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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. 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

  3. Red Alder (Alnus rubra) Distribution Influences Nitrate Discharge to Coastal Estuaries: Comparison of Two Oregon Watersheds

    EPA Science Inventory

    We determined nutrient export from the Yaquina and Alsea Rivers as part of a larger program for evaluating nutrient sources to coastal waters. The Yaquina and Alsea data indicated that one river typically contained twice the amount of dissolved nitrate-N, although temperature, co...

  4. 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...

  5. 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...

  6. Gaseous nitrogen losses and mineral nitrogen transformation along a water table gradient in a black alder (Alnus glutinosa (L.) Gaertn.) forest on organic soils

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    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 in the laboratory experiment. Measured N2O fluxes 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 spatio-temporal 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 conducted incubation experiment. 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 ground water level was found to prevent net nitrification, resulting in a

  7. 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

  8. Biogeography of ectomycorrhizal fungi associated with alders (Alnus spp.) in relation to biotic and abiotic variables at the global scale.

    PubMed

    Põlme, Sergei; Bahram, Mohammad; Yamanaka, Takashi; Nara, Kazuhide; Dai, Yu Cheng; Grebenc, Tine; Kraigher, Hojka; Toivonen, Mika; Wang, Pi-Han; Matsuda, Yosuke; Naadel, Triin; Kennedy, Peter G; Kõljalg, Urmas; Tedersoo, Leho

    2013-06-01

    · Much of the macroecological information about microorganisms is confounded by the lack of standardized methodology, paucity of metadata and sampling effect of a particular substrate or interacting host taxa. · This study aims to disentangle the relative effects of biological, geographical and edaphic variables on the distribution of Alnus-associated ectomycorrhizal (ECM) fungi at the global scale by using comparable sampling and analysis methods. · Ribosomal DNA sequence analysis revealed 146 taxa of ECM fungi from 22 Alnus species across 96 sites worldwide. Use of spatial and phylogenetic eigenvectors along with environmental variables in model selection indicated that phylogenetic relations among host plants and geographical links explained 43 and 10%, respectively,in ECM fungal community composition, whereas soil calcium concentration positively influenced taxonomic richness. · Intrageneric phylogenetic relations among host plants and regional processes largely account for the global biogeographic distribution of Alnus-associated ECM fungi. The biogeography of ECM fungi is consistent with ancient host migration patterns from Eurasia to North America and from southern Europe to northern Europe after the last glacial maximum, indicating codispersal of hosts and their mycobionts.

  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. δ15N patterns of Douglas-fir and red alder riparian forests in the Oregon Coast Range

    USGS Publications Warehouse

    Scott, E.E.; Perakis, S.S.; Hibbs, D.E.

    2008-01-01

    We used naturally occurring stable isotopes of N to compare N dynamics in near-stream and upslope environments along riparian catenas in N-fixing red alder (Alnus rubra) and Douglas-fir (Pseudotsuga menziesii) forests in the Coast Range of western Oregon. Based on the existing literature, we expected soil δ15N to be enriched closer to streams owing to inputs of isotopically heavy, marine-derived N by spawning salmon, higher rates of denitrification near the stream, or both. However, it has been unclear what effect red alder might have on soil δ15N patterns near streams. We found a consistent −1‰ δ15N signature in red alder foliage, and δ15N of total N in soils under red alder averaged 2.2‰ along sampling transects extending 20 m upslope from the stream. Surprisingly, δ15N of total N in soil under Douglas-fir was progressively depleted nearer to streams, opposite from the pattern expected from N losses by denitrification or N inputs from anadromous salmon. Instead, δ15N of total N in soil under Douglas-fir converged toward soil δ15N values typical of red alder sites. We consider that the historic presence of red alder may have contributed a legacy of lower soil δ15N nearer to streams on sites that are currently dominated by young Douglas-fir forest.

  12. 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.

  13. Mixed, short rotation culture of red alder and black cottonwood: growth, coppicing, nitrogen fixation, and allelopathy

    SciTech Connect

    Heilman, P.; Stettler, R.F.

    1985-01-01

    Alnus rubra seedlings were grown in a 1:1 mixture at a spacing of 1.2 x 1.2 m with 28 Populus clones (25 clones pf P. trichocarpa, 2 of P. deltoides x P. trichocarpa, and one P. deltoides x P. nigra) in a study established in W. Washington in March 1979. Trees were harvested at 4 yr old. At harvest, average heights were: pure Populus, 10.2 m; Populus in the mixed stand 11.0 m; and alder 8.4 m. Most Populus sprouted satisfactorily after harvest (6.6 shoots/plant when pure, 7.6 shoots/plant in the mixture), but alder sprouted poorly (3.6 shoots/plant). Above-ground biomass at harvest was 15.9 t/ha p.a. for the mixture and 16.7 t/ha p.a. for pure Populus, although the mixture had been more productive at 2 yr. Nitrogenase activity (nitrogen fixation as measured by acetylene reduction) of alder declines in the 4th season; competition was the most important factor influencing this decline. Soil N content had no effect on fixation. A pot study showed that ground Populus leaf and litter material inhibited the growth of red alder seedlings, although soil collected from Populus plots had no effect. Results indicated that allelopathy is probably a minor factor under field conditions, at most, and that growing mixed stands may, on balance, be beneficial. 20 references.

  14. Pityriasis rubra pilaris

    MedlinePlus

    ... PA: Elsevier; 2016:chap 11. Tobin AM, Kirby B. Pityriasis rubra pilaris. In: Lebwohl MG, Heymann WR, Berth-Jones J, Coulson I, eds. Treatment of Skin Disease: Comprehensive Therapeutic Strategies . 4th ed. Philadelphia, PA: Elsevier Saunders; 2014:chap ...

  15. 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...

  16. In-planta sporulation phenotype: a major life history trait to understand the evolution of Alnus-infective Frankia strains.

    PubMed

    Pozzi, Adrien C; Bautista-Guerrero, Hector H; Nouioui, Imen; Cotin-Galvan, Laëtitia; Pepin, Régis; Fournier, Pascale; Menu, Frédéric; Fernandez, Maria P; Herrera-Belaroussi, Aude

    2015-09-01

    Two major types of Frankia strains are usually recognized, based on the ability to sporulate in-planta: spore-positive (Sp+) and spore-negative (Sp-). We carried out a study of Sp+ and Sp- Frankia strains based on nodules collected on Alnus glutinosa, Alnus incana and Alnus viridis. The nodules were phenotyped using improved histology methods, and endophytic Frankia strain genotype was determined using a multilocus sequence analysis approach. An additional sampling was done to assess the relation between Sp+ phenotype frequency and genetic diversity of Frankia strains at the alder stand scale. Our results revealed that (i) Sp+ and Sp- Alnus-infective Frankia strains are genetically different even when sampled from the same alder stand and the same host-plant species; (ii) there are at least two distinct phylogenetic lineages of Sp+ Frankia that cluster according to the host-plant species and without regard of geographic distance and (iii) genetic diversity of Sp+ strains is very low at the alder stand scale compared with Sp- strains. Difference in evolutionary history and genetic diversity between Sp+ and Sp- Frankia allows us to discuss the possible ecological role of in-planta sporulation. PMID:25335453

  17. Granulosis rubra nasi

    PubMed Central

    Sargunam, Cynthia; Thomas, Jayakar; Ahmed, N. Ashwak

    2013-01-01

    Granulosis rubra nasi is a rare disorder of the eccrine glands, inherited as an autosomal dominant trait. It is clinically characterized by hyperhidrosis of the central part of the face, most conspicuous on the tip of the nose, followed by appearance of diffuse erythema over the nose, cheeks, chin, and upper lip. It is commonly seen in childhood, but can also occur in adults. This is a case report of a 27-year-old male patient who presented with excessive sweating over the nose. Physical examination of the nose revealed erythema and multiple telangiectatic vesicles. Biopsy findings supported the diagnosis of granulosis rubra nasi. This case is being reported for its rarity since to the best of our knowledge, it has not been reported in Indian subjects so far. PMID:23984236

  18. Growth and N2 fixation in an Alnus hirsuta (Turcz.) var. sibirica stand in Japan.

    PubMed

    Tobita, Hiroyuki; Hasegawa, Shigeaki F; Yazaki, Kenichi; Komatsu, Masabumi; Kitao, Mitsutoshi

    2013-11-01

    To estimate the N2 fixation ability of the alder (Alnus hirsuta (Turcz.) var. sibirica), we examined the seasonal variation in nitrogenase activity of nodules using the acetylene reduction method in an 18-year-old stand naturally regenerated after disturbance by road construction in Japan. To evaluate the contribution of N2 fixation to the nitrogen (N) economy in this alder stand, we also measured the phenology of the alder, the litterfall, the decomposition rate of the leaf litter, and N accumulation in the soil. The acetylene reduction activity per unit nodule mass (ARA) under field conditions appeared after bud break, peaked the maximum in midsummer after full expansion of the leaves, and disappeared after all leaves had fallen. There was no consistent correlation between ARA and tree size (dbh). The amount of N2 fixed in this alder stand was estimated at 56.4 kg ha-1 year-1 when a theoretical molar ratio of 3 was used to convert the amount of reduced acetylene to the amount of fixed N2. This amount of N2 fixation corresponded to the 66.4 percent of N in the leaf litter produced in a year. These results suggested that N2 fixation still contributed to the large portion of N economy in this alder stand. PMID:24287656

  19. Structural differences in diarylheptanoids analogues from Alnus viridis and Alnus glutinosa influence their activity and selectivity towards cancer cells.

    PubMed

    Dinić, Jelena; Novaković, Miroslav; Podolski-Renić, Ana; Vajs, Vlatka; Tešević, Vele; Isaković, Aleksandra; Pešić, Milica

    2016-04-01

    Diarylheptanoids represent a group of plant secondary metabolites that possess multiple biological properties and are increasingly recognized for their therapeutic potential. A comparative study was performed on structurally analogous diarylheptanoids isolated from the bark of green (Alnus viridis) and black alder (Alnus glutinosa) to address their biological effects and determine structure-activity relationship. The structures and configurations of all compounds were elucidated by NMR, HR-ESI-MS, UV and IR. Diarylheptanoids actions were studied in human non-small cell lung carcinoma cells (NCI-H460) and normal keratinocytes (HaCaT). A. viridis compounds 3v, 5v, 8v and 9v that possess a carbonyl group at C-3 were considerably more potent than compounds without this group. A. viridis/A. glutinosa analogue pairs, 5v/5g and 9v/9g, which differ in the presence of 3' and 3″-OH groups, were evaluated for anticancer activity and selectivity. 5v and 9v that do not possess 3' and 3″-OH groups showed significantly higher cytotoxicity compared to analogues 5g and 9g. In addition, these two A. viridis compounds induced a more prominent apoptosis in both cell lines and an increase in subG0 cell cycle phase, compared to their A. glutinosa analogues. 5v and 9v treatment triggered intracellular superoxide anion accumulation and notably decreased mitochondrial transmembrane potential. In HaCaT cells, 9v and 9g with a 4,5 double bond caused a more prominent loss of mitochondrial transmembrane potential compared to 5v and 5g which possess a 5-methoxy group instead. Although green alder diarylheptanoids 5v and 9v displayed higher cytotoxicity, their analogues from black alder 5g and 9g could be more favorable for therapeutic use since they were more active in cancer cells than in normal keratinocytes. These results indicate that minor differences in the chemical structure can greatly influence the effect of diarylheptanoids on apoptosis and redox status and determine their

  20. 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

  1. Ectomycorrhizae between Alnus acuminata H.B.K. and Naucoria escharoides (Fr.:Fr.) Kummer from Argentina.

    PubMed

    Becerra, Alejandra; Daniele, Graciela; Domínguez, Laura; Nouhra, Eduardo; Horton, Tom

    2002-04-01

    Field ectomycorrhizae of Naucoria escharoides on Alnus acuminata ("andean alder", "aliso del cerro") are described in detail for the first time. Naturally occurring ectomycorrhizal roots were sampled beneath sporocarps of N. escharoides. The samples were taken from four natural forest plots at two homogeneous A. acuminata sites (Tucumán and Catamarca Provinces, Argentina). The ectomycorrhizae were characterized morphologically and compared by means of PCR/RFLP analysis of the internal transcribed spacer region of the nuclear rDNA. The most important morphological features of the ectomycorrhizae are a white to pale yellow mantle, simple to monopodial branches, hyaline emanating hyphae, abundant hyphal bundles emerging more or less perpendicularly from a plectenchymatous mantle, and an acute or rounded apex with or without a mantle. N. escharoides fruitbodies have white basal mycelium with emanating hyphae similar to those of andean alder ectomycorrhizae. The RFLP profiles of sporocarps and mycorrhizae were the same. PMID:12035728

  2. Development of ectomycorrhizae on containerized sweet birch and European alder seedlings for planting on low quality sites

    SciTech Connect

    Walker, R.F.; West, D.C.; McLaughlin, S.B.

    1982-01-01

    A study was initiated to assess the potential of Pisolithus tinctorius as an ectomycorrhizal associate of containerized sweet birch (Betula lenta) and European alder (Alnus glutinosa) seedlings and to determine the effect of this fungal symbiont on seedling growth. In a test of sweet birch and European alder grown in Leach tubes, P. tinctorius formed abundant ectomycorrhizae on sweet birch when introduced via a vegetative mycelial inoculum. Cenococcum geophilum, originating from sclerotia present in the potting medium, and Thelephora terrestris, introduced via wind-borne propagules, formed ectomycorrhizae on the sweet birch seedlings inoculated with P. tinctorius and on the sweet birch control seedlings. C. geophilum also formed ectomycorrhizae on the inoculated and control European alder seedlings, but an inoculation with P. tinctorius did not result in the formation of P. tinctorius ectomycorrhizae on this host. Sweet birch seedlings infected with P. tinctorius had a greater dry weight, height, root collar diameter, and volume and a lower shoot/root ratio than the sweet birch control seedlings, and European alder seedlings with abundant C. geophilum ectomycorrhizae exhibited a similar improvement in growth in comparison with European alder with lesser C. geophilum infections. The inoculation of containerized sweet birch and European alder seedlings in the nursery with the appropriate ectomycorrhizal symbiont may facilitate the establishment of these species on harsh sites such as surface mine spoils. 57 references, 3 tables.

  3. Ectomycorrhizas of Cortinarius helodes and Gyrodon monticola with Alnus acuminata from Argentina.

    PubMed

    Becerra, Alejandra; Nouhra, Eduardo; Daniele, Graciela; Domínguez, Laura; McKay, Donaraye

    2005-01-01

    Field ectomycorrhizas of Cortinarius helodes Moser, Matheny & Daniele (sp. nov) and Gyrodon monticola Sing. on Alnus acuminata Kunth (Andean alder, aliso del cerro) are described based on morphological and anatomical features. Ectomycorrhizal roots were sampled beneath fruitbodies of C. helodes and G. monticola from two homogeneous A. acuminata forest sites located in Tucuman and Catamarca Provinces in Argentina. C. helodes ectomycorrhizas showed a thick white to beige mantle exuding a milky juice when injured, were bluish toward the apex, and had hyphal strands in the mantle. G. monticola ectomycorrhizas showed some conspicuous features like highly differentiated rhizomorphs, inflated brown cells on the mantle surface, and hyaline and brown emanating hyphae with dolipores. Restriction fragment length polymorphism analysis of the nuclear rDNA internal transcribed spacer provided a distinctive profile for each of the collections of fruitbodies and the mycorrhizal morphotypes. PMID:14648309

  4. Anti-adipogenic activities of Alnus incana and Populus balsamifera bark extracts, part I: sites and mechanisms of action.

    PubMed

    Martineau, Louis C; Hervé, Jessica; Muhamad, Asim; Saleem, Ammar; Harris, Cory S; Arnason, John T; Haddad, Pierre S

    2010-09-01

    Obesity is an epidemic in most developed countries and novel therapeutic approaches are needed. In the course of a screening project of medicinal plants used by the Eastern James Bay Cree of Canada and having potential for the treatment of diabetes, we have identified several products that inhibit adipogenesis, suggesting potential antiobesity activities. The inhibitory activity of two of these, the extract of the inner bark of the deciduous trees Alnus incana ssp. rugosa (Speckled Alder) and Populus balsamifera L. (Balsam Poplar), was analyzed using the 3T3-L1 cell model of adipogenesis. Intracellular triglyceride accumulation, pre-adipocyte proliferation, and PPAR- γ activity were measured. Alnus incana extracts acted early in the differentiation process but did not affect clonal expansion of pre-adipocytes nor the morphological transformation from fibroblast-like to rounded fat-laden cells. Alnus incana extracts were found to act as partial agonists toward PPAR- γ activity. In contrast, Populus balsamifera extracts completely abrogated adipogenesis, severely limited clonal expansion of pre-adipocytes and generally maintained cells in an undifferentiated fibroblast-like morphology. Populus balsamifera extracts exerted antagonistic action against PPAR- γ activity. It is concluded that, through their actions on the adipocyte, these plant products may be useful for the treatment of obesity and related metabolic diseases.

  5. The Phytophthora species assemblage and diversity in riparian alder ecosystems of western Oregon, USA.

    PubMed

    Sims, Laura Lee; Sutton, Wendy; Reeser, Paul; Hansen, Everett M

    2015-01-01

    Phytophthora species were systematically sampled, isolated, identified and compared for presence in streams, soil and roots of alder (Alnus species) dominated riparian ecosystems in western Oregon. We describe the species assemblage and evaluate Phytophthora diversity associated with alder. We recovered 1250 isolates of 20 Phytophthora species. Only three species were recovered from all substrates (streams, soil, alder roots): P. gonapodyides, the informally described "P. taxon Pgchlamydo", and P. siskiyouensis. P. alni ssp. uniformis along with five other species not previously recovered in Oregon forests are included in the assemblage: P.citricola s.l., P. gregata, P. gallica, P. nicotianae and P. parsiana. Phytophthora species diversity was greatest in downstream riparian locations. There was no significant difference in species diversity comparing soil and unwashed roots (the rhizosphere) to stream water. There was a difference between the predominating species from the rhizosphere compared to stream water. The most numerous species was the informally described "P. taxon Oaksoil", which was mainly recovered from, and most predominant in, stream water. The most common species from riparian forest soils and alder root systems was P. gonapodyides.

  6. The Influence of Speckled Alder on Nitrogen Accumulation in Adirondack Wetlands

    NASA Astrophysics Data System (ADS)

    Kiernan, B. D.; Hurd, T. M.; Raynal, D. J.

    2001-05-01

    Shrub-dominated wetlands of the Adirondacks typically support vigorous populations of nitrogen-fixing speckled alder Alnus incana (L.) Moench var. americana Regel), and are the second most abundant wetland type in the Adirondack region. In symbiotic association with an actinomycete of the genus Frankia, this shrub fixes 37-43 kg N/ha/yr in monotypic stands. This study was undertaken to quantify the abundance of alder in wetlands typed as "Scrub-shrub 1" (SS1; known as alder/willow wetlands) in the National Wetlands Inventory, and to determine the accumulation of nitrate and ammonium in alder wetland substrates. Twenty wetlands from the Oswegatchie-Black (OB) and Upper Hudson (UH) watersheds were randomly selected using the Adirondack Park Agency's GIS data base which includes wetland cover types assigned using remotely sensed data. Wetlands designated as "SS1" (scrub-shrub vegetation) and "SS1/EM1" (scrub-shrub with emergent herbaceous vegetation) were included in the sample. Six wetlands varying in alder abundance were chosen to estimate N accumulation in the substrate, with measurement of dissolved inorganic N in groundwater and ion exchange resin extracts. In the OB watershed, A. incana averaged 30 % of total shrub density in SS1 wetlands and 36 % in SS1/EM1 wetlands. Alder accounted for 49 % of all stems in UH SS1 wetlands, 28 % in the SS1/EM1 wetlands and in total accounted for 35 % of all stems in this study. Nitrate in IER extracts and groundwater was significantly higher in high-density alder wetlands (p < 0.05). Eight of the 20 wetlands included in this study were estimated to have less than 3,000 alder stems/ha, and five were estimated to have greater than 10,000 stems/ha. The other seven wetlands averaged 6,000 stems/ha. At nine sites, foliar N equaled or exceeded estimated atmospheric deposition (~10 kg/ha/yr), and was likely derived from N fixation. We conclude that 50 % of the SS1/EM1 wetlands and at least 75 % of the SS1 wetlands in these watersheds

  7. Anti-adipogenic activities of Alnus incana and Populus balsamifera bark extracts, part II: bioassay-guided identification of actives salicortin and oregonin.

    PubMed

    Martineau, Louis C; Muhammad, Asim; Saleem, Ammar; Hervé, Jessica; Harris, Cory S; Arnason, John T; Haddad, Pierre S

    2010-10-01

    Among modern day metabolic diseases, obesity has reached epidemic proportions worldwide and novel therapeutic support strategies are urgently needed. Adipocytes are interesting targets in this context. Using ethnobotanical and bioassay screening techniques, we have identified two Boreal Forest plants used by the James Bay Cree that potently inhibit adipogenesis, namely ALNUS INCANA ssp. RUGOSA (Speckled Alder) and POPULUS BALSAMIFERA (Balsam Poplar). The mode of action of this inhibitory activity was reported in a companion paper. The current study report the results of a classical bioassay-guided fractionation approach aimed at identifying the active principles responsible for the inhibition of adipogenesis, as measured using triglyceride accumulation in the 3T3-L1 adipocyte model cell line. The glycosides oregonin and salicortin were isolated and identified as the respective active principles for ALNUS INCANA and POPULUS BALSAMIFERA. These compounds thus offer promise as novel agents to mitigate the incidence or the progression of obesity.

  8. How can effect the synergy of climate change, soil units and vegetation groups the potential global distribution of plants up to 2300: a modelling study for prediction of potential global distribution and migration of the N2 fixing species Alnus spp.

    NASA Astrophysics Data System (ADS)

    Sakalli, A.

    2015-01-01

    Plant migration is a well known adaptation strategy of plant groups or species with evidence from historical to present observation and monitoring studies. Importance of N2-fixing plants has increased in last decades. Alnus (alder) is an important plant group because of its nitrogen fixation ability. Alders are generally distributed in humid locations of boreal, temperate and tropical climate zones, where the nitrogen fixation is an important nitrogen source for other plants. To model the nitrogen fixation by alder, data about the global distribution of alder is absolutely required. In this study a new method and model are presented to predict the distribution of N2-fixing genus on global scale and its migration in the future by using climate change scenarios. Three linear functions were defined for the determination of climate niche of alders. The distribution and migration model (Alnus-Distribution-Model (ADM)) was improved with the aid of the soil units from FAO-Unesco Soil Database, and vegetation types from Schmithüsen's biogeographical atlas. The model was also developed to predict the impact of climate change on alder distribution by using climate data from experiments performed by the Community Climate System Model version 4 (CCSM4) including the representative concentration pathways (RCPs) mitigation scenarios, and extensions of the scenarios beyond 2100 to 2300. The model covered basic approaches to understand the combine effect of climate, soil and vegetation on plant distribution and migration in the current time and future.

  9. 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. PMID:27170470

  10. Molecular diversity of Frankia in root nodules of Alnus incana grown with inoculum from polluted urban soils.

    PubMed

    Ridgway, K P; Marland, L A; Harrison, A F; Wright, J; Young, J P W; Fitter, A H

    2004-11-01

    ABSTRACT The establishment and growth of trees can be compromised by soil contamination which can reduce populations of key microbial symbionts. We describe the colonisation of grey alder (Alnus incana) by Frankia from 10 urban soils with varying degrees of organic and inorganic pollution. Principal components analysis (PCA) of soil chemical profiles showed a separation of remediated and unremediated soils. A. incana seedlings were used as trap plants to capture the microsymbiont from soil. After 6 months growth, nodulation was lowest on trees grown with the most contaminated soils. Plant biomass was positively correlated with root nodule biomass and negatively correlated with PAH concentration. DNA was isolated from nodules for the analysis of Frankia genetic diversity. The polymerase chain reaction (PCR) was used to amplify the 16S-23S intergenic spacer (IGS) of Frankia ribosomal DNA. PCR products were subject to restriction digestion yielding 10 restriction fragment length polymorphism (RFLP) types from 72 nodules analysed. Our results demonstrate that each soil supports a distinct nodulating Frankia community. Partial 16S sequencing placed most strains in Frankia clusters 1a and 1b, which are typically Alnus-infecting, but sequences from several nodules obtained from a gasworks soil belonged to cluster 3, normally associated with Elaeagnus. These results show for the first time that polluted soils can be an effective source of Alnus-infective Frankia. Inoculation with site-adapted Frankia under greenhouse conditions could thus be an appropriate strategy to increase the symbiotic capacity of A. incana and to improve its chances of survival and growth when planted on polluted soils. PMID:19712365

  11. Influence of roadside pollution on the phylloplane microbial community of Alnus nepalensis (Betulaceae).

    PubMed

    Joshi, S R

    2008-09-01

    The North Eastern region of India is undergoing industrial development at a faster rate than expected. Roads form the main system of transportation and communication owing to the hilly topography of the region. Automobiles discharge a number of gaseous and trace metal contaminants. Human activities like stone grinding, road construction and sand milling also increase the atmospheric dust and heavy metal contaminant level. These contaminants get settled on leaf surfaces at roadsides and enter in contact with phylloplane microorganisms. This study compares microorganisms on leaf surfaces of alder (Alnus nepalensis (Betulaceae)) on roadside and non-roadside environments. Two sites dominated by alder were selected. One at a busy road intersection on the National Highway no. 44 in Shillong with high traffic density (8 000-9 000 heavy vehicles/day), taken as the polluted site and the other one in a forest approximately 500 m away from the roadside considered as the unpolluted site. Analysis of phylloplane microorganisms, lead, zinc, copper, cadmium and sulphur was carried out from leaves. The bacterial population was higher at the unpolluted site. Bacterial population showed a significant negative correlation with lead, zinc, copper, cadmium and sulphur. Similarly, fungal population was higher at the unpolluted site. A total of 29 fungal species were isolated from the phylloplane of A. nepalensis (polluted site 16 species; unpolluted site 28 species). Some fungal forms like Mortierella sp., Fusarium oxysporum and Aureobasidium pollulans were dominant in the polluted site. Numbers of phylloplane fungi and bacteria were significantly reduced in the polluted site. The correlation coefficient indicated a detrimental effect of metals like lead, zinc, copper, cadmium and sulphur on the microbial community of leaf surfaces. The specificity of certain fungi to the unpolluted site may be attributed to their sensitivity to pollution. The predominance of Aureobasidium pollulans

  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. Dendrochronology and lakes: using tree-rings of alder to reconstruct lake levels

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    Climate change is considered a major threat for ecosystems around the world. Assessing its effects is challenging, amongst others, as we are unsure how ecosystems may respond to climate conditions they were not exposed to before. However, increased insight may be obtained by analyzing responses of ecosystems to past climate variability. In this respect, lake ecosystems appear as valuable sentinels, because they provide direct and indirect indicators of change through effects of climate. Lake-level fluctuations of closed catchments, for example, reflect a dynamic water balance, provide detailed insight in past moisture variations, and thereby allow for assessments of effects of anticipated climate change. Up to now, lake-level data are mostly obtained from gauging records and reconstructions from sediments and landforms. However, these records are in many cases only available over relatively short time periods, and, since geoscientific work is highly demanding, lake-level reconstructions are lacking for many regions. Here, we present and discuss an alternative method to reconstruct lake levels, which is based on tree-ring data of black alder (Alnus glutinosa L.). This tree species tolerates permanently waterlogged and temporally flooded conditions (i.e. riparian vegetation), and is often found along lakeshores. As the yearly growth of trees varies depending upon the experienced environmental conditions, annual rings of black alder from lakeshore vegetation likely capture information on variations in water table, and may therefore be used to reconstruct lake levels. Although alder is a relatively short-lived tree species, the frequent use of its' decay-resistant wood in foundations of historical buildings offers the possibility of extending living tree-chronologies back in time for several centuries. In this study, the potential to reconstruct lake-level fluctuations from tree-ring chronologies of black alder is explored for three lake ecosystems in the Mecklenburg

  14. Global biogeography of Alnus-associated Frankia actinobacteria.

    PubMed

    Põlme, Sergei; Bahram, Mohammad; Kõljalg, Urmas; Tedersoo, Leho

    2014-12-01

    Macroecological patterns of microbes have received relatively little attention until recently. This study aimed to disentangle the determinants of the global biogeographic community of Alnus-associated actinobacteria belonging to the Frankia alni complex. By determining a global sequence similarity threshold for the nitrogenase reductase (nifH) gene, we separated Frankia into operational taxonomic units (OTUs) and tested the relative effects of Alnus phylogeny, geographic relatedness, and climatic and edaphic variables on community composition at the global scale. Based on the optimal nifH gene sequence similarity threshold of 99.3%, we distinguished 43 Frankia OTUs from root systems of 22 Alnus species on four continents. Host phylogeny was the main determinant of Frankia OTU-based community composition, but there was no effect on the phylogenetic structure of Frankia. Biogeographic analyses revealed the strongest cross-continental links over the Beringian land bridge. Despite the facultative symbiotic nature of Frankia, phylogenetic relations among Alnus species play a prominent role in structuring root-associated Frankia communities and their biogeographic patterns. Our results suggest that Alnus species exert strong phylogenetically determined selection pressure on compatible Actinobacteria. PMID:25124146

  15. 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.

  16. 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

  17. Bioactive constituents and medicinal importance of genus Alnus

    PubMed Central

    Sati, Sushil Chandra; Sati, Nitin; Sati, O. P.

    2011-01-01

    The genus Alnus has been reviewed for its chemical constituents and biological activities including traditional importance of some common species. The plants of this genus contain terpenoids, flavonoids, diarylheptanoids, phenols, steroids, and tannins. Diarylheptanoids are the dominant constituents within the genus Alnus, few of them exhibited antioxidant effects and inhibitory activity against nuclear factor kappaB activation, nitric oxide and tumor necrosis factor-α production, human umbilical vein endothelial cells, farnesyl protein transferase, cell-mediated low-density lipoprotein oxidation, HIF-1 in AGS cells, and the HIV-1-induced cytopathic effect in MT-4 cells. Some ellagitannines showed hepatoprotective activity even in a dose of 1 mg/kg which is ten-fold smaller compared with the dose of traditional flavonoid-based drugs. The members of genus Alnus are well known for their traditional uses in the treatment of various diseases like cancer, hepatitis, inflammation of uterus, uterine cancer, rheumatism, dysentery, stomachache, diarrhea, fever, etc. The aim of the present review is to summarize the various researches related to the chemistry and pharmacology of genus Alnus. PMID:22279375

  18. 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.

  19. 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...

  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. 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...

  2. 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). PMID:25058932

  3. 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. PMID:23202636

  4. 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).

  5. 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.

  6. Bevacizumab-induced pityriasis rubra pilaris-like eruption.

    PubMed

    Brown, Shannon; Fletcher, J Wesley; Fiala, Katherine H

    2016-07-01

    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

  7. Photosynthetic and leaf water potential responses of Alnus glutinosa saplings to stem-base inoculaton with Phytophthora alni subsp. alni.

    PubMed

    Clemenz, Christian; Fleischmann, Frank; Häberle, Karl-Heinz; Matyssek, Rainer; Osswald, Wolfgang

    2008-11-01

    Three-year-old Alnus glutinosa (L.) Gaertn. (alder) saplings were single or double inoculated at the stem base with Phytophthora alni subsp. alni Brasier & S.A. Kirk under natural climatic conditions. Lesion formation on the bark showed a biphasic pattern of development, with extension occurring at a moderate rate in spring, and more rapidly during late summer. However, large variability was encountered in pathogen development within the population of infected saplings, ranging from high susceptibility to almost complete resistance. Infection resulted in severe growth retardation, and death within two years of inoculation in 75% of the saplings. During disease development, rates of transpiration and CO(2) uptake were significantly reduced. Consequently, minimum leaf water potentials were less negative in infected saplings than in control saplings. Surviving saplings matched control trees in photosynthetic capacity, transpiration rate and water potential during the second year of infection. Leaf starch concentration of infected saplings was significantly higher than in control saplings, possibly indicating that the destruction of bark tissue by the pathogen impaired phloem transport from leaves to roots.

