes et al. 2013) , analysis showed an ˜20 K difference in the reaction rate between the reported results and the previous recommendations. In light of these discrepancies, an uncertainty estimation of previous recommendations illuminated an uncertainty of at least 20 K for the dehydration reaction of tertiary-butanol and the retro Diels-Alder reaction of cyclohexene, thus resolving the discrepancies. The determination of the H + O2 branching reaction and decomposition reactions of isopropanol used an indirect determination technique. The uncertainty of the H + O2 branching reaction rate is shown to be underestimated by previous

  18. Root tensile strength of grey alder and mountain maple grown on a coarse grained eco-engineered slope in the Swiss Alps related to wood anatomical features

    NASA Astrophysics Data System (ADS)

    Kink, Dimitri; Bast, Alexander; Meyer, Christine; Meier, Wolfgang; Egli, Markus; Gärtner, Holger

    2014-05-01

    . In order to confirm this assumption and possibly find more important root properties which have an influence on soil stabilization, the root systems of seven trees (three grey alder, four mountain maple) were excavated and analyzed. The study site is a catchment, where shallow landslides are common. It is located in the Prättigau valley in the Eastern Swiss Alps and was eco-engineered in 1997. The substrate is coarse-grained morainic material, mean annual air temperature reaches 4.64°C, average precipitation is 1170 mm, and the altitude is about 1000 m a.s.l.. The root system of each tree was uncovered carefully by hand to keep the roots undamaged, before removal it was photographed in situ to document the root distribution. The root systems were then cut into single root pieces of about 20 cm length and the position of each sample was documented. The root samples were then hierarchically classified in several root classes. The tensile strength of more than 500 samples was determined. In addition, the values for age, diameter, and root moisture were ascertained. Since it was assumed, that the cellular structure of the roots has an influence on the tensile strength, two microscopic thin-sections were prepared from all successfully tested root samples. The microscopic analysis focused on anatomical parameters such as the size and number of vessels, their distribution as well as their conductivity. The results for the final correlation between the anatomical characteristics and the root's tensile strength are presented for both tree species.

  19. TERRESTRIAL AND MARINE SOURCES OF NUTRIENTS TO AN OREGON COASTAL RIVER

    EPA Science Inventory

    In the Pacific Northwest of North America, anadromous fish can transport significant quantities of nutrients and energy from the ocean to the watersheds where they return, reproduce and die. In addition, the widespread distribution of N2-fixing alders (Alnus spp.) can influence ...

  20. High performance addition-type thermoplastics (ATTs) - Evidence for the formation of a Diels-Alder adduct in the reaction of an acetylene-terminated material and a bismaleimide

    NASA Technical Reports Server (NTRS)

    Pater, R. H.; Soucek, M. D.; Chang, A. C.; Partos, R. D.

    1991-01-01

    Recently, the concept and demonstration of a new versatile synthetic reaction for making a large number of high-performance addition-type thermoplastics (ATTs) were reported. The synthesis shows promise for providing polymers having an attractive combination of easy processability, good toughness, respectable high temperature mechanical performance, and excellent thermo-oxidative stability. The new chemistry involves the reaction of an acetylene-terminated material with a bismaleimide or benzoquinone. In order to clarify the reaction mechanism, model compound studies were undertaken in solutions as well as in the solid state. The reaction products were purified by flash chromatography and characterized by conventional analytical techniques including NMR, FT-IR, UV-visible, mass spectroscopy, and high pressure liquid chromatography. The results are presented of the model compound studies which strongly support the formation of a Diels-Alder adduct in the reaction of an acetylene-terminated compound and a bismaleimide or benzoquinone.

  1. Multilocus sequence typing confirms the close genetic interrelatedness of three distinct flavescence dorée phytoplasma strain clusters and group 16SrV phytoplasmas infecting grapevine and alder in Europe.

    PubMed

    Arnaud, Guillaume; Malembic-Maher, Sylvie; Salar, Pascal; Bonnet, Patrick; Maixner, Michael; Marcone, Carmine; Boudon-Padieu, Elisabeth; Foissac, Xavier

    2007-06-01

    Vineyards of southern France and northern Italy are affected by the flavescence dorée (FD) phytoplasma, a quarantine pathogen transmitted by the leafhopper of Nearctic origin Scaphoideus titanus. To better trace propagation of FD strains and identify possible passage between the vineyard and wild plant compartments, molecular typing of phytoplasma strains was applied. The sequences of the two genetic loci map and uvrB-degV, along with the sequence of the secY gene, were determined among a collection of FD and FD-related phytoplasmas infecting grapevine, alder, elm, blackberry, and Spanish broom in Europe. Sequence comparisons and phylogenetic analyses consistently indicated the existence of three FD phytoplasma strain clusters. Strain cluster FD1 (comprising isolate FD70) displayed low variability and represented 17% of the disease cases in the French vineyard, with a higher incidence of the cases in southwestern France. Strain cluster FD2 (comprising isolates FD92 and FD-D) displayed no variability and was detected both in France (83% of the cases) and in Italy, whereas the more-variable strain cluster FD3 (comprising isolate FD-C) was detected only in Italy. The clonal property of FD2 and its wide distribution are consistent with diffusion through propagation of infected-plant material. German Palatinate grapevine yellows phytoplasmas (PGY) appeared variable and were often related to some of the alder phytoplasmas (AldY) detected in Italy and France. Finally, phylogenetic analyses concluded that FD, PGY, and AldY were members of the same phylogenetic subclade, which may have originated in Europe.

  2. Monitoring plant tissue nitrogen isotopes to assess nearshore inputs of nitrogen to Lake Crescent, Olympic National Park, Washington

    USGS Publications Warehouse

    Cox, Stephen E.; Moran, Patrick W.; Huffman, Raegan L.; Fradkin, Steven C.

    2016-05-31

    Mats of filamentous-periphytic algae present in some nearshore areas of Lake Crescent, Olympic National Park, Washington, may indicate early stages of eutrophication from nutrient enrichment of an otherwise highly oligotrophic lake. Natural abundance ratios of stable isotopes of nitrogen (δ15N) measured in plant tissue growing in nearshore areas of the lake indicate that the major source of nitrogen used by these primary producing plants is derived mainly from atmospherically fixed nitrogen in an undeveloped forested ecosystem. Exceptions to this pattern occurred in the Barnes Point area where elevated δ15N ratios indicate that effluent from septic systems also contribute nitrogen to filamentous-periphytic algae growing in the littoral zone of that area. Near the Lyre River outlet of Lake Crescent, the δ15N of filamentous-periphytic algae growing in close proximity to the spawning areas of a unique species of trout show little evidence of elevated δ15N indicating that nitrogen from on-site septic systems is not a substantial source of nitrogen for these plants. The δ15N data corroborate estimates that nitrogen input to Lake Crescent from septic sources is comparatively small relative to input from motor vehicle exhaust and vegetative sources in undeveloped forests, including litterfall, pollen, and symbiotic nitrogen fixation. The seasonal timing of blooms of filamentous-periphytic algal near the lake shoreline is also consistent with nitrogen exported from stands of red alder trees (Alnus rubra). Isotope biomonitoring of filamentous-periphytic algae may be an effective approach to monitoring the littoral zone for nutrient input to Lake Crescent from septic sources.