  8. Miliaria rubra of the lower limbs in underground miners.

    PubMed

    Donoghue, A M; Sinclair, M J

    2000-08-01

    This report documents a case series of miliaria rubra of the lower limbs in miners at a deep underground metalliferous mine in tropical arid Australia. During the summer months of February and March 1999, all cases of miliaria rubra of the lower limbs in underground miners seen at the mine's medical centre were clinically examined and administered a questionnaire. Twenty-five patients were seen, an incidence of 56.4 cases per million man-hours. Miliaria rubra was most often located between the ankle and knee (88% of cases). Twenty-four percent had concurrent folliculitis and 20% had concurrent tinea. Thirty-two percent had a personal history of asthma. Walking through ground-water and splashing of the legs was common. Three to 4 weeks of sedentary duties in air conditioning was generally required to achieve resolution of miliaria rubra. The incidence of miliaria rubra of the lower limbs is 38% of the incidence of heat exhaustion at the same mine. The length of disablement is greater, however. Atopics may be at increased risk of miliaria rubra. Control measures are discussed.

  9. The pentadehydro-Diels-Alder reaction.

    PubMed

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

    2016-04-28

    In the classic Diels-Alder [4 + 2] cycloaddition reaction, the overall degree of unsaturation (or oxidation state) 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 Diels-Alder reaction, butadiene and ethylene combine to produce cyclohexene. More recent developments include variants in which the number of hydrogen atoms in the reactant pair and in the resulting product is reduced by, for example, four in the tetradehydro-Diels-Alder (TDDA) and by six in the hexadehydro-Diels-Alder (HDDA) reactions. Any oxidation state higher than tetradehydro (that is, lacking more than four hydrogens) leads to the production of a reactive intermediate that is more highly oxidized than benzene. This increases the power of the overall process substantially, because trapping of the reactive intermediate can be used to increase the structural complexity of the final product in a controllable and versatile manner. Here we report an unprecedented overall 4π + 2π cycloaddition reaction that generates a different, highly reactive intermediate known as an α,3-dehydrotoluene. This species is in 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 process a pentadehydro-Diels-Alder (PDDA) reaction-a nomenclature chosen for chemical taxonomic reasons rather than mechanistic ones. 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.

  10. The pentadehydro-Diels-Alder reaction.

    PubMed

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

    2016-04-28

    In the classic Diels-Alder [4 + 2] cycloaddition reaction, the overall degree of unsaturation (or oxidation state) 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 Diels-Alder reaction, butadiene and ethylene combine to produce cyclohexene. More recent developments include variants in which the number of hydrogen atoms in the reactant pair and in the resulting product is reduced by, for example, four in the tetradehydro-Diels-Alder (TDDA) and by six in the hexadehydro-Diels-Alder (HDDA) reactions. Any oxidation state higher than tetradehydro (that is, lacking more than four hydrogens) leads to the production of a reactive intermediate that is more highly oxidized than benzene. This increases the power of the overall process substantially, because trapping of the reactive intermediate can be used to increase the structural complexity of the final product in a controllable and versatile manner. Here we report an unprecedented overall 4π + 2π cycloaddition reaction that generates a different, highly reactive intermediate known as an α,3-dehydrotoluene. This species is in 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 process a pentadehydro-Diels-Alder (PDDA) reaction-a nomenclature chosen for chemical taxonomic reasons rather than mechanistic ones. 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

  11. 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

  12. 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

  13. 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

  14. A Review of Pityriasis Rubra Pilaris and Rheumatologic Associations

    PubMed Central

    Chan, Happy; Liu, Fu Tong

    2004-01-01

    Pityriasis rubra pilaris (PRP) is a rare group of hyperkeratotic, papulosquamous disease that can be acquired or inherited. There have been reported cases of rheumatologic associations, mainly arthritis and dermatomyositis. In this review article, we will explore the clinical presentation and classification, rheumatologic associations and treatment modalities of PRP. In addition, we will also report a case of PRP with seronegative arthritis. PMID:15154613

  15. 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.

  16. 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.

  17. Seasonal fluctuations in leaf phenolic composition under UV manipulations reflect contrasting strategies of alder and birch trees.

    PubMed

    Kotilainen, Titta; Tegelberg, Riitta; Julkunen-Tiitto, Riitta; Lindfors, Anders; O'Hara, Robert B; Aphalo, Pedro J

    2010-11-01

    Seasonal variation in leaf phenolic composition may be important for acclimation of plants to seasonal changes in their biotic and abiotic environment. For a realistic assessment of how plants respond to solar UV-B (280-315 nm) and UV-A (315-400 nm) radiation, seasonal variation in both environment and plant responses needs to be taken into account. This also has implications for studies concerning stratospheric ozone depletion and resulting increased UV-B radiation, as other environmental variables and/or plant phenology could interact with UV radiation. To elucidate this, we established a field experiment using plastic films attenuating different parts of the solar UV spectrum. The concentration of individual phenolic compounds was measured during one growing season in leaves of grey alder (Alnus incana) and white birch (Betula pubescens) trees. Our results showed changes in concentration of, e.g. hydrolyzable tannins in birch that suggest an effect of UV-A alone and e.g. chlorogenic acids in alder indicate a quadratic effect of UV-B irradiance and both linear and quadratic effect for UV-A in second-degree polynomial fits. Further, there was interaction between treatment and sampling time for some individual metabolites; hence, the UV response varied during the season. In addition to the UV effects, three temporal patterns emerged in the concentrations of particular groups of phenolics. Possible implications for both sampling methods and timing are discussed. Moreover, our results highlight differences in responses of the two tree species, which are taken to indicate differences in their ecological niche differentiation.

  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. 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

  20. Advocacy and hope for the patient with pityriasis rubra pilaris.

    PubMed

    Nunemacher, Kathy J

    2008-10-01

    Pityriasis rubra pilaris (PRP) is a rare skin disease that can cause severe physical and psychological manifestations. A short case study of an adult with PRP who was denied access to medications and his journey towards improved health is discussed. Through advocacy and support, health care providers can make a difference in the care of patients with PRP and improve their quality of life. PMID:19051784

  1. New prodigiosin-like pigment from Alteromonas rubra.

    PubMed Central

    Gerber, N N; Gauthier, M J

    1979-01-01

    The red prodigiosin-like pigment from Alteromonas rubra was shown to be a mixture of prodigiosin (pigment 1) and a new cyclic isomer (pigment 2). The new structure was elucidated by mass and nuclear magnetic resonance spectra. Careful examinations of the prodigiosins produced by Serratia marcescens, Vibrio psychoerythrus, and an unidentified red bacterium (LL-100-6) failed to disclose any of the new pigment, pigment 2. PMID:384909

  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. Permanent draft genome of Rhodopirellula rubra SWK7.

    PubMed

    Klindworth, Anna; Richter, Michael; Richter-Heitmann, Tim; Wegner, Carl-Eric; Frank, Carsten S; Harder, Jens; Glöckner, Frank Oliver

    2014-02-01

    The genome of Rhodopirellula rubra strain SWK7 was sequenced as a permanent draft to complement the full genome sequence of the type strain Rhodopirellula baltica SH1(T). This isolate is part of a larger study to infer the biogeography of Rhodopirellula species in European marine waters, as well as to amend the genus description of R. baltica. This genomics resource article is the fourth among a series of five publications reporting in a total of eight new permanent draft genomes of Rhodopirellula species.

  5. Permanent draft genome of Rhodopirellula rubra SWK7.

    PubMed

    Klindworth, Anna; Richter, Michael; Richter-Heitmann, Tim; Wegner, Carl-Eric; Frank, Carsten S; Harder, Jens; Glöckner, Frank Oliver

    2014-02-01

    The genome of Rhodopirellula rubra strain SWK7 was sequenced as a permanent draft to complement the full genome sequence of the type strain Rhodopirellula baltica SH1(T). This isolate is part of a larger study to infer the biogeography of Rhodopirellula species in European marine waters, as well as to amend the genus description of R. baltica. This genomics resource article is the fourth among a series of five publications reporting in a total of eight new permanent draft genomes of Rhodopirellula species. PMID:24291061

  6. 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

  7. 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.

  8. 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.

  9. 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) ...

  10. 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. PMID:26487352

  11. 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.

  12. Understanding the mechanism of polar Diels-Alder reactions.

    PubMed

    Domingo, Luis R; Sáez, José A

    2009-09-01

    A good correlation between the activation energy and the polar character of Diels-Alder reactions measured as the charge transfer at the transition state structure has been found. This electronic parameter controls the reaction rate to an even greater extent than other recognized structural features. The proposed polar mechanism, which is characterized by the electrophilic/nucleophilic interactions at the transition state structure, can be easily predicted by analyzing the electrophilicity/nucleophilicity indices defined within the conceptual density functional theory. Due to the significance of the polarity of the reaction, Diels-Alder reactions should be classified as non-polar (N), polar (P), and ionic (I).

  13. Extracorporeal photochemotherapy for the treatment of exanthematic pityriasis rubra pilaris.

    PubMed

    Haenssle, H A; Bertsch, H P; Emmert, S; Wolf, C; Zutt, M

    2004-05-01

    Pityriasis rubra pilaris (PRP) is a rare papulosquamous skin disease of unknown aetiology that has been categorized into five clinical types based on age at onset, cutaneous features and prognosis. We present a patient with chronic exanthematic type II atypical adult PRP, whose skin status was significantly improved with monthly extracorporeal photochemotherapy (ECP). Various therapeutic regimens including narrow-band UV-B, bath PUVA therapy, systemic fumaric acid esters and systemic cyclosporin had failed. Oral retinoids could not be administered due to a type IIa hyperlipoproteinemia with profound hepatic steatosis and elevated liver transaminases. The observed clinical benefit may encourage future clinical studies analysing the effectiveness of ECP in otherwise unresponsive cases of type II PRP.

  14. 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.

  15. Mechanism of the isomerization of isopentenyl pyrophosphate in Rhodotorual rubra-1.

    PubMed

    Hayman, E P; Chichester, C O; Simpson, K L

    1975-07-01

    Stereospecifically labeled mevalonic acid was incorporated into the carotenoids of Rhodotorula. The randomized results are discussed in relation to mechanisms proposed for the conversion of isopentenyl pyrophosphate to dimethylallyl pyrophosphate and the prenol transferase enzyme system to Rhondotorula rubra.

  16. Mechanisms of competitive displacement of native ant fauna by invading Myrmica rubra (Hymenoptera: Formicidae) populations.

    PubMed

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

    2014-12-01

    Exotic ants have become invasive in many regions around the world, with variable ecological impacts. Postinvasion, native ant communities are often found to be depauperate, though the causes of this apparent lack of coexistence are rarely well known. Myrmica rubra (L.), a Palearctic Myrmecine ant, is currently expanding its range as an invasive in North America. This aggressive ant forms dense, patchy local infestations and appears to aggressively displace native ant fauna. We measured behavioral interactions and rates of recruitment in experimental field assays pitting native foragers against captive colonies of M. rubra at tuna-jelly or aphid baits in uninfested areas of Mt. Desert Island, ME. Behavioral interactions were idiosyncratic with respect to the native opponent, but M. rubra generally showed significantly higher levels of recruitment, aggression, and displacement of native foragers. As with other invasive ant species shown to have broken the "dominance-discovery trade-off," M. rubra was consistently faster to discover baits and disproportionately displaced native foragers, providing a plausible proximate mechanism for native ant exclusion. Finally, we surveyed ant recruitment at baits for 24 h in August 2004 at four sites with varying M. rubra abundance but found little evidence of temporal niche partitioning. Taken together, these results indicate competitive superiority by M. rubra with respect to native ant communities of the northeastern North America and suggest direct aggression and competitive exclusion at food resources can lead to local native displacement.

  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. 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.

  20. 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

  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. High stereoselectivity on low temperature Diels-Alder reactions.

    PubMed

    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 degrees 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 alpha- or beta-methyl substituted 2-cycloenones was also observed. PMID:16542029

  3. Norbornenes in inverse electron-demand Diels-Alder reactions.

    PubMed

    Vrabel, Milan; Kölle, Patrick; Brunner, Korbinian M; Gattner, Michael J; López-Carrillo, Verónica; de Vivie-Riedle, Regina; Carell, Thomas

    2013-09-27

    Significant differences in the reactivity of norbornene derivatives in the inverse electron-demand Diels-Alder reaction with tetrazines were revealed by kinetic studies. Substantial rate enhancement for the exo norbornene isomers was observed. Quantum-chemical calculations were used to rationalize and support the observed experimental data.

  4. Catalytic enantioselective intramolecular aza-diels-alder reactions.

    PubMed

    Min, Chang; Lin, Chih-Tsung; Seidel, Daniel

    2015-05-26

    A readily available chiral Brønsted acid was identified as an efficient catalyst for intramolecular Povarov reactions. Polycyclic amines containing three contiguous stereogenic centers were obtained with excellent stereocontrol in a single step from secondary anilines and aldehydes possessing a pendent dienophile. These transformations constitute the first examples of catalytic enantioselective intramolecular aza-Diels-Alder reactions.

  5. 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. PMID:1352442

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

    PubMed Central

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

    1992-01-01

    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. Images PMID:1352442

  7. Physiological effects of major up-regulated Alnus glutinosa peptides on Frankia sp. ACN14a.

    PubMed

    Carro, Lorena; Pujic, Petar; Alloisio, Nicole; Fournier, Pascale; Boubakri, Hasna; Poly, Franck; Rey, Marjolaine; Heddi, Abdelaziz; Normand, Philippe

    2016-07-01

    Alnus glutinosa has been shown previously to synthesize, in response to nodulation by Frankia sp. ACN14a, an array of peptides called Alnus symbiotic up-regulated peptides (ASUPs). In a previous study one peptide (Ag5) was shown to bind to Frankia nitrogen-fixing vesicles and to modify their porosity. Here we analyse four other ASUPs, alongside Ag5, to determine whether they have different physiological effects on in vitro grown Frankia sp. ACN14a. The five studied peptides were shown to have different effects on nitrogen fixation, respiration, growth, the release of ions and amino acids, as well as on cell clumping and cell lysis. The mRNA abundance for all five peptides was quantified in symbiotic nodules and one (Ag11) was found to be more abundant in the meristem part of the nodule. These findings point to some peptides having complementary effects on Frankia cells. PMID:27082768

  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. PMID:26399165

  9. 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.

  10. 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.

  11. 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. PMID:26595095

  12. 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.

  13. 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. PMID:23751216

  14. 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

  15. Recent Progress in Dehydro(genative) Diels-Alder Reaction.

    PubMed

    Li, Wenbo; Zhou, Liejin; Zhang, Junliang

    2016-01-26

    In recent years, remarkable progress has been made in dehydro or dehydrogenative Diels-Alder (D-A) reactions. This Minireview gives an overview of the major two strategies for dehydro(genative) Diels-Alder reactions, which differ in dehydrogenation and D-A cyclization sequence. Reactions in which D-A cycloaddition is followed by dehydrogenation are useful methods for the synthesis of various aromatic compounds, whereas advancements in dehydro genative procedures with oxidants or catalysts prior to D-A cycloaddition offer yet further new routes to functionalized cycloadducts. Recent leading findings are highlighted and the current state of the art, scope, and limitations of these processes are discussed in this Minireview. PMID:26786814

  16. Cobalt(III) porphyrin catalyzed aza-Diels-Alder reaction.

    PubMed

    Wakabayashi, Ryota; Kurahashi, Takuya; Matsubara, Seijiro

    2012-09-21

    An efficient protocol for the aza-Diels-Alder reaction of electron-deficient 1,3-dienes with unactivated imines in the presence of a cationic cobalt(III) porphyrin complex was developed. The transformation proceeded smoothly to afford the desired piperidine scaffold within 2 h at ambient temperature. Highly chemoselective cycloaddition of imines with dienes in the presence of a variety of carbonyl compounds was also demonstrated.

  17. Microsatellite loci development for red elm (Ulmus rubra Muhl.) and cross-species amplification with Siberian elm (Ulmus pumila L.)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ulmus pumila is an elm species, non-native to the United States which hybridizes with Ulmus rubra. In order to study the genetic structure and hybridization patterns between these two elm species, we developed fifteen primer pairs for microsatellite loci in U. rubra and tested their cross-amplifica...

  18. The role of red alder in riparian forest structure along headwater streams in southeastern Alaska

    USGS Publications Warehouse

    Orlikowska, E.H.; Deal, R.L.; Hennon, P.E.; Wipfli, M.S.

    2004-01-01

    We assessed the influence of red alder on tree species composition, stand density, tree size distribution, tree mortality, and potential for producing large conifers, in 38-42 yr old riparian forests along 13 headwater streams in the Maybeso and Harris watersheds on Prince of Wales Island, Alaska. Red alder ranged from 0 to 53% of the total live basal area of the stands. Tree density, basal area of live and dead trees, and mean diameter of live conifers were not significantly related to the percent of alder as a proportion of total stand live basal area within these riparian forests. The mean diameter of the 100 largest conifers per hectare (the largest trees) was similar among different sites and appeared unrelated to the amount of alder in the stands. The mean diameter of dead conifers increased slightly with increasing proportion of red alder. Most dead trees were small and died standing. Red alder was much more concentrated immediately along stream margins (within 0-1 m distance from the stream bank vs. > 1 m). The presence of red alder did not inhibit the production of large-diameter conifers, and both alder and conifers provided small woody debris for fishless headwater streams in southeastern Alaska. Red alder is an important structural component of young-growth riparian stands.

  19. 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 ...

  20. 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. PMID:15660942

  1. Patterns of Hybridization and Introgression Between Invasive Ulmus Pumila (Ulmaceae) and Native U. Rubra

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ulmus pumila (Siberian elm) is an invasive elm species, non-native to the United States, which hybridizes with Ulmus rubra (red elm), a U.S. native. While Siberian elm is highly tolerant to Dutch elm disease (DED), red elm populations in North America have been strongly affected by DED. Putative p...

  2. 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...

  3. 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.

  4. 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.

  5. 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.

  6. 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. PMID:12096738

  7. 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.

  8. Two new phenolic compounds from the leaves of Alnus sibirica Fisch. ex Turcz.

    PubMed

    Kim, Manh Heun; Park, Kwan Hee; Kim, So Ra; Park, Kwang Jun; Oh, Myeong Hwan; Heo, Jun Hyeok; Yoon, Ki Hoon; Yin, Jun; Yoon, Kyu Hyung; Lee, Min Won

    2016-01-01

    Two new phenolic compounds, 4-O-glucopyranosyl-5-O-caffeoylshikimic acid (1) and 2,3-digalloyl oregonin (2), were isolated along with eight known phenolic compounds (3-10) from an 80% acetone extract of Alnus sibirica leaves. The chemical structures of these compounds were elucidated using 1D/2D nuclear magnetic resonance and high resolution-MS. The anti-oxidative activities of these compounds were determined by assaying their 1,1-diphenyl-2-picrylhydrazyl radical and nitroblue tetrazolium superoxide anion scavenging activity. All of the isolated phenolic compounds (1-10) exhibited potent anti-oxidative activities. In particular, 2 and 4, which are diarylheptanoids, and 10 which is ellagitannin exhibited excellent anti-oxidative activities with almost the same potency as that of the positive controls L-ascorbic acid and allopurinol.

  9. Two new phenolic compounds from the leaves of Alnus sibirica Fisch. ex Turcz.

    PubMed Central

    Kim, Manh Heun; Park, Kwan Hee; Kim, So Ra; Park, Kwang Jun; Oh, Myeong Hwan; Heo, Jun Hyeok; Yoon, Ki Hoon; Yin, Jun; Yoon, Kyu Hyung; Lee, Min Won

    2016-01-01

    Two new phenolic compounds, 4-O-glucopyranosyl-5-O-caffeoylshikimic acid (1) and 2,3-digalloyl oregonin (2), were isolated along with eight known phenolic compounds (3–10) from an 80% acetone extract of Alnus sibirica leaves. The chemical structures of these compounds were elucidated using 1D/2D nuclear magnetic resonance and high resolution-MS. The anti-oxidative activities of these compounds were determined by assaying their 1,1-diphenyl-2-picrylhydrazyl radical and nitroblue tetrazolium superoxide anion scavenging activity. All of the isolated phenolic compounds (1–10) exhibited potent anti-oxidative activities. In particular, 2 and 4, which are diarylheptanoids, and 10 which is ellagitannin exhibited excellent anti-oxidative activities with almost the same potency as that of the positive controls L-ascorbic acid and allopurinol. PMID:26211877

  10. 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

  11. Hemimandibulectomy and vascularized fibula flap in bisphosphonate-induced mandibular osteonecrosis with polycythaemia rubra vera.

    PubMed

    Ghazali, N; Collyer, J C; Tighe, J V

    2013-01-01

    This report presents the successful management of an advanced and refractory bisphosphonate-related osteonecrosis of the jaws (BRONJ) by hemimandibulectomy and an osteocutaneous fibula flap reconstruction in a patient with polycythaemia rubra vera, a rare haematological condition in which there is increased risk of thrombosis and haemorrhage. Union of the vascularized bone with the mandible depends on obtaining a BRONJ-free margin and rigid fixation of the bony ends. Magnetic resonance imaging can provide accurate delineation of necrotic bone and area of osteomyelitis. Placement of a 1cm margin beyond this can envisage a BRONJ-free margin. Aggressive medical management of polycythaemia rubra vera by venesection, asprin and cytoreduction therapy along with anticoagulant prophylaxis against thromboembolic events in the first 2 weeks following major surgery can provide the basis of a good surgical and flap outcome. Nevertheless, the possibility of unpredictable haemorrhage must be considered throughout. PMID:22520725

  12. Carbon Dioxide Fixation in Roots and Nodules of Alnus glutinosa1

    PubMed Central

    McClure, Peter R.; Coker, George T.; Schubert, Karel R.

    1983-01-01

    Detached roots and nodules of the N2-fixing species, Albus glutinosa (European black alder), actively assimilate CO2. The maximum rates of dark CO2 fixation observed for detached nodules and roots were 15 and 3 micromoles CO2 fixed per gram dry weight per hour, respectively. The net incorporation of CO2 in these tissues was catalyzed by phosphoenolpyruvate carboxylase which produces organic acids, some of which are used in the synthesis of the amino acids, aspartate, glutamate, and citrulline and by carbamyl phosphate synthetase. The latter accounts for approximately 30 to 40% of the CO2 fixed and provides carbamyl phosphate for the synthesis of citrulline. Results of labeling studies suggest that there are multiple pools of malate present in nodules. The major pool is apparently metabolically inactive and of unknown function while the smaller pool is rapidly utilized in the synthesis of amino acids. Dark CO2 fixation and N2 fixation in nodules decreased after treatment of nodulated plants with nitrate while the percentage of the total 14C incorporated into organic acids increased. Phosphoenolpyruvate carboxylase and carbamyl phosphate synthetase play key roles in the synthesis of amino acids including citrulline and in the metabolism of N2-fixing nodules and roots of alder. PMID:16662882

  13. Scaling foliar respiration to the stand level throughout the growing season in a Quercus rubra forest.

    PubMed

    Xu, Cheng-Yuan; Griffin, Kevin L

    2008-04-01

    Stand-level, canopy foliar carbon loss (R(can)) was modeled for a virtual Quercus rubra L. monoculture at two sites differing in soil water availability in a northeastern deciduous forest (USA) throughout the 2003 growing season. Previously reported foliar respiratory temperature responses of Q. rubra were used to parameterize a full distributed physiology model that estimates R(can) by integrating the effects of season, site and canopy position, and represents the best estimation of R(can). Model sensitivity to five simplified parameterization scenarios was tested, and a reasonable procedure of simplification was established. Neglecting effects of season, site or canopy position on respiration causes considerable relative error in R(can) estimation. By contrast, assuming a constant E(0) (a temperature response variable of the respiration model), or a constant night temperature (mean nighttime temperature) caused only a small relative error (< 10%) compared with the full model. From June 8 to October 28, 2003, modeled R(can) of the virtual Q. rubra monoculture was, on average, 45.3 mmol CO(2) m(-2) night(-1) on a ground-area basis (or 334 mmol CO(2) kg(-1) night(-1) on a biomass basis) and 101 mmol CO(2) m(-2) night(-1) (or 361 mmol CO(2) kg(-1) night(-1)) at the drier site and the more mesic site, respectively. To model R(can) of Q. rubra (or other Quercus species with similar respiratory properties), variations in the base respiration rate across season, site and canopy position need to be fully accounted for, but E(0) may be assumed constant. Modeling R(can) at the mean nighttime temperature would not strongly affect estimated canopy carbon loss.

  14. 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.

  15. Scaling foliar respiration to the stand level throughout the growing season in a Quercus rubra forest.

    PubMed

    Xu, Cheng-Yuan; Griffin, Kevin L

    2008-04-01

    Stand-level, canopy foliar carbon loss (R(can)) was modeled for a virtual Quercus rubra L. monoculture at two sites differing in soil water availability in a northeastern deciduous forest (USA) throughout the 2003 growing season. Previously reported foliar respiratory temperature responses of Q. rubra were used to parameterize a full distributed physiology model that estimates R(can) by integrating the effects of season, site and canopy position, and represents the best estimation of R(can). Model sensitivity to five simplified parameterization scenarios was tested, and a reasonable procedure of simplification was established. Neglecting effects of season, site or canopy position on respiration causes considerable relative error in R(can) estimation. By contrast, assuming a constant E(0) (a temperature response variable of the respiration model), or a constant night temperature (mean nighttime temperature) caused only a small relative error (< 10%) compared with the full model. From June 8 to October 28, 2003, modeled R(can) of the virtual Q. rubra monoculture was, on average, 45.3 mmol CO(2) m(-2) night(-1) on a ground-area basis (or 334 mmol CO(2) kg(-1) night(-1) on a biomass basis) and 101 mmol CO(2) m(-2) night(-1) (or 361 mmol CO(2) kg(-1) night(-1)) at the drier site and the more mesic site, respectively. To model R(can) of Q. rubra (or other Quercus species with similar respiratory properties), variations in the base respiration rate across season, site and canopy position need to be fully accounted for, but E(0) may be assumed constant. Modeling R(can) at the mean nighttime temperature would not strongly affect estimated canopy carbon loss. PMID:18244949

  16. The effect of pressure on microwave-enhanced Diels-Alder reactions. A case study.

    PubMed

    Kaval, Nadya; Dehaen, Wim; Kappe, C Oliver; Van der Eycken, Erik

    2004-01-21

    It is demonstrated that microwave-assisted Diels-Alder reactions of substituted 2(1H)-pyrazinones with ethylene are significantly more effective utilizing pre-pressurized (up to 10 bar) reaction vessels.

  17. 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

    2012-06-01

    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.

  18. Electron transfer-initiated Diels-Alder cycloadditions of 2'-hydroxychalcones.

    PubMed

    Cong, Huan; Ledbetter, Dustin; Rowe, Gerard T; Caradonna, John P; Porco, John A

    2008-07-23

    An efficient approach to cyclohexenyl chalcones employing highly electron rich 2'-hydroxychalcone dienophiles via electron transfer-initiated Diels-Alder cycloaddition is described. Using the methodology, the total synthesis of nicolaiodesin C has been accomplished. PMID:18576647

  19. Mitochondrial DNA sequence and gene organization in the [corrected] Australian blacklip [corrected] abalone Haliotis rubra (leach).

    PubMed

    Maynard, Ben T; Kerr, Lyndal J; McKiernan, Joanne M; Jansen, Eliza S; Hanna, Peter J

    2005-01-01

    The complete mitochondrial DNA of the blacklip abalone Haliotis rubra (Gastropoda: Mollusca) was cloned and 16,907 base pairs were sequenced. The sequence represents an estimated 99.85% of the mitochondrial genome, and contains 2 ribosomal RNA, 22 transfer RNA, and 13 protein-coding genes found in other metazoan mtDNA. An AT tandem repeat and a possible C-rich domain within the putative control region could not be fully sequenced. The H. rubra mtDNA gene order is novel for mollusks, separated from the black chiton Katharina tunicata by the individual translocations of 3 tRNAs. Compared with other mtDNA regions, sequences from the ATP8, NAD2, NAD4L, NAD6, and 12S rRNA genes, as well as the control region, are the most variable among representatives from Mollusca, Arthropoda, and Rhynchonelliformea, with similar mtDNA arrangements to H. rubra. These sequences are being evaluated as genetic markers within commercially important Haliotis species, and some applications and considerations for their use are discussed. PMID:16206015

  20. 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. PMID:27014774

  1. 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 ??15N 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. ?? 2005 Regents of the University of Colorado.

  2. 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.

  3. 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. PMID:24234763

  4. 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. PMID:26485638

  5. 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.

  6. 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. PMID:26091871

  7. Modeling climate impact on an emerging disease, the Phytophthora alni-induced alder decline.

    PubMed

    Aguayo, Jaime; Elegbede, Fabrice; Husson, Claude; Saintonge, François-Xavier; Marçais, Benoît

    2014-10-01

    Alder decline caused by Phytophthora alni is one of the most important emerging diseases in natural ecosystems in Europe, where it has threatened riparian ecosystems for the past 20 years. Environmental factors, such as mean site temperature and soil characteristics, play an important role in the occurrence of the disease. The objective of the present work was to model and forecast the effect of environment on the severity of alder Phytophthora outbreaks, and to determine whether recent climate change might explain the disease emergence. Two alder sites networks in NE and SW France were surveyed to assess the crown health of trees; the oomycete soil inoculum was also monitored in the NE network. The main factors explaining the temporal annual variation in alder crown decline or crown recovery were the mean previous winter and previous summer temperatures. Both low winter temperatures and high summer temperatures were unfavorable to the disease. Cold winters promoted tree recovery because of poor survival of the pathogen, while hot summer temperature limited the incidence of tree decline. An SIS model explaining the dynamics of the P. alni-induced alder decline was developed using the data of the NE site network and validated using the SW site network. This model was then used to simulate the frequency of declining alder over time with historical climate data. The last 40 years' weather conditions have been generally favorable to the establishment of the disease, indicating that others factors may be implicated in its emergence. The model, however, showed that the climate of SW France was much more favorable for the disease than that of the Northeast, because it seldom limited the overwintering of the pathogen. Depending on the European area, climate change could either enhance or decrease the severity of the alder decline.

  8. Ecological and genetic effects of cutting in an Alnus trabeculosa Hand.-Mazz. (Betulaceae) population.

    PubMed

    Miyamoto, N; Karamoto, N; Takahashi, M

    2003-09-01

    In order to assess the ecological and genetic effects of cutting, we compared two portions of Alnus trabeculosa population at Yuda (Iwate Prefecture, Japan): one that has been cut about 30 years ago and one that has remained uncut. These portions were compared in terms of the degree of sprouting, genetic variation and gene distribution using isozyme markers. First, we determined the multilocus genotype (MLG) of all ramets, then sorted them into individuals according to the distribution of the MLGs. The average (+/- SE) of largest distance between ramets in one individual was 2.1 (+/- 0.18) m, which is consistent with the distance (2.0 (+/- 0.20) m) obtained by tracing physical connections between ramets. We found no significant differences in genetic variation between the two portions, but there were significant differences in their degree of sprouting. Furthermore, there were striking differences in gene distribution: the cut portion showed greater clustering of individuals with identical genetic components, which may be due to regeneration in the gaps made by cutting, reflecting the location of the mother trees, and seed and pollen dispersal from them. PMID:12939636

  9. Vaccinium myrtillus leaves and Frangula alnus bark derived extracts as potential antistaphylococcal agents.

    PubMed

    Sadowska, Beata; Paszkiewicz, Małgorzata; Podsędek, Anna; Redzynia, Małgorzata; Różalska, Barbara

    2014-01-01

    Due to constantly increasing antibiotic resistance of pathogens and participation of the biofilms they make in various types of infections, a development of alternative therapeutic strategies becomes an urgent need. Taking advantage of the biological activity of plant-derived compounds can solve this problem. In this study antimicrobial, including those synergistic with classic antibiotics, and cytotoxic properties of newly-obtained extracts from Vaccinium myrtillus leaves (VLE) and Frangula alnus bark (FBE) were evaluated. Both tested extracts exhibited relevant antistaphylococcal activity (MIC range 0.75-1.5 mg/mL) accompanied by a relativly low cytotoxic effect on mammalian cells (BI > 1). Phytochemical analysis of the extracts tested showed a high total content of phenolic compounds with the predominance of hydroxycinnamic acids in VLE and hydroxybenzoic acids and flavanols in FBE. Widely described in the literature antimicrobial properties of phenolics were probably connected with the biological activity of the extracts tested. We also report that the presence of VLE or FBE at sub-MIC concentrations enhances biocidal potential of vancomycin and linezolid. Therefore, we are considering a possibility of an alternative therapy for local infections caused by S. aureus by combining classic antibiotics with plant-derived extracts. PMID:24649485

  10. Facile Diels-Alder reactions with pyridines promoted by tungsten.

    PubMed

    Graham, Peter M; Delafuente, David A; Liu, Weijun; Myers, William H; Sabat, Michal; Harman, W D

    2005-08-01

    The isoquinuclidine (2-azabicyclo[2.2.2]octane) core is found in numerous molecules of biological and medicinal importance, including the widely investigated Iboga alkaloids and their related bisindole Cantharanthus alkaloids (Sundberg, R. J.; Smith, S. Q. Alkaloids (San Diego, CA, United States) 2002, 59, 281-386). A diverse range of synthetic methods for the stereoselective construction of this architecture is required for the efficient development of related pharmaceuticals. Here, we report a fundamentally new methodology that constructs the isoquinuclidine core directly from pyridines, using a pi-basic tungsten complex to disrupt the aromatic stabilization of these otherwise inert heterocycles. By this approach, common pyridines are found to undergo stereoselective Diels-Alder reactions with electron-deficient alkenes under mild reaction conditions, thus providing access to a broad range of functionalized isoquinuclidines. Further, by using the common terpene alpha-pinene, a single enantiomer of the tungsten fragment can be isolated and used to provide access to enantio-enriched isoquinuclidines from pyridines.