  3. Cascading effects of induced terrestrial plant defences on aquatic and terrestrial ecosystem function

    PubMed Central

    Jackrel, Sara L.; Wootton, J. Timothy

    2015-01-01

    Herbivores induce plants to undergo diverse processes that minimize costs to the plant, such as producing defences to deter herbivory or reallocating limited resources to inaccessible portions of the plant. Yet most plant tissue is consumed by decomposers, not herbivores, and these defensive processes aimed to deter herbivores may alter plant tissue even after detachment from the plant. All consumers value nutrients, but plants also require these nutrients for primary functions and defensive processes. We experimentally simulated herbivory with and without nutrient additions on red alder (Alnus rubra), which supplies the majority of leaf litter for many rivers in western North America. Simulated herbivory induced a defence response with cascading effects: terrestrial herbivores and aquatic decomposers fed less on leaves from stressed trees. This effect was context dependent: leaves from fertilized-only trees decomposed most rapidly while leaves from fertilized trees receiving the herbivory treatment decomposed least, suggesting plants funnelled a nutritionally valuable resource into enhanced defence. One component of the defence response was a decrease in leaf nitrogen leading to elevated carbon : nitrogen. Aquatic decomposers prefer leaves naturally low in C : N and this altered nutrient profile largely explains the lower rate of aquatic decomposition. Furthermore, terrestrial soil decomposers were unaffected by either treatment but did show a preference for local and nitrogen-rich leaves. Our study illustrates the ecological implications of terrestrial herbivory and these findings demonstrate that the effects of selection caused by terrestrial herbivory in one ecosystem can indirectly shape the structure of other ecosystems through ecological fluxes across boundaries. PMID:25788602

  4. Genetics Home Reference: familial pityriasis rubra pilaris

    MedlinePlus

    ... means redness; and "pilaris" suggests the involvement of hair follicles in this disorder. Affected individuals have a salmon- ... develop bumps called follicular keratoses that occur around hair follicles. The skin on the palms of the hands ...

  5. Density functional theory and atoms-in-molecule study on the role of two-electron stabilizing interactions in retro Diels-Alder reaction of cycloadducts derived from substituted cyclopentadiene and p-benzoquinone.

    PubMed

    Patil, Mahendra P; Sunoj, Raghavan B

    2006-11-07

    A systematic investigation on the cycloreversion reaction of the cycloadduct formed between substituted cyclopentadiene and p-benzoquinone (1-19) is reported at the B3LYP/6-311+G**//B3LYP/6-31G* level of theory. The computed activation barrier exhibits a fairly high sensitivity to the nature of substituents at the C7-position. Gibbs free energy of activation for 1 and 19 are found to be 20.3 and 30.1 kcal mol(-1), respectively, compared to 7, which is estimated to be 24.7 kcal mol(-1). Quantitative analysis of the electronic effects operating in both the cycloadduct as well as the corresponding transition state for the retro Diels-Alder (rDA) reaction performed using the natural bond orbital (NBO) and atoms in molecule (AIM) methods have identified important two-electron stabilizing interactions. Among four major delocalizations, sigma(C7-X) to sigma*(C1-C5) [and to sigma*(C2-C6)] is identified as the key contributing factor responsible for ground state C1-C5 bond elongation, which in turn is found to be crucial in promoting the rDA reaction. A good correlation between the population of antibonding orbital [sigma*(C1-C5)] of the ground state cycloadduct and Gibbs free energy of activation is observed. The importance of factors that modulate ground state structural features in controlling the energetics of rDA reaction is described.

  6. N-O chemistry for antibiotics: discovery of N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds as selective antibacterial agents using nitroso Diels-Alder and ene chemistry.

    PubMed

    Wencewicz, Timothy A; Yang, Baiyuan; Rudloff, James R; Oliver, Allen G; Miller, Marvin J

    2011-10-13

    The discovery, syntheses, and structure-activity relationships (SAR) of a new family of heterocyclic antibacterial compounds based on N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds are described. A structurally diverse library of ∼100 heterocyclic molecules generated from Lewis acid-mediated nucleophilic ring-opening reactions with nitroso Diels-Alder cycloadducts and nitroso ene reactions with substituted alkenes was evaluated in whole cell antibacterial assays. Compounds containing the N-alkyl-N-(pyridin-2-yl)hydroxylamine structure demonstrated selective and potent antibacterial activity against the Gram-positive bacterium Micrococcus luteus ATCC 10240 (MIC(90) = 2.0 μM or 0.41 μg/mL) and moderate activity against other Gram-positive strains including antibiotic resistant strains of Staphylococcus aureus (MRSA) and Enterococcus faecalis (VRE). A new synthetic route to the active core was developed using palladium-catalyzed Buchwald-Hartwig amination reactions of N-alkyl-O-(4-methoxybenzyl)hydroxylamines with 2-halo-pyridines that facilitated SAR studies and revealed the simplest active structural fragment. This work shows the value of using a combination of diversity-oriented synthesis (DOS) and parallel synthesis for identifying new antibacterial scaffolds.

  7. Intramolecular Diels-Alder Reaction of N-Alkyl-2-cyano-1-azadienes: A Study of the Eschenmoser Cycloreversion of Dihydrooxazines as a Route to N-Alkyl-2-cyano-1-azadienes.

    PubMed

    Motorina, Irina A.; Fowler, Frank W.; Grierson, David S.

    1997-04-04

    In connection with the development of the intramolecular Diels-Alder reaction (IMDA) of 1-azadienes, the 5,6-dihydro-4H-1,2-oxazine 12has been evaluated as a synthon equivalent of the 2-cyano-1-azadiene system. It was found that the dihydrooxazonium salt 27, generated in situ from the cyclic hydroxamic acid derivative 26, is converted directly to azadiene 4a via tautomerization to the corresponding enamine and a particularly facile Eschenmoser type cycloreversion process. Conditions were subsequently found for the preparation of synthon 12. N-Alkylation of this intermediate with alkyl bromides in the presence of Ag(+) ion also resulted in direct formation of the 2-cyano-1-azadiene products 38a-dand 4a. Microwave irradiation of a benzene solution of azadiene 4a proved to be a convenient means to effect its IMDA conversion to indolizidine 5a. To avoid decomposition of azadiene 38c, its intramolecular cycloaddition giving 40 (60%) was achieved by flash vacuum thermolysis.

  8. Lipase-catalyzed domino kinetic resolution/intramolecular Diels-Alder reaction: one-pot synthesis of optically active 7-oxabicyclo[2.2.1]heptenes from furfuryl alcohols and beta-substituted acrylic acids.

    PubMed

    Akai, Shuji; Naka, Tadaatsu; Omura, Sohei; Tanimoto, Kouichi; Imanishi, Masashi; Takebe, Yasushi; Matsugi, Masato; Kita, Yasuyuki

    2002-09-16

    The first lipase-catalyzed domino reaction is described in which the acyl moiety formed during the enzymatic kinetic resolution of furfuryl alcohols (+/-)-3 with a 1-ethoxyvinyl ester 2 was utilized as a part of the constituent structure for the subsequent Diels-Alder reaction. The preparation of ester 2 from carboxylic acid 1 and the subsequent domino reaction were carried out in a one-pot reaction. Therefore, this procedure provides a convenient preparation of the optically active 7-oxabicyclo[2.2.1]heptene derivatives 5, which has five chiral, non-racemic carbon centers, from achiral 1 and racemic 3. The overall efficiency of this process was dependent on the substituent at the C-3 position of 3, and the use of the 3-methylfurfuryl derivatives, (+/-)-3 b and (+/-)-3 f, exclusively produced diastereoselectivity with excellent enantioselectivity to give (2R)-syn-5 (91->/=99 % ee) and (S)-3 (96->/=99 % ee). Similar procedures starting from the 3-bromofurfuryl alcohols (+/-)-3 h-j provided the cycloadducts (2R)-syn-5 j-q (93->/=99 % ee), in which the bromo group was utilized for the installation of bulky substituents to the 7-oxabicycloheptene core.

  9. Linking Watershed Nitrogen Sources with Nitrogen Dynamics in Rivers of Western Oregon, USA

    NASA Astrophysics Data System (ADS)

    Sobota, D. J.; Compton, J.; Goodwin, K. E.

    2012-12-01

    We constructed contemporary nitrogen (N) budgets for 25 river basins in the Willamette River Basin (WRB) of western Oregon, USA, to improve the understanding of how recent trends in human-driven N loading have influenced riverine N dynamics in the region. Nearly 20% of WRB stream length is currently in fair or poor condition because of high N concentrations. Additionally, nitrate contamination of drinking water affects at least 8,000 people in the WRB. We hypothesized that 1) the majority of N inputs in the WRB would originate from agricultural activities in lowland portions of watersheds, 2) annual riverine N yield (kg/ha/yr) would correspond to annual per area watershed N inputs, and 3) riverine N yields would be seasonal and highest during winter due to the region's Mediterranean climate. We calculated average annual N inputs for each study basin by summing newly available datasets describing spatially explicit N inputs of synthetic fertilizer, atmospheric deposition, crop biological N2 fixation, biological N2 fixation by red alder (Alnus rubra Bong.), livestock manure, and point sources for the period 1996 - 2007. Annual and seasonal riverine N exports were estimated with the USGS model LOADEST calibrated to N concentration data collected during the study period. We estimated that two-thirds of total N input to the WRB study basins in the 2000s came from synthetic fertilizer application. Nearly all fertilizer application occurred on the lowlands near watershed mouths. We found a wide range of riverine N yields from the study basins, ranging from one to 70 kg N/ha/yr. Across the study basins, N export was more strongly correlated to fertilizer application rates than to percent of agricultural area in the watershed. Low watershed N yields reflected a high proportion of watershed area in the forested Cascade Mountain Range, which received low N inputs mainly from atmospheric deposition. N yields from study basins were strongly seasonal, with at least 50%, and

  10. Effects of invasive European bird cherry (Prunus padus) on leaf litter processing by aquatic invertebrate shredder communities in urban Alaskan streams

    USGS Publications Warehouse

    Roon, David A.; Wipfli, Mark S.; Wurtz, Tricia L.

    2014-01-01

    European bird cherry (Prunus padus) (EBC) is an invasive ornamental tree that is spreading rapidly in riparian forests of urban Alaska. To determine how the spread of EBC affects leaf litter processing by aquatic invertebrate shredders, we conducted complementary leaf pack experiments in two streams located in Anchorage, Alaska. The first experiment contrasted invasive EBC with three native tree species—thin-leaf alder (Alnus tenuifolia), paper birch (Betula neoalaskana), and black cottonwood (Populus trichocarpa)—in one reach of Chester Creek; finding that EBC leaf litter broke down significantly faster than birch and cottonwood, but at a similar rate to alder. The second experiment contrasted EBC with alder in four reaches of Campbell and Chester creeks; finding that while EBC leaf litter broke down significantly faster than alder in Chester Creek, EBC broke down at a similar rate to alder in Campbell Creek. Although EBC sometimes supported fewer shredders by both count and mass, shredder communities did not differ significantly between EBC and native plants. Collectively, these data suggest that invasive EBC is not currently exhibiting strong negative impacts on leaf litter processing in these streams, but could if it continues to spread and further displaces native species over time.

  11. Comparative Study of the Volatile Components of Fresh and Fermented Flowers of Alnus sieboldiana (Betulaceae).

    PubMed

    Ab Ghani, Nurunajah; Ismail, Nor Hadiani; Asakawa, Yoshinori

    2016-02-01

    Analysis of the volatile components present in the fresh male and female flowers and young leaves shows that 2-phenylethanol is the major component in all these three organs, which play a significant role in the strong resinous aromatic odor. The male flowers contained styrene as a second major compound. The level of styrene does not affect the male flowers odor concentration. The level of β-phenylethyl cinnamate and trans-methyl cinnamate in the fermented male flowers decreased as the fermentation time increased. This was due to the Penicillium enzymatic action on the fermented male flowers.

  12. Do Invertebrate Activity and Current Velocity Affect Fungal Assemblage Structure in Leaves?

    NASA Astrophysics Data System (ADS)

    Ferreira, Verónica; Graça, Manuel A. S.

    2006-02-01

    In this study we assessed the effect of current velocity and shredder presence, manipulated in artificial channels, on the structure of the fungal assemblage colonizing alder (Alnus glutinosa (L.) Gaertner) leaves incubated in coarse and fine mesh bags. Fungal sporulation rates, cumulative conidial production and number of species of aquatic hyphomycetes were higher in leaves exposed to high rather than to low current velocity. The opposite was observed regarding Simpson's index (D) on the fungal assemblage. Some species of aquatic hyphomycetes were consistently stimulated in high current channels. No effect of shredders or of mesh type was observed.

  13. The exohedral Diels-Alder reactivity of the titanium carbide endohedral metallofullerene Ti2C2@D(3h)-C78: comparison with D(3h)-C78 and M3N@D(3h)-C78 (M=Sc and Y) reactivity.

    PubMed

    Garcia-Borràs, Marc; Osuna, Sílvia; Luis, Josep M; Swart, Marcel; Solà, Miquel

    2012-06-04

    The chemical functionalization of endohedral (metallo)fullerenes has become a main focus of research in the last few years. It has been found that the reactivity of endohedral (metallo)fullerenes may be quite different from that of the empty fullerenes. Encapsulated species have an enormous influence on the thermodynamics, kinetics, and regiochemistry of the exohedral addition reactions undergone by these species. A detailed understanding of the changes in chemical reactivity due to incarceration of atoms or clusters of atoms is essential to assist the synthesis of new functionalized endohedral fullerenes with specific properties. Herein, we report the study of the Diels-Alder cycloaddition between 1,3-butadiene and all nonequivalent bonds of the Ti(2)C(2)@D(3h)-C(78) metallic carbide endohedral metallofullerene (EMF) at the BP86/TZP//BP86/DZP level of theory. The results obtained are compared with those found by some of us at the same level of theory for the D(3h)-C(78) free cage and the M(3)N@D(3h)-C(78) (M=Sc and Y) metallic nitride EMFs. It is found that the free cage is more reactive than the Ti(2)C(2)@D(3h)-C(78) EMF and this, in turn, has a higher reactivity than M(3)N@D(3h)-C(78). The results indicate that, for Ti(2)C(2)@D(3h)-C(78), the corannulene-type [5,6] bonds c and f, and the type B [6,6] bond 3 are those thermodynamically and kinetically preferred. In contrast, the D(3h)-C(78) free cage has a preference for addition to the [6,6] 1 and 6 bonds and the [5,6] b bond, whereas M(3)N@D(3h)-C(78) favors additions to the [6,6] 6 (M=Sc) and [5,6] d (M=Y) bonds. The reasons for the regioselectivity found in Ti(2)C(2)@D(3h)-C(78) are discussed.