  11. Fulminant Budd-Chiari syndrome associated with polycythemia rubra vera and factor V Leiden mutation.

    PubMed

    Akyildiz, Murat; Karasu, Zeki; Dheir, Hamad; Osmanoglu, Necla; Akay, Sinan; Ilter, Tankut

    2006-01-01

    Budd-Chiari syndrome (BCS) is a severe disorder characterized by hepatic venous outflow obstruction. Hypercoagulable states are the major etiological factors for the development of BCS and can be identified in about 75% of patients. Multiple etiological factors can be found in the same patient. Hematologic abnormalities, especially myeloproliferative disorders, are the most common causes of BCS. Furthermore, the prevalence of factor V Leiden mutation is three times greater in patients with BCS. Although the clinical course tends to be chronic, BCS may, on rare occasions, cause acute liver failure. Herein, we report a patient who had factor V Leiden mutation and polycythemia rubra vera, presented as fulminant BCS. PMID:16378893

  12. Sofosbuvir-Induced Erythrodermic Pityriasis Rubra Pilaris-Like Drug Eruption.

    PubMed

    Cheung, Evelyn J; Jedrych, Jaroslaw J; English, Joseph C

    2015-10-01

    Until 2011, the standard-of-care therapy for patients with hepatitis C consisted of interferon and ribavirin. The recent advent of new targeted therapies against this virus has provided more options of treatment for infected patients. Sofosbuvir, a nucleotide inhibitor of hepatitis C virus (HCV) RNA polymerase, was recently approved by the US Food and Drug Administration in 2013. Various Phase 3 trials with sofosbuvir combination therapy have reported an incidence of rash between 7% and 18%. We here describe a case of sofosbuvir-induced erythrodermic pityriasis rubra pilaris-like drug eruption.

  13. The breeding system of wild red ruffed lemurs (Varecia rubra): a preliminary report.

    PubMed

    Vasey, Natalie

    2007-01-01

    Captive studies have shown that ruffed lemurs (Varecia) have an unusual suite of reproductive traits combined with extremely high maternal reproductive costs. These traits include the bearing of litters, nesting of altricial young, and absentee parenting. To characterize the breeding system of this enigmatic lemur, reproductive traits must be contextualized in the wild. Here, I provide a preliminary report of mating and infant care in one community of wild red ruffed lemurs (Varecia rubra). Observations span a 15-month period covering two birth seasons and one mating season on the Masoala Peninsula, Madagascar. Factors that are not possible to replicate in captivity are reported, such as mating pattern, natality and mortality rates, the location of nests within the home range, and the structuring of infant care within a natural community. V. rubra at Andranobe have a fission-fusion, multifemale-multimale grouping pattern and a polygamous mating system. They do not mate monogamously or live strictly in family-based groups as suggested by previous workers. During the first 2 months of life, nests and infant stashing localities are situated within each mother's respective core area, and inhabitants of each core area within the communal home range provide care for young. As part of their absentee parenting system, infants are left in concealed, protected, and supportive spots high in the canopy, while mothers travel distantly. This practice is termed 'infant stashing'. Alloparenting appears to be an integral part of V. rubra's overall reproductive strategy in the wild, as it was performed by all age-sex classes. Among the alloparental behaviors observed were infant guarding, co-stashing, infant transport, and allonursing. Alloparenting and absentee parenting may mitigate high maternal reproductive costs. Furthermore, V. rubra may have a breeding system in which genetic partners (i.e., mating partners) do not always correspond to infant care-providers. Combined with

  14. Antibacterial Δ(1) -3-ketosteroids from the South China Sea gorgonian coral Subergorgia rubra.

    PubMed

    Sun, Xue-Ping; Cao, Fei; Shao, Chang-Lun; Wang, Mei; Zhang, Xiu-Li; Wang, Chang-Yun

    2015-07-01

    Three new Δ(1) -3-ketosteroids characterized with a 9-OH, subergosterones A-C (1-3), together with five known analogs 4-8, were obtained from the gorgonian coral Subergorgia rubra collected from the South China Sea. The structures of 1-3, including their absolute configurations, were determined by comprehensive spectroscopic methods and electronic circular dichroism (ECD) experiments. Compounds 2 and 3 exhibited inhibitory antibacterial activities against Bacillus cereus with MIC values of 1.56 μM.

  15. A 2-substituted prodiginine, 2-(p-hydroxybenzyl)prodigiosin, from Pseudoalteromonas rubra.

    PubMed

    Fehér, Domonkos; Barlow, Russell S; Lorenzo, Patricia S; Hemscheidt, Thomas K

    2008-11-01

    In the course of work aimed at the discovery of new pharmaceutical lead compounds from marine bacteria, a lipophilic extract of the bacterium Pseudoalteromonas rubra displayed significant cytotoxicity against SKOV-3, a human ovarian adenocarcinoma cell line. Bioassay-directed fractionation of this extract resulted in the isolation of a series of known and new prodiginine-type azafulvenes. The structure of the major metabolite was elucidated by interpretation of spectroscopic data as a 2-substituted prodigiosin, which we named 2-(p-hydroxybenzyl)prodigiosin (HBPG).

  16. Complete genome sequence of Pseudoalteromonas rubra SCSIO 6842, harboring a putative conjugative plasmid pMBL6842.

    PubMed

    Li, Baiyuan; Wang, Pengxia; Zeng, Zhenshun; Cai, Xingsheng; Wang, Guanghua; Wang, Xiaoxue

    2016-04-20

    Pseudoalteromonas is a genus of Gram-negative and is ubiquitously distributed in the ocean. Many Pseudoalteromonas species are capable of producing pigments, which can serve as an alternative source to replace synthetic pigments used in the food industry. Prodigiosins belong to a family of secondary metabolite characterized by a common pyrrolyl pyrromethane skeleton, and have been successfully applied to yogurt, milk and carbonated drinks as substitutes for synthetic additives. The strain Pseudoalteromonas rubra SCSIO 6842 can produce cycloprodigiosin and harbors a conjugative plasmid. Here we report the complete genome of P. rubra SCSIO 6842 for a better understanding of the molecular basis of cycloprodigiosin production and regulation. PMID:26970053

  17. Complete genome sequence of Pseudoalteromonas rubra SCSIO 6842, harboring a putative conjugative plasmid pMBL6842.

    PubMed

    Li, Baiyuan; Wang, Pengxia; Zeng, Zhenshun; Cai, Xingsheng; Wang, Guanghua; Wang, Xiaoxue

    2016-04-20

    Pseudoalteromonas is a genus of Gram-negative and is ubiquitously distributed in the ocean. Many Pseudoalteromonas species are capable of producing pigments, which can serve as an alternative source to replace synthetic pigments used in the food industry. Prodigiosins belong to a family of secondary metabolite characterized by a common pyrrolyl pyrromethane skeleton, and have been successfully applied to yogurt, milk and carbonated drinks as substitutes for synthetic additives. The strain Pseudoalteromonas rubra SCSIO 6842 can produce cycloprodigiosin and harbors a conjugative plasmid. Here we report the complete genome of P. rubra SCSIO 6842 for a better understanding of the molecular basis of cycloprodigiosin production and regulation.

  18. 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 ...

  19. 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.

  20. Transpiration of shrub species, Alnus firma under changing atmospheric environments in montane area, Japan

    NASA Astrophysics Data System (ADS)

    Miyazawa, Y.; Maruyama, A.; Inoue, A.

    2014-12-01

    In the large caldera of Mt. Aso in Japan, grasslands have been traditionally managed by the farmers. Due to changes in the social structure of the region, a large area of the grassland has been abandoned and was invaded by the shrubs with different hydrological and ecophysiological traits. Ecophysiological traits and their responses to seasonally changing environments are fundamental to project the transpiration rates under changing air and soil water environments, but less is understood. We measured the tree- and leaf-level ecophysiological traits of a shrub, Alnus firma in montane region where both rainfall and soil water content drastically changes seasonally. Sap flux reached the annual peak in evaporative summer (July-August) both in 2013 and 2014, although the duration was limited within a short period due to the prolonged rainy season before summer (2014) and rapid decrease in the air vapor pressure deficit (D) in late summer. Leaf ecophysiological traits in close relationship with gas exchange showed modest seasonal changes and the values were kept at relatively high levels typical in plants with nitrogen fixation under nutrient-poor environments. Stomatal conductance, which was measured at leaf-level measurements and sap flux measurements, showed responses to D, which coincided with the theoretical response for isohydric leaves. A multilayer model, which estimates stand-level transpiration by scaling up the leaf-level data, successfully captured the temporal trends in sap flux, suggesting that major processes were incorporated. Thus, ecophysiological traits of A. firma were characterized by the absence of responses to seasonally changing environments and the transpiration rate was the function of the interannually variable environmental conditions.

  1. 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

    2016-03-01

    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.

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

    PubMed

    Tuvi-Arad, Inbal; Avnir, David

    2012-08-01

    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.

  3. 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

  4. Collagen fiber immobilized Myrica rubra tannin and its adsorption to UO2(2+).

    PubMed

    Liao, Xuepin; Lu, Zhongbi; Du, Xiao; Liu, Xin; Shi, Bi

    2004-01-01

    Tannins, which are rich in ortho-hydroxyl groups, have a high affinity for UO2(2+). In this paper, Myrica rubra tannin was immobilized on collagen fiber by an aldehydic cross-linking reaction to prepare a novel adsorbent for uranium (UO2(2+)) recovery from wastewater. The adsorption equilibrium, the adsorption kinetics, and the effects of temperature and pH on the adsorption equilibrium were investigated in detail. It was found that the Myrica rubra tannin immobilized on collagen fiber exhibits an excellent adsorption capacity for UO2(2+). The adsorption capacity at 293 K and pH 5.0 was as high as 1.19 mmol UO2(2+)/g (283.3 mgU/g) when the initial concentration of UO2(2+) in solution was 7.5 mmol/L. The adsorption isotherms could be described by the Freundlich equation, and the increase of temperature promoted the adsorption to UO2(2+) . The adsorption kinetics data were fitted very well by the pseudosecond-order rate model, and the equilibrium adsorption capacity calculated by the pseudo-second-order rate model was almost the same as that determined by the actual measurement with the error < or = 4%. The pH has a significant effect on the adsorption process. According to our experiments, the suitable pH scope should be 5-8.

  5. Competition between classical and hexadehydro-Diels–Alder (HDDA) reactions of HDDA triynes with furan

    PubMed Central

    Nguyen, Quang Luu; Baire, Beeraiah; Hoye, Thomas R.

    2015-01-01

    We report here thermal reactions between furan and one of three related triyne substrates. Each triyne is capable of reacting initially in two modes: (i) unimolecular hexadehydro-Diels-Alder (HDDA) reaction or (ii) bimolecular Diels-Alder reaction between one of its alkynes with furan. The relative rates of these initial events are such that two of the substrates react essentially in only one of modes (i) or (ii). The third is intermediate in behavior; its bifurcation is dependent on the concentration of the furan reactant. These results teach, more generally, principles relevant to the design of efficient HDDA-based reaction cascades. PMID:26028780

  6. 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

  7. 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.

  8. Hybridization between red elm (Ulmus rubra Muhl.) and Siberian elm (Ulmus pumila L.) confirmed using microsatellite markers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ulmus pumila (Siberian elm) is an invasive elm species, non-native to the United States, which hybridizes with Ulmus rubra (red elm), a U.S. native. In order to study the population genetic structure of each species and the genetic hybridization patterns between the two species, we developed fiftee...

  9. PSI photoinhibition is more related to electron transfer from PSII to PSI rather than PSI redox state in Psychotria rubra.

    PubMed

    Huang, Wei; Yang, Ying-Jie; Zhang, Jiao-Lin; Hu, Hong; Zhang, Shi-Bao

    2016-07-01

    Although it has been believed that wild-type plants are capable of protecting photosystem I (PSI) under high light, our previous study indicates that PSI is sensitive to high light in the shade-established tree species Psychotria rubra. However, the underlying physiological mechanisms are unclear. In this study, we examined the roles of electron transfer from PSII to PSI and PSI redox state in PSI photoinhibition in P. rubra by treatments with lincomycin (Lin), diuron (DCMU), and methyl viologen (MV). After exposure to 2000 μmol photons m(-2) s(-1) for 2 h, PSI activity decreased by 35, 29, 3, and 49 % in samples treated with H2O, Lin, DCMU, and MV, respectively. Meanwhile, the MV-treated samples showed higher P700 oxidation ratio than the H2O-treated samples, suggesting the PSI photoinhibition under high light was accompanied by high levels of P700 oxidation ratio. PSI photoinhibition was alleviated in the DCMU-treated samples but was accelerated in the MV-treated samples, suggesting that PSI photoinhibition in P. rubra was mainly controlled by electron transfer from PSII to PSI. Taking together, PSI photoinhibition is more related to electron transfer from PSII to PSI rather than PSI redox state in P. rubra, which is different from the mechanisms of PSI photoinhibition in Arabidopsis thaliana and cucumber.

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

    PubMed

    Hacke, U.; Sauter, J. J.

    1996-06-01

    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.

  11. Bioactivity-guided identification of antimicrobial metabolites in Alnus glutinosa bark and optimization of oregonin purification by Centrifugal Partition Chromatography.

    PubMed

    Abedini, Amin; Chollet, Sébastien; Angelis, Apostolis; Borie, Nicolas; Nuzillard, Jean-Marc; Skaltsounis, Alexios-Leandros; Reynaud, Romain; Gangloff, Sophie C; Renault, Jean-Hugues; Hubert, Jane

    2016-09-01

    Barks from conifers and broadleaved trees constitute abundant wastes generated from wood harvesting and logging activities. Extracts of such residues obtained from Alnus trees have been reported as interesting resources with potent antibacterial activities. The present study aims to determine the antimicrobial activity of a crude methanol extract prepared from the bark of Alnus glutinosa against a panel of 22 bacteria and yeasts and to optimize a purification method enabling the high production of the most active substances. Fractionation of the crude extract was performed by Centrifugal Partition Chromatography (CPC) using a three-phase solvent system composed of n-heptane, methyl-ter-butyl ether, acetonitrile and water. The major known compounds contained in the fractions produced by CPC were chemically profiled by (13)C NMR dereplication, resulting in the unambiguous identification of oregonin, hirsutanonol, betulinic acid, and alusenone 1a. The antibacterial evaluation of the fractions by bioautography on Staphylococcus aureus revealed that oregonin, in addition to being the major metabolite of the crude extract (∼32% w/w), was the most active with an antibacterial inhibitory effect comparable to antibiotics. The purification of oregonin was optimized at the laboratory-scale by CPC. A single injection of 3.7g of crude extract resulted in a recovery of 72% (850mg) of the available oregonin at purity higher than 94%.

  12. Bioactivity-guided identification of antimicrobial metabolites in Alnus glutinosa bark and optimization of oregonin purification by Centrifugal Partition Chromatography.

    PubMed

    Abedini, Amin; Chollet, Sébastien; Angelis, Apostolis; Borie, Nicolas; Nuzillard, Jean-Marc; Skaltsounis, Alexios-Leandros; Reynaud, Romain; Gangloff, Sophie C; Renault, Jean-Hugues; Hubert, Jane

    2016-09-01

    Barks from conifers and broadleaved trees constitute abundant wastes generated from wood harvesting and logging activities. Extracts of such residues obtained from Alnus trees have been reported as interesting resources with potent antibacterial activities. The present study aims to determine the antimicrobial activity of a crude methanol extract prepared from the bark of Alnus glutinosa against a panel of 22 bacteria and yeasts and to optimize a purification method enabling the high production of the most active substances. Fractionation of the crude extract was performed by Centrifugal Partition Chromatography (CPC) using a three-phase solvent system composed of n-heptane, methyl-ter-butyl ether, acetonitrile and water. The major known compounds contained in the fractions produced by CPC were chemically profiled by (13)C NMR dereplication, resulting in the unambiguous identification of oregonin, hirsutanonol, betulinic acid, and alusenone 1a. The antibacterial evaluation of the fractions by bioautography on Staphylococcus aureus revealed that oregonin, in addition to being the major metabolite of the crude extract (∼32% w/w), was the most active with an antibacterial inhibitory effect comparable to antibiotics. The purification of oregonin was optimized at the laboratory-scale by CPC. A single injection of 3.7g of crude extract resulted in a recovery of 72% (850mg) of the available oregonin at purity higher than 94%. PMID:27428455

  13. 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.

  14. 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

  15. Assembly of the Isoindolinone Core of Muironolide A by Asymmetric Intramolecular Diels-Alder Cycloaddition

    PubMed Central

    Flores, Beatris; Molinski, Tadeusz F.

    2011-01-01

    The hexahydro-1H-isoindolin-1-one core of muironolide A was prepared by asymmetric intramolecular Diels Alder cycloaddition using a variant of the MacMillan organocatalyst which sets the C4,C5 and C11 stereocenters. PMID:21751773

  16. 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…

  17. Concise total synthesis of (-)-auxofuran by a click Diels-Alder strategy.

    PubMed

    Boukouvalas, John; Loach, Richard P

    2013-09-20

    The first synthesis of auxofuran, a newly discovered auxin-like signaling molecule of streptomycetes, has been achieved in seven steps and 59% overall yield from commercial starting materials. Central to the synthetic route is a click-unclick Diels-Alder cycloaddition/cycloreversion regimen enabling rapid access to an advanced intermediate from an unactivated alkyne.

  18. Regioselectivity of Diels-Alder Reactions Between 6,7-Dehydrobenzofuran and 2-Substituted Furans

    PubMed Central

    Brown, Neil; Buszek, Keith R.

    2014-01-01

    We describe the first report of the generation of 6,7-dehydrobenzofuran (6,7-benzofuranyne) from 6,7-dihalobenzofurans via metal-halogen exchange and elimination, in a manner similar to our previous work with 6,7-indole arynes. This benzofuranyne undergoes highly regioselective Diels-Alder cycloadditions with 2-substituted furans. PMID:25278635

  19. Sulfinyl-mediated stereoselective Overman rearrangements and Diels-Alder cycloadditions.

    PubMed

    Fernández de la Pradilla, Roberto; Colomer, Ignacio; Viso, Alma

    2012-06-15

    The Overman rearrangement of allylic sulfinyl trichloroacetimidates affords sulfinyl trichloroacetamides with high stereoselectivity and excellent yields. Bis-allylic substrates lead to amido 2-sulfinyl butadiene derivatives in excellent yields, with total chemo- and diastereoselectivity. The Diels-Alder cycloaddition of related dienes is controlled by the sulfoxide moiety.

  20. Ugi/Himbert Arene/Allene Diels-Alder Cycloaddition to Synthesize Strained Polycyclic Skeleton.

    PubMed

    Cheng, Guangsheng; He, Xiang; Tian, Lumin; Chen, Jiawen; Li, Chunju; Jia, Xueshun; Li, Jian

    2015-11-01

    The present work disclosed an efficient multicomponent reaction of isocyanide, allenic acid, aldehyde (ketone), and aniline. This protocol undergoes Ugi reaction followed by an intramolecular arene/allene Diels-Alder sequence, thus providing a rapid access to synthesize strained polycyclic skeletons.

  1. Functionalization of organic semiconductor crystals via the Diels-Alder reaction.

    PubMed

    Qualizza, Brittni A; Prasad, Srividya; Chiarelli, M Paul; Ciszek, Jacob W

    2013-05-18

    A surface adlayer is generated on organic single crystals (tetracene and rubrene) using the site specific Diels-Alder reaction and a series of vapor phase dienophiles. X-ray photoelectron spectroscopy (XPS) confirms adsorption on the surfaces of tetracene and rubrene and mass spectrometry demonstrates the reaction's applicability to a range of dienophiles. PMID:23571721

  2. 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.

  3. The population genomic signature of environmental selection in the widespread insect-pollinated tree species Frangula alnus at different geographical scales.

    PubMed

    De Kort, H; Vandepitte, K; Mergeay, J; Mijnsbrugge, K V; Honnay, O

    2015-11-01

    The evaluation of the molecular signatures of selection in species lacking an available closely related reference genome remains challenging, yet it may provide valuable fundamental insights into the capacity of populations to respond to environmental cues. We screened 25 native populations of the tree species Frangula alnus subsp. alnus (Rhamnaceae), covering three different geographical scales, for 183 annotated single-nucleotide polymorphisms (SNPs). Standard population genomic outlier screens were combined with individual-based and multivariate landscape genomic approaches to examine the strength of selection relative to neutral processes in shaping genomic variation, and to identify the main environmental agents driving selection. Our results demonstrate a more distinct signature of selection with increasing geographical distance, as indicated by the proportion of SNPs (i) showing exceptional patterns of genetic diversity and differentiation (outliers) and (ii) associated with climate. Both temperature and precipitation have an important role as selective agents in shaping adaptive genomic differentiation in F. alnus subsp. alnus, although their relative importance differed among spatial scales. At the 'intermediate' and 'regional' scales, where limited genetic clustering and high population diversity were observed, some indications of natural selection may suggest a major role for gene flow in safeguarding adaptability. High genetic diversity at loci under selection in particular, indicated considerable adaptive potential, which may nevertheless be compromised by the combined effects of climate change and habitat fragmentation. PMID:25944466

  4. Draft genome sequence of Frankia sp. strain QA3, a nitrogen-fixing actinobacterium isolated from the root nodule of Alnus nitida.

    PubMed

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

    2013-01-01

    Members of the 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. strain QA3, a nitrogen-fixing actinobacterium isolated from root nodules of Alnus nitida. PMID:23516220

  5. Draft Genome Sequence of Frankia sp. Strain QA3, a Nitrogen-Fixing Actinobacterium Isolated from the Root Nodule of Alnus nitida

    PubMed Central

    Sen, Arnab; Beauchemin, Nicholas; Bruce, David; Chain, Patrick; Chen, Amy; Walston Davenport, Karen; Deshpande, Shweta; Detter, Chris; Furnholm, Teal; Ghodbhane-Gtari, Faten; Goodwin, Lynne; Gtari, Maher; Han, Cliff; Han, James; Huntemann, Marcel; Ivanova, Natalia; Kyrpides, Nikos; Land, Miriam L.; Markowitz, Victor; Mavrommatis, Kostas; Nolan, Matt; Nouioui, Imen; Pagani, Ioanna; Pati, Amrita; Pitluck, Sam; Santos, Catarina L.; Sur, Saubashya; Szeto, Ernest; Tavares, Fernando; Teshima, Hazuki; Thakur, Subarna; Wall, Luis; Woyke, Tanja; Wishart, Jessie

    2013-01-01

    Members of the 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. strain QA3, a nitrogen-fixing actinobacterium isolated from root nodules of Alnus nitida. PMID:23516220

  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. Aluminum and temperature alteration of cell membrane permeability of Quercus rubra

    SciTech Connect

    Junping Chen; Sucoff, E.I.; Stadelmann, E.J. )

    1991-06-01

    Al toxicity is the major factor limiting plant growth in acid soils. This report extends research on Al-induced changes in membrane behavior of intact root cortex cells of Northern red oak (Quercus rubra). Membrane permeability was determined by the plasmometric method for individual intact cells at temperatures from 2 or 4 to 35 C. Al (0.37 millimolar) significantly increased membrane permeability to urea and monoethyl urea and decreased permeability to water. Al significantly altered the activation energy required to transport water (+ 32%), urea (+ 9%), and monoethyl urea ({minus}7%) across cell membranes. Above 9 C, Al increased the lipid partiality of the cell membranes; below 7 C, Al decreased it. Al narrowed by 6 C the temperature range over which plasmolysis occurred without membrane damage. These changes in membrane behavior are explainable if Al reduced membrane lipid fluidity and kink frequency and increases packing density and the occurrence of straight lipid chains.

  8. Mitochondrial protective effects of Myrica rubra extract against acetaminophen-induced toxicity.

    PubMed

    Gou, Wenwen; Xu, Lizhi; Wang, Yucai; Yu, Wen; Zhong, Zengtao; Gao, Jing; Chen, Huimei; Wang, Yaping

    2013-01-01

    The present study investigates the hepatoprotective activity of Myrica rubra Sieb. et Zucc. extract (MCE) against acetaminophen (AAP)-induced liver damage and elucidates the possible mechanisms behind the hepatoprotection observed. Serum alanine aminotransferase and serum aspartate aminotransferase activities were detected and liver histopathology was observed. Mitochondrial swelling, mitochondrial membrane potential, and voltage-dependent anion channel (VDAC) gene transcription were also investigated. The results showed that 50, 150, and 450 mg/kg MCE could restore AAP-induced changes in mice liver in a dose-dependent manner. The mechanisms behind the hepatoprotective effects of MCE may be related to the mitochondrial protection of liver cells, especially of VDAC, an important protein on the outer membrane of the mitochondria. PMID:24117068

  9. 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

  10. Granulosis rubra nasi: a rare condition treated successfully with topical tacrolimus

    PubMed Central

    Kumar, Piyush; Gosai, Anubhav; Mondal, Ashim Kumar; Lal, Niharika Ranjan; Gharami, Ramesh Chandra

    2012-01-01

    A 20 years-old girl presented with multiple asymptomatic reddish vesicles on face for four years. It used to get worse in summer and was associated with localized hyperhidrosis. The lesions were notable for disappearance on diascopy. Histopathology from the vesicle showed mononuclear cell infiltration in the upper dermis, especially around eccrine sweat apparatus, along with dilatation of superficial capillaries and lymphatics. Based on clinical presentation and histopathology, diagnosis of Granulosis rubra nasi (GRN) was made. GRN usually resolves at puberty; however, rarely it may persist in adulthood. We here report a case of GRN having lesions persisting in adulthood. Moreover, she showed excellent response to topical tacrolimus, a finding not observed in literature. PMID:25386315

  11. Highly enantioselective production of (R)-halohydrins with whole cells of Rhodotorula rubra KCh 82 culture.

    PubMed

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

    2014-12-04

    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.

  12. 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.

  13. Subergorgiaols A-L, 9,10-secosteroids from the South China Sea gorgonian Subergorgia rubra.

    PubMed

    Sun, Xue-Ping; Cao, Fei; Shao, Chang-Lun; Chen, Min; Liu, Hai-Juan; Zheng, Cai-Juan; Wang, Chang-Yun

    2015-02-01

    Twelve new 9,10-secosteroids designated as subergorgiaols A-L (1-12), along with four known analogues (13-16), were isolated from the gorgonian Subergorgia rubra collected from the South China Sea. Their planar structures and the relative configurations were elucidated by comprehensive spectroscopic methods including NOESY spectra. The absolute configuration of 1 was established by a dimolybdenum tetraacetate [Mo2(AcO)4] induced circular dichroism (ICD) procedure and the modified Mosher's method. Compounds 1-12 represent the first series of 9,10-secosteroids characterized with a hydroxy group at C-8, which are 8-OH derivatives of astrogorgiadiols/calicoferols. Compound 4 exhibited cytotoxicity against the cervical carcinoma cell line (CaSki) with an IC50 value of 2.4 μM, and 6 showed toxicity toward brine shrimp Artemia salina with an LC50 value of 2.0 μM.

  14. Mechanism of angiogenic effects of saponin from ginseng Radix rubra in human umbilical vein endothelial cells.

    PubMed Central

    Morisaki, N.; Watanabe, S.; Tezuka, M.; Zenibayashi, M.; Shiina, R.; Koyama, N.; Kanzaki, T.; Saito, Y.

    1995-01-01

    1. The effects of saponin from Ginseng Radix rubra on angiogenesis (tube formation) and its key steps (protease secretion, proliferation and migration) in human umbilical vein endothelial cells (HUVEC) were examined to elucidate the mechanism of the tissue repairing effects of Ginseng Radix rubra. The effect on a wound healing model was also studied. 2. Tube formation was measured by an in vitro system. The activity and immunoreactivity of tissue-type plasminogen activator (tPA) as a protease for angiogenesis and the immunoreactivity of its inhibitor, plasminogen activator inhibitor-1 (PAI-1), were measured in conditioned medium of HUVEC stimulated for 24 h with saponin. Cell proliferation was measured by counting the cell numbers at 2-7 days after seeding. Migration was measured by Boyden's chamber method. The effect on wound healing was studied in the skin of diabetic rats. 3. Saponin at 10-100 micrograms ml-1 significantly stimulated tube formation by HUVEC in a dose-dependent manner. Saponin in a similar concentration-range increased the secretion of tPA from HUVEC as estimated by immunoreactivity and enzyme activity. On the other hand, PAI-1 immunoreactivity was slightly increased at 10 micrograms ml-1 of saponin, but then was significantly decreased at 50 and 100 micrograms ml-1. Cell proliferation was only slightly enhanced by 1-100 micrograms ml-1 of saponin, but migration was significantly enhanced by 10-100 micrograms ml-1 in a dose-dependent manner. Moreover, saponin stimulated wound healing with enhanced angiogenesis in vivo.(ABSTRACT TRUNCATED AT 250 WORDS) Images Figure 1 Figure 8 PMID:7582543

  15. Hypolipidemic effects of Myrica rubra extracts and main compounds in C57BL/6j mice.

    PubMed

    He, Kai; Li, Xuegang; Xiao, Yubo; Yong, Yang; Zhang, Zaiqi; Li, Shuping; Zhou, Taimei; Yang, Daqing; Gao, Pincao; Xin, Xiaoliang

    2016-08-10

    The present study evaluated the antihyperlipidemic activity of myricetin, myricetrin, the alcohol fraction (AF) and the ethyl acetate fraction (EF) obtained from the bark of Myrica rubra (MR) in high-fat and high-cholesterol (HFHC) induced hyperlipidemic C57BL/6j mice. Mice were treated with myricetin, myricetrin, AF and EF with a dose of 130 mg per kg per day for 35 days. After treatment, serum parameters including total cholesterol (TC), triglyceride (TG), low-density lipoprotein cholesterol (LDL-C), total bile acids (TBA), etc., were examined. The results revealed that EF showed the highest weight lowering activity (P < 0.01). All tested samples decreased the levels of the TC, TG, LDL-C, TBA and LPS (lipopolysaccharide) content in the serum of mice to different extents. Liver fat deposition was significantly reduced after myricetin, myricetrin, AF and EF therapy (P < 0.01). Additionally, the cell size of epididymal adipose tissue was also decreased in myricetin, AF and EF groups (P < 0.05). The antihyperlipidemic activity of these samples may be attributed to the inhibition of lipid synthesis via suppressing the expression of HMGCR (3-hydroxy-3-methylglutaryl coenzyme A reductase) and ACC1 (acetyl-CoA carboxylase), promoting the metabolism and excretion of lipids via up-regulating the expression of SREBP2 (sterol regulatory element binding proteins), LDLR (low density lipoprotein receptor), UCP2 (uncoupling protein 2) and CYP7A1 (cholesterol 7α-hydroxylase). These results may provide a powerful foundation for seeking and utilizing Myrica rubra bio-active compounds for the treatment of hyperlipidemia and cardiovascular diseases. PMID:27459037

  16. 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.

  17. 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.

  18. Abundance and Relative Distribution of Frankia Host Infection Groups Under Actinorhizal Alnus glutinosa and Non-actinorhizal Betula nigra Trees.