  14. Geographic variation in red alder. Forest Service research paper

    SciTech Connect

    Lester, D.T.; DeBell, D.S.

    1989-04-01

    A test of 10 provenances was established in 1969 on the central coast of Oregon. The provenances tested included Juneau, Alaska, and Sandpoint, Idaho, in addition to eight well-spaced locations in Oregon, Washington, and in the southern end of Vancouver island, British Columbia. Periodic measurements through 15 years of plantation development revealed differences among provenances in height, diameter, and height/diameter ratio. The calculated variables, bole volume and aboveground biomass, showed large differences among provenances. Two provenances from northwestern Washington consistently were the most vigorous, two (Juneau, Alaska, and Sandpoint, Idaho) were the least vigorous, and the remaining six provenances shifted somewhat in ranking over time.

  15. Presumed consent for transplantation: a dead issue after Alder Hey?

    PubMed Central

    English, V; Sommerville, A

    2003-01-01

    In the wake of scandals about the unauthorised retention of organs following postmortem examination, the issue of valid consent (or the lack of it) has returned to the forefront. Emphasis is put on obtaining explicit authorisation from the patient or family prior to any medical intervention, including those involving the dead. Although the controversies in the UK arose from the retention of human material for education or research rather than therapy, concern has been expressed that public mistrust could also adversely affect organ donation for transplantation. At the same time, however, the British Medical Association (BMA) continues to call for a shift to a system of presumed consent for organ transplantation. This apparent inconsistency can be justified because valid distinctions exist between the reasons requiring explicit consent for retention and the acceptability of presumed consent for transplantation. This paper argues for introducing a system of presumed consent for organ donation, given the overwhelming expressions of public support for transplantation. Ongoing legislative review in the UK provides an ideal chance to alter the default position to one where potential donors can simply acquiesce or opt out of donation. Combined with consultation with their relatives, this could be a much better method of realising individuals' wishes. It would also achieve a better balance between the duties owed to the deceased and those owed to people awaiting a transplant. PMID:12796433

  16. Crystal structures and conformations of two Diels-Alder adduct derivatives: 1,8-bis-(thio-phen-2-yl)-14-oxa-tetra-cyclo-[6.5.1.0(2,7).0(9,13)]tetra-deca-2(7),3,5-trien-10-one and 1,8-diphenyl-14-oxa-tetra-cyclo[6.5.1.0(2,7).0(9,13)] tetra-deca-2,4,6-trien-10-one.

    PubMed

    Gopinath, S; Narayanan, P; Sethusankar, K; Nandakumar, Meganathan; Mohanakrishnan, Arasambattu K

    2015-02-01

    The title compounds, C21H16O2S2 (I) and C25H20O2 (II), are products of a tandem 'pincer' Diels-Alder reaction consisting of [2 + 2] cyclo-additions between benzo[c]furan and cyclo-penta-none. Each comprises a fused tetra-cyclic ring system containing two five-membered rings (in envelope conformations with the O atom as the flap) and six-membered rings (in boat conformations). In addition, two thio-phene rings in (I) and two phenyl rings in (II) are attached to the tetra-cyclic ring system. The cyclo-penta-none ring adopts a twisted conformation in (I) and an envelope conformation in (II). In (I), the thio-phene rings are positionally disordered over two sets of sites, with occupancy ratios of 0.901 (2):0.099 (2) and 0.666 (2):0.334 (2). In (II), the oxygen atom of the cyclo-penta-none ring is rotationally disordered over two sites with an occupancy ratio of 0.579 (4):0.421 (4). The mol-ecular structure of (I) is stabilized by an intra-molecular C-H⋯O hydrogen bond, which generates an S(7) ring motif. In the crystal, the mol-ecules are linked via weak C-H⋯O hydrogen bonds, which generate R (2) 2(16) ring motifs in (I) and C(8) chains in (II). In both structures, the crystal packing also features C-H⋯π inter-actions. The crystal studied of compound (I) was twinned by non-merohedry. The twin component is related by the twin law [-1 0 0 -0.101 1 -0.484 0 0 -1] operated by a twofold rotation axis parallel to the b axis. The structure of (I) was refined with a twin scale factor of 0.275 (2).

  17. Postglacial vegetation history of Mitkof Island, Alexander Archipelago, southeastern Alaska

    USGS Publications Warehouse

    Ager, T.A.; Carrara, P.E.; Smith, Jody L.; Anne, V.; Johnson, J.

    2010-01-01

    An AMS radiocarbon-dated pollen record from a peat deposit on Mitkof Island, southeastern Alaska provides a vegetation history spanning ???12,900??cal yr BP to the present. Late Wisconsin glaciers covered the entire island; deglaciation occurred > 15,400??cal yr BP. The earliest known vegetation to develop on the island (???12,900??cal yr BP) was pine woodland (Pinus contorta) with alder (Alnus), sedges (Cyperaceae) and ferns (Polypodiaceae type). By ???12,240??cal yr BP, Sitka spruce (Picea sitchensis) began to colonize the island while pine woodland declined. By ???11,200??cal yr BP, mountain hemlock (Tsuga mertensiana) began to spread across the island. Sitka spruce-mountain hemlock forests dominated the lowland landscapes of the island until ???10,180??cal yr BP, when western hemlock (Tsuga heterophylla) began to colonize, and soon became the dominant tree species. Rising percentages of pine, sedge, and sphagnum after ???7100??cal yr BP may reflect an expansion of peat bog habitats as regional climate began to shift to cooler, wetter conditions. A decline in alders at that time suggests that coastal forests had spread into the island's uplands, replacing large areas of alder thickets. Cedars (Chamaecyparis nootkatensis, Thuja plicata) appeared on Mitkof Island during the late Holocene.

  18. Postglacial vegetation history of Mitkof Island, Alexander Archipelago, southeastern Alaska

    NASA Astrophysics Data System (ADS)

    Ager, Thomas A.; Carrara, Paul E.; Smith, Jane L.; Anne, Victoria; Johnson, Joni

    2010-03-01

    An AMS radiocarbon-dated pollen record from a peat deposit on Mitkof Island, southeastern Alaska provides a vegetation history spanning ˜12,900 cal yr BP to the present. Late Wisconsin glaciers covered the entire island; deglaciation occurred > 15,400 cal yr BP. The earliest known vegetation to develop on the island (˜12,900 cal yr BP) was pine woodland ( Pinus contorta) with alder ( Alnus), sedges (Cyperaceae) and ferns (Polypodiaceae type). By ˜12,240 cal yr BP, Sitka spruce ( Picea sitchensis) began to colonize the island while pine woodland declined. By ˜11,200 cal yr BP, mountain hemlock ( Tsuga mertensiana) began to spread across the island. Sitka spruce-mountain hemlock forests dominated the lowland landscapes of the island until ˜10,180 cal yr BP, when western hemlock ( Tsuga heterophylla) began to colonize, and soon became the dominant tree species. Rising percentages of pine, sedge, and sphagnum after ˜7100 cal yr BP may reflect an expansion of peat bog habitats as regional climate began to shift to cooler, wetter conditions. A decline in alders at that time suggests that coastal forests had spread into the island's uplands, replacing large areas of alder thickets. Cedars ( Chamaecyparis nootkatensis, Thuja plicata) appeared on Mitkof Island during the late Holocene.

  19. Phenology, dichogamy, and floral synchronization in a northern red oak (Quercus Rubra L.) seed orchard

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We developed a novel scoring system to assess spring phenology in a northern red oak clonal seed orchard. The system was used to score between 304 and 364 ramets for three reproductive seasons and place clones into early, middle, and late phenology groups. While the absolute number of clones in ea...

  20. Festuca rubra evaluation for potential use in green stripping for wildfire control

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Much of western U.S. land is experiencing increased drought, higher temperatures, and increased soil salinity levels, which lead to rangeland degradation. These factors contribute to encroachment of weedy species into previously productive range and agricultural lands, which dramatically increases ...

  1. Analysing branching pattern in plantations of young red oak trees (Quercus rubra L., Fagaceae).

    PubMed

    Heuret, Patrick; Guédon, Yann; Guérard, Natacha; Barthélémy, Daniel

    2003-03-01

    Branching patterns of the growth units of monocyclic or bicyclic annual shoots on the main axis of 5-year-old red oaks were studied in a plantation in south-western France. For each growth unit, the production of axillary structures associated with each node was described in the form of a sequence. For a given category of growth units, homogeneous zones (i.e. zones in which composition in terms of type of axillary production does not change substantially) were identified on such sequences using a dedicated statistical model called a hidden semi-Markov chain. For instance, on the first growth unit of bicyclic annual shoots, a zone with 1-year-delayed branches was found systematically below a zone with buds and one-cycle-delayed branches. Branching patterns shown by the growth unit of monocyclic annual shoots and on the second growth unit of bicyclic annual shoots were very similar. Branches with a 1-year delay in development tended to be polycyclic at the top of the growth unit and monocyclic lower down. The number of nodes shown by the branched zone of the growth unit of monocyclic annual shoots was stable, irrespective of the total number of nodes of the growth unit. In contrast, the second growth unit of bicyclic annual shoots exhibited a correlation between the number of nodes in the branching zone and the total number of nodes. The contribution made by this method to understanding plant functioning is discussed.

  2. Analysing Branching Pattern in Plantations of Young Red Oak Trees (Quercus rubra L., Fagaceae)

    PubMed Central

    HEURET, PATRICK; GUÉDON, YANN; GUÉRARD, NATACHA; BARTHÉLÉMY, DANIEL

    2003-01-01

    Branching patterns of the growth units of monocyclic or bicyclic annual shoots on the main axis of 5‐year‐old red oaks were studied in a plantation in south‐western France. For each growth unit, the production of axillary structures associated with each node was described in the form of a sequence. For a given category of growth units, homogeneous zones (i.e. zones in which composition in terms of type of axillary production does not change substantially) were identified on such sequences using a dedicated statistical model called a hidden semi‐Markov chain. For instance, on the first growth unit of bicyclic annual shoots, a zone with 1‐year‐delayed branches was found systematically below a zone with buds and one‐cycle‐delayed branches. Branching patterns shown by the growth unit of monocyclic annual shoots and on the second growth unit of bicyclic annual shoots were very similar. Branches with a 1‐year delay in development tended to be polycyclic at the top of the growth unit and monocyclic lower down. The number of nodes shown by the branched zone of the growth unit of monocyclic annual shoots was stable, irrespective of the total number of nodes of the growth unit. In contrast, the second growth unit of bicyclic annual shoots exhibited a correlation between the number of nodes in the branching zone and the total number of nodes. The contribution made by this method to understanding plant functioning is discussed. PMID:12588728

  3. A 14,000 year vegetation history of a hypermaritime island on the outer Pacific coast of Canada based on fossil pollen, spores and conifer stomata

    NASA Astrophysics Data System (ADS)

    Lacourse, Terri; Delepine, J. Michelle; Hoffman, Elizabeth H.; Mathewes, Rolf W.

    2012-11-01

    Pollen and conifer stomata analyses of lake sediments from Hippa Island on the north coast of British Columbia were used to reconstruct the vegetation history of this small hypermaritime island. Between 14,000 and 13,230 cal yr BP, the island supported diverse herb-shrub communities dominated by Cyperaceae, Artemisia and Salix. Pinus contorta and Picea sitchensis stomata indicate that these conifers were present among the herb-shrub communities, likely as scattered individuals. Transition to open P. contorta woodland by 13,000 cal yr BP was followed by increases in Alnus viridis, Alnus rubra and P. sitchensis. After 12,000 cal yr BP, Pinus-dominated communities were replaced by dense P. sitchensis and Tsuga heterophylla forest with Lysichiton americanus and fern understory. Thuja plicata stomata indicate that this species was present by 8700 cal yr BP, but the pollen record suggests that its populations did not expand to dominate regional rainforests, along with Tsuga and Picea, until after 6600 cal yr BP. Conifer stomata indicate that species may be locally present for hundreds to thousands of years before pollen exceed thresholds routinely used to infer local species arrival. When combined, pollen and conifer stomata can provide a more accurate record of paleovegetation than either when used alone.

  4. Postglacial vegetation history of Orcas Island, northwestern Washington

    NASA Astrophysics Data System (ADS)

    Leopold, Estella B.; Dunwiddie, Peter W.; Whitlock, Cathy; Nickmann, Rudy; Watts, William A.

    2016-05-01

    The revegetation of islands following retreat of Pleistocene glaciers is of great biogeographical interest. The San Juan Islands, Washington, feature regionally distinctive xerophytic plant communities, yet their vegetation history, as it relates to past climate and sea level, is poorly known. We describe a 13,700-year-old pollen record from Killebrew Lake Fen and compare the vegetation reconstruction with others from the region. The data suggest that the narrow channels surrounding Orcas Island were not a barrier to early postglacial immigration of plants. Between 13,700 and 12,000 cal yr BP, Pinus, Tsuga, Picea, Alnus viridis, and possibly Juniperus maritima were present in a mosaic that supported Bison antiquus and Megalonyx. The rise of Alnus rubra-type pollen and Pteridium spores at ca. 12,000 cal yr BP suggests a warming trend and probably more fires. Temperate conifer taxa, including Cupressaceae, Pseudotsuga, Tsuga heterophylla, and Abies, increased after 11,000 cal yr BP and especially in the last 7000 cal yr BP. After 6000 cal yr BP, Pseudotsuga and Cupressaceae dominated the vegetation. The last 1500 yr were the wettest period of the record. Due to its rain shadow location, Orcas Island experienced drier conditions than on the mainland during most of the postglacial period.

  5. Movements and wetland selection by brood-rearing black ducks

    USGS Publications Warehouse

    Ringelman, J.K.; Longcore, J.R.