    PubMed

    Samant, Suvidha; Huo, Tian; Dawson, Jeffrey O; Hahn, Dittmar

    2016-02-01

    Quantitative polymerase chain reaction (qPCR) was used to assess the abundance and relative distribution of host infection groups of the root-nodule forming, nitrogen-fixing actinomycete Frankia in four soils with similar physicochemical characteristics, two of which were vegetated with a host plant, Alnus glutinosa, and two with a non-host plant, Betula nigra. Analyses of DAPI-stained cells at three locations, i.e., at a distance of less than 1 m (near stem), 2.5 m (middle crown), and 3-5 m (crown edge) from the stems of both tree species revealed no statistically significant differences in abundance. Frankiae generally accounted for 0.01 to 0.04 % of these cells, with values between 4 and 36 × 10(5) cells (g soil)(-1). In three out of four soils, abundance of frankiae was significantly higher at locations "near stem" and/or "middle crown" compared to "crown edge," while numbers at these locations were not different in the fourth soil. Frankiae of the Alnus host infection group were dominant in all samples accounting for about 75 % and more of the cells, with no obvious differences with distance to stem. In three of the soils, all of these cells were represented by strain Ag45/Mut15. In the fourth soil that was vegetated with older A. glutinosa trees, about half of these cells belonged to a different subgroup represented by strain ArI3. In all soils, the remaining cells belonged to the Elaeagnus host infection group represented by strain EAN1pec. Casuarina-infective frankiae were not found. Abundance and relative distribution of Frankia host infection groups were similar in soils under the host plant A. glutinosa and the non-host plant B. nigra. Results did thus not reveal any specific effects of plant species on soil Frankia populations. PMID:26143359

  19. Phylogeny and assemblage composition of Frankia in Alnus tenuifolia nodules across a primary successional sere in interior Alaska.

    PubMed

    Anderson, M D; Taylor, D L; Ruess, R W

    2013-07-01

    In nitrogen (N) fixing symbioses, host-symbiont specificity, genetic variation in bacterial symbionts and environmental variation represent fundamental constraints on the ecology, evolution and practical uses of these interactions, but detailed information is lacking for many naturally occurring N-fixers. This study examined phylogenetic host specificity of Frankia in field-collected nodules of two Alnus species (A. tenuifolia and A. viridis) in interior Alaska and, for A. tenuifolia, distribution, diversity, spatial autocorrelation and correlation with specific soil factors of Frankia genotypes in nodules collected from replicated habitats representing endpoints of a primary sere. Frankia genotypes most commonly associated with each host belonged to different clades within the Alnus-infective Frankia clade, and for A. tenuifolia, were divergent from previously described Frankia. A. tenuifolia nodules from early and late succession habitats harboured distinct Frankia assemblages. In early succession, a single genotype inhabited 71% of nodules with no discernable autocorrelation at any scale, while late succession Frankia were more diverse, differed widely among plants within a site and were significantly autocorrelated within and among plants. Early succession Frankia genotype occurrence was strongly correlated with carbon/nitrogen ratio in the mineral soil fraction, while in late succession, the most common genotypes were correlated with different soil variables. Our results suggest that phylogenetic specificity is a significant factor in the A. tenuifolia-Frankia interaction and that significant habitat-based differentiation may exist among A. tenuifolia-infective genotypes. This is consistent with our hypothesis that A. tenuifolia selects specific Frankia genotypes from early succession soils and that this choice is attenuated in late succession. PMID:23731390

  20. Phylogeny and assemblage composition of Frankia in Alnus tenuifolia nodules across a primary successional sere in interior Alaska.

    PubMed

    Anderson, M D; Taylor, D L; Ruess, R W

    2013-07-01

    In nitrogen (N) fixing symbioses, host-symbiont specificity, genetic variation in bacterial symbionts and environmental variation represent fundamental constraints on the ecology, evolution and practical uses of these interactions, but detailed information is lacking for many naturally occurring N-fixers. This study examined phylogenetic host specificity of Frankia in field-collected nodules of two Alnus species (A. tenuifolia and A. viridis) in interior Alaska and, for A. tenuifolia, distribution, diversity, spatial autocorrelation and correlation with specific soil factors of Frankia genotypes in nodules collected from replicated habitats representing endpoints of a primary sere. Frankia genotypes most commonly associated with each host belonged to different clades within the Alnus-infective Frankia clade, and for A. tenuifolia, were divergent from previously described Frankia. A. tenuifolia nodules from early and late succession habitats harboured distinct Frankia assemblages. In early succession, a single genotype inhabited 71% of nodules with no discernable autocorrelation at any scale, while late succession Frankia were more diverse, differed widely among plants within a site and were significantly autocorrelated within and among plants. Early succession Frankia genotype occurrence was strongly correlated with carbon/nitrogen ratio in the mineral soil fraction, while in late succession, the most common genotypes were correlated with different soil variables. Our results suggest that phylogenetic specificity is a significant factor in the A. tenuifolia-Frankia interaction and that significant habitat-based differentiation may exist among A. tenuifolia-infective genotypes. This is consistent with our hypothesis that A. tenuifolia selects specific Frankia genotypes from early succession soils and that this choice is attenuated in late succession.

  1. Abundance and Relative Distribution of Frankia Host Infection Groups Under Actinorhizal Alnus glutinosa and Non-actinorhizal Betula nigra Trees.

    PubMed

    Samant, Suvidha; Huo, Tian; Dawson, Jeffrey O; Hahn, Dittmar

    2016-02-01

    Quantitative polymerase chain reaction (qPCR) was used to assess the abundance and relative distribution of host infection groups of the root-nodule forming, nitrogen-fixing actinomycete Frankia in four soils with similar physicochemical characteristics, two of which were vegetated with a host plant, Alnus glutinosa, and two with a non-host plant, Betula nigra. Analyses of DAPI-stained cells at three locations, i.e., at a distance of less than 1 m (near stem), 2.5 m (middle crown), and 3-5 m (crown edge) from the stems of both tree species revealed no statistically significant differences in abundance. Frankiae generally accounted for 0.01 to 0.04 % of these cells, with values between 4 and 36 × 10(5) cells (g soil)(-1). In three out of four soils, abundance of frankiae was significantly higher at locations "near stem" and/or "middle crown" compared to "crown edge," while numbers at these locations were not different in the fourth soil. Frankiae of the Alnus host infection group were dominant in all samples accounting for about 75 % and more of the cells, with no obvious differences with distance to stem. In three of the soils, all of these cells were represented by strain Ag45/Mut15. In the fourth soil that was vegetated with older A. glutinosa trees, about half of these cells belonged to a different subgroup represented by strain ArI3. In all soils, the remaining cells belonged to the Elaeagnus host infection group represented by strain EAN1pec. Casuarina-infective frankiae were not found. Abundance and relative distribution of Frankia host infection groups were similar in soils under the host plant A. glutinosa and the non-host plant B. nigra. Results did thus not reveal any specific effects of plant species on soil Frankia populations.

  2. 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.

  3. Total Synthesis of (+)-Cytosporolide A via a Biomimetic Hetero-Diels-Alder Reaction.

    PubMed

    Takao, Ken-Ichi; Noguchi, Shuji; Sakamoto, Shu; Kimura, Mizuki; Yoshida, Keisuke; Tadano, Kin-Ichi

    2015-12-23

    The first total synthesis of (+)-cytosporolide A was achieved by a biomimetic hetero-Diels-Alder reaction of (-)-fuscoatrol A with o-quinone methide generated from (+)-CJ-12,373. The dienophile, highly oxygenated caryophyllene sesquiterpenoid (-)-fuscoatrol A, was synthesized from the synthetic intermediate in our previous total synthesis of (+)-pestalotiopsin A. The o-quinone methide precursor, isochroman carboxylic acid (+)-CJ-12,373, was synthesized through a Kolbe-Schmitt reaction and an oxa-Pictet-Spengler reaction. The hetero-Diels-Alder reaction of these two compounds proceeded with complete chemo-, regio-, and stereoselectivity to produce the complicated pentacyclic ring system of the cytosporolide skeleton. This total synthesis unambiguously demonstrates that natural cytosporolide A has the structure previously suggested. PMID:26633257

  4. Molecular Complexity via C–H Activation: A Dehydrogenative Diels-Alder Reaction

    PubMed Central

    Stang, Erik M.; White, M. Christina

    2011-01-01

    Traditionally, C–H oxidation reactions install oxidized functionality onto a preformed molecular skeleton, resulting in a local molecular change. The use of C–H activation chemistry to construct complex molecular scaffolds is a new area with tremendous potential in synthesis. We report a Pd(II)/bis-sulfoxide catalyzed dehydrogenative Diels-Alder reaction that converts simple terminal olefins into complex cycloadducts in a single operation. PMID:21842902

  5. TEMPO-Mediated Aza-Diels-Alder Reaction: Synthesis of Tetrahydropyridazines Using Ketohydrazones and Olefins.

    PubMed

    Yang, Xiu-Long; Peng, Xie-Xue; Chen, Fei; Han, Bing

    2016-05-01

    A novel, facile, and efficient method for the synthesis of tetrahydropyridazines by a one-pot tandem reaction of easily accessible ketohydrazones and olefins in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) has been successfully developed. The reaction involves the initial generation of azoalkenes from direct oxidative dehydrogenation of ketohydrazones using TEMPO as the commercially available oxidant, followed by a subsequent aza-Diels-Alder reaction with olefins.

  6. Molecular complexity via C-H activation: a dehydrogenative Diels-Alder reaction.

    PubMed

    Stang, Erik M; White, M Christina

    2011-09-28

    Traditionally, C-H oxidation reactions install oxidized functionality onto a preformed molecular skeleton, resulting in a local molecular change. The use of C-H activation chemistry to construct complex molecular scaffolds is a new area with tremendous potential in synthesis. We report a Pd(II)/bis-sulfoxide-catalyzed dehydrogenative Diels-Alder reaction that converts simple terminal olefins into complex cycloadducts in a single operation.

  7. Synthesis and Diels-Alder reactions of a benzo[5]radialene derivative.

    PubMed

    von Richthofen, Andreas A; Marzorati, Liliana; Ducati, Lucas C; Di Vitta, Claudio

    2014-08-01

    Apart from their exotic structure, radialenes have been employed as precursors of more complex polycyclic molecules. In this work we report the synthesis of the first compound having the benzo[5]radialene substructure, starting from simple materials. Such a compound proved to be a convenient diene in Diels-Alder reactions, for the preparation of highly functionalized fluorenes and benzo[b]fluorenes in a quimio- and stereocontrolled fashion.

  8. Intramolecular [4 + 2] trapping of a hexadehydro-Diels-Alder (HDDA) benzyne by tethered arenes.

    PubMed

    Pogula, Vedamayee D; Wang, Tao; Hoye, Thomas R

    2015-02-20

    We report here the efficient, intramolecular trapping in a Diels-Alder (DA) sense of thermally generated benzynes by one of two pendant arene rings. A more electron-rich ring (p-methoxyphenyl) reacted substantially faster than a simple phenyl ring, which was, in turn, slightly more reactive vs a 4-carbomethoxyphenyl ring. Photoinduced di-π-methane rearrangement of the initial DA adducts gave rise to unusual isomeric polycyclic adducts.

  9. A Thermal Dehydrogenative Diels–Alder Reaction of Styrenes for the Concise Synthesis of Functionalized Naphthalenes

    PubMed Central

    Kocsis, Laura S.; Benedetti, Erica

    2012-01-01

    Functionalized naphthalenes are valuable building blocks in many important areas. A microwave-assisted, intramolecular dehydrogenative Diels-Alder reaction of styrenyl derivatives to provide cyclopenta[b]naphthalene substructures not previously accessible using existing synthetic methods is described. The synthetic utility of these uniquely functionalized naphthalenes was demonstrated by a single-step conversion of one of these cycloadducts to a fluorophore bearing a structural resemblance to Prodan. PMID:22913473

  10. New L-Serine Derivative Ligands as Cocatalysts for Diels-Alder Reaction

    PubMed Central

    Sousa, Carlos A. D.; Rodríguez-Borges, José E.; Freire, Cristina

    2013-01-01

    New L-serine derivative ligands were prepared and tested as cocatalyst in the Diels-Alder reactions between cyclopentadiene (CPD) and methyl acrylate, in the presence of several Lewis acids. The catalytic potential of the in situ formed complexes was evaluated based on the reaction yield. Bidentate serine ligands showed good ability to coordinate medium strength Lewis acids, thus boosting their catalytic activity. The synthesis of the L-serine ligands proved to be highly efficient and straightforward. PMID:24383009

  11. 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.

  12. Hydraulic conductivity of red oak (Quercus rubra L.) leaf tissue does not respond to light.

    PubMed

    Rockwell, F E; Holbrook, N M; Zwieniecki, M A

    2011-04-01

    The permeability of leaf tissue to water has been reported to increase under illumination, a response reputed to involve aquaporins. We studied this 'light response' in red oak (Quercus rubra L.), the species in which the phenomenon was first detected during measurements of leaf hydraulic conductance with the high-pressure flow meter (HPFM). In our HPFM measurements, we found that pre-conditioning leaves in darkness was not sufficient to bring them to their minimum conductance, which was attained only after an hour of submersion and pressurization. However, pre-conditioning leaves under anoxic conditions resulted in an immediate reduction in conductance. Leaves light- and dark-acclimated while on the tree showed no differences in the time course of HPFM measurement under illumination. We also studied the effect of light level and anoxia on rehydration kinetics, finding that anoxia slowed rehydration, but light had no effect either in the lab (rehydration under low light, high humidity) or on the tree (acclimation under high light, 10 min of dark prior to rehydration). We conclude that the declines in conductance observed in the HPFM must involve a resistance downstream of the extracellular air space, and that in red oak the hydraulic conductivity of leaf tissue is insensitive to light. PMID:21309791

  13. 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

  14. Sublethal toxicity of trace metals to larvae of the blacklip abalone, Haliotis rubra.

    PubMed

    Gorski, Jacquelle; Nugegoda, Dayanthi

    2006-05-01

    The availability of literature regarding sublethal and chronic toxicity of heavy metals to early life stages of marine species is restricted to a few species of invertebrate mollusks. The early life stage of abalone, an important gastropod both environmentally and commercially, has been involved in limited research investigating the effects of heavy metal toxicity. Fertilized eggs of Haliotis rubra were exposed to a range of dissolved nominal concentrations of cadmium, copper, iron, lead, mercury, and zinc in individual solutions for 48 h. After 48 h of exposure, the test was completed by recording survival success and morphological abnormalities of veliger larvae in each heavy metal treatment. The mean 48-h median effective concentrations affecting normal morphological development of veliger larvae determined in this test shows a decreasing order of toxicity of copper (7 mg/L), mercury (21 mg/L), zinc (35 mg/L), iron (4102 mg/L), cadmium (4515 mg/L), and lead (5111 mg/L). PMID:16704070

  15. [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.

  16. 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

  17. 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.

  18. 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.

  19. Extreme consumption of Beta vulgaris var. rubra can cause metal ion accumulation in the liver.

    PubMed

    Blázovics, Anna; Sárdi, Eva; Szentmihályi, Klára; Váli, L; Takács-Hájos, Mária; Stefanovits-Bányai, Eva

    2007-09-01

    Redox homeostasis can be considered as the cumulative action of all free radical reactions and antioxidant defences in different tissues, which provide suitable conditions for life. Transition metal ions are ubiquitous in biological systems. Beta vulgaris var. rubra (table beet root) contains several bioactive agents (e.g. betain, betanin, vulgaxanthine, polyphenols, folic acid) and different metal elements (e.g. Al, B, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Zn), which act on the various physiological routes. Therefore we studied the effect of this metal rich vegetable on element content of the liver in healthy rats. Male Wistar rats (n = 7) (200 +/- 20 g) were treated with lyophilised powder of table beet root (2 g/kg b.w.) added into the rat chow for 10 days. Five healthy animals served as control. We found significant accumulation of Cu, Fe, Mg, Mn, Zn and P in the liver, which was proved by ICP-AES measurements. We suppose that the extreme consumption of table beet root can cause several disturbances not only in cases of healthy patients but, e.g. in patients suffering with metal accumulating diseases, e.g. porphyria cutanea tarda, haemochromatosis or Wilson disease-although moderate consumption may be beneficial in iron-deficiency anaemia and inflammatory bowel diseases. PMID:17899785

  20. 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

  1. Polymorphisms in different EST-SSR types derived from the Chinese bayberry Myrica rubra, Myricaceae) transcriptome.

    PubMed

    Zhang, S Y; Feng, C; Xu, C J; Zhu, C Q; Chen, K S

    2015-06-01

    Most plant expressed sequence tag-simple sequence repeats (EST-SSRs) are not polymorphic, and it is important to learn the characteristics of highly polymorphic EST-SSRs. In this study, 357 compound and 5557 non-compound EST-SSRs, identified from the transcriptome of the Chinese bayberry (Myrica rubra 'Biqi'), were divided into 11 types based on their characteristics. Polymorphisms in all 11 EST-SSR types were investigated in 10 cultivars. The percentages of polymorphic loci ranged from 12.9 to 87.5%, with 2-ntL having the highest, followed by 3-ntL, Compound B, and Compound A. The number of alleles and the polymorphic information content of 2-ntL and Compound B were the highest, followed by 2-ntM and Compound A. Therefore, we recommend that 2-ntL, Compound B, and Compound A EST-SSRs should be preferentially selected for the screening of polymorphic EST-SSRs in the Chinese bayberry. Our results should facilitate genetic and breeding studies of this species, and provide a reference for similar study in other plant species.

  2. Paralytic shellfish toxins, including deoxydecarbamoyl-STX, in wild-caught Tasmanian abalone (Haliotis rubra).

    PubMed

    Harwood, D Tim; Selwood, Andrew I; van Ginkel, Roel; Waugh, Craig; McNabb, Paul S; Munday, Rex; Hay, Brenda; Thomas, Krista; Quilliam, Michael A; Malhi, Navreet; Dowsett, Natalie; McLeod, Catherine

    2014-11-01

    For the first time wild-caught Tasmanian abalone, Haliotis rubra, have been reported to contain paralytic shellfish toxins (PSTs). This observation followed blooms of the toxic dinoflagellate Gymnodinium catenatum. No illnesses were reported, but harvesting restrictions were enforced in commercial areas. Abalone were assayed using HPLC-FLD methodology based on AOAC official method 2005.06. An uncommon congener, deoxydecarbamoyl-STX (doSTX), was observed in addition to regulated PSTs as unassigned chromatographic peaks. A quantitative reference material was prepared from contaminated Tasmanian abalone viscera and ampouled at 54.2 μmol/L. The LD50 of doSTX via intraperitoneal injection was 1069 nmol/kg (95% confidence limits 983-1100 nmol/kg), indicating it is nearly 40 times less toxic than STX. A toxicity equivalence factor of 0.042 was generated using the mouse bioassay. Levels of PSTs varied among individuals from the same site, although the toxin profile remained relatively consistent. In the foot tissue, STX, decarbamoyl-STX and doSTX were identified. On a molar basis doSTX was the dominant congener in both foot and viscera samples. The viscera toxin profile was more complex, with other less toxic PST congeners observed and was similar to mussels from the same site. This finding implicates localised dinoflagellate blooms as the PST source in Tasmanian abalone.

  3. 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. PMID:23377397

  4. Ustekinumab as an Alternative Treatment Option for Chronic Pityriasis Rubra Pilaris

    PubMed Central

    Chowdhary, Mudit; Davila, Ulysses; Cohen, David J.

    2015-01-01

    Pityriasis rubra pilaris (PRP) is an exceptionally rare, chronic inflammatory dermatosis of unknown etiology. Patients classically present with small, follicular keratosis and salmon-colored plaques that begin at the head and neck and slowly progress to widespread erythroderma including the palms and soles. It is difficult to distinguish PRP from other inflammatory dermatoses; however, features that help aid in the diagnosis include ‘islands’ of spared skin, orangish hue and typical findings on biopsy. There are no specific guidelines on therapy and treatment options include corticosteroids, vitamin D analogs, retinoids, methotrexate, cyclosporine, azathioprine and tumor necrosis factor alpha antagonists. Unfortunately options are limited for patients when these drugs do not work. We report a case of chronic PRP, refractory to conventional treatment, successfully treated with ustekinumab monotherapy. The patient was treated with 90 mg subcutaneous ustekinumab injections and began to show improvement within only 8 weeks. Long-term control of the disease has been attained without any significant side effects. We report this case to show that ustekinumab can be used as an alternative treatment method for patients with chronic, unremitting PRP. Treatment response is remarkably rapid and the infrequent dosing leads to patient compliance and a significantly improved quality of life. PMID:25969677

  5. 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.

  6. 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.

  7. Dimerization of quercetin, Diels-Alder vs. radical-coupling approach: a joint thermodynamics, kinetics, and topological study.

    PubMed

    Fourré, Isabelle; Di Meo, Florent; Podloucká, Pavlína; Otyepka, Michal; Trouillas, Patrick

    2016-08-01

    Quercetin is a prototypical antioxidant and prominent member of flavonoids, a large group of natural polyphenols. The oxidation of quercetin may lead to its dimerization, which is a paradigm of the more general polyphenol oligomerization. There exist two opposing mechanisms to describe the dimerization process, namely radical-coupling or Diels-Alder reactions. This work presents a comprehensive rationalization of this dimerization process, acquired from density functional theory (DFT) calculations. It is found that the two-step radical-coupling pathway is thermodynamically and kinetically preferred over the Diels-Alder reaction. This is in agreement with the experimental results showing the formation of only one isomer, whereas the Diels-Alder mechanism would yield two isomers. The evolution in bonding, occurring during these two processes, is investigated using the atoms in molecules (AIM) and electron localization function (ELF) topological approaches. It is shown that some electron density is accumulated between the fragments in the transition state of the radical-coupling reaction, but not in the transition state of the Diels-Alder process. Graphical Abstract Quantum chemistry calculations of the dimerization process of quercetin show that a radical coupling approach is preferred to a Diels-Alder type reaction, in agreement with experimental results. Analysis of the bonding evolution highlights the reaction mechanism. PMID:27449669

  8. 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.

  9. 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. PMID:26504154

  10. 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

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

    PubMed

    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

    2015-08-01

    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

  12. 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.

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

    PubMed

    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

    2015-08-01

    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.

  14. 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

  15. 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

  16. Topical management of striae distensae (stretch marks): prevention and therapy of striae rubrae and albae.

    PubMed

    Ud-Din, S; McGeorge, D; Bayat, A

    2016-02-01

    Striae distensae (SD) are common dermal lesions, with significant physical and psychological impact. Many therapeutic modalities are available but none can completely eradicate SD. The most common therapy is the application of topicals used both therapeutically and prophylactically. Even though there are many commercially available topical products, not all have sufficient level of evidence to support their continued use in SD. The aim here was to assess the evidence for the use of topicals in SD and to propose a structured approach in managing SD. A systematic search of published literature and manufacturer website information for topicals in SD was carried out. The results showed that there are few studies (n = 11) which investigate the efficacy of topicals in management of SD. Trofolastin and Alphastria creams demonstrated level-2 evidence of positive results for their prophylactic use in SD. Additionally, tretinoin used therapeutically showed varying results whilst cocoa butter and olive oil did not demonstrate any effect. Overall, there is a distinct lack of evidence for each topical formulation. The majority of topicals failed to mention their effect on early vs. later stages of SD (striae rubrae compared to striae albae) and their role in both prevention and treatment. In conclusion, there is no topical formulation, which is shown to be most effective in eradicating or improving SD. A structured approach in identification and targeted management of symptoms and signs with the appropriate topical is required. Randomized controlled trials are necessary to assess the efficacy of topical products for treatment and prevention of different stages of SD. PMID:26486318

  17. 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.

  18. 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

  19. 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)).

  20. 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. PMID:26414161

  1. Rhodopirellula lusitana sp. nov. and Rhodopirellula rubra sp. nov., isolated from the surface of macroalgae.

    PubMed

    Bondoso, Joana; Albuquerque, Luciana; Lobo-da-Cunha, Alexandre; da Costa, Milton S; Harder, Jens; Lage, Olga Maria

    2014-05-01

    Twenty two strains of Rhodopirellula were isolated from the epiphytic community of several marine macroalgae and separated into two groups, designated as group B and group C. In this study, we characterized these groups as two novel species belonging to the genus Rhodopirellula. These strains were represented by pleomorphic cells that were arranged in rosettes and formed pink- or red-pigmented colonies. The organisms were chemoorganotrophic and required vitamin B12 for growth. Their optimal temperature for growth was around 25°C. Major fatty acids were C18:1 ω9c, C16:0 and C16:1 ω7c/C16:1 ω6c. Phosphatidylcholine and phosphatidylglycerol were the major polar lipids. Unidentified phospholipids were also present. The 16S rDNA sequence analysis confirmed the affiliation of these organisms to the order Planctomycetales, genus Rhodopirellula, with R. baltica as the closest phylogenetic relative. The analysis of a partial sequence of the gene encoding the β-subunit of RNA polymerase (rpoB) confirmed the phylogenetic separation of the isolates into two different species of the genus Rhodopirellula. The 16S rRNA sequences from strains of group B revealed their widespread occurrence across the world, whereas strains of group C were not observed before. On the basis of physiological, biochemical, chemotaxonomic and genetic characteristics we propose that our isolates represent two new species of Rhodopirellula, Rhodopirellula rubra sp. nov. (type strain is LF2(T)=DSM 25,459=CECT 8075) and Rhodopirellula lusitana sp. nov. (type strain is UC17(T)=DSM 25,457=LMG 27,777). PMID:24631661

  2. 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.

  3. Recent Advances in Inverse-Electron-Demand Hetero-Diels-Alder Reactions of 1-Oxa-1,3-Butadienes.

    PubMed

    Pałasz, Aleksandra

    2016-06-01

    This review is an endeavor to highlight the progress in the inverse-electron-demand hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes in recent years. The huge number of examples of 1-oxadienes cycloadditions found in the literature clearly demonstrates the incessant importance of this transformation in pyran ring synthesis. This type of reaction is today one of the most important methods for the synthesis of dihydropyrans which are the key building blocks in structuring of carbohydrate and other natural products. Two different modes, inter- and intramolecular, of inverse-electron-demand hetero-Diels-Alder reactions of 1-oxadienes are discussed. The domino Knoevenagel hetero-Diels-Alder reactions are also described. In recent years the use of chiral Lewis acids, chiral organocatalysts, new optically active heterodienes or dienophiles have provided enormous progress in asymmetric synthesis. Solvent-free and aqueous hetero-Diels-Alder reactions of 1-oxabutadienes were also investigated. The reactivity of reactants, selectivity of cycloadditions, and chemical stability in aqueous solutions and under physiological conditions were taken into account to show the potential application of the described reactions in bioorthogonal chemistry. New bioorthogonal ligation by click inverse-electron-demand hetero-Diels-Alder cycloaddition of in situ-generated 1-oxa-1,3-butadienes and vinyl ethers was developed. It seems that some of the hetero-Diels-Alder reactions described in this review can be applied in bioorthogonal chemistry because they are selective, non-toxic, and can function in biological conditions taking into account pH, an aqueous environment, and temperature. PMID:27573264

  4. Recent Advances in Inverse-Electron-Demand Hetero-Diels-Alder Reactions of 1-Oxa-1,3-Butadienes.

    PubMed

    Pałasz, Aleksandra

    2016-06-01

    This review is an endeavor to highlight the progress in the inverse-electron-demand hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes in recent years. The huge number of examples of 1-oxadienes cycloadditions found in the literature clearly demonstrates the incessant importance of this transformation in pyran ring synthesis. This type of reaction is today one of the most important methods for the synthesis of dihydropyrans which are the key building blocks in structuring of carbohydrate and other natural products. Two different modes, inter- and intramolecular, of inverse-electron-demand hetero-Diels-Alder reactions of 1-oxadienes are discussed. The domino Knoevenagel hetero-Diels-Alder reactions are also described. In recent years the use of chiral Lewis acids, chiral organocatalysts, new optically active heterodienes or dienophiles have provided enormous progress in asymmetric synthesis. Solvent-free and aqueous hetero-Diels-Alder reactions of 1-oxabutadienes were also investigated. The reactivity of reactants, selectivity of cycloadditions, and chemical stability in aqueous solutions and under physiological conditions were taken into account to show the potential application of the described reactions in bioorthogonal chemistry. New bioorthogonal ligation by click inverse-electron-demand hetero-Diels-Alder cycloaddition of in situ-generated 1-oxa-1,3-butadienes and vinyl ethers was developed. It seems that some of the hetero-Diels-Alder reactions described in this review can be applied in bioorthogonal chemistry because they are selective, non-toxic, and can function in biological conditions taking into account pH, an aqueous environment, and temperature.

  5. Scandium(III)-zeolites as new heterogeneous catalysts for imino-Diels-Alder reactions.

    PubMed

    Olmos, Andrea; Louis, Benoit; Pale, Patrick

    2012-04-16

    This study demonstrates the first zeolite-catalyzed synthesis of piperidine derivatives, including peptidomimetics and indoloquinolizidine alkaloids. The approach developed utilizes a highly effective one-pot reaction cascade, through imine formation and imino-Diels-Alder reactions, promoted by scandium-loaded zeolites as a heterogeneous catalyst. The methodology described benefits from very low catalyst loadings (≤5 mol % of Sc(III) ), commercially and readily available starting materials, and mild reaction conditions. Furthermore, the Sc(III) -zeolite catalyst can be readily reused more than 10 times without any loss in efficiency.

  6. A practical new chiral controller for asymmetric Diels-Alder and alkylation reactions.

    PubMed

    Sarakinos, G; Corey, E J

    1999-12-01

    [formula: see text] The enantiomerically pure hydroxy sulfones (+)- and (-)-2 have been prepared from 1,2-epoxycyclohexane by a simple and practical procedure. The acrylate esters of these alcohols undergo BCl3-catalyzed Diels-Alder reactions with a variety of dienes at -78 to -55 degrees C in CH2Cl2 or C7H8 with high dienophile face selectivity (Table 1). The chiral esters so formed are readily cleaved with recovery of the controllers (+)- or (-)-2. Esters of (+)- and (-)-2 can be converted to Z-potassium enolates and alkylated with high face selectivity. PMID:10836034

  7. The Nitrosocarbonyl Hetero-Diels–Alder Reaction as a Useful Tool for Organic Syntheses

    PubMed Central

    Bodnar, Brian S.

    2014-01-01

    Organic transformations that result in the formation of multiple covalent bonds within the same reaction are some of the most powerful tools in synthetic organic chemistry. Nitrosocarbonyl hetero-Diels–Alder (HDA) reactions allow for the simultaneous stereospecific introduction of carbon–nitrogen and carbon–oxygen bonds in one synthetic step, and provide direct access to 3,6-dihydro-1,2-oxazines. This Review describes the development of the nitrosocarbonyl HDA reaction and the utility of the resulting oxazine ring in the synthesis of a variety of important, biologically active molecules. PMID:21520360

  8. Rates of Hexadehydro-Diels–Alder (HDDA) Cyclizations: Impact of the Linker Structure

    PubMed Central

    2015-01-01

    The rates of the hexadehydro-Diels–Alder (HDDA) reaction of substrates containing, minimally, a 1,3,8-triyne subunit are reported. Several series of related substrates, differing in the nature of the three-atom tether that links the 1,3-diyne and diynophile, were examined. Seemingly small changes in substrate structure result in large differences in cyclization rate, spanning more than 8 orders of magnitude. The reactivity trends revealed by these studies should prove useful in guiding substrate design and choice of reaction conditions in future applications. PMID:25153729

  9. Intramolecular Dehydro-Diels–Alder Reaction Affords Selective Entry to Arylnaphthalene or Aryldihydronaphthalene Lignans

    PubMed Central

    2015-01-01

    Intramolecular dehydro-Diels–Alder (DDA) reactions are performed affording arylnaphthalene or aryldihydronaphthalene lactones selectively as determined by choice of reaction solvent. This constitutes the first report of an entirely selective formation of arylnaphthalene lactones utilizing DDA reactions of styrene-ynes. The synthetic utility of the DDA reaction is demonstrated by the synthesis of taiwanin C, retrohelioxanthin, justicidin B, isojusticidin B, and their dihydronaphthalene derivatives. Computational methods for chemical shift assignment are presented that allow for regioisomeric lignans to be distinguished. PMID:25061845

  10. Hetero-Diels–Alder reactions of hetaryl and aryl thioketones with acetylenic dienophiles

    PubMed Central

    Grzelak, Paulina; Mikina, Maciej; Linden, Anthony

    2015-01-01

    Summary Selected hetaryl and aryl thioketones react with acetylenecarboxylates under thermal conditions in the presence of LiClO4 or, alternatively, under high-pressure conditions (5 kbar) at room temperature yielding thiopyran derivatives. The hetero-Diels–Alder reaction occurs in a chemo- and regioselective manner. The initially formed [4 + 2] cycloadducts rearrange via a 1,3-hydrogen shift sequence to give the final products. The latter were smoothly oxidized by treatment with mCPBA to the corresponding sulfones. PMID:26124858

  11. 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.