    1982-01-01

    Movements and wetland selection by brood-rearing black ducks (Anas rubripes) were studied in Maine during 1977-80. Eight radio-marked hens moved their broods an average of 1.2 km from the nest to rearing pond, but only 1 hen initiated secondary brood movements. Half of the 85 broods reared in the study area used only 3 wetlands, and most rearing ponds contained active beaver (Castor canadensis) colonies. Brood-rearing hens preferred Emergent ponds over lakes and Evergreen Scrub-Shrub wetlands, and did not occupy Dead Scrub-Shrub, Unconsolidated Bottom, or Aquatic Bed wetlands. Rearing ponds were large and possessed extensive areas of flooded mountain alder (Alnus incana), willow (Salix spp.), and herbaceous vegetation. Wetlands avoided by brood-rearing hens were those with large areas of open water, submergent aquatics, or ericaceous shrub vegetation.

  6. A 20th century calendar of snow avalanche activity within the Bødalen valley, inner Nordfjord, western Norway

    NASA Astrophysics Data System (ADS)

    Decaulne, A.; Eggertsson, O.; Laute, K.; Beylich, A. A.

    2012-04-01

    The forest-covered valley floor of the Bødalen valley located in the inner Nordfjord, western Norway offers the great opportunity for snow-avalanche reconstruction using tree rings. By sampling at different points within the forest stand, both on birch (Betula pubescens) and alder (Alnus), we are able to extract the magnitude and return period of major snow-avalanche events in the valley. The years of 1967, 1974, 1985, 1994 and 2001 appear like very avalanche-rich, and the years of 1992 and 2007 appear as extreme, with snow-avalanche signals being recorded at the majority of the trees. Although the investigated valley is quite remote during the winter time, the gained knowledge of the recent snow-avalanche history provides a picture of the potential activity that can be expected also elsewhere in the Nordfjord region, and escpecially in the inhabited areas as well as along important transportation corridors that do not have such records available.

  7. Comparison of planted soil infiltration systems for treatment of log yard runoff.

    PubMed

    Hedmark, Asa; Scholz, Miklas; Aronsson, Par; Elowson, Torbjorn

    2010-07-01

    Treatment of log yard runoff is required to avoid contamination of receiving watercourses. The research aim was to assess if infiltration of log yard runoff through planted soil systems is successful and if different plant species affect the treatment performance at a field-scale experimental site in Sweden (2005 to 2007). Contaminated runoff from the log yard of a sawmill was infiltrated through soil planted with Alnus glutinosa (L.) Gärtner (common alder), Salix schwerinii X viminalis (willow variety "Gudrun"), Lolium perenne (L.) (rye grass), and Phalaris arundinacea (L.) (reed canary grass). The study concluded that there were no treatment differences when comparing the four different plants with each other, and there also were no differences between the tree and the grass species. Furthermore, the infiltration treatment was effective in reducing total organic carbon (55%) and total phosphorus (45%) concentrations in the runoff, even when the loads on the infiltration system increased from year to year.

  8. Tree-mediated methane emissions from tropical and temperate peatlands.

    NASA Astrophysics Data System (ADS)

    Pangala, S. R.; Gauci, V.; Hornibrook, E. R. C.; Gowing, D. J.

    2012-04-01

    Methane production and transport processes in peatlands are fairly well understood, but growing evidence for emission of methane through trees has highlighted the need to revisit methane transport processes. In wetland trees, morphological adaptations such as development of hypertrophied lenticels, aerenchyma and adventitious roots in response to soil anoxia mediates gas transport, transporting both oxygen from the atmosphere to oxygen-deprived roots and soil-produced methane from the root-zone to the atmosphere. Although, tree-mediated methane emissions from temperate tree species have been confirmed, methane emissions from tropical tree species and processes that control tree-mediated methane emissions remain unclear. This study explains the role of trees in transporting soil-produced methane to the atmosphere and uncovers the principal mechanisms of tree-mediated methane emissions. Methane emissions from eight tropical tree species and two temperate tree species were studied in situ. The mechanisms and controls on tree-mediated methane emissions were investigated using three year old common alder (Alnus glutinosa; 50 trees) grown under two artificially controlled water-table positions. Methane fluxes from whole mesocosms, the soil surface and tree stems were measured using static closed chambers. Both temperate and tropical tree species released significant quantities of methane, with tropical trees dominating ecosystem level methane fluxes. In temperate peatlands, both the methane gas transport mechanism and quantity of methane emitted from stems is tree-species dependent. In Alnus glutinosa, no correlations were observed between stomatal behaviour and tree-mediated methane emissions, however, stem methane emissions were positively correlated with both stem lenticel density and dissolved soil methane concentration. In Alnus glutinosa, no emissions were observed from leaf surfaces. The results demonstrate that exclusion of tree-mediated methane emissions from

  9. ADVANCED INTRAMOLECULAR DIELS-ALDER STUDY TOWARD THE SYNTHESIS OF (-)-MORPHINE: STRUCTURE CORRECTION OF A PREVIOUSLY REPORTED DIELS-ALDER PRODUCT. (R826113)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  10. Grazing preference and utilization of soil fungi by Folsomia candida (Collembola)

    NASA Astrophysics Data System (ADS)

    Hedenec, Petr; Frouz, Jan

    2016-04-01

    Soil fungi are important food resources for soil fauna. Here we ask whether the collembolan Folsomia candida shows selectivity in grazing between four saprophytic fungi (Penicillium chrysogenum, Penicillium expansum, Absidia glauca, and Cladosporium herbarum), whether grazing preference corresponds to effects on collembolan reproduction, and whether the effects of fungi on grazing and reproduction depends on the fungal substrate, which included three kinds of litter (Alnus glutinosa, Salix caprea, and Quercus robur) and one kind of agar (yeast extract). On agar, Cladosporium herbarum and Absidia glauca were the most preferred fungi and supported the highest collembolan reproduction. On fungal-colonized litter, grazing preference was more affected by litter type than by fungal species whereas collembolan reproduction was affected by both litter type and fungal species. On fungal-colonized litter, the litter type that was most preferred for grazing did not support the highest reproduction, i.e., there was an inconsistency between food preference and suitability. Alder and willow were preferred over oak for grazing, but alder supported the least reproduction.

  11. Stream and floodplain restoration in a riparian ecosystem disturbed by placer mining

    USGS Publications Warehouse

    Karle, Kenneth F.; Densmore, Roseann V.

    1994-01-01

    Techniques for the hydrologic restoration of placer-mined streams and floodplains were developed in Denali National Park and Preserve Alaska, USA. The hydrologic study focused on a design of stream and floodplain geometry using hydraulic capacity and shear stress equations. Slope and sinuosity values were based on regional relationships. Design requirements include a channel capacity for a 1.5-year (bankfull) discharge and a floodplain capacity for a 1.5- to 100-year discharge. Concern for potential damage to the project from annual flooding before natural revegetation occurs led to development of alder (Alnus crispa) brush bars to dissipate floodwater energy and encourage sediment deposition. The brush bars, constructed of alder bundles tied together and anchored laterally adjacent to the channel, were installed on the floodplain in several configurations to test their effectiveness. A moderate flood near the end of the two-year construction phase of the project provided data on channel design, stability, floodplain erosion, and brush bar effectiveness. The brush bars provided substantial protection, but unconsolidated bank material and a lack of bed armour for a new channel segment led to some bank erosion, slope changes and an increase in sinuosity in several reaches of the study area.