  12. Syntheses of arabinose-derived pyrrolidine catalysts and their applications in intramolecular Diels-Alder reactions.

    PubMed

    Shing, Tony K M; Wu, Kwun W; Wu, Ho T; Xiao, Qicai

    2015-02-14

    Six chiral hydroxylated pyrrolidine catalysts were synthesized from commercially available D-arabinose in seven steps. Various aromatic substituents α to the amine can be introduced readily by a Grignard reaction, which enables facile optimization of the catalyst performance. The stereoselectivities of these catalysts have been assessed by comparing with those of MacMillan's imidazolidinone in a known intramolecular Diels-Alder (IMDA) reaction of a triene. Two additional IMDA reactions of symmetrical dienals with concomitant desymmetrisation further established the potential use of these novel amine catalysts. These pyrrolidines are valuable catalysts for other synthetic transformations. PMID:25503272

  13. Silver Nanoparticle-Catalyzed Diels-Alder Cycloadditions of 2′-Hydroxychalcones

    PubMed Central

    Cong, Huan; Becker, Clinton F.; Elliott, Sean J.; Grinstaff, Mark W.; Porco, John A.

    2010-01-01

    Metal nanoparticles are currently being employed as catalysts for a number of classical chemical transformations. In contrast, identification of novel reactions of nanoparticles, especially towards the synthesis of complex natural products and derivatives, is highly underdeveloped and represents a bourgeoning area in chemical synthesis. Herein, we report silica-supported silver nanoparticles as solid, recyclable catalysts for Diels-Alder cycloadditions of 2′-hydroxychalcones and dienes in high yield and turnover number. The use of silver nanoparticle catalysts is further demonstrated by the total synthesis of the cytotoxic natural product panduratin A employing a highly electron-rich dienophile and Lewis acid-sensitive diene. PMID:20443601

  14. Diels–Alder Reactions of Allene with Benzene and Butadiene: Concerted, Stepwise, and Ambimodal Transition States

    PubMed Central

    2015-01-01

    Multiconfigurational complete active space methods (CASSCF and CASPT2) have been used to investigate the (4 + 2) cycloadditions of allene with butadiene and with benzene. Both concerted and stepwise radical pathways were examined to determine the mechanism of the Diels–Alder reactions with an allene dienophile. Reaction with butadiene occurs via a single ambimodal transition state that can lead to either the concerted or stepwise trajectories along the potential energy surface, while reaction with benzene involves two separate transition states and favors the concerted mechanism relative to the stepwise mechanism via a diradical intermediate. PMID:25216056

  15. Diels-Alder reactions of allene with benzene and butadiene: concerted, stepwise, and ambimodal transition states.

    PubMed

    Pham, Hung V; Houk, K N

    2014-10-01

    Multiconfigurational complete active space methods (CASSCF and CASPT2) have been used to investigate the (4 + 2) cycloadditions of allene with butadiene and with benzene. Both concerted and stepwise radical pathways were examined to determine the mechanism of the Diels-Alder reactions with an allene dienophile. Reaction with butadiene occurs via a single ambimodal transition state that can lead to either the concerted or stepwise trajectories along the potential energy surface, while reaction with benzene involves two separate transition states and favors the concerted mechanism relative to the stepwise mechanism via a diradical intermediate.

  16. Preparation of 2-BF3-substituted 1,3-dienes and their Diels-Alder/cross-coupling reactions.

    PubMed

    De, Subhasis; Welker, Mark E

    2005-06-01

    [reaction: see text] 2-BF3-substituted 1,3-butadienes with potassium and tetrabutylammonium counterions have been prepared in gram quantities from chloroprene via a simple synthetic procedure. The potassium salt of this new main group element substituted diene has been characterized by 1H, 13C, 11B, and 19F NMR. Diels-Alder reactions of these dienes with ethyl acrylate and methyl vinyl ketone are reported, as well as subsequent Pd-catalyzed cross-coupling reactions of those Diels-Alder adducts. PMID:15932228

  17. Thermoactinospora rubra gen. nov., sp. nov., a thermophilic actinomycete isolated from Tengchong, Yunnan province, south-west China.

    PubMed

    Zhou, En-Min; Tang, Shu-Kun; Sjøholm, Carsten; Song, Zhao-Qi; Yu, Tian-Tian; Yang, Ling-Ling; Ming, Hong; Nie, Guo-Xing; Li, Wen-Jun

    2012-06-01

    Two novel Gram-positive, spore-forming, thermophilic actinomycetes, designated as strain YIM 77501(T) and YIM 77570, were isolated from a sandy soil sample collected at Tengchong National Volcanic Geological Park, Yunnan province, south-west China. Phylogenetic analysis based on the 16S rRNA gene sequences suggested that the two isolates fell within the family Streptosporangiaceae. The strains formed extensively branched substrate and aerial mycelia which carried masses of long, straight or irregular spore chains composed of warty ornamented spores. Cell walls of the two strains contained meso-diaminopimelic acid and glucose, galactose, mannose and ribose were detected as whole-cell sugars. The predominant menaquinones were MK-9(H(4)) and MK-9(H(6)). The major polar lipids were diphosphatidylglycerol, phosphatidylethanolamine, N-acetylglucosamine-containing phospholipids and phosphatidylinositol, phosphatidylinositolmannosides. The major cellular fatty acids were iso-C(16:0) and 10-methyl C(17:0). The DNA G+C content was 74-76 mol%. On the basis of the morphological and chemotaxonomic characteristics as well as the phylogenetic analysis, these strains represents a novel species of a new genus within the family Streptosporangiaceae, for which the name Thermoactinospora rubra gen. nov., sp. nov. is proposed. The type strain of T. rubra is YIM 77501(T) (=DSM 45614(T) = CCTCC AA 2011014(T)).

  18. 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.

  19. 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

  20. 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.

  1. 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.

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

    PubMed

    Ninh, Chi; Bettinger, Christopher J

    2013-07-01

    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.

  3. No sympatric speciation here: multiple data sources show that the ant Myrmica microrubra is not a separate species but an alternate reproductive morph of Myrmica rubra.

    PubMed

    Steiner, F M; Schlick-Steiner, B C; Konrad, H; Moder, K; Christian, E; Seifert, B; Crozier, R H; Stauffer, C; Buschinger, A

    2006-05-01

    No aspect of speciation is as controversial as the view that new species can evolve sympatrically, among populations in close physical contact. Social parasitism has been suggested to yield necessary disruptive selection for sympatric speciation. Recently, mitochondrial DNA phylogeography has shown that the ant Myrmica microrubra is closely related to its host, Myrmica rubra, leading to the suggestion that sympatric speciation has occurred. We investigated the relationships between the two ant forms using mitochondrial and nuclear DNA sequences, microsatellite genotyping and morphometrics. Molecular phylogenetic and population structure analyses showed that M. microrubra does not evolve separately to its host but rather shares a gene pool with it. Probability analysis showed that mitochondrial DNA data previously adduced in favour of sympatric speciation do not in fact do so. Morphometrically, M. microrubra is most readily interpreted as a miniature queen form of M. rubra, not a separate species. Myrmica microrubra is not an example of speciation. The large (typical M. rubra) and small (M. microrubra) queen forms are alternative reproductive strategies of the same species. Myrmica microrubraSeifert 1993 is consequently synonymized here with M. rubra Linnaeus, 1758.

  4. Hybridization and introgression patterns between native red elm (Ulmus rubra Muhl.) and exotic, invasive Siberian elm (Ulmus pumila L.) examined using species-specific microsatellite markers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ulmus pumila (Siberian elm) is an invasive elm species, non-native to the United States, which hybridizes with Ulmus rubra (red elm), a U.S. native. While Siberian elm is highly tolerant to Dutch elm disease (DED), red elm populations in North America have been decimated by DED. In order to study ...

  5. Diversity and specificity of Frankia strains in nodules of sympatric Myrica gale, Alnus incana, and Shepherdia canadensis determined by rrs gene polymorphism.

    PubMed

    Huguet, V; Batzli, J M; Zimpfer, J F; Normand, P; Dawson, J O; Fernandez, M P

    2001-05-01

    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

  6. 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...

  7. Asymmetric synthesis of bicyclic dihydropyrans via organocatalytic inverse-electron-demand oxo-Diels-Alder reactions of enolizable aliphatic aldehydes.

    PubMed

    Li, Jun-Long; Yang, Kai-Chuan; Li, Yi; Li, Qiang; Zhu, Hong-Ping; Han, Bo; Peng, Cheng; Zhi, Yong-Gang; Gou, Xiao-Jun

    2016-08-23

    A highly enantioselective organocatalytic inverse-electron-demand oxo-Diels-Alder reaction involving aqueous acetaldehyde has been discovered. The reaction, in which cyclic enones serve as dienes in the presence of readily available secondary amine catalysts, allows facile construction of optically active bicyclic dihydropyrans. Other typical enolizable aliphatic aldehydes can also serve as competent dienophiles in the reaction. PMID:27436351

  8. No evidence found for Diels-Alder reaction products in soybean oil oxidized at the frying temperature by NMR study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    It has been generally accepted that the Diels-Alder reaction mechanism is one of the major reaction mechanisms to produce dimers and polymers during heating process of vegetable oil. Soybean oil oxidized at 180 °C for 24 hrs with 1.45 surface area-to-volume ratio showed 36.1% polymer peak area in g...

  9. The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry.

    PubMed

    Polgar, Lorenzo Massimo; van Duin, Martin; Picchioni, Francesco

    2016-08-25

    A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified with furfurylamine to graft furan groups to the rubber backbone. These pendant furan groups are then cross-linked with a bis-maleimide via a Diels-Alder coupling reaction. Both reactions can be performed under a broad range of experimental conditions and can easily be applied on a large scale. The material properties of the resulting Diels-Alder cross-linked rubbers are similar to a peroxide-cured ethylene/propylene/diene rubber (EPDM) reference. The cross-links break at elevated temperatures (> 150 °C) via the retro-Diels-Alder reaction and can be reformed by thermal annealing at lower temperatures (50-70 °C). Reversibility of the system was proven with infrared spectroscopy, solubility tests and mechanical properties. Recyclability of the material was also shown in a practical way, i.e., by cutting a cross-linked sample into small parts and compression molding them into new samples displaying comparable mechanical properties, which is not possible for conventionally cross-linked rubbers.

  10. CYCLOADDITION REACTIONS OF AZIDE, FURAN, AND PYRROLE UNITS WITH BENZYNES GENERATED BY THE HEXADEHYDRO-DIELS–ALDER (HDDA) REACTION

    PubMed Central

    Chen, Junhua; Baire, Beeraiah

    2014-01-01

    Benzynes can be generated by the intramolecular thermal cycloisomerization of triynes–the title HDDA reaction. We report here that these can be trapped by cycloaddition reaction with trimethylsilyl azide (1,3-dipolar) or a furan or pyrrole (4+2 Diels–Alder). PMID:24910496

  11. The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry.

    PubMed

    Polgar, Lorenzo Massimo; van Duin, Martin; Picchioni, Francesco

    2016-01-01

    A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified with furfurylamine to graft furan groups to the rubber backbone. These pendant furan groups are then cross-linked with a bis-maleimide via a Diels-Alder coupling reaction. Both reactions can be performed under a broad range of experimental conditions and can easily be applied on a large scale. The material properties of the resulting Diels-Alder cross-linked rubbers are similar to a peroxide-cured ethylene/propylene/diene rubber (EPDM) reference. The cross-links break at elevated temperatures (> 150 °C) via the retro-Diels-Alder reaction and can be reformed by thermal annealing at lower temperatures (50-70 °C). Reversibility of the system was proven with infrared spectroscopy, solubility tests and mechanical properties. Recyclability of the material was also shown in a practical way, i.e., by cutting a cross-linked sample into small parts and compression molding them into new samples displaying comparable mechanical properties, which is not possible for conventionally cross-linked rubbers. PMID:27583665

  12. 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…

  13. 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?".

  14. 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.

  15. 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. PMID:25875156

  16. 1,4-Difluoro-2,5-dimethoxybenzene as a precursor for iterative double benzyne-furan Diels-Alder reactions.

    PubMed

    Morton, Gillian E; Barrett, Anthony G M

    2005-04-29

    [reaction: see text] The use of 1,4-difluoro-2,5-dimethoxybenzene as a novel precursor for iterative two-directional benzyne-furan Diels-Alder reactions, using a range of 2- and 3-substituted furans, is reported. Substituted oxabenzonorbornadienes were synthesized following the initial Diels-Alder reaction, which upon ring opening under acidic conditions gave substituted naphthol derivatives. Highly substituted anthracenols were generated in the second benzyne-furan Diels-Alder reaction following acid-catalyzed isomerization of the cycloadducts.

  17. 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.

  18. Landscape heterogeneity controls growth variability of alder, willow, and birch shrubs in response to observed increases in temperature and snow

    NASA Astrophysics Data System (ADS)

    Tape, K. D.; Hallinger, M.; Buras, A.; Wilmking, M.

    2013-12-01

    Over the last decade, evidence has emerged for a circumarctic trend of increasing shrub cover in tundra regions. On the Alaskan tundra, repeat photography has shown spatial differences in shrub patch dynamics: since 1950, most patches expanded while some remained stable. In this study we explore the underpinnings of this landscape heterogeneity by sampling the three dominant shrubs of the Alaskan tundra--alder, willow and birch--and creating shrub ring width chronologies to determine the influence of climate variability on shrub growth. Shrubs of expanding patches of all three species grew at higher rates than shrubs of stable patches. Alder and willow shrubs in expanding patches exhibited mainly positive growth trends, while their counterparts in stable patches exhibited mainly negative growth trends. Birch shrub growth declined in expanding and stable patches. Alder and willow shrub growth rates and responses to climate were controlled more by soil characteristics than by their genus; expanding alder and willow shrubs showed significant positive correlations with spring and summer temperatures, whereas alder and willow shrubs of stable patches were negatively influenced by winter precipitation. The widely-scattered stable shrub patches sampled here are considered ';moist tussock tundra,' which covers 13.4% of the low arctic landscape. In moist tussock tundra, and presumably also wet tussock tundra, the negative influence of deeper snow on shrubs outweighed the positive influence of deeper snow on ground temperature and nutrient stocks articulated by the snow-shrub-microbe hypothesis. Thus, while shrubs of expanding patches have generally profited from warmer summers, shrubs of stable patches have suffered from increased soil moisture resulting from increased snowmelt water. These results underscore the spatial and temporal complexity in shrub-climate dynamics, which will require considerable finesse to appropriately integrate into modeling efforts.

  19. 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.

  20. 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.

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

    DOE PAGES

    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 themore » diffusion pathways in SDAPP are very different than in Nafion.« less

  2. A mechanochemical study of the effects of compression on a Diels-Alder reaction.

    PubMed

    Jha, Sanjiv K; Brown, Katie; Todde, Guido; Subramanian, Gopinath

    2016-08-21

    We examine the effects of compressive external forces on the mechanisms of the parent Diels-Alder (DA) reaction between butadiene and ethylene. Reaction pathways and transition states were calculated using the nudged elastic band method within a mechanochemical framework at the CASSCF(6,6)/6-31G**, as well as the B3LYP/6-311++G** levels of theory. Our results suggest that compressive hydrostatic pressure lowers the energy barrier for the parent DA reaction while suppressing the undesirable side reaction, thereby leading to a direct increase in the yield of cyclohexene. Compressive pressure also increases the exothermicity of the parent DA reaction, which would lead to increased temperatures in a reaction vessel and thereby indirectly increase the yield of cyclohexene. Our estimates indicate that the compression used in our study corresponds to a range of 68 MPa-1410 MPa.

  3. A mechanochemical study of the effects of compression on a Diels-Alder reaction

    NASA Astrophysics Data System (ADS)

    Jha, Sanjiv K.; Brown, Katie; Todde, Guido; Subramanian, Gopinath

    2016-08-01

    We examine the effects of compressive external forces on the mechanisms of the parent Diels-Alder (DA) reaction between butadiene and ethylene. Reaction pathways and transition states were calculated using the nudged elastic band method within a mechanochemical framework at the CASSCF(6,6)/6-31G**, as well as the B3LYP/6-311++G** levels of theory. Our results suggest that compressive hydrostatic pressure lowers the energy barrier for the parent DA reaction while suppressing the undesirable side reaction, thereby leading to a direct increase in the yield of cyclohexene. Compressive pressure also increases the exothermicity of the parent DA reaction, which would lead to increased temperatures in a reaction vessel and thereby indirectly increase the yield of cyclohexene. Our estimates indicate that the compression used in our study corresponds to a range of 68 MPa-1410 MPa.

  4. 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.

  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. A Diels-Alder reaction triggered by a [4 + 3] metallacycloaddition.

    PubMed

    Vivancos, Ángela; Vattier, Florencia; López-Serrano, Joaquín; Paneque, Margarita; Poveda, Manuel L; Álvarez, Eleuterio

    2015-04-01

    The Tp(Me2)Ir(III) complex 1-OH2 (Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate), which contains a labile molecule of water and an iridium-bonded alkenyl moiety (-C(R)═C(R)-(R=CO2Me)) as part of a benzo-annulated five-membered iridacycle, reacts readily with the conjugated dienes butadiene and 2,3-dimethylbutadiene to afford the corresponding Diels-Alder products. Experimental and DFT studies are in accordance with an initial [4 + 3] cyclometalation reaction between the diene and the five-coordinated 16-electron organometallic fragment 1 (generated from 1-OH2 by facile water dissociation). The reaction can be extended to a related TpIr(III) complex (Tp = hydrotris(pyrazolyl)borate) that also features a labile ligand (i.e., 2-THF).

  7. 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

  8. A mechanochemical study of the effects of compression on a Diels-Alder reaction.

    PubMed

    Jha, Sanjiv K; Brown, Katie; Todde, Guido; Subramanian, Gopinath

    2016-08-21

    We examine the effects of compressive external forces on the mechanisms of the parent Diels-Alder (DA) reaction between butadiene and ethylene. Reaction pathways and transition states were calculated using the nudged elastic band method within a mechanochemical framework at the CASSCF(6,6)/6-31G**, as well as the B3LYP/6-311++G** levels of theory. Our results suggest that compressive hydrostatic pressure lowers the energy barrier for the parent DA reaction while suppressing the undesirable side reaction, thereby leading to a direct increase in the yield of cyclohexene. Compressive pressure also increases the exothermicity of the parent DA reaction, which would lead to increased temperatures in a reaction vessel and thereby indirectly increase the yield of cyclohexene. Our estimates indicate that the compression used in our study corresponds to a range of 68 MPa-1410 MPa. PMID:27544105

  9. 18F-Based Pretargeted PET Imaging Based on Bioorthogonal Diels–Alder Click Chemistry

    PubMed Central

    2015-01-01

    A first-of-its-kind 18F 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[18F]NOTA-labeled tetrazine radioligand were harnessed for the visualization of CA19.9-expressing BxPC3 pancreatic cancer xenografts. Biodistribution and 18F-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. PMID:26479967

  10. Sensory evaluation, physicochemical properties and aroma-active profiles in a diverse collection of Chinese bayberry (Myrica rubra) cultivars.

    PubMed

    Cheng, Huan; Chen, Jianle; Chen, Shiguo; Xia, Qile; Liu, Donghong; Ye, Xingqian

    2016-12-01

    The present study aimed to differentiate the flavor (taste and odor) profiles of 11 Chinese bayberry cultivars (Myrica rubra). The physicochemical analysis for taste indicated the bayberry cultivars were quite different in soluble sugars, organic acids, color, total phenolics and anthocyanin contents. Sucrose was the main soluble sugar in bayberry fruit. Principal component analysis (PCA) of physicochemical properties indicated bayberries could be divided into 5 groups, and the Bi qi cultivar contained the highest brix/acid ratio demonstrating the sweetest taste. PCA of aroma-active profile for odor (analyzed by SPME-GC-MS-O) indicated bayberries could be divided into 3 groups: α-pinene ("pine" odor) for group 1 (four cultivars), β-caryophyllene and isocaryophyllene ("woody" odor) for group 2 (six cultivars), and ethyl acetate ("overripe" odor) for group 3 (one cultivar). Our research on the physicochemical and active-aroma of 11 bayberry cultivars will help to select suitable cultivars to increase consumer satisfaction. PMID:27374545

  11. Functional analysis of differentially expressed proteins in Chinese bayberry (Myrica rubra Sieb. et Zucc.) fruits during ripening.

    PubMed

    Chen, Yi-Yong; Zhang, Ze-Huang; Zhong, Can-Yu; Song, Xiao-Min; Lin, Qi-Hua; Huang, Chun-Mei; Huang, Rong-Hui; Chen, Wei

    2016-01-01

    This study developed a proteome reference map of Myrica rubra fruits at the green, pink and red stages during ripening using two-dimensional gel electrophoresis (2-DE). Forty-six differentially expressed proteins were detected in the gel, of which 43 were successfully identified by matrix-assisted laser desorption ionization time-of-flight/time-of-flight mass spectrometry and protein database searching. We found that malic enzyme related to the decrease of organic acid acidity was up-regulated. The high abundance of pyruvate decarboxylase and alcohol dehydrogenase may contribute to fruit peculiar fragrant characteristics. Phenylalanine ammonia-lyase, chalcone synthase 11, UDP-glucose:flavonoid 3-O-glucosyltransferase, and anthocyanidin synthase, enzymes involved in the anthocyanin metabolic pathway, were all up-regulated. The physiological data agree with fruit proteome results. These findings provided insights into the metabolic processes and regulatory mechanisms during Chinese bayberry fruit ripening. PMID:26213036

  12. 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.

  13. 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. PMID:27638736

  14. 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. PMID:20527138

  15. 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.

  16. 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. PMID:25234391

  17. 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

  18. 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

  19. 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

  20. Exploring Reaction Mechanism on Generalized Force Modified Potential Energy Surfaces (G-FMPES) for Diels-Alder Reaction

    NASA Astrophysics Data System (ADS)

    Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath

    We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.

  1. 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.

  2. Structure and function of Frankia vesicles in dinitrogen fixing actinorhizal plants

    SciTech Connect

    Torrey, J.G.

    1990-01-01

    Frankia, a filamentous bacterium which induces N{sub 2}-fixing root nodules on the roots of a wide range of woody dicotyledonous plants, is the first known actinomycete which fixes dinitrogen when growing in free-living culture. The nitrogenase enzyme is induced in many strains of this organism by withholding fixed nitrogen compounds from its nutrient medium. Our studies have concerned the physiology, biochemistry and structural development of the N{sub 2}-fixing apparatus in Frankia grown in vitro and in root nodules of host plants. Diverse strains of Frankia were isolated and cultured from different host plants and vesicle form and function were studied. Two strains were studied, HFPArI3, an isolate from nodules of the red alder Alnus rubra and HFPCcI3 isolated from root nodules of the tropical tree Casuarina cunninghamiana. The goal was to understand the structure and function which leads to optimum effectiveness for dinitrogen fixation. 13 refs.

  3. 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.

  4. 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. PMID:15589661

  5. 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.

  6. 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

  7. Visible-light induced isoindoles formation to trigger intermolecular Diels-Alder reactions in the presence of air.

    PubMed

    Lin, Chao; Zhen, Le; Cheng, Yong; Du, Hong-Jin; Zhao, Hui; Wen, Xiaoan; Kong, Ling-Yi; Xu, Qing-Long; Sun, Hongbin

    2015-06-01

    Visible-light induced isoindole formation triggered an intermolecular Diels-Alder reaction with dienophiles such as acetylenedicarboxylate and maleimides in the presence of air. The reaction resulted in excellent diastereoselctivity and high yields under mild reaction conditions. This protocol provides an atom-economical, transition-metal-free (TM-free) and straightforward approach to structurally diverse bridged-ring heterocycles from easily accessible molecules.

  8. Spectacular Rate Enhancement of the Diels-Alder Reaction at the Ionic Liquid/n-Hexane Interface.

    PubMed

    Beniwal, Vijay; Manna, Arpan; Kumar, Anil

    2016-07-01

    The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity.

  9. Design and synthesis of fused polycycles via Diels–Alder reaction and ring-rearrangement metathesis as key steps

    PubMed Central

    Ravikumar, Ongolu

    2015-01-01

    Summary Atom efficient processes such as the Diels–Alder reaction (DA) and the ring-rearrangement metathesis (RRM) have been used to design new polycycles. In this regard, ruthenium alkylidene catalysts are effective in realizing the RRM of bis-norbornene derivatives prepared by DA reaction and Grignard addition. Here, fused polycycles are assembled which are difficult to produce by conventional synthetic routes. PMID:26425184

  10. 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

    2016-07-01

    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.

  11. 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

    2016-07-01

    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. PMID:27299858

  12. 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.

  13. Effects of fungal inocula and habitat conditions on alder and eucalyptus leaf litter decomposition in streams of northern Spain.

    PubMed

    Pérez, Javier; Galán, Javier; Descals, Enrique; Pozo, Jesús

    2014-02-01

    We investigated how fungal decomposer (aquatic hyphomycetes) communities colonizing alder and eucalyptus leaf litter respond to changes in habitat characteristics (transplantation experiment). We examined the breakdown of leaf materials and the associated fungal communities at two contrasting sites, a headwater stream (H) and a midreach (M). Agroforestry increased from headwater to midreach. One month after the start of experiments at both sites, some leaf samples from the midreach site were transplanted to the headwater site (M-H treatment). Although both sites showed similar dissolved inorganic nutrient concentrations, eucalyptus leaves initially incubated at the midreach site (M, M-H) increased their breakdown rate compared to those incubated along the experiment at the headwater site (H). Alder breakdown rate was not enhanced, suggesting that their consumption was not limited by nutrient availability. Sporulation rates clearly differed between leaf types (alder > eucalyptus) and streams (H > M), but no transplantation effect was detected. When comparing conidial assemblages after transplantation, an inoculum effect (persistence of early colonizing species) was clear in both leaf species. Substrate preference and shifts in the relative importance of some fungal species along the process were also observed. Overall, our results support the determining role of the initial conditioning phase on the whole litter breakdown process, highlighting the importance of intrinsic leaf characteristics and those of the incubation habitat.

  14. Anxiolytic effects of Plumeria rubra var. acutifolia (Poiret) L. flower extracts in the elevated plus-maze model of anxiety in mice.

    PubMed

    Chatterjee, Manavi; Verma, Rajkumar; Lakshmi, Vijai; Sengupta, Shibani; Verma, Anil Kumar; Mahdi, Abbas Ali; Palit, Gautam

    2013-04-01

    Interest in alternative medicine and plant-derived medications that affect the "mind" is growing rapidly since last two decades. The aim of the present study was to investigate the effects of ethanolic extract of flower of Plumeria rubra (PR) along with its fractions in the elevated plus-maze (EPM) model of anxiety. The P. rubra extract or its fractions was administered orally to male Swiss mice, at graded doses, 1h prior to behavioural assessment. The PR extract at the dose of 100mg/kg p.o., significantly increased the time spent in the open arms of the EPM. Further, the anxiolytic properties of hexane, chloroform and butanolic soluble and insoluble fractions at one-fifth of the original dose were also observed in the EPM task. Out of which butanol insoluble fraction showed significant anxiolytic activity comparable to standard anxiolytic drug, diazepam. Further, pretreatment with crude ethanolic extract and butane insoluble fraction showed no significant effects in the horizontal activity, total distance travelled and stereotypy count in the animal activity monitor and had no motor in-coordination side effects in the rotarod test in mice. These observations suggest that the flower extract of P. rubra and its insoluble butanolic fraction might possess significant anxiolytic potential to be pursued further for drug development process.

  15. Trans-cyclooctene tag with improved properties for tumor pretargeting with the diels-alder reaction.

    PubMed

    Rossin, Raffaella; van Duijnhoven, Sander M J; Läppchen, Tilman; van den Bosch, Sandra M; Robillard, Marc S

    2014-09-01

    Radioimmunotherapy (RIT) of solid tumors is hampered by low tumor-to-nontumor (T/NT) ratios of the radiolabeled monoclonal antibodies resulting in low tumor doses in patients. Pretargeting technologies can improve the effectiveness of RIT in cancer therapy by increasing this ratio. We showed that a pretargeting strategy employing in vivo chemistry in combination with clearing agents, proceeds efficiently in tumor-bearing mice resulting in high T/NT ratios. A dosimetry study indicated that the chemical pretargeting technology, which centered on the bioorthogonal Diels-Alder click reaction between a radiolabeled tetrazine probe and a trans-cyclooctene-oxymethylbenzamide-tagged CC49 antibody (CC49-TCO(1)), can match the performance of clinically validated high-affinity biological pretargeting approaches in mice ( Rossin J Nucl Med. 2013 , 54 , 1989 - 1995 ). Nevertheless, the increased protein surface hydrophobicity of CC49-TCO(1) led to a relatively rapid blood clearance and concomitant reduced tumor uptake compared to native CC49 antibody. Here, we present the in vivo evaluation of a TCO-oxymethylacetamide-tagged CC49 antibody (CC49-TCO(2)), which is highly reactive toward tetrazines and less hydrophobic than CC49-TCO(1). CC49-TCO(2) was administered to healthy mice to determine its blood clearance and the in vivo stability of the TCO. Next, pretargeting biodistribution and SPECT studies with CC49-TCO(2), tetrazine-functionalized clearing agent, and radiolabeled tetrazine were carried out in nude mice bearing colon carcinoma xenografts (LS174T). CC49-TCO(2) had an increased circulation half-life, a 1.5-fold higher tumor uptake, and a 2.6-fold improved in vivo TCO stability compared to the more hydrophobic TCO-benzamide-CC49. As a consequence, and despite the 2-fold lower reactivity of CC49-TCO(2) toward tetrazines compared with CC49-TCO(1), administration of radiolabeled tetrazine afforded a significantly increased tumor accumulation and improved T/NT ratios in mice

  16. 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.

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

    DOE PAGES

    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 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

  18. 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.

  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. PMID:26248230

  20. 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.

  1. Gas exchange in Quercus rubra (northern red oak) during a drought: analysis of relations among photosynthesis, transpiration, and leaf conductance.

    PubMed

    Weber, J. A.; Gates, D. M.

    1990-12-01

    Development of water stress in leaves of mature Quercus rubra L. caused a marked midday depression in photosynthesis (A) and transpiration (E). At external CO(2) partial pressures of 100-110 Pa, a constant temperature of 30 degrees C and a constant photosynthetic photon flux density of about 1000 micromol m(-2) s(-1), A was 8 micromol m(-2) at low leaf water potentials (-1.5 to -2.0 MPa), whereas it was 20 micromol m(-2) s(-1) in non-stressed leaves (-1.0 MPa). At lower external CO(2) partial pressures, the effect of low leaf water potential on A was less. The midday depression in gas exchange was relieved by an overnight rain of 2.5 cm. No difference in carboxylation efficiency or CO(2) compensation point was found between leaves before and after rain, The relationship between A and E was linear for a given external CO(2) partial pressure, but the slope varied with CO(2) concentration. Modification of the model of stomatal response proposed by Ball et al. (1987) produced a linear relationship between leaf conductance and a factor incorporating A, relative humidity, and CO(2). The data indicate that gas exchange in leaves of mature northern red oak respond rapidly to relief of drought with no indication of long-term photoinhibition. PMID:14972919

  2. Severe, Disfiguring, Pityriasis Rubra Pilaris in a Woman in the Dominican Republic: Histopathologic Diagnosis and Response to Antiretroviral Therapy.

    PubMed

    Lerebours-Nadal, Leonel; Beck-Sague, Consuelo M; Parker, Douglas; Gosman, Amanda; Saavedra, Arturo; Engel, Kristy; Dean, Andrew G

    2016-01-01

    Pityriasis rubra pilaris (PRP) is a poorly understood dermatologic condition usually accompanied by keratoderma and intense erythroderma with islands of unaffected skin. The PRP categories include HIV-associated PRP VI. A 23-year-old HIV-infected, dark-skinned woman in the Dominican Republic developed an extremely severe, disfiguring process characterized first by a dry scaly rash involving her face, trunk, and extremities with hyperpigmentation and islands of spared skin and minimal erythroderma, followed by alopecia and development of a thick horny layer on the scalp and face. The condition, histologically proven to be PRP, was accompanied by fever, wasting, and decline in CD4 count. Initiation of combination antiretroviral therapy (cART) was followed by rapid and sustained resolution of PRP. Nine years after ART initiation, she remains well, with viral suppression and immune recovery, without PRP recurrence but with sparse hair regrowth and facial scarring. In some dark-skinned patients, severe PRP may not feature characteristic erythroderma but will respond to combination ART.

  3. Spatial heterogeneity in the relative impacts of foliar quality and predation pressure on red oak, Quercus rubra, arthropod communities.

    PubMed

    Zehnder, Caralyn B; Stodola, Kirk W; Cooper, Robert J; Hunter, Mark D

    2010-12-01

    Predation pressure and resource availability often interact in structuring herbivore communities, with their relative influence varying in space and time. The operation of multiple ecological pressures and guild-specific herbivore responses may combine to override simple predictions of how the roles of plant quality and predation pressure vary in space. For 2 years at the Coweeta LTER in the Southern Appalachian Mountains, we conducted a bird exclosure experiment on red oak (Quercus rubra) saplings to investigate the effects of bird predation on red oak arthropod communities. We established bird exclosures at six sites along an elevational gradient and estimated variation in foliar nitrogen and bird predation pressure along this gradient. Foliar nitrogen concentrations increased with elevation while our index of bird predation pressure was variable across sites. Greater arthropod densities were detected inside exclosures; however, this result was mainly driven by the response of phloem feeders which were much more prevalent inside exclosures than on control trees. There was little evidence for an effect of bird predation on the other arthropod guilds. Consequently, there was no evidence of a trophic cascade either in terms of leaf damage or tree growth. Finally, we found more variation in arthropod density among trees within sites than variation in arthropod density among sites, indicating the importance of micro-site variation in structuring arthropod communities. PMID:20711610

  4. 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.

  5. Severe, Disfiguring, Pityriasis Rubra Pilaris in a Woman in the Dominican Republic: Histopathologic Diagnosis and Response to Antiretroviral Therapy.

    PubMed

    Lerebours-Nadal, Leonel; Beck-Sague, Consuelo M; Parker, Douglas; Gosman, Amanda; Saavedra, Arturo; Engel, Kristy; Dean, Andrew G

    2016-01-01

    Pityriasis rubra pilaris (PRP) is a poorly understood dermatologic condition usually accompanied by keratoderma and intense erythroderma with islands of unaffected skin. The PRP categories include HIV-associated PRP VI. A 23-year-old HIV-infected, dark-skinned woman in the Dominican Republic developed an extremely severe, disfiguring process characterized first by a dry scaly rash involving her face, trunk, and extremities with hyperpigmentation and islands of spared skin and minimal erythroderma, followed by alopecia and development of a thick horny layer on the scalp and face. The condition, histologically proven to be PRP, was accompanied by fever, wasting, and decline in CD4 count. Initiation of combination antiretroviral therapy (cART) was followed by rapid and sustained resolution of PRP. Nine years after ART initiation, she remains well, with viral suppression and immune recovery, without PRP recurrence but with sparse hair regrowth and facial scarring. In some dark-skinned patients, severe PRP may not feature characteristic erythroderma but will respond to combination ART. PMID:26514629

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

    PubMed

    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

  7. Shade, leaf growth and crown development of Quercus rubra, Quercus velutina, Prunus serotina and Acer rubrum seedlings.

    PubMed

    Gottschalk, Kurt W.

    1994-01-01

    The study was conducted in an open field to determine the optimum irradiance for establishment and growth of two oak species and two major associated woody species. Half-sib seedlings of black cherry (Prunus serotina Ehrh.), red maple (Acer rubrum L.), northern red oak (Quercus rubra L.) and black oak (Q. velutina Lam.) were grown for two years under shade-cloth tents. Eight shade treatments (94, 70, 57, 45, 37, 27, 20 and 8% of full sunlight) with three replications each were used. Measurements were made on seedlings harvested at the end of the first and second growing seasons. In the second year, shading significantly decreased the number of leaves for all species except black cherry, but only significantly decreased leaf area in northern red oak. Shading significantly decreased average leaf size of red maple. Average leaf size of black cherry was largest in the intermediate shade treatments and decreased significantly with increased and decreased shade. Leaf weight/leaf area (mg cm(-2)) increased significantly in a quadratic pattern with decreasing shade for all four species. Leaf area ratio (cm(2) g(-1)) decreased significantly with decreasing shade for all species except red maple in the first year and black oak in the second year. Total branch development increased significantly with decreasing shade in red maple and northern red oak, whereas indeterminate branches increased significantly with decreasing shade only in black cherry, and short branches increased significantly with decreasing shade only in red maple. PMID:14967644

  8. 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

  9. Permanent Draft Genome Sequence of Frankia sp. Strain AvcI1, a Nitrogen-Fixing Actinobacterium Isolated from the Root Nodules of Alnus viridis subsp. crispa Grown in Canada.

    PubMed

    Swanson, Erik; Oshone, Rediet; Simpson, Stephen; Morris, Krystalynne; Abebe-Akele, Feseha; Thomas, W Kelley; Tisa, Louis S

    2015-01-01

    Frankia strain AvcI1, isolated from root nodules of Alnus viridis subsp. crispa, is a member of Frankia lineage Ia, which is able to reinfect plants of the Betulaceae and Myricaceae families. Here, we report a 7.7-Mbp draft genome sequence with a G+C content of 72.41% and 6,470 candidate protein-encoding genes. PMID:26722013

  10. Permanent Draft Genome Sequence of Frankia sp. Strain AvcI1, a Nitrogen-Fixing Actinobacterium Isolated from the Root Nodules of Alnus viridis subsp. crispa Grown in Canada

    PubMed Central

    Swanson, Erik; Oshone, Rediet; Simpson, Stephen; Morris, Krystalynne; Abebe-Akele, Feseha; Thomas, W. Kelley

    2015-01-01

    Frankia strain AvcI1, isolated from root nodules of Alnus viridis subsp. crispa, is a member of Frankia lineage Ia, which is able to reinfect plants of the Betulaceae and Myricaceae families. Here, we report a 7.7-Mbp draft genome sequence with a G+C content of 72.41% and 6,470 candidate protein-encoding genes. PMID:26722013

  11. 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.

  12. 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.

  13. Modification of multi-walled carbon nanotubes by Diels-Alder and Sandmeyer reactions.

    PubMed

    Gergely, A; Telegdi, J; Mészáros, E; Pászti, Z; Tárkanyi, G; Kármán, F H; Kálmán, E

    2007-08-01

    Random (L) and aligned (A) multi-walled carbon nanotubes (MWNTs) were modified by Diels-Alder (DA) [4+2] cycloaddition, Sandmeyer (SM) reaction and by catalytic oxidation (OX). The properties of modified carbon nanotubes were studied by dispersability tests, elemental analysis, thermogravimetry/mass spectrometry, X-ray photoelectron spectroscopy, and NMR spectroscopy. The cycloaddition reaction could only be successfully performed with the L-MWNTs in molten and in solution state by using an aluminum chloride homogeneous catalyst. The efficiency and thermal stability of the solution phase cycloaddition were much higher than in the case of modification in the molten phase. The functionalization of both types of MWNTs by Sandmeyer reaction was carried out by copper(I) and iron(ll) ions that helped in the radical decomposition of diazonium salts. Successful functionalization of nanotubes is achieved by a long decomposition time of the thermally activated diazonium salts. To the contrary, in the case of radical decomposition of diazonium salts, the time is not a decisive parameter. The dispersability tests have proved the changes in the physical features of modified carbon nanotubes depending on the hydrophobic and hydrophilic character of the solvents. The presence of the modifying groups and their fragments from the functionalized MWNTs has been demonstrated by thermogravimetry/mass spectrometry (TG/MS). Relatively high concentration of sulfur atoms was detected by X-ray photoelectron spectroscopy in nanotubes modified by sulfur substituent groups. In the case of catalytic oxidation, the X-ray photoelectron spectroscopic signal of oxygen bound to nanotubes showed considerable change as compared to pristine nanotubes. Due to the high thermal stability of modified multi-walled carbon nanotubes, the functionalized derivatives are applicable in several industrial fields. PMID:17685300

  14. π-conjugated polymer-fullerene covalent hybrids via ambient conditions Diels-Alder ligation.

    PubMed

    Yameen, Basit; Puerckhauer, Tanja; Ludwig, Jens; Ahmed, Ishtiaq; Altintas, Ozcan; Fruk, Ljiljana; Colsmann, Alexander; Barner-Kowollik, Christopher

    2014-08-13

    The established ability of graphitic carbon-nanomaterials to undergo ambient condition Diels-Alder reactions with cyclopentadienyl (Cp) groups is herein employed to prepare fullerene-polythiophene covalent hybrids with improved electron transfer and film forming characteristics. A novel precisely designed polythiophene (M n 9.8 kD, Đ 1.4) with 17 mol% of Cp-groups bearing repeat unit is prepared via Grignard metathesis polymerization. The UV/Vis absorption and fluorescence (λex 450 nm) characteristics of polythiophene with pendant Cp-groups (λmax 447 nm, λe-max 576 nm) are comparable to the reference poly(3-hexylthiophene) (λmax 450 nm, λe-max 576 nm). The novel polythiophene with pendant Cp-groups is capable of producing solvent-stable free-standing polythiophene films, and non-solvent assisted self-assemblies resulting in solvent-stable nanoporous-microstructures. (1) H-NMR spectroscopy reveals an efficient reaction of the pendant Cp-groups with C60 . The UV/Vis spectroscopic analyses of solution and thin films of the covalent and physical hybrids disclose closer donor-acceptor packing in the case of covalent hybrids. AFM images evidence that the covalent hybrids form smooth films with finer lamellar-organization. The effect is particularly remarkable in the case of poorly soluble C60 . A significant enhancement in photo-voltage is observed for all devices constituted of covalent hybrids, highlighting novel avenues to developing efficient electron donor-acceptor combinations for light harvesting systems. PMID:24711288

  15. Harnessing the Bioorthogonal Inverse Electron Demand Diels-Alder Cycloaddition for Pretargeted PET Imaging

    PubMed Central

    Lewis, Jason S.

    2015-01-01

    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 64Cu-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 64Cu or 89Zr. 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. PMID:25742199

  16. 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.

  17. 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.

  18. Origins of stereoselectivity in the Diels-Alder addition of chiral hydroxyalkyl vinyl ketones to cyclopentadiene: a quantitative computational study.

    PubMed

    Bakalova, Snezhana M; Kaneti, Jose

    2008-12-18

    Modest basis set level MP2/6-31G(d,p) calculations on the Diels-Alder addition of S-1-alkyl-1-hydroxy-but-3-en-2-ones (1-hydroxy-1-alkyl methyl vinyl ketones) to cyclopentadiene correctly reproduce the trends in known experimental endo/exo and diastereoface selectivity. B3LYP theoretical results at the same or significantly higher basis set level, on the other hand, do not satisfactorily model observed endo/exo selectivities and are thus unsuitable for quantitative studies. The same is valid also with regard to subtle effects originating from, for example, conformational distributions of reactants. The latter shortcomings are not alleviated by the fact that observed diastereoface selectivities are well-reproduced by DFT calculations. Quantitative computational studies of large cycloaddition systems would require higher basis sets and better account for electron correlation than MP2, such as, for example, CCSD. Presently, however, with 30 or more non-hydrogen atoms, these computations are hardly feasible. We present quantitatively correct stereochemical predictions using a hybrid layered ONIOM computational approach, including the chiral carbon atom and the intramolecular hydrogen bond into a higher level, MP2/6-311G(d,p) or CCSD/6-311G(d,p), layer. Significant computational economy is achieved by taking account of surrounding bulky (alkyl) residues at 6-31G(d) in a low HF theoretical level layer. We conclude that theoretical calculations based on explicit correlated MO treatment of the reaction site are sufficiently reliable for the prediction of both endo/exo and diastereoface selectivity of Diels-Alder addition reactions. This is in line with the understanding of endo/exo selectivity originating from dynamic electron correlation effects of interacting pi fragments and diastereofacial selectivity originating from steric interactions of fragments outside of the Diels-Alder reaction site. PMID:18637663

  19. Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural

    PubMed Central

    Pacheco, Joshua J.; Davis, Mark E.

    2014-01-01

    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. PMID:24912153

  20. 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

  1. 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. PMID:24912153

  2. Actinorhizal Alder Phytostabilization Alters Microbial Community Dynamics in Gold Mine Waste Rock from Northern Quebec: A Greenhouse Study.

    PubMed

    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

  3. Actinorhizal Alder Phytostabilization Alters Microbial Community Dynamics in Gold Mine Waste Rock from Northern Quebec: A Greenhouse Study.

    PubMed

    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

  4. 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.

  5. 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

  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. Tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds.

    PubMed

    Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando; Del Pozo, Carlos; Fustero, Santos

    2015-01-01

    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

  8. Design and synthesis of polycyclic sulfones via Diels–Alder reaction and ring-rearrangement metathesis as key steps

    PubMed Central

    Gunta, Rama

    2015-01-01

    Summary Here, we describe a new and simple synthetic strategy to various polycyclic sulfones via Diels–Alder reaction and ring-rearrangement metathesis (RRM) as the key steps. This approach delivers tri- and tetracyclic sulfones with six (n = 1), seven (n = 2) or eight-membered (n = 3) fused-ring systems containing trans-ring junctions unlike the conventional all cis-ring junctions generally obtained during the RRM sequence. Interestingly the starting materials used are simple and commercially available. PMID:26425192

  9. Theoretical Study on Regioselectivity of the Diels-Alder Reaction between 1,8-Dichloroanthracene and Acrolein.

    PubMed

    Sultan, Mujeeb A; Karama, Usama; Almansour, Abdulrahman I; Soliman, Saied M

    2016-01-01

    A theoretical study of the regioselectivity of the Diels-Alder reaction between 1,8-dichloroanthracene and acrolein is performed using DFT at the B3LYP/6-31G(d,p) level of theory. The FMO analysis, global and local reactivity indices confirmed the reported experimental results. Potential energy surface analysis showed that the cycloadditions (CAs) favor the formation of the anti product. These results are in good agreement with the reported results obtained experimentally where the anti is the major product. PMID:27669204

  10. 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.

  11. 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. PMID:26788111

  12. 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

  13. Dichlorination of (hexadehydro-Diels-Alder generated) benzynes and a protocol for interrogating the kinetic order of bimolecular aryne trapping reactions.

    PubMed

    Niu, Dawen; Wang, Tao; Woods, Brian P; Hoye, Thomas R

    2014-01-01

    The efficient dichlorination of benzynes prepared by the hexadehydro-Diels-Alder (HDDA) reaction is reported. Cycloisomerization of a triyne substrate in the presence of dilithium tetrachlorocuprate is shown to provide dichlorinated products A by capture of the benzyne intermediate. A general strategy for discerning the kinetic order of an external aryne trapping agent is presented. It merely requires measurement of the competition between bimolecular vs unimolecular trapping events (here, dichlorination vs intramolecular Diels-Alder (IMDA) reaction to give A vs B, respectively) as a function of the concentration of the trapping agent.

  14. Copper(II)-catalyzed room temperature aerobic oxidation of hydroxamic acids and hydrazides to acyl-nitroso and azo intermediates, and their Diels-Alder trapping.

    PubMed

    Chaiyaveij, Duangduan; Cleary, Leah; Batsanov, Andrei S; Marder, Todd B; Shea, Kenneth J; Whiting, Andrew

    2011-07-01

    CuCl(2), in the presence of a 2-ethyl-2-oxazoline ligand, is an effective catalyst for the room temperature, aerobic oxidation of hydroxamic acids and hydrazides, to acyl-nitroso and azo dienophiles respectively, which are efficiently trapped in situ via both inter- and intramolecular hetero-Diels-Alder reactions with dienes. Both inter- and intramolecular variants of the Diels-Alder reaction are suitable under the reaction conditions using a variety of solvents. Under the same conditions, an acyl hydrazide was also oxidized to give an acyl-azo dienophile which was trapped intramolecularly by a diene. PMID:21644530

  15. Synthesis of 3,4-dihydro-1,8-naphthyridin-2(1H)-ones via microwave-activated inverse electron-demand Diels–Alder reactions

    PubMed Central

    Fadel, Salah; Hajbi, Youssef; Khouili, Mostafa; Lazar, Said

    2014-01-01

    Summary Substituted 3,4-dihydro-1,8-naphthyridin-2(1H)-ones have been synthesized with the inverse electron-demand Diels–Alder reaction from 1,2,4-triazines bearing an acylamino group with a terminal alkyne side chain. Alkynes were first subjected to the Sonogashira cross-coupling reaction with aryl halides, the product of which then underwent an intramolecular inverse electron-demand Diels–Alder reaction to yield 5-aryl-3,4-dihydro-1,8-naphthyridin-2(1H)-ones by an efficient synthetic route. PMID:24605148

  16. 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.

  17. 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

  18. 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%.

  19. Characterizing Ipomopsis rubra (Polemoniaceae) germination under various thermal scenarios with non-parametric and semi-parametric statistical methods.

    PubMed

    Pérez, Hector E; Kettner, Keith

    2013-10-01

    Time-to-event analysis represents a collection of relatively new, flexible, and robust statistical techniques for investigating the incidence and timing of transitions from one discrete condition to another. Plant biology is replete with examples of such transitions occurring from the cellular to population levels. However, application of these statistical methods has been rare in botanical research. Here, we demonstrate the use of non- and semi-parametric time-to-event and categorical data analyses to address questions regarding seed to seedling transitions of Ipomopsis rubra propagules exposed to various doses of constant or simulated seasonal diel temperatures. Seeds were capable of germinating rapidly to >90 % at 15-25 or 22/11-29/19 °C. Optimum temperatures for germination occurred at 25 or 29/19 °C. Germination was inhibited and seed viability decreased at temperatures ≥30 or 33/24 °C. Kaplan-Meier estimates of survivor functions indicated highly significant differences in temporal germination patterns for seeds exposed to fluctuating or constant temperatures. Extended Cox regression models specified an inverse relationship between temperature and the hazard of germination. Moreover, temperature and the temperature × day interaction had significant effects on germination response. Comparisons to reference temperatures and linear contrasts suggest that summer temperatures (33/24 °C) play a significant role in differential germination responses. Similarly, simple and complex comparisons revealed that the effects of elevated temperatures predominate in terms of components of seed viability. In summary, the application of non- and semi-parametric analyses provides appropriate, powerful data analysis procedures to address various topics in seed biology and more widespread use is encouraged.

  20. Immunomodulating Activity of Nymphaea rubra Roxb. Extracts: Activation of Rat Dendritic Cells and Improvement of the TH1 Immune Response

    PubMed Central

    Cheng, Jai-Hong; Lee, Shau-Yu; Lien, Yi-Yang; Lee, Meng-Shiou; Sheu, Shyang-Chwen

    2012-01-01

    Polysaccharides play a key role in enhancing immune function and facilitating cellular communication. Here, we purified Nymphaea rubra Roxb. polysaccharides (NR-PS) by treating them with pullulanase. They were then cultured with immature dendritic cells (DCs) derived from rat bone marrow hematopoietic cells (BMHCs). After treatment with bioactive NR-PS with a degree of polymerization (DP) value of 359.8, we found that the DCs underwent morphological changes indicative of activation. CD80/86 (87.16% ± 8.49%) and MHC class II (52.01% ± 10.11%) expression levels were significantly up-regulated by this treatment compared to the controls (65.45% ± 0.97% and 34.87% ± 1.96%). In parallel, endocytosis was also reduced (167.94% ± 60.59%) after treatment with 25 μg/mL of NR-PS as measured by the medium fluorescence intensity compared to the control (261.67% ± 47.26%). Furthermore, the DCs after treatment with 25 μg/mL NR-PS showed increased IL-12 (102.09 ± 10.16 to 258.78 ± 25.26 pg/mL) and IFN-γ (11.76 ± 0.11 to 15.51 ± 1.66 pg/mL) secretion together with reduced IL-10 secretion (30.75 ± 3.35 to 15.37 ± 2.35 pg/mL), which indicates a TH1 immune response. In conclusion, NR-PS exhibits stimulatory effects on rat DCs and promotes the secretion of TH1 cytokines. Taken together, our studies are the first to show that NR-PS is an immunomodulator affecting the maturation and functioning of DCs. PMID:23109818

  1. A new genus and species of fish leeches Dolichobdella rubra, gen. n., sp. n., (Clitellata, Hirudinida, Piscicolidae) from the northern Sea ofJapan

    NASA Astrophysics Data System (ADS)

    Utevsky, Serge Y.; Chernyshev, Alexei V.

    2013-02-01

    A new species of fish leeches, Dolichobdella rubra gen. n., sp. n., was found in samples collected by RV Akademik M.A. Lavrentyev in the northern Sea of Japan from 470-528 m during the joint Russian-German expedition SoJaBio (Sea of Japan Biodiversity Studies) in August 2010. The leech does not exceed 13 mm in length and has the following morphological characteristics: body elongated, smooth, lacking gills and pulsatile vesicles; eyes and ocelli absent; coloration reddish; female gonopore larger than male one; 6pairs of testisacs; accessory glands, conductive tissue and copulatory area present; ovisacs short; bursa long; coelomic system reduced.

  2. From tolerance to acute metabolic deregulation: contribution of proteomics to dig into the molecular response of alder species under a polymetallic exposure.

    PubMed

    Printz, Bruno; Sergeant, Kjell; Lutts, Stanley; Guignard, Cédric; Renaut, Jenny; Hausman, Jean-Francois

    2013-11-01

    Alnus spp. are actinorhizal trees commonly found in wet habitats and able to grow effectively in soil slightly contaminated with metal trace- elements. Two clones belonging to two Alnus species, namely, A. incana and A. glutinosa, were grown in hydroponics and exposed for 9 weeks to a Cd + Ni + Zn polymetallic constraint. Although responding by a similar decrease in total biomass production, the proteomic analysis associated with the study of various biochemical parameters including carbohydrate and mineral analyses revealed that the two clones have a distinct stress-responsive behavior. All parameters indicated that the roots, the organ in direct contact with the media, are more affected than the leaves. In fact, in A. glutinosa the response was almost completely confined to the roots, whereas many proteins change significantly in the roots and in the leaves of the treated A. incana. In both clones, the changes affected a broad range of metabolic processes such as redox regulation and energy metabolism and induced the production of pathogenesis-related proteins. In particular, changes in the accumulation of bacterial proteins that were not identified as coming from the known symbionts of Alnus were reported. Further investigation should be performed to identify their origin and exact role in the plant response to the polymetallic exposure tested here. PMID:24015726

  3. Extraordinary Mechanism of the Diels-Alder Reaction: Investigation of Stereochemistry, Charge Transfer, Charge Polarization, and Biradicaloid Formation.

    PubMed

    Sexton, Thomas; Kraka, Elfi; Cremer, Dieter

    2016-02-25

    The Diels-Alder reaction between 1,3-butadiene and ethene is investigated from far-out in the entrance channel to the very last step in the exit channel thus passing two bifurcation points and extending the range of the reaction valley studied with URVA (Unified Reaction Valley Approach) by 300% compared to previous studies. For the first time, the pre- and postchemical steps of the reaction are analyzed at the same level of theory as the actual chemical processes utilizing the path curvature and its decomposition into internal coordinate or curvilinear coordinate components. A first smaller charge transfer to the dienophile facilitates the rotation of gauche butadiene into its cis form. The actual chemical processes are initiated by a second larger charge transfer to the dienophile that facilitates pyramidalization of the reacting carbon centers, bond equalization, and biradicaloid formation of the reactants. The transition state is aromatically stabilized and moved by five path units into the entrance channel in line with the Hammond-Leffler postulate. The pseudorotation of the boat form into the halfchair of cyclohexene is analyzed. Predictions are made for the Diels-Alder reaction based on a 11-phase mechanism obtained by the URVA analysis. PMID:26785172

  4. Low dielectric, nanoporous fluorinated polyimide films prepared from PCL-PI-PCL triblock copolymer using retro-Diels-Alder reaction.

    PubMed

    Ju, Junping; Wang, Qihua; Wang, Tingmei; Wang, Chao

    2013-08-15

    The triblock copolymers with the majority phase comprising fluorinated polyimide and the minor phase consisting of poly (ε-caprolactone) (PCL) were synthesized through Diels-Alder reaction between PI-Maleimide and PCL-Furfuryl Amine. The chemical composition and structure of the copolymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Films of the copolymers were spined and microphase-separation of the thin film was achieved by solvent annealing in N,N-dimethylformamide (DMF) vapor. The microphase-separation morphology was investigated by atomic force microscopy (AFM). Based on the microphase-separation structures, nanoporous fluorinated polyimide films were obtained after removal of the PCL block can removed via a retro-DA (Diels-Alder) reaction using a simple heating and immersing procedure. The nanoporous thin film was characterized by Transmission electron microscopy (TEM). The dielectric property of the nanoporous fluorinated polyimide films was investigated. It was found that the nanopores introduction could effectively reduce the dielectric constant from 2.82 of PI dense films to 2.10 of nanoporous PI films.

  5. Biodegradable hyaluronic acid hydrogels to control release of dexamethasone through aqueous Diels-Alder chemistry for adipose tissue engineering.

    PubMed

    Fan, Ming; Ma, Ye; Zhang, Ziwei; Mao, Jiahui; Tan, Huaping; Hu, Xiaohong

    2015-11-01

    A robust synthetic strategy of biopolymer-based hydrogels has been developed where hyaluronic acid derivatives reacted through aqueous Diels-Alder chemistry without the involvement of chemical catalysts, allowing for control and sustain release of dexamethasone. To conjugate the hydrogel, furan and maleimide functionalized hyaluronic acid were synthesized, respectively, as well as furan functionalized dexamethasone, for the covalent immobilization. Chemical structure, gelation time, morphologies, swelling kinetics, weight loss, compressive modulus and dexamethasone release of the hydrogel system in PBS at 37°C were studied. The results demonstrated that the aqueous Diels-Alder chemistry provides an extremely selective reaction and proceeds with high efficiency for hydrogel conjugation and covalent immobilization of dexamethasone. Cell culture results showed that the dexamethasone immobilized hydrogel was noncytotoxic and preserved proliferation of entrapped human adipose-derived stem cells. This synthetic approach uniquely allows for the direct fabrication of biologically functionalized gel scaffolds with ideal structures for adipose tissue engineering, which provides a competitive alternative to conventional conjugation techniques such as copper mediated click chemistry.

  6. An interpenetrating HA/G/CS biomimic hydrogel via Diels-Alder click chemistry for cartilage tissue engineering.

    PubMed

    Yu, Feng; Cao, Xiaodong; Zeng, Lei; Zhang, Qing; Chen, Xiaofeng

    2013-08-14

    In order to mimic the natural cartilage extracellular matrix, a novel biological degradable interpenetrating network hydrogel was synthesized from the gelatin (G), hyaluronic acid (HA) and chondroitin sulfate (CS) by Diels-Alder "click" chemistry. HA was modified with furylamine and G was modified with furancarboxylic acid respectively. (1)H NMR spectra and elemental analysis showed that the substitution degrees of HA-furan and G-furan were 71.5% and 44.5%. Then the hydrogels were finally synthesized by cross-linking furan-modified HA and G derivatives with dimaleimide poly(ethylene glycol) (MAL-PEG-MAL). The mechanical and degradation properties of the hydrogels could be tuned simply through varying the molar ratio between furan and maleimide. Rheological, mechanical and degradation studies demonstrated that the Diels-Alder "click" chemistry is an efficient method for preparing high performance biological interpenetrating hydrogels. This biomimic hydrogel with improved mechanical properties could have great potential applications in cartilage tissue engineering. PMID:23769536

  7. Studies on the biosynthesis of paraherquamide A and VM99955. A theoretical study of intramolecular Diels-Alder cycloaddition.

    PubMed

    Domingo, Luis R; Zaragozá, Ramón J; Williams, Robert M

    2003-04-01

    Intramolecular Diels-Alder reactions of 2-azadiene models have been studied quantum chemically at the B3LYP/6-31G level in order to elucidate the stereochemical features of the cyclization step involved in the biosynthesis of paraherquamide A and VM99955. These cycloadditions take place through concerted transition states associated with [4 + 2] processes. Analysis of the energies along the competitive paths reveals that while the cycloadditions of the oxindoles present a large anti selectivity, the indoles show a low syn selectivity for the formation of the C20 stereogenic center that is larger for the reduced tertiary amide form. The presence of the C14 methyl of the beta-methylproline ring produces a low hindrance along the reaction coordinate for the syn approach of the isoprene framework, in agreement with the low facial selectivity found experimentally. An analysis of the electrophilicity and activation parameters for experimental models of the inter- and intramolecular Diels-Alder reactions reveals several significant factors controlling these biosynthetic cyclizations. The results are in reasonable agreement with the available experimental data.

  8. 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

  9. 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

  10. Accurate Diels-Alder reaction energies from efficient density functional calculations.

    PubMed

    Mezei, Pál D; Csonka, Gábor I; Kállay, Mihály

    2015-06-01

    We assess the performance of the semilocal PBE functional; its global hybrid variants; the highly parametrized empirical M06-2X and M08-SO; the range separated rCAM-B3LYP and MCY3; the atom-pairwise or nonlocal dispersion corrected semilocal PBE and TPSS; the dispersion corrected range-separated ωB97X-D; the dispersion corrected double hybrids such as PWPB95-D3; the direct random phase approximation, dRPA, with Hartree-Fock, Perdew-Burke-Ernzerhof, and Perdew-Burke-Ernzerhof hybrid reference orbitals and the RPAX2 method based on a Perdew-Burke-Ernzerhof exchange reference orbitals for the Diels-Alder, DARC; and self-interaction error sensitive, SIE11, reaction energy test sets with large, augmented correlation consistent valence basis sets. The dRPA energies for the DARC test set are extrapolated to the complete basis set limit. CCSD(T)/CBS energies were used as a reference. The standard global hybrid functionals show general improvements over the typical endothermic energy error of semilocal functionals, but despite the increased accuracy the precision of the methods increases only slightly, and thus all reaction energies are simply shifted into the exothermic direction. Dispersion corrections give mixed results for the DARC test set. Vydrov-Van Voorhis 10 correction to the reaction energies gives superior quality results compared to the too-small D3 correction. Functionals parametrized for energies of noncovalent interactions like M08-SO give reasonable results without any dispersion correction. The dRPA method that seamlessly and theoretically correctly includes noncovalent interaction energies gives excellent results with properly chosen reference orbitals. As the results for the SIE11 test set and H2(+) dissociation show that the dRPA methods suffer from delocalization error, good reaction energies for the DARC test set from a given method do not prove that the method is free from delocalization error. The RPAX2 method shows good performance for the DARC

  11. Diels-Alder hydrogels with enhanced stability: First step toward controlled release of bevacizumab.

    PubMed

    Kirchhof, Susanne; Gregoritza, Manuel; Messmann, Viktoria; Hammer, Nadine; Goepferich, Achim M; Brandl, Ferdinand P

    2015-10-01

    Eight-armed PEG was functionalized with furyl and maleimide groups (8armPEG20k-Fur and 8armPEG20k-Mal); degradable hydrogels were obtained by cross-linking via Diels-Alder chemistry. To increase the stability to degradation, the macromonomers were modified by introducing a hydrophobic 6-aminohexanoic acid spacer between PEG and the reactive end-groups (8armPEG20k-Ahx-Fur and 8armPEG20k-Ahx-Mal). In an alternative approach, the number of reactive groups per macromonomer was increased by branching the terminal ends of eight-armed PEG with lysine (Lys) and Ahx residues (8armPEG20k-Lys-Ahx-Fur2 and 8armPEG20k-Lys-Ahx-Mal2). The hydrolytic resistance of the synthesized macromonomers was determined by UV spectroscopy; the obtained hydrogels were characterized by rheology and degradation studies. The degradation time of 5% (w/v) 8armPEG20k-Ahx hydrogels (28days) was twice as long as the degradation time of 5% (w/v) 8armPEG20k hydrogels (14days); this is explained by increased hydrolytic resistance of the maleimide group. Using dendritic 8armPEG20k-Lys-Ahx macromonomers substantially increased the stability of the resulting hydrogels; degradation of 5% (w/v) 8armPEG20k-Lys-Ahx hydrogels occurred after 34 weeks. 8armPEG20k hydrogels had the largest mesh size of all tested hydrogels, while hydrogels made from dendritic 8armPEG20k-Lys-Ahx macromonomers showed the smallest value. To evaluate their potential for the controlled release of therapeutic antibodies, the hydrogels were loaded with bevacizumab. The incorporated bevacizumab was released over 10 days (8armPEG20k) and 42days (8armPEG20k-Ahx), respectively; release from 8armPEG20k-Lys-Ahx hydrogels was not completed after 105 days. In summary, we believe that 8armPEG20k-Ahx or 8armPEG20k-Lys-Ahx hydrogels could serve as controlled release system for therapeutic antibodies such as bevacizumab.

  12. 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.

  13. Synthesis of the Reported Pyranonaphthoquinone Structure of the Indoleamine-2,3-dioxygenase Inhibitor Annulin B by Regioselective Diels-Alder Reaction.