  12. Stable Isotope Probing of Peat and Forest Floor Amendments

    NASA Astrophysics Data System (ADS)

    Quideau, Sylvie; Béasse, Mark

    2013-04-01

    In Alberta, Canada, land reclamation efforts utilize peat as an organic amendment to help reclaim decommissioned oil sands mine sites to upland boreal forests. This study investigates the rhizosphere microbial communities of two pioneer species, aspen (Populus tremuloides Michx.), a species not known for strong associations with the soil microbial community, and alder (Alnus crispa Ait.), a species well known for mutualism with actinomycetes. Specifically, the objective was to determine how different organic amendments (peat versus forest floor) influenced the rhizosphere microbial communities and how this could be linked to plant growth. Seedlings were grown for 20 weeks in forest floor material, peat, and a combination of both. They were pulse labelled with 13CO2 (g) and subsequently harvested for plant growth measurements. While analysis of plant growth attributes did not indicate any effect of the organic amendment on aspen growth, alder reported significantly less growth in peat treatments. The rhizosphere soils were extracted for compound-specific analysis of δ13C in microbial phospholipid fatty acids. Stable isotope probing showed greater carbon flow between trees and their rhizosphere communities when seedlings were grown in forest floor material.

  13. Experimental woodcock management at the Moosehorn National Wildlife Refuge

    USGS Publications Warehouse

    Sepik, G.F.; Owen, R.B.; Coulter, M.W.; Keppie, Daniel M.; Owen, Ray B.

    1977-01-01

    The purpose of this study is to develop woodcock(Philohela minor) management techniques that can be easily used by the small landowner or incorporated with other land management operations such as commercial timber harvesting. The Moosehorn National Wildlife Refuge contains areas which are characteristic of the abandoned farms now being purchased for recreation or retirement as well as areas suitable for commercial forest management. Woodcock management, beginning in 1973, has centered on rejuvenation of diurnal habitat and creation of summer fields and singing grounds. Strips (10 mwide, 25 to 125 mlong and separated by 40 m) were clear~cut in two alder (Alnus sp.) stands resulting in increased diurnal use in at least one cover, increased singing male use and good alder regeneration. Small clear-cuts (30 X30 m) in a large contiguous woodland (1200 ha) with a history of few singing males resulted in an increased number of singing males despite an overall decrease in the number of singing males throughout the refuge. Management strategies and recommendations also are given.

  14. Biotic and abiotic variables influencing plant litter breakdown in streams: a global study.

    PubMed

    Boyero, Luz; Pearson, Richard G; Hui, Cang; Gessner, Mark O; Pérez, Javier; Alexandrou, Markos A; Graça, Manuel A S; Cardinale, Bradley J; Albariño, Ricardo J; Arunachalam, Muthukumarasamy; Barmuta, Leon A; Boulton, Andrew J; Bruder, Andreas; Callisto, Marcos; Chauvet, Eric; Death, Russell G; Dudgeon, David; Encalada, Andrea C; Ferreira, Verónica; Figueroa, Ricardo; Flecker, Alexander S; Gonçalves, José F; Helson, Julie; Iwata, Tomoya; Jinggut, Tajang; Mathooko, Jude; Mathuriau, Catherine; M'Erimba, Charles; Moretti, Marcelo S; Pringle, Catherine M; Ramírez, Alonso; Ratnarajah, Lavenia; Rincon, José; Yule, Catherine M

    2016-04-27

    Plant litter breakdown is a key ecological process in terrestrial and freshwater ecosystems. Streams and rivers, in particular, contribute substantially to global carbon fluxes. However, there is little information available on the relative roles of different drivers of plant litter breakdown in fresh waters, particularly at large scales. We present a global-scale study of litter breakdown in streams to compare the roles of biotic, climatic and other environmental factors on breakdown rates. We conducted an experiment in 24 streams encompassing latitudes from 47.8° N to 42.8° S, using litter mixtures of local species differing in quality and phylogenetic diversity (PD), and alder (Alnus glutinosa) to control for variation in litter traits. Our models revealed that breakdown of alder was driven by climate, with some influence of pH, whereas variation in breakdown of litter mixtures was explained mainly by litter quality and PD. Effects of litter quality and PD and stream pH were more positive at higher temperatures, indicating that different mechanisms may operate at different latitudes. These results reflect global variability caused by multiple factors, but unexplained variance points to the need for expanded global-scale comparisons.

  15. Methane Emission through Trees in Temperate and Tropical Wetlands

    NASA Astrophysics Data System (ADS)

    Pangala, S. R.; Gauci, V.; Hornibrook, E. R.; Gowing, D.

    2012-12-01

    Methane produced in wetland soil generally is thought to be emitted by a combination of three key processes: 1) diffusion through water-filled pores, 2) abrupt release of bubbles (ebullition), and 3) via internal spaces within the stems of herbaceous plants adapted to live in waterlogged soils. The capacity for trees to mediate methane emissions has received limited attention despite mesocosm studies of seedlings and saplings demonstrating that wetland trees have a significant capacity to transport soil-produced methane to the atmosphere. Notably ~60% of global wetlands are forested. We present in situ measurements of methane flux from a temperate carr (swamp) composed of alder (Alnus glutinosa) and birch (Betula pubescens) situated in the United Kingdom and a tropical forested peat swamp located in Borneo. The in situ data are complemented by a mesocosm experiment in which methane emissions were measured from alder saplings subjected to two water-regime treatments. In both the in situ and mesocosm studies, emissions from trees are compared to methane flux from the ground surface, the latter occurring via pore water diffusion, ebullition or via the aerenchyma of herbaceous plants. We show that tree stem emissions are controlled by a number of factors including tree species, soil pore-water concentration and stem lenticel density. Our results demonstrate that the omission of tree-mediated methane fluxes from measurement campaigns conducted in forested wetland can significantly underestimate the total ecosystem flux of methane.

  16. Trees are important conduits for emission of methane from temperate and tropical wetlands

    NASA Astrophysics Data System (ADS)

    Gauci, Vincent; Pangala, Sunitha; Gowing, David; Hornibrook, Edward

    2013-04-01

    Methane produced in wetland soil generally is thought to be emitted to the atmosphere primarily via diffusion through pore water, release of gas bubbles (i.e., ebullition), and gas phase diffusion through the aerenchyma of herbaceous plants. The role of trees as a conduit for methane export from soil to the atmosphere has received limited attention despite evidence from mesocosm experiments showing that seedlings and saplings of wetland trees have a significant capacity to transport soil-produced gases. Notably ~60% of global wetlands are forested. We present in situ measurements of methane flux from a temperate carr (swamp) composed of alder (Alnus glutinosa) and birch (Betula pubescens) situated in the United Kingdom and a tropical forested peat swamp located in Borneo. The in situ data are complemented by a mesocosm experiment in which methane emissions were measured from alder saplings subjected to two water-regime treatments. In both the in situ and mesocosm studies, emissions from trees are compared to methane flux from the ground surface, the latter occurring via pore water diffusion, ebullition or the aerenchyma of herbaceous plants. We show that tree stem emissions are controlled by a number of factors including tree species, soil pore-water concentration and stem lenticel density. Our results demonstrate that the omission of tree-mediated methane fluxes from measurement campaigns conducted in forested wetland can significantly underestimate total ecosystem flux of methane.