    PubMed

    Inman, Martyn; Carvalho, Catarina; Lewis, William; Moody, Christopher J

    2016-09-01

    Annulin B, isolated from the marine hydroid isolated from Garveia annulata, is a potent inhibitor of the tryptophan catabolizing enzyme indoleamine-2,3-dioxygenase (IDO). A synthesis of the reported pyranonaphthoquinone structure is described, in which the key step is a regioselective Diels-Alder reaction between a pyranobenzoquinone dienophile and a silyl ketene acetal diene. PMID:27513176

  14. Kinetic study of the Diels-Alder reaction of Li⁺@C₆₀ with cyclohexadiene: greatly increased reaction rate by encapsulated Li⁺.

    PubMed

    Ueno, Hiroshi; Kawakami, Hiroki; Nakagawa, Koji; Okada, Hiroshi; Ikuma, Naohiko; Aoyagi, Shinobu; Kokubo, Ken; Matsuo, Yutaka; Oshima, Takumi

    2014-08-01

    We studied the kinetics of the Diels-Alder reaction of Li(+)-encapsulated [60]fullerene with 1,3-cyclohexadiene and characterized the obtained product, [Li(+)@C60(C6H8)](PF6(-)). Compared with empty C60, Li(+)@C60 reacted 2400-fold faster at 303 K, a rate enhancement that corresponds to lowering the activation energy by 24.2 kJ mol(-1). The enhanced Diels-Alder reaction rate was well explained by DFT calculation at the M06-2X/6-31G(d) level of theory considering the reactant complex with dispersion corrections. The calculated activation energies for empty C60 and Li(+)@C60 (65.2 and 43.6 kJ mol(-1), respectively) agreed fairly well with the experimentally obtained values (67.4 and 44.0 kJ mol(-1), respectively). According to the calculation, the lowering of the transition state energy by Li(+) encapsulation was associated with stabilization of the reactant complex (by 14.1 kJ mol(-1)) and the [4 + 2] product (by 5.9 kJ mol(-1)) through favorable frontier molecular orbital interactions. The encapsulated Li(+) ion catalyzed the Diels-Alder reaction by lowering the LUMO of Li(+)@C60. This is the first detailed report on the kinetics of a Diels-Alder reaction catalyzed by an encapsulated Lewis acid catalyst rather than one coordinated to a heteroatom in the dienophile.

  15. Synthesis of polysubstituted β-amino cyclohexane carboxylic acids via Diels-Alder reaction using Ni(II)-complex stabilized β-alanine derived dienes.

    PubMed

    Ding, Xiao; Wang, Hengshuai; Wang, Jiang; Wang, Sinan; Lin, Daizong; Lv, Li; Zhou, Yu; Luo, Xiaomin; Jiang, Hualiang; Aceña, José Luis; Soloshonok, Vadim A; Liu, Hong

    2013-02-01

    This paper describes the design and synthesis of a new class of β-alanine derived dienes stabilized by Ni(II)-complex. Preliminary study of their Diels-Alder cycloaddition reactions with several types of dienophiles demonstrates their significant synthetic potential for the preparation of various polyfunctional β-aminocyclohexane carboxylic acids.

  16. 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…

  17. 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…

  18. 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…

  19. 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.…

  20. 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…

  1. 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…

  2. Warming and drought differentially influence the production and resorption of elemental and metabolic nitrogen pools in Quercus rubra.

    PubMed

    Suseela, Vidya; Tharayil, Nishanth; Xing, Baoshan; Dukes, Jeffrey S

    2015-11-01

    The process of nutrient retranslocation from plant leaves during senescence subsequently affects both plant growth and soil nutrient cycling; changes in either of these could potentially feed back to climate change. Although elemental nutrient resorption has been shown to respond modestly to temperature and precipitation, we know remarkably little about the influence of increasing intensities of drought and warming on the resorption of different classes of plant metabolites. We studied the effect of warming and altered precipitation on the production and resorption of metabolites in Quercus rubra. The combination of warming and drought produced a higher abundance of compounds that can help to mitigate climatic stress by functioning as osmoregulators and antioxidants, including important intermediaries of the tricarboxylic acid (TCA) cycle, amino acids including proline and citrulline, and polyamines such as putrescine. Resorption efficiencies (REs) of extractable metabolites surprisingly had opposite responses to drought and warming; drought treatments generally increased RE of metabolites compared to ambient and wet treatments, while warming decreased RE. However, RE of total N differed markedly from that of extractable metabolites such as amino acids; for instance, droughted plants resorbed a smaller fraction of elemental N from their leaves than plants exposed to the ambient control. In contrast, plants in drought treatment resorbed amino acids more efficiently (>90%) than those in ambient (65-77%) or wet (42-58%) treatments. Across the climate treatments, the RE of elemental N correlated negatively with tissue tannin concentration, indicating that polyphenols produced in leaves under climatic stress could interfere with N resorption. Thus, senesced leaves from drier conditions might have a lower nutritive value to soil heterotrophs during the initial stages of litter decomposition despite a higher elemental N content of these tissues. Our results suggest that N

  3. Warming and drought differentially influence the production and resorption of elemental and metabolic nitrogen pools in Quercus rubra.

    PubMed

    Suseela, Vidya; Tharayil, Nishanth; Xing, Baoshan; Dukes, Jeffrey S

    2015-11-01

    The process of nutrient retranslocation from plant leaves during senescence subsequently affects both plant growth and soil nutrient cycling; changes in either of these could potentially feed back to climate change. Although elemental nutrient resorption has been shown to respond modestly to temperature and precipitation, we know remarkably little about the influence of increasing intensities of drought and warming on the resorption of different classes of plant metabolites. We studied the effect of warming and altered precipitation on the production and resorption of metabolites in Quercus rubra. The combination of warming and drought produced a higher abundance of compounds that can help to mitigate climatic stress by functioning as osmoregulators and antioxidants, including important intermediaries of the tricarboxylic acid (TCA) cycle, amino acids including proline and citrulline, and polyamines such as putrescine. Resorption efficiencies (REs) of extractable metabolites surprisingly had opposite responses to drought and warming; drought treatments generally increased RE of metabolites compared to ambient and wet treatments, while warming decreased RE. However, RE of total N differed markedly from that of extractable metabolites such as amino acids; for instance, droughted plants resorbed a smaller fraction of elemental N from their leaves than plants exposed to the ambient control. In contrast, plants in drought treatment resorbed amino acids more efficiently (>90%) than those in ambient (65-77%) or wet (42-58%) treatments. Across the climate treatments, the RE of elemental N correlated negatively with tissue tannin concentration, indicating that polyphenols produced in leaves under climatic stress could interfere with N resorption. Thus, senesced leaves from drier conditions might have a lower nutritive value to soil heterotrophs during the initial stages of litter decomposition despite a higher elemental N content of these tissues. Our results suggest that N

  4. Therapeutic Efficacy and Safety of Paeoniae Radix Rubra Formulae in Relieving Hyperbilirubinemia Induced by Viral Hepatitis: A Meta-Analysis

    PubMed Central

    Huang, Yin-Qiu; Ma, Xiao; Wang, Jian; Zhao, Yan-Ling; Wang, Jia-Bo; Chen, Zhe; Zhu, Yun; Shan, Li-Mei; Wei, Shi-Zhang; Wang, Ji; Xiao, Xiao-He

    2016-01-01

    Objective: Hyperbilirubinemia is one of the most devastating pathologies induced by various liver diseases. Formulae related to Paeoniae Radix Rubra (PRR) at high doses have been applied to treat hyperbilirubinemia in traditional Chinese medicine (TCM). The aim of this systematic review and meta-analysis is to assess the efficacy and safety of formulae relevant to high-dose PRR in patients suffering from hyperbilirubinemia induced by viral hepatitis. Methods: We performed a meta-analysis of randomized-controlled clinical trials to evaluate the efficacy and safety of formulae that apply a high dose of PRR for hyperbilirubinemia. Seven databases were searched until April, 2015. All studies were included according to detailed criteria and assessed for methodological quality. The outcome measurements were recorded for further analysis using the RevMan 5.2.11 software. Results: Fifteen articles involving 1323 patients with hyperbilirubinemia were included. Formulae with high-dose PRR might promote the efficacy of either a combined application ([OR: 3.98, 95% CI (2.91, 5.43)]; P < 0.01) or a single application ([OR: 4.00, 95% CI (1.50, 10.68)]; P < 0.01) for hyperbilirubinemia. The indices of TBIL, ALT, and AST significantly decreased ([MD: –75.57, 95% CI (−94.88, −56.26)], [MD: −26.54, 95% CI (−36.19, −16.88)], and ([MD: −28.94, 95% CI (−46.26, −11.61)]; P < 0.01), respectively. In addition, formulae with high-dose PRR could enhance the treatment efficacy of hyperbilirubinemia triggered by hepatitis B ([OR: 2.98, 95% CI (1.75, 5.05)]; P < 0.01). Furthermore, the efficacy was enhanced with an increasing dosage of PRR. Two articles reported that no side effects occurred in clinical trials, and three studies noted that patients presented light digestive tract symptoms. Conclusion: Formulae relevant to high-dose PRR ameliorate hyperbilirubinemia and might constitute a promising therapeutic approach. For widespread acceptance by practitioners, more

  5. Factors Controlling the Reactivity and Selectivity of the Diels-Alder Reactions Involving 1,2-Azaborines.

    PubMed

    García-Rodeja, Yago; Fernández, Israel

    2016-08-01

    The factors controlling the reactivity and endo/exo selectivity of the Diels-Alder reactions involving 1,2-azaborines have been computationally explored within the density functional theory framework. It is found that the AlCl3-catalyzed [4 + 2]-cycloaddition reaction between these dienes and N-methylmaleimide proceeds concertedly and leads almost exclusively to the corresponding endo cycloadduct, which is in good agreement with previous experimental observations. In addition, the effect of the substituent directly attached to the boron atom of the 1,2-azaborine on the process is also analyzed in detail. To this end, the combination of the activation strain model of reactivity and the energy decomposition analysis methods has been applied to gain a quantitative understanding into the origins of the endo selectivity of the process as well as the influence of the boron and nitrogen substituent on the barrier heights of the transformations. PMID:27383907

  6. 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

  7. Synthesis of complex benzenoids via the intermediate generation of o-benzynes through the hexadehydro-Diels-Alder reaction.

    PubMed

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

    2013-03-01

    The hexadehydro-Diels-Alder (HDDA) cascade enables the synthesis of complex benzenoid products with various substitution patterns through aryne intermediates. The first stage of this cascade involves the generation of a highly reactive ortho-benzyne intermediate by a net [4+2] cycloisomerization of a triyne substrate. The benzyne can be rapidly 'trapped' either intramolecularly or intermolecularly with myriad nucleophilic or π-bond-donating reactants. As a representative example of a general procedure for synthesizing highly substituted benzenoids, this protocol describes the synthesis of a typical triyne substrate and its use as the reactant in an HDDA cascade to form a phthalide. The synthetic procedure detailed herein (four chemical reactions) takes 16-20 h of active effort over a period of several days for the preparation of the triyne precursor and ∼2 h of active effort over a 3-d period for the generation and trapping of the benzyne and isolation of the phthalide product.

  8. Synthesis of complex benzenoids via the intermediate generation of o-benzynes through the hexadehydro-Diels–Alder reaction

    PubMed Central

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

    2014-01-01

    The hexadehydro-Diels–Alder (HDDA) cascade enables the synthesis of complex benzenoid products with various substitution patterns via aryne intermediates. The first stage of this cascade involves generation of a highly reactive ortho-benzyne intermediate by a net [4+2] cycloisomerization of a triyne substrate. The benzyne can be rapidly ‘trapped’ either intra- or intermolecularly with a myriad of nucleophilic or π-bond-donating reactants. As a representative example of a general procedure to synthesize highly substituted benzenoids, this protocol describes the synthesis of a typical triyne substrate and its use as the reactant in an HDDA cascade to form a phthalide. The synthetic procedure detailed herein (four chemical reactions) takes 16–20 h of active effort over a several day period for preparation of the triyne precursor and ~2 h of active effort over a 3-day period for generation and trapping of the benzyne and isolation of the phthalide product. PMID:23411632

  9. Elucidation of Diels-Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst.

    PubMed

    Do, Phuong T M; McAtee, Jesse R; Watson, Donald A; Lobo, Raul F

    2013-01-01

    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 structure of many of the byproducts produced in this reaction when HY zeolite is employed as a catalyst has 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. PMID:23316419

  10. Elucidation of Diels-Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst

    PubMed Central

    Do, Phuong T.M.; McAtee, Jesse R.; Watson, Donald A.; Lobo, Raul F.

    2012-01-01

    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 structure of many of the byproducts produced in this reaction when HY zeolite is employed as a catalyst has 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. PMID:23316419

  11. 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; 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 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

  12. 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.

  13. Irreversible endo-selective diels-alder reactions of substituted alkoxyfurans: a general synthesis of endo-cantharimides.

    PubMed

    Foster, Robert W; Benhamou, Laure; Porter, Michael J; Bučar, Dejan-Krešimir; Hailes, Helen C; Tame, Christopher J; Sheppard, Tom D

    2015-04-13

    The [4+2] cycloaddition of 3-alkoxyfurans with N-substituted maleimides provides the first general route for preparing endo-cantharimides. Unlike the corresponding reaction with 3H furans, the reaction can tolerate a broad range of 2-substitued furans including alkyl, aromatic, and heteroaromatic groups. The cycloaddition products were converted into a range of cantharimide products with promising lead-like properties for medicinal chemistry programs. Furthermore, the electron-rich furans are shown to react with a variety of alternative dienophiles to generate 7-oxabicyclo[2.2.1]heptane derivatives under mild conditions. DFT calculations have been performed to rationalize the activation effect of the 3-alkoxy group on a furan Diels-Alder reaction.

  14. Diels-Alder attachment of a planar organic molecule to a dangling bond dimer on a hydrogenated semiconductor surface.

    PubMed

    Godlewski, Szymon; Kawai, Hiroyo; Engelund, Mads; Kolmer, Marek; Zuzak, Rafal; Garcia-Lekue, Aran; Novell-Leruth, Gerard; Echavarren, Antonio M; Sanchez-Portal, Daniel; Joachim, Christian; Saeys, Mark

    2016-06-22

    Construction of single-molecule electronic devices requires the controlled manipulation of organic molecules and their properties. This could be achieved by tuning the interaction between the molecule and individual atoms by local "on-surface" chemistry, i.e., the controlled formation of chemical bonds between the species. We demonstrate here the reversible attachment of a planar conjugated polyaromatic molecule to a pair of unpassivated dangling bonds on a hydrogenated Ge(001):H surface via a Diels-Alder [4+2] addition using the tip of a scanning tunneling microscope (STM). Due to the small stability difference between the covalently bonded and a nearly undistorted structure attached to the dangling bond dimer by long-range dispersive forces, we show that at cryogenic temperatures the molecule can be switched between both configurations. The reversibility of this covalent bond forming reaction may be applied in the construction of complex circuits containing organic molecules with tunable properties.

  15. 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.

  16. Origin of the synchronicity on the transition structures of polar Diels-Alder reactions. Are these reactions [4 + 2] processes?

    PubMed

    Domingo, Luis R; José Aurell, M; Pérez, Patricia; Contreras, Renato

    2003-05-16

    The transition structures (TSs) for a series of related Diels-Alder reactions between cyclopentadiene and mono-, di-, tri-, and tetracyanoethylene derivatives have been studied with use of DFT methods at the B3LYP/6-31G computational level. The increase of the electron-withdrawing substitution on ethylene increases the rate of these polar cycloadditions. However, the symmetric arrangement of cis and trans 1,2-di- and tetracyanoethylenes decreases the effectiveness of the substitution, which can be related to the symmetry found at the corresponding TSs. A DFT analysis of the global and local electrophilicity power of these series of cyano ethylenes provides a sound explanation about the nature of these synchronous processes. The present theoretical study is in agreement with the experimental outcomes.

  17. 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.

  18. Estimation of whole-tree and stand-level methane emissions from the stems of Alnus japonica in a cool-temperate forested peatland

    NASA Astrophysics Data System (ADS)

    Terazawa, Kazuhiko; Yamada, Kenji; Sakata, Tadashi; Nakamura, Takatoshi; Ishizuka, Shigehiro

    2016-04-01

    We measured methane (CH4) fluxes at the stem surfaces of canopy trees in a forested peatland of northern Japan to estimate: 1) the CH4 emission rates from the stems of individual trees and 2) the stem CH4 emission rates at the stand level. The study site was located ca. 1 km south of Lake Tofutsu, a brackish lake in eastern Hokkaido. An experimental plot was established in an area dominated by Alnus japonica trees. For seven A. japonica, the stem CH4 fluxes were measured using a static closed-chamber method. Three of the sample trees were used to estimate the whole-tree stem CH4 emissions. The CH4 flux was measured at six heights (0.15 - 5.15 m above the ground at 1 m intervals) on the stem of each tree, using a scaffold constructed beside the tree. The stand-level stem CH4 emissions were estimated from the CH4 fluxes measured 0.15 m above the ground; the relationship between stem height and CH4 flux and the relationship between diameter at breast height and whole-tree CH4 emissions were determined. Stem CH4 emission rates were highest at the lowest measurement position on the stem (height 0.15 m), and decreased with stem height for all measurements. Nevertheless, significant CH4 emissions were detected 5.15 m above the ground. The relationship between stem height and CH4 emissions fit a power function. The estimated CH4 emission rate from the stem surface of an individual tree was 1.91 ± 1.24 and 0.68 ± 0.18 mg tree-1 h-1 for late-August and mid-September, respectively. The estimated stem CH4 emissions at the stand level varied seasonally, with the highest rate of 556 mg ha-1 h-1 in September.

  19. Trehangelins A, B and C, novel photo-oxidative hemolysis inhibitors produced by an endophytic actinomycete, Polymorphospora rubra K07-0510.

    PubMed

    Nakashima, Takuji; Okuyama, Ryuki; Kamiya, Yoshiyuki; Matsumoto, Atsuko; Iwatsuki, Masato; Inahashi, Yuki; Yamaji, Kenzaburo; Takahashi, Yōko; Ōmura, Satoshi

    2013-06-01

    Three new natural products, designated trehangelins A, B and C, were isolated by solvent extraction, silica gel and octadecylsilyl silica gel column chromatographies and subsequent preparative HPLC from the cultured broth of an endophytic actinomycete strain, Polymorphospora rubra K07-0510. The trehangelins consisted of a trehalose moiety and two angelic acid moieties. Trehangelins A (IC50 value, 0.1 mg ml(-1)) and C (IC50 value, 0.4 mg ml(-1)), with symmetric structures, showed potent inhibitory activity against hemolysis of red blood cells induced by light-activated pheophorbide a. However, trehangelin B, with an asymmetric structure, displayed only a slight inhibition (IC50 value, 1.0 mg ml(-1)). PMID:23591606

  20. 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.

  1. On the Diels-Alder approach to solely biomass-derived polyethylene terephthalate (PET): conversion of 2,5-dimethylfuran and acrolein into p-xylene.

    PubMed

    Shiramizu, Mika; Toste, F Dean

    2011-10-24

    Polyethylene terephthalate (PET) is a polymeric material with high global demand. Conventionally, PET is produced from fossil-fuel-based materials. Herein, we explored the feasibility of a sustainable method for PET production by using solely bio-renewable resources. Specifically, 2,5-dimethylfuran (derived from lignocellulosic biomass through 5-(hydroxymethyl)furfural) and acrolein (produced from glycerol, a side product of biodiesel production) were converted into the key intermediate p-xylene (a precursor of terephthalic acid). This synthesis consists of a sequential Diels-Alder reaction, oxidation, dehydration, and decarboxylation. In particular, the pivotal first step, the Diels-Alder reaction, was studied in detail to provide useful kinetic and thermodynamic data. Although it was found that this reaction requires low temperature to proceed efficiently, which presents a limitation on economic feasibility on an industrial scale, the concept was realized and bio-derived p-xylene was obtained in 34% overall yield over four steps. PMID:21922576

  2. 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., Jr.

    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

  3. 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

  4. Understanding the mechanism of non-polar Diels-Alder reactions. A comparative ELF analysis of concerted and stepwise diradical mechanisms.

    PubMed

    Domingo, Luis R; Chamorro, Eduardo; Pérez, Patricia

    2010-12-21

    The electron-reorganization along the concerted and stepwise pathways associated with the non-polar Diels-Alder reaction between cyclopentadiene (Cp, 1) and ethylene (2) has been studied using the topological analysis of the electron localization function (ELF) at the B3LYP/6-31G(d) level of theory. ELF results for the concerted mechanism stresses that the electron-reorganization demanded on the diene and ethylene reagents to reach two pseudo-diradical structures is responsible for the high activation energy. A comparative ELF analysis of some relevant points of the non-polar Diels-Alder reaction between Cp and styrene (10) suggests that these concerted mechanisms do not have a pericyclic electron-reorganization.

  5. Adaptation of a Small-Molecule Hydrogen-Bond Donor Catalyst to an Enantioselective Hetero-Diels–Alder Reaction Hypothesized for Brevianamide Biosynthesis

    PubMed Central

    2015-01-01

    Chiral diamine-derived hydrogen-bond donors were evaluated for their ability to effect stereocontrol in an intramolecular hetero-Diels–Alder (HDA) reaction hypothesized in the biosynthesis of brevianamides A and B. Collectively, these results provide proof of principle that small-molecule hydrogen-bond catalysis, if even based on a hypothetical biosynthesis construct, holds significant potential within enantioselective natural product synthesis. PMID:25697748

  6. New and Concise Syntheses of the Bicyclic Oxamazin Core Using an Intramolecular Nitroso Diels-Alder Reaction and Ring-Closing Olefin Metathesis

    PubMed Central

    Watson, Kyle D.; Carosso, Serena

    2013-01-01

    Herein two new and concise synthetic approaches for making an unsaturated bicyclic oxamazin core are reported. The first involves the use of an intramolecular Diels-Alder reaction to form both of the fused rings in one step. The second approach incorporates ring-closing olefin metathesis in the final step to form the second fused ring of the core. The scope of the second approach was also expanded further to afford larger ringed bicyclic systems. PMID:23276301

  7. New and concise syntheses of the bicyclic oxamazin core using an intramolecular nitroso Diels-Alder reaction and ring-closing olefin metathesis.

    PubMed

    Watson, Kyle D; Carosso, Serena; Miller, Marvin J

    2013-01-18

    Herein two new and concise synthetic approaches for making an unsaturated bicyclic oxamazin core are reported. The first involves the use of an intramolecular Diels-Alder reaction to form both of the fused rings in one step. The second approach incorporates ring-closing olefin metathesis in the final step to form the second fused ring of the core. The scope of the second approach was also expanded further to afford larger ringed bicyclic systems.

  8. 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

  9. Highly stereoselective generation of complex oxy-bicyclic scaffolds via an atom-economic Pd(II)-catalyzed hydroalkynylation, isomerization and Diels-Alder cycloaddition sequence.

    PubMed

    Shen, Ruwei; Chen, Ke; Deng, Qiulin; Yang, Jianjun; Zhang, Lixiong

    2014-02-21

    An atom-economic tandem Pd(II)-catalyzed hydroalkynylation, alkyne-allene isomerization, and Diels-Alder cycloaddition is reported. The reaction employs readily available starting substrates, proceeds in a highly ordered fashion, features high regio- and stereoselectivity, and tolerates a wide range of functionality and structural motifs, thus offering an attractive strategy for producing new molecular complexity and diversity from easily available starting materials. A mechanistic study with density functional theoretical calculations was conducted to rationalize the observed stereoselectivity.

  10. N2 fixation and cycling in Alnus glutinosa, Betula pendula and Fagus sylvatica woodland exposed to free air CO2 enrichment.

    PubMed

    Millett, Jonathan; Godbold, Douglas; Smith, Andrew R; Grant, Helen

    2012-06-01

    We measured the effect of elevated atmospheric CO(2) on atmospheric nitrogen (N(2)) fixation in the tree species Alnus glutinosa growing in monoculture or in mixture with the non-N(2)-fixing tree species Betula pendula and Fagus sylvatica. We addressed the hypotheses that (1) N(2) fixation in A. glutinosa will increase in response to increased atmospheric CO(2) concentrations, when growing in monoculture, (2) the impact of elevated CO(2) on N(2) fixation in A. glutinosa is the same in mixture and in monoculture and (3) the impacts of elevated CO(2) on N cycling will be evident by a decrease in leaf δ(15)N and by the soil-leaf enrichment factor (EF), and that these impacts will not differ between mixed and single species stands. Trees were grown in a forest plantation on former agricultural fields for four growing seasons, after which the trees were on average 3.8 m tall and canopy closure had occurred. Atmospheric CO(2) concentrations were maintained at either ambient or elevated (by 200 ppm) concentrations using a free-air CO(2) enrichment (FACE) system. Leaf δ(15)N was measured and used to estimate the amount (N(dfa)) and proportion (%N(dfa)) of N derived from atmospheric fixation. On average, 62% of the N in A. glutinosa leaves was from fixation. The %N(dfa) and N(dfa) for A. glutinosa trees in monoculture did not increase under elevated CO(2), despite higher growth rates. However, N(2) fixation did increase for trees growing in mixture, despite the absence of significant growth stimulation. There was evidence that fixed N(2) was transferred from A. glutinosa to F. sylvatica and B. pendula, but no evidence that this affected their CO(2) response. The results of this study show that N(2) fixation in A. glutinosa may be higher in a future elevated CO(2) world, but that this effect will only occur where the trees are growing in mixed species stands.

  11. 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.

  12. 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. PMID:21313828

  13. 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. PMID:23327466

  14. 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.

  15. 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. PMID:18088142

  16. On the importance of hydrogen bonding in the promotion of Diels-Alder reactions of unactivated aldehydes: a computational study

    NASA Astrophysics Data System (ADS)

    Chemouri, Hafida; Mekelleche, Sidi Mohamed

    2014-03-01

    The kinetic solvent effects on the Diels-Alder (DA) reaction of N,N-dimethylamino-3-trimethylsilyl butadiene with p-anisaldehyde are studied by density functional calculations at the B3LYP/6-31C(d) level of theory. Experimentally, it has been found that the acceleration of this reaction is not due to the increase of the polarity of the solvent but it is rather due to hydrogen bonding (HB). Intrinsic reaction coordinate calculations combined with electron localisation function analysis show that this reaction follows a one-step two-stage mechanism with a highly asynchronous sigma bond formation process. The calculations, performed using an explicit solvent model based on the coordination of the carbonyl group with one molecule of the solvent, show a considerable decrease of the activation energy when going from the gas phase (ɛ = 1) to solution phase and this diminution is found to be more important in isopropyl alcohol (ɛ = 18.3) in comparison with acetonitrile (ɛ = 37.5). Our calculations also show that the acceleration of this DA reaction is due to the increase of the electrophilicity power of the solvated carbonyl compound and consequently the increase of the polarity of the reaction in the presence of protic solvents. The obtained results put in evidence the relevance of HB in the promotion of DA reactions of unactivated ketones as experimentally expected.

  17. Nonstatistical dynamics in the thermal C2-C6/diels-alder cyclization of enyne-allenes: effect of topology.

    PubMed

    Samanta, Debabrata; Rana, Anup; Schmittel, Michael

    2015-02-20

    The thermal C(2)-C(6) (Schmittel) cyclization of an enyne-allene with two aryl rings at the allene terminus experimentally leads to three formal Diels-Alder (DA) cycloaddition products, two of which (involving the dimethylamino phenyl unit) are shown to form in a nonstatistical process. DFT computations on the reaction paths reveal that the two aryl rings (Ph vs PhNMe2) do not interact in a dynamic manner as their minimum energy pathways (MEPs) are separated by a large barrier. The preferential formation of the more-hindered DA product 8 (ortho to the dimethylamino group) over the less-hindered product 9 (para to the dimethylamino group), despite the higher energy TS for 8, suggests the occurrence of nonstatistical dynamics in the cyclization onto the dimethylamino phenyl unit, though. Potential energy surface (PES) computations indicate that the large amount of nonstatistical dynamics (97%) arises from facile IRC dynamics (left picture) that is compared with the non-IRC dynamics of a related system (∼76%, right picture, J. Org. Chem. 2014, 79, 2368). PMID:25647469

  18. 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

    2015-09-01

    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.

  19. Highly reactive trans-cyclooctene tags with improved stability for Diels-Alder chemistry in living systems.

    PubMed

    Rossin, Raffaella; van den Bosch, Sandra M; Ten Hoeve, Wolter; Carvelli, Marco; Versteegen, Ron M; Lub, Johan; Robillard, Marc S

    2013-07-17

    One of the challenges of pretargeted radioimmunotherapy, which centers on the capture of a radiolabeled probe by a preinjected tumor-bound antibody, is the potential immunogenicity of biological capturing systems. A bioorthogonal chemical approach may circumvent this drawback, but effective in vivo chemistry in mice, larger animals, and eventually humans, requires very high reagent reactivity, sufficient stability, and retained selectivity. We report here that the reactivity of the fastest bioorthogonal reaction, the inverse-electron-demand-Diels-Alder cycloaddition between a tetrazine probe and a trans-cyclooctene-tagged antibody, can be increased 10-fold (k2 = 2.7 × 10(5) M(-1) s(-1)) via the trans-cyclooctene, approaching the speed of biological interactions, while also increasing its stability. This was enabled by the finding that the trans-cyclooctene tag is probably deactivated through isomerization to the unreactive cis-cyclooctene isomer by interactions with copper-containing proteins, and that increasing the steric hindrance on the tag can impede this process. Next, we found that the higher reactivity of axial vs equatorial linked TCO can be augmented by the choice of linker. The new, stabilized, and more reactive tag allowed for improved tumor-to-nontumor ratios in pretargeted tumor-bearing mice.

  20. 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

    2015-09-01

    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. PMID:26005158

  1. Aquatic hyphomycete communities associated with decomposing alder leaf litter in reference headwater streams of the Basque Country (northern Spain).

    PubMed

    Pérez, Javier; Descals, Enrique; Pozo, Jesús

    2012-08-01

    The community of aquatic hyphomycetes associated with decomposing alder leaf litter was studied during autumn-winter in nine headwater reference streams of the Basque Country (northern Spain). In order to study the spatial variability in composition and community structure, three streams from each of three different river basins were compared. The colonization dynamics and community changes throughout the decomposition process were also followed in three of the rivers (one per basin). The taxonomic richness and community structure of these fungi varied among rivers, including similar streams of a given watershed. However, neither species diversity nor total abundance was statistically related to environmental variables. Only the conidial production of two of the species, Flagellospora curvula and Lunulospora curvula appeared to be enhanced by nitrate availability in the water. The taxonomic richness and the reproductive activity (sporulation rate) were positively related to the leaf litter decomposition rate. The changes in conidial production along the process were similar for all the streams and helped explain leaf litter quality dynamics.

  2. Riparian forest composition affects stream litter decomposition despite similar microbial and invertebrate communities.

    PubMed

    Kominoski, John S; Marczak, Laurie B; Richardson, John S

    2011-01-01

    Cross-boundary flows of energy and nutrients link biodiversity and functioning in adjacent ecosystems. The composition of forest tree species can affect the structure and functioning of stream ecosystems due to physical and chemical attributes, as well as changes in terrestrial resource subsidies. We examined how variation in riparian canopy composition (coniferous, deciduous, mixed) affects adjacent trophic levels (invertebrate and microbial consumers) and decomposition of organic matter in small, coastal rainforest streams in southwestern British Columbia. Breakdown rates of higher-quality red alder (Alnus rubra) litter were faster in streams with a greater percentage of deciduous than coniferous riparian canopy, whereas breakdown rates of lower-quality western hemlock (Tsuga heterophylla) litter were independent of riparian forest composition. When invertebrates were excluded using fine mesh, breakdown rates of both litter species were an order of magnitude less and were not significantly affected by riparian forest composition. Stream invertebrate and microbial communities were similar among riparian forest composition, with most variation attributed to leaf litter species. Invertebrate taxa richness and shredder biomass were higher in A. rubra litter; however, taxa evenness was greatest for T. heterophylla litter and both litter species in coniferous streams. Microbial community diversity (determined from terminal restriction fragment length polymorphisms) was unaffected by riparian forest or litter species. Fungal allele richness was higher than bacterial allele richness, and microbial communities associated with lower-quality T. heterophylla litter had higher diversity (allele uniqueness and richness) than those associated with higher-quality A. rubra litter. Percent variation in breakdown rates was mostly attributed to riparian forest composition in the presence of invertebrates and microbes; however, stream consumer biodiversity at adjacent trophic levels

  3. 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.

  4. 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. PMID:23094336

  5. 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. PMID:27322873

  6. 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.

  7. 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.