  17. Distinct temperature sensitivity among taiga and tundra shrubs in Alaska

    NASA Astrophysics Data System (ADS)

    Andreu-Hayles, L.; Anchukaitis, K. J.; D'Arrigo, R.

    2014-12-01

    Shrub expansion into Arctic and alpine tundra ecosystems is well documented, mostly over the last 50 years, based on remote sensing data, aerial photography, and in-situ observations. Warming temperatures are considered the main driver of the observed change in shrub vegetation patterns. Here, we assess the relationship between temperatures and shrub growth from five populations of Salix spp. (willow) and Alnus spp. (alder) in Alaska growing within the tundra and the boreal forest (~taiga) using dendrochronological techniques. The three tundra shrub sites are located on the Dalton Highway north from Toolik Lake (~69ºN 148ºW), whereas the two taiga shrub sites are located closer to Fairbanks at the Twelve Mile Summit site (~65ºN 146ºW). Because shrub ages vary among the studied populations lead to different time spans for the ring-width chronologies generated, a common period with available satellite data spanning from 1982 to 2010 was selected for this study. All tundra shrub chronologies shared a strong positive response to summer temperatures despite growing in heterogeneous site conditions and belonging to different species. In contrast, in the taiga, summer temperatures enhance willow growth, whereas alder growth appears almost insensitive to temperature over the interval studied. Extending the analyses back in time, a very strong positive relationship was found between alder ring-width and June temperatures prior to 1970. This phenomenon, a weakening of the previously existing relationship between growth and temperatures, was also detected in white spruce (Picea glauca) growing at the same site, and it is known in the literature as the 'divergence problem'. Thus, at this taiga location, alder shrubs and trees seem to have similar growth patterns. Summer temperatures no longer seem to enhance taiga alder growth. Shrubs of different species exposed to the same climatic conditions can exhibit varied growth responses. The distinct temperature sensitivities

  18. Effects of low-dosed imidacloprid pulses on the functional role of the caged amphipod Gammarus roeseli in stream mesocosms.

    PubMed

    Böttger, R; Feibicke, M; Schaller, J; Dudel, G

    2013-07-01

    Effects of two series of imidacloprid pulses on caged amphipods (Gammarus roeseli) and their shredder efficiency for litter decomposition were studied for 70 days as part of a comprehensive stream mesocosm experiment. The duration of each imidacloprid pulse of 12µgL(-1) was 12h. About 250mL cages with an initial stock of 10 adult gammarids together with different conditioned litter substrates were used. Beside alder leaves (Alnus glutinosa), straw (× Triticosecale) was also used in different trials and tested for its suitability to serve as litter substrate. Results from tracer and microprobe measurements approved the suitability of the test system under low-flow condition of 10cms(-1) in the surrounding stream water. Population development followed a logistic growth function with a carrying capacity of 200 Ind cage(-1) for alder and 161 for straw. In the course of the study, the F1 generation reached sexual maturity and F2 offspring appeared. Increased nitrogen contents of gammarid-free trials compared to stocked ones after 70 days indicated that biofilm on both substrates was an important food source for G. roeseli. However, increased shredding activity by gammarids was only detected for alder during the second pulse series. During the remaining time and also for straw, losses of coarse particular organic matter were quite constant and slow indicating the dominance of transport limited decomposition processes on the litter surfaces. No effect of imidacloprid pulses on population levels and litter decomposition could be detected. However, the number of brood carrying females was reduced in the treatments compared to the control groups in the last 3 weeks of the study. In conclusion, repeated low-level and short-term exposition may have adverse long-term effects on G. roeseli in the field with regard to both the population size and the functional role as key shredder.

  19. The effect of saprophagous macrofauna on litter decomposition

    NASA Astrophysics Data System (ADS)

    Frouz, Jan

    2016-04-01

    Previous experiments show that feeding of the larvae of Bibionidae on lef litter cause short term increase of respiration but in long term the decomposition of bibio feces is slower than decomposition of litter from which feces were produced. To understand why excrements of decompose more slowly than leaf litter, we fed Bibio marci larvae the litter of tree species differing in litter quality (Alnus glutinosa, Salix caprea, and Quercus robur) and then measured respiration induced by litter and excrements. We also measured respiration induced by the same litter artificially modified to mimic faunal effects; the litter was modified by grinding, grinding with alkalinization to pH 11, grinding with coating by kaolinite, and grinding with both alkalinization and coating. Decomposition of excrements tended to be slower for willow and was significantly slower for oak and alder than for the corresponding litter. With oak, decomposition was slower for all artificially modified litter than for non-modified litter. The reduction in the decomposition was similar for excrements and for alder and willow litter that was ground, coated, and alkalinized. In alder, a similar reduction was found in ground and alkalinized litter. 13C NMR indicated that gut passage increases aliphatic components and decreases polysaccharides. Pyrolysis indicated that gut passage increases the ratio of guaiacyl to hydroxymethyl derivatives in lignin. Our findings indicate that the decreased decomposition rate of excrements might result from the removal of easily available polysaccharides, the increase in aliphatic components, an increase in the resistant components of lignin, the accumulation of microbial cell walls, and the binding of nitrogen into complexes with aromatic components. Several of these mechanisms are supported or determined by litter alkalinization during gut passage.

  20. Effects of Elevated CO2 on Litter Chemistry and Subsequent Invertebrate Detritivore Feeding Responses

    PubMed Central

    Dray, Matthew W.; Crowther, Thomas W.; Thomas, Stephen M.; A’Bear, A. Donald; Godbold, Douglas L.; Ormerod, Steve J.; Hartley, Susan E.; Jones, T. Hefin

    2014-01-01

    Elevated atmospheric CO2 can change foliar tissue chemistry. This alters leaf litter palatability to macroinvertebrate detritivores with consequences for decomposition, nutrient turnover, and food-web structure. Currently there is no consensus on the link between CO2 enrichment, litter chemistry, and macroinvertebrate-mediated leaf decomposition. To identify any unifying mechanisms, we presented eight invertebrate species from aquatic and terrestrial ecosystems with litter from Alnus glutinosa (common alder) or Betula pendula (silver birch) trees propagated under ambient (380 ppm) or elevated (ambient +200 ppm) CO2 concentrations. Alder litter was largely unaffected by CO2 enrichment, but birch litter from leaves grown under elevated CO2 had reduced nitrogen concentrations and greater C/N ratios. Invertebrates were provided individually with either (i) two litter discs, one of each CO2 treatment (‘choice’), or (ii) one litter disc of each CO2 treatment alone (‘no-choice’). Consumption was recorded. Only Odontocerum albicorne showed a feeding preference in the choice test, consuming more ambient- than elevated-CO2 birch litter. Species’ responses to alder were highly idiosyncratic in the no-choice test: Gammarus pulex and O. albicorne consumed more elevated-CO2 than ambient-CO2 litter, indicating compensatory feeding, while Oniscus asellus consumed more of the ambient-CO2 litter. No species responded to CO2 treatment when fed birch litter. Overall, these results show how elevated atmospheric CO2 can alter litter chemistry, affecting invertebrate feeding behaviour in species-specific ways. The data highlight the need for greater species-level information when predicting changes to detrital processing–a key ecosystem function–under atmospheric change. PMID:24465985