  8. Effects of temperature and light on photosynthesis of dominant species of a northern hardwood forest. [Populus grandidentata, Quercus rubra, Betula papyrifera

    SciTech Connect

    Jurik, T.W. ); Weber, J.A. ); Gates, D.M. )

    1988-06-01

    The response of CO{sub 2} exchange rate (CER) to temperature and light was determined for 14 dominant plant species of a northern deciduous hardwood forest in northern lower Michigan. Leaves at the top of the canopy had temperature optima near 25 C for CER, whereas leaves in the understory had optima near 20 C. There was no change in optimum temperature over the growing season, and overall shapes of response curves were similar among species. The lack of change in temperature optima may be a result of little change in growing conditions rather than a lack of ability to acclimatize. Nine of 11 species in the understory had no significant differences in light-saturated, maximum CERs, whereas at the top of the canopy Populus grandidentata had a higher maximum CER than Quercus rubra and Betula papyrifera. The species in the understory also differed little in light-saturation points for CER. Species at the top of the canopy had higher values for maximum CER, light-saturation point for CER, and maximum conductance than did species in the understory.

  9. 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.

  10. Purification of Flavonoids from Chinese Bayberry (Morella rubra Sieb. et Zucc.) Fruit Extracts and α-Glucosidase Inhibitory Activities of Different Fractionations.

    PubMed

    Yan, Shuxia; Zhang, Xianan; Wen, Xin; Lv, Qiang; Xu, Changjie; Sun, Chongde; Li, Xian

    2016-01-01

    Chinese bayberry (Morella rubra Sieb. et Zucc.) fruit have a diverse flavonoid composition responsible for the various medicinal activities, including anti-diabetes. In the present study, efficient simultaneous purification of four flavonoid glycosides, i.e., cyanidin-3-O-glucoside (1), myricetin-3-O-rhamnoside (2), quercetin-3-O-galactoside (3), quercetin-3-O-rhamnoside (4), from Chinese bayberry pulp was established by the combination of solid phase extract (SPE) by C18 Sep-Pak(®) cartridge column chromatography and semi-preparative HPLC (Prep-HPLC), which was followed by HPLC and LC-MS identification. The purified flavonoid glycosides, as well as different fractions of fruit extracts of six bayberry cultivars, were investigated for α-glucosidase inhibitory activities. The flavonol extracts (50% methanol elution fraction) of six cultivars showed strong α-glucosidase inhibitory activities (IC50 = 15.4-69.5 μg/mL), which were higher than that of positive control acarbose (IC50 = 383.2 μg/mL). Four purified compounds 1-4 exerted α-glucosidase inhibitory activities, with IC50 values of 1444.3 μg/mL, 418.8 μg/mL, 556.4 μg/mL, and 491.8 μg/mL, respectively. Such results may provide important evidence for the potential anti-diabetic activity of different cultivars of Chinese bayberry fruit and the possible bioactive compounds involved. PMID:27589714

  11. 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.

  12. Anti-inflammatory properties of red ginger (Zingiber officinale var. Rubra) extract and suppression of nitric oxide production by its constituents.

    PubMed

    Shimoda, Hiroshi; Shan, Shao-Jie; Tanaka, Junji; Seki, Azusa; Seo, Joung-Wook; Kasajima, Naoki; Tamura, Satoru; Ke, Yan; Murakami, Nobutoshi

    2010-02-01

    Red ginger (Zingiber officinale var. Rubra) has been prescribed as an analgesic for arthritis pain in Indonesian traditional medicine. The surface color of the rhizome is purple because of the anthocyanidins in its peel. We prepared 40% ethanolic extract from dried red ginger (red ginger extract [RGE]) and evaluated its anti-inflammatory activity using acute and chronic inflammation models. In an acetic acid-induced mouse writhing model, RGE (10-100 mg/kg) suppressed both the frequency of writhing and the increase in permeability of abdominal capillaries. On the other hand, continuous treatment with RGE (10 mg/kg) significantly (P < .05) suppressed footpad edema in a rat adjuvant arthritis model. To clarify the anti-inflammatory mechanism of RGE, we examined the effect on prostaglandin (PG) and nitric oxide (NO) production from mouse leukemic monocytes (RAW264 cells) stimulated by lipopolysaccharide. RGE (3 and 10 microg/mL) significantly (P < .05) suppressed PGE(2) production, while it also suppressed NO production at 100 microg/mL. After bioassay-guided separation of RGE, we found that [6]-shogaol and gingerdiols suppressed NO production. Red dye fractions presumed to be proanthocyanidins also suppressed NO production at 100 microg/mL. Consequently, we found a potent suppressive effect of RGE on acute and chronic inflammation, and inhibition of macrophage activation seems to be involved in this anti-inflammatory effect. [6]-Shogaol, gingerdiols, and proanthocyanidins were identified as constituents that inhibited NO production.

  13. Short Rotation Woody Crops Program. Quarterly progress report, March 1-May 31, 1985. [Sycamore, alders, black locust, larch, poplars, saltbush

    SciTech Connect

    Wright, L.L.; Perlack, R.D.; Wenzel, C.R.; Trimble, J.L.; Ranney, J.W.

    1985-08-01

    This report covers the progress of the Short Rotation Woody Crops Program (SRWCP) during the third quarter of fiscal year 1985. This report summarizes ORNL management activities, technical activities at ORNL and subcontract institutions, and the technology transfer that is occurring as a result of subcontractor and ORNL activities. Third-year results of a nutrient utilization study confirmed that there were no benefits to quarterly fertilization with urea nitrogen. Testing of one prototype short-rotation intensive culture harvester was conducted on a sycamore plantation on Scott Paper Company land in southern Alabama. Coppice yields of European black alder reported by Iowa State University indicate potential productivity of about 7.2 dry Mg . ha/sup -1/ . year/sup -1/ if the best trees are selected. Coppice yields were more than double first-rotation yields. About 31,000 black locust and larch trees were established in 12 genetic tests at 4 sites in Michigan. Seedling rotation productivity rates of 4-year-old hybrid poplar, based on harvest data, were reported by Pennsylvania State University. Rates varied from 4.8 dry Mg . ha/sup -1/ . year/sup -1/ to 10.7 dry Mg . ha/sup -1/ . year/sup -1/, depending on site, management strategy, and planting year. An efficient method for in vitro micropropagation of elite genotypes of fourwing saltbush was developed by Plant Resources Institute. A new study to evaluate yield/density relationships was established by the USDA Forest Service, Pacific Northwest Forest and Range Experiment Station. Dissertation research on the crown geometry of plantation-grown American sycamore was completed.

  14. Enantioselective synthesis of dihydrocoumarin derivatives by chiral scandium(III)-complex catalyzed inverse-electron-demand hetero-Diels-Alder reaction.

    PubMed

    Hu, Haipeng; Liu, Yangbin; Guo, Jing; Lin, Lili; Xu, Yali; Liu, Xiaohua; Feng, Xiaoming

    2015-03-01

    An asymmetric inverse-electron-demand hetero-Diels-Alder reaction between o-quinone methides and azlactones to generate potentially pharmacological active dihydrocoumarins has been achieved efficiently by using a chiral N,N'-dioxide-Sc(III) complex as the catalyst. The desired products were obtained in high yields with excellent enantioselectivities and diastereoselectivities (up to 94% yield, 96% ee and >19 : 1 dr) under mild reaction conditions. A concerted reaction pathway was confirmed by Operando IR and control experiments.

  15. 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.

  16. Multicomponent Double Diels-Alder/Nazarov Tandem Cyclization of Symmetric Cross-Conjugated Diynones to Generate [6-5-6] Tricyclic Products.

    PubMed

    Carmichael, Rachael A; Chalifoux, Wesley A

    2016-06-20

    The construction of complex polycyclic terpenoid products in an efficient and step-economical manner using multicomponent and tandem processes is highly valuable. Herein, we report a tandem cyclization sequence that initiates with a multicomponent double Diels-Alder reaction of cross-conjugated diynones, followed by a Nazarov cyclization to efficiently produce [6-5-6] tricyclic products with excellent regio- and diastereoselectivity. This methodology generates five new carbon-carbon bonds, three rings, quaternary or vicinal quaternary carbons, and stereogenic centers in a one-pot reaction. PMID:27124516

  17. 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).

  18. 1,4-Cyclohexadienes--easy access to a versatile building block via transition-metal-catalysed Diels-Alder reactions.

    PubMed

    Hilt, Gerhard

    2014-06-01

    1,4-Cyclohexadiene derivatives are easily accessed via transition-metal cycloadditions of 1,3-dienes with alkynes. The mild reaction conditions of several transition-metal-catalysed reactions allows the incorporation of various functional groups to access functionalised 1,4-cyclohexadienes. The control of the regiochemistry in the intermolecular cobalt-catalysed Diels-Alder reaction is realised utilising different ligand designs. The functionalised 1,4-cyclohexadiene derivatives are valuable building blocks in follow-up transformations. Finally, the oxidation of the 1,4-cyclohexadienes can be accomplished under mild conditions to generate the corresponding arene derivatives.

  19. 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

    2015-03-01

    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.

  20. Toward an understanding of the acceleration of Diels-Alder reactions by a pseudo-intramolecular process achieved by molecular recognition. A DFT study.

    PubMed

    Domingo, Luis R; Aurell, M José; Arnó, Manuel; Saez, José A

    2007-05-25

    The pseudo-intramolecular Diels-Alder (DA) reaction between a 2-substituted furan (1) and a N-maleimide derivative (2) has been analyzed using DFT methods. Formation of two hydrogen bonds between the appendages on furan and maleimide derivatives favors thermodynamically the formation of a molecular complex (MC1) through an efficient molecular recognition process. The large enthalpy stabilization associated with the molecular recognition overcomes the unfavorable activation entropy associated with the bimolecular process. As a consequence, the subsequent DA reaction is clearly accelerated through a pseudo-intramolecular process.

  1. Synthesis of Dihydrophenanthridines and Oxoimidazolidines from Anilines and Ethylglyoxylate via Aza Diels-Alder Reaction of Arynes and KF-Induced Annulation.

    PubMed

    Reddy, R Santhosh; Lagishetti, Chandraiah; Chen, Shuo; Kiran, I N Chaithanya; He, Yun

    2016-09-16

    The transition-metal-free multicomponent coupling of arynes, anilines, and ethylglyoxylate, proceeding via an inverse electron-demand aza Diels-Alder cycloaddition and N-arylation, has been demonstrated. This protocol allows rapid access to N-aryl dihydrophenanthridine derivatives in moderate to high yields at room temperature from readily available starting materials. In addition, an unprecedented fluoride induced annulation of ethyl(arylimino)acetates led to the formation of highly functionalized oxoimidazolidine derivatives in good yields under mild conditions. PMID:27571345

  2. 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

  3. 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

  4. 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

  5. Carbon Dioxide Fixation in Roots and Nodules of Alnus glutinosa: I. Role of Phosphoenolpyruvate Carboxylase and Carbamyl Phosphate Synthetase in Dark CO(2) Fixation, Citrulline Synthesis, and N(2) Fixation.

    PubMed

    McClure, P R; Coker, G T; Schubert, K R

    1983-03-01

    Detached roots and nodules of the N(2)-fixing species, Albus glutinosa (European black alder), actively assimilate CO(2). The maximum rates of dark CO(2) fixation observed for detached nodules and roots were 15 and 3 micromoles CO(2) fixed per gram dry weight per hour, respectively. The net incorporation of CO(2) in these tissues was catalyzed by phosphoenolpyruvate carboxylase which produces organic acids, some of which are used in the synthesis of the amino acids, aspartate, glutamate, and citrulline and by carbamyl phosphate synthetase. The latter accounts for approximately 30 to 40% of the CO(2) fixed and provides carbamyl phosphate for the synthesis of citrulline. Results of labeling studies suggest that there are multiple pools of malate present in nodules. The major pool is apparently metabolically inactive and of unknown function while the smaller pool is rapidly utilized in the synthesis of amino acids. Dark CO(2) fixation and N(2) fixation in nodules decreased after treatment of nodulated plants with nitrate while the percentage of the total (14)C incorporated into organic acids increased. Phosphoenolpyruvate carboxylase and carbamyl phosphate synthetase play key roles in the synthesis of amino acids including citrulline and in the metabolism of N(2)-fixing nodules and roots of alder. PMID:16662882

  6. 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

  7. Isotopologue ratios of N2O and N2 measurements underpin the importance of denitrification in differently N-loaded riparian alder forests.

    PubMed

    Mander, Ulo; Well, Reinhard; Weymann, Daniel; Soosaar, Kaido; Maddison, Martin; Kanal, Arno; Lõhmus, Krista; Truu, Jaak; Augustin, Jürgen; Tournebize, Julien

    2014-10-21

    Known as biogeochemical hotspots in landscapes, riparian buffer zones exhibit considerable potential concerning mitigation of groundwater contaminants such as nitrate, but may in return enhance the risk for indirect N2O emission. Here we aim to assess and to compare two riparian gray alder forests in terms of gaseous N2O and N2 fluxes and dissolved N2O, N2, and NO3(-) in the near-surface groundwater. We further determine for the first time isotopologue ratios of N2O dissolved in the riparian groundwater in order to support our assumption that it mainly originated from denitrification. The study sites, both situated in Estonia, northeastern Europe, receive contrasting N loads from adjacent uphill arable land. Whereas N2O emissions were rather small at both sites, average gaseous N2-to-N2O ratios inferred from closed-chamber measurements and He-O laboratory incubations were almost four times smaller for the heavily loaded site. In contrast, groundwater parameters were less variable among sites and between landscape positions. Campaign-based average (15)N site preferences of N2O (SP) in riparian groundwater ranged between 11 and 44 ‰. Besides the strong prevalence of N2 emission over N2O fluxes and the correlation pattern between isotopologue and water quality data, this comparatively large range highlights the importance of denitrification and N2O reduction in both riparian gray alder stands. PMID:25264900

  8. Regioselectivity of Sc2C2@C3v(8)-C82: Role of the Sumanene-Type Hexagon in Diels-Alder Reaction.

    PubMed

    Zhao, Pei; Zhao, Xiang; Ehara, Masahiro

    2016-09-16

    Recently, several experiments have demonstrated high chemical reactivity of the sumanene-type hexagon in Sc2C2@C82. To further uncover its reactivity, the Diels-Alder reaction to all the nonequivalent C-C bonds of C82 and Sc2C2@C82 has been investigated by density functional theory calculations. For the free fullerene, the [5,6] bond 7 is the thermodynamically most favored, whereas the addition on the [6,6] bond 3 has the lowest activation energy. Diels-Alder reaction has no preference for addition sites in the sumanene-type hexagon. However, in the case of the endohedral fullerene, the [6,6] bond 19 in the special hexagon becomes the most reactive site according to both kinetic and thermodynamic considerations. Further analyses reveal that bond 19 in Sc2C2@C82 exhibits the shortest bond length and third largest π-orbital axis vector. In addition, the LUMOs of bond 19 are also symmetry-allowed to interact with butadiene. PMID:27538115

  9. Cross-Linked Hydrogels Formed through Diels-Alder Coupling of Furan- and Maleimide-Modified Poly(methyl vinyl ether-alt-maleic acid).

    PubMed

    Stewart, S Alison; Backholm, Matilda; Burke, Nicholas A D; Stöver, Harald D H

    2016-02-23

    The Diels-Alder [4 + 2] cycloaddition between furan- and maleimide-functional polyanions was used to form cross-linked synthetic polymer hydrogels. Poly(methyl vinyl ether-alt-maleic anhydride) was reacted with furfurylamine or N-(2-aminoethyl)maleimide in acetonitrile to form pairs of furan- and maleimide-functionalized poly(methyl vinyl ether-alt-maleic acid)s. Mixtures of these mutually reactive polyanions in water gelled within 15 min to 18 h, depending on degree of functionalization and polymer concentrations. Solution and magic-angle spinning (1)H NMR were used to confirm the formation of the Diels-Alder adduct, to analyze competing hydrolytic side reactions, and demonstrate postgelation functionalization. The effect of the degree of furan and maleimide functionalization, polymer concentration, pH, and calcium ion concentration, on gelation time, gel mechanical properties, and equilibrium swelling, are described. Release of dextran as a model drug was studied using fluorescence spectroscopy, as a function of gel composition and calcium treatment. PMID:26800849

  10. Toward an understanding of the unexpected regioselective hetero-Diels-Alder reactions of asymmetric tetrazines with electron-rich ethylenes: a DFT study.

    PubMed

    Domingo, Luis R; Picher, M Teresa; Sáez, José A

    2009-04-01

    The regioselective hetero-Diels-Alder (HDA) reaction of asymmetric tetrazines (TTZs) with electron-rich (ER) ethylenes has been studied with use of DFT methods at the B3LYP/6-31G* level of theory. The reaction is a domino process that comprises three consecutive reactions: (i) a HDA reaction between the TTZ and the ER ethylene; (ii) a retro-Diels-Alder reaction with loss of nitrogen; and (iii) a beta-hydrogen elimination with formation of the final pyridazines. The first polar HDA reaction, which is associated to the nucleophilic attack of the ER ethylene to the electrophilically activated TTZ, is the rate and regioselectivity determining step of the domino process. The unexpected regioselectivity of these HDA reactions is explained within the polar cycloaddition model by using the conceptual DFT. Although the nucleophilic attack of the ER ethylene over the para position relative to the methylsulfinyl substituent could favor the charge transfer, it is energetically more unfavorable because it diminishes the electron density at the electronegative TTZ core.

  11. 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

  12. Immunomodulating activity of Nymphaea rubra Roxb. extracts: activation of rat dendritic cells and improvement of the T(H)1 immune response.

    PubMed

    Cheng, Jai-Hong; Lee, Shau-Yu; Lien, Yi-Yang; Lee, Meng-Shiou; Sheu, Shyang-Chwen

    2012-01-01

    Polysaccharides play a key role in enhancing immune function and facilitating cellular communication. Here, we purified Nymphaea rubra Roxb. polysaccharides (NR-PS) by treating them with pullulanase. They were then cultured with immature dendritic cells (DCs) derived from rat bone marrow hematopoietic cells (BMHCs). After treatment with bioactive NR-PS with a degree of polymerization (DP) value of 359.8, we found that the DCs underwent morphological changes indicative of activation. CD80/86 (87.16% ± 8.49%) and MHC class II (52.01% ± 10.11%) expression levels were significantly up-regulated by this treatment compared to the controls (65.45% ± 0.97% and 34.87% ± 1.96%). In parallel, endocytosis was also reduced (167.94% ± 60.59%) after treatment with 25 μg/mL of NR-PS as measured by the medium fluorescence intensity compared to the control (261.67% ± 47.26%). Furthermore, the DCs after treatment with 25 μg/mL NR-PS showed increased IL-12 (102.09 ± 10.16 to 258.78 ± 25.26 pg/mL) and IFN-γ (11.76 ± 0.11 to 15.51 ± 1.66 pg/mL) secretion together with reduced IL-10 secretion (30.75 ± 3.35 to 15.37 ± 2.35 pg/mL), which indicates a T(H)1 immune response. In conclusion, NR-PS exhibits stimulatory effects on rat DCs and promotes the secretion of T(H)1 cytokines. Taken together, our studies are the first to show that NR-PS is an immunomodulator affecting the maturation and functioning of DCs.

  13. Immunomodulating activity of Nymphaea rubra Roxb. extracts: activation of rat dendritic cells and improvement of the T(H)1 immune response.

    PubMed

    Cheng, Jai-Hong; Lee, Shau-Yu; Lien, Yi-Yang; Lee, Meng-Shiou; Sheu, Shyang-Chwen

    2012-01-01

    Polysaccharides play a key role in enhancing immune function and facilitating cellular communication. Here, we purified Nymphaea rubra Roxb. polysaccharides (NR-PS) by treating them with pullulanase. They were then cultured with immature dendritic cells (DCs) derived from rat bone marrow hematopoietic cells (BMHCs). After treatment with bioactive NR-PS with a degree of polymerization (DP) value of 359.8, we found that the DCs underwent morphological changes indicative of activation. CD80/86 (87.16% ± 8.49%) and MHC class II (52.01% ± 10.11%) expression levels were significantly up-regulated by this treatment compared to the controls (65.45% ± 0.97% and 34.87% ± 1.96%). In parallel, endocytosis was also reduced (167.94% ± 60.59%) after treatment with 25 μg/mL of NR-PS as measured by the medium fluorescence intensity compared to the control (261.67% ± 47.26%). Furthermore, the DCs after treatment with 25 μg/mL NR-PS showed increased IL-12 (102.09 ± 10.16 to 258.78 ± 25.26 pg/mL) and IFN-γ (11.76 ± 0.11 to 15.51 ± 1.66 pg/mL) secretion together with reduced IL-10 secretion (30.75 ± 3.35 to 15.37 ± 2.35 pg/mL), which indicates a T(H)1 immune response. In conclusion, NR-PS exhibits stimulatory effects on rat DCs and promotes the secretion of T(H)1 cytokines. Taken together, our studies are the first to show that NR-PS is an immunomodulator affecting the maturation and functioning of DCs. PMID:23109818

  14. 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). PMID:20598871

  15. 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

  16. 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.

  17. The properties given at the time of publication for the designated type strain of Leifsonia rubra Reddy et al. 2003, CMS 76r, do not correspond with those of MTCC 4210, DSM 15304, CIP 107783 and JCM 12471 that are deposited as representing the type strain: Opinion 96. Judicial Commission of the International Committee on Systematics of Prokaryotes.

    PubMed

    Tindall, B J

    2014-10-01

    The Judicial Commission affirms that, according to information presented to it, the type strain of Leifsonia rubra Reddy et al. 2003 designated in the original publication as strain CMS 76r and deposited as MTCC 4210, DSM 15304, CIP 107783 and JCM 12471 does not have properties corresponding with those of the strains held in those collections under those accession numbers. The species Leifsonia rubra Reddy et al. 2003 was not represented by an authentic deposit of a type strain at the time of effective publication in the pages of the International Journal of Systematic and Evolutionary Microbiology.

  18. Design of cross-linked semicrystalline poly(ε-caprolactone)-based networks with one-way and two-way shape-memory properties through Diels-Alder reactions.

    PubMed

    Raquez, Jean-Marie; Vanderstappen, Sophie; Meyer, Franck; Verge, Pierre; Alexandre, Michael; Thomassin, Jean-Michel; Jérôme, Christine; Dubois, Philippe

    2011-08-29

    Cross-linked poly(ε-caprolactone) (PCL)-based polyesterurethane (PUR) systems have been synthesized through Diels-Alder reactions by reactive extrusion. The Diels-Alder and retro-Diels-Alder reactions proved to be useful for enhancing the molecular motion of PCL-based systems, and therefore their crystallization ability, in the design of cross-linked semicrystalline polymers with one-way and two-way shape-memory properties. Successive reactions between α,ω-diol PCL (PCL(2) ), furfuryl alcohol, and methylene diphenyl 4,4'-diisocyanate straightforwardly afforded the α,ω-furfuryl PCL-based PUR systems, and subsequent Diels-Alder reactions with N,N-phenylenedimaleimide afforded the thermoreversible cycloadducts. The cross-linking density could be modulated by partially replacing PCL-diol with PCL-tetraol. Interestingly, the resulting PUR systems proved to be semicrystalline cross-linked polymers, the melting temperature of which (close to 45 °C) represented the switching temperature for their shape-memory properties. Qualitative and quantitative measurements demonstrated that these PUR systems exhibited one-way and two-way shape-memory properties depending on their cross-linking density.

  19. Design of cross-linked semicrystalline poly(ε-caprolactone)-based networks with one-way and two-way shape-memory properties through Diels-Alder reactions.

    PubMed

    Raquez, Jean-Marie; Vanderstappen, Sophie; Meyer, Franck; Verge, Pierre; Alexandre, Michael; Thomassin, Jean-Michel; Jérôme, Christine; Dubois, Philippe

    2011-08-29

    Cross-linked poly(ε-caprolactone) (PCL)-based polyesterurethane (PUR) systems have been synthesized through Diels-Alder reactions by reactive extrusion. The Diels-Alder and retro-Diels-Alder reactions proved to be useful for enhancing the molecular motion of PCL-based systems, and therefore their crystallization ability, in the design of cross-linked semicrystalline polymers with one-way and two-way shape-memory properties. Successive reactions between α,ω-diol PCL (PCL(2) ), furfuryl alcohol, and methylene diphenyl 4,4'-diisocyanate straightforwardly afforded the α,ω-furfuryl PCL-based PUR systems, and subsequent Diels-Alder reactions with N,N-phenylenedimaleimide afforded the thermoreversible cycloadducts. The cross-linking density could be modulated by partially replacing PCL-diol with PCL-tetraol. Interestingly, the resulting PUR systems proved to be semicrystalline cross-linked polymers, the melting temperature of which (close to 45 °C) represented the switching temperature for their shape-memory properties. Qualitative and quantitative measurements demonstrated that these PUR systems exhibited one-way and two-way shape-memory properties depending on their cross-linking density. PMID:21744399

  20. High π-Facial and exo-Selectivity for the Intramolecular Diels-Alder Cycloaddition of Dodeca-3,9,11-trien-5-one Precursors to 2-epi-Symbioimine and Related Compounds.

    PubMed

    Xiang, Ming; Wu, Yiwei; Burke, Jason P; Chruma, Jason J

    2016-09-16

    An unconstrained exocyclic stereogenic center and a removable trimethylsilyl group are combined to induce high π-facial selectivity and near-exclusive exo-selectivity in the intramolecular Diels-Alder cycloaddition of dodeca-3,9,11-trien-5-ones. This strategy provides direct access to polysubstituted trans-1-decalones related to the symbioimines in good yield and acceptable diastereoselectivity.

  1. High π-Facial and exo-Selectivity for the Intramolecular Diels-Alder Cycloaddition of Dodeca-3,9,11-trien-5-one Precursors to 2-epi-Symbioimine and Related Compounds.

    PubMed

    Xiang, Ming; Wu, Yiwei; Burke, Jason P; Chruma, Jason J

    2016-09-16

    An unconstrained exocyclic stereogenic center and a removable trimethylsilyl group are combined to induce high π-facial selectivity and near-exclusive exo-selectivity in the intramolecular Diels-Alder cycloaddition of dodeca-3,9,11-trien-5-ones. This strategy provides direct access to polysubstituted trans-1-decalones related to the symbioimines in good yield and acceptable diastereoselectivity. PMID:27563727

  2. Modification of the protein expression pattern induced in the nitrogen-fixing actinomycete Frankia sp. strain ACN14a-tsr by root exudates of its symbiotic host Alnus glutinosa and cloning of the sodF gene.

    PubMed

    Hammad, Y; Maréchal, J; Cournoyer, B; Normand, P; Domenach, A M

    2001-06-01

    Two-dimensional (2-D) polyacrylamide gel electrophoresis was used to detect proteins induced in Frankia sp. strain ACN14a-tsr by root exudates of its symbiotic host, Alnus glutinosa. The 5 most prominent proteins were purified from 2-D gels and characterized by N-terminal sequencing. All of these proteins had a high percentage of similarity with known stress proteins. One protein match was the Fe superoxide dismutase (Fe-SOD), another was a tellurite resistance protein (Ter), the third was a bacterioferritin comigratory protein (Bcp); and two matches, differing only by their isoelectric point, were the same small heat shock protein (Hsp), a major immune reactive protein found in mycobacteria. This suggests that the symbiotic microorganism Frankia, first responds with a normal stress response to toxic root products of its symbiotic host plant. To confirm its identity, the gene corresponding to the Fe-SOD protein, sodF was isolated from a genomic library by a PCR-approach and sequenced. It is the first stress response gene characterized in Frankia.

  3. Metalloporphyrin-Based Hypercrosslinked Polymers Catalyze Hetero-Diels-Alder Reactions of Unactivated Aldehydes with Simple Dienes: A Fascinating Strategy for the Construction of Heterogeneous Catalysts.

    PubMed

    Dou, Zhiyu; Xu, Li; Zhi, Yongfeng; Zhang, Yuwei; Xia, Hong; Mu, Ying; Liu, Xiaoming

    2016-07-11

    We describe a novel and intriguing strategy for the construction of efficient heterogeneous catalysts by hypercrosslinking catalyst molecules in a one-pot Friedel-Crafts alkylation reaction. The new hypercrosslinked polymers (HCPs) as porous solid catalysts exhibit the combined advantages of homogeneous and heterogeneous catalysis, owing to their high surface area, good stability, and tailoring of catalytic centers on the frameworks. Indeed, a new class of metalloporphyrin-based HCPs were successfully synthesized using modified iron(III) porphyrin complexes as building blocks, and the resulting networks were found to be excellent recyclable heterogeneous catalysts for the hetero-Diels-Alder reaction of unactivated aldehydes with 1,3-dienes. Moreover, this new strategy showed wide adaptability, and many kinds of homogeneous-like solid-based catalysts with high catalytic performance and excellent recyclability were also constructed.

  4. 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.

  5. Understanding reactivity and regioselectivity in Diels-Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study.

    PubMed

    Giri, Germán F; Sarotti, Ariel M; Spanevello, Rolando A

    2015-10-13

    The effect of an extra EWG in the reactivity and regioselectivity in Diels-Alder reactions of β-cyanolevoglucosenone and 4 different dienes was studied by a joint computational and experimental study. Conceptual DFT analysis successfully predicted an important enhancement in the reactivity, and correctly anticipated the regioselectivity in the reactions with isoprene. However, this static treatment failed when dealing the regiochemical preference of the reactions involving a substituted anthracene as diene. MPW1K/6-31G* calculations correctly reproduced the experimental observations. Based on the collected data, we found that when dealing with dienes and dienophiles with no clear electronically activated position, the ease of pyramidalization of the interacting atoms dictates the regioselectivity of the DA reaction. PMID:26318382

  6. Catalytic asymmetric hetero-Diels-Alder reactions of enones with isatins to access functionalized spirooxindole tetrahydropyrans: scope, derivatization, and discovery of bioactives.

    PubMed

    Cui, Hai-Lei; Chouthaiwale, Pandurang V; Yin, Feng; Tanaka, Fujie

    2016-02-01

    The development of concise methods for the synthesis of functionalized small molecules is important in the search for new bioactive molecules. To contribute to this, we have developed oxa-hetero-Diels-Alder reactions of enones with isatins catalyzed by amine-based catalyst systems. Various spirooxindole tetrahydropyranones were synthesized either in enantiomerically enriched forms or as racemic forms depending on the catalyst system. The reaction products were further transformed at the ketone carbonyl group and the indole nitrogen. Using these reactions, functionalized spirooxindole tetrahydropyran derivatives with functional groups in four directions in a three-dimensional space were concisely obtained. From these synthesized compounds, an inhibitor of human ion channel Nav1.7 with μM-level activity was identified, indicating that the developed reaction methods are useful for providing molecules for the discovery of new biofunctional molecules.

  7. ent-Kaurane-Based Regio- and Stereoselective Inverse Electron Demand Hetero-Diels-Alder Reactions: Synthesis of Dihydropyran-Fused Diterpenoids†

    PubMed Central

    Ding, Chunyong; Wang, Lili; Chen, Haijun; Wild, Christopher; Ye, Na; Ding, Ye; Wang, Tianzhi; White, Mark A.; Shen, Qiang; Zhou, Jia

    2014-01-01

    A mild and concise approach for the construction of 3,4-dihydro-2H-pyran ring integrated into the A-ring of the natural product oridonin using an optimized inverse electron demand hetero-Diels-Alder (IED HDA) reaction is reported herein. A self-dimerization of the exocyclic enone installed in the A-ring through a homo-HDA reaction was identified to exclusively give a dimeric ent-kaurane diterpenoid with the spirochroman core. Moreover, the efficient cross-HDA cycloadditions of this enone with various vinyl ethers or vinyl sulfides, instead of its own homo-HDA dimerization, were achieved in regio- and stereoselective manners, thus providing the access to novel dihydropyran-fused diterpenoids as potential anticancer agents to overcome chemoresistance. PMID:25225052

  8. Diels-Alder Reaction of Anthranilic Acids: A Versatile Route to Dense Monolayers on Flat Edge and Basal Plane Graphitic Carbon Substrates.

    PubMed

    Farquhar, Anna K; Fitchett, Christopher M; Dykstra, Haidee M; Waterland, Mark R; Brooksby, Paula A; Downard, Alison J

    2016-09-01

    Methods that reliably yield monolayers of covalently anchored modifiers on graphene and other planar graphitic materials are in demand. Covalently bonded groups can add functionality to graphitic carbon for applications ranging from sensing to supercapacitors and can tune the electronic and optical properties of graphene. Limiting modification to a monolayer gives a layer with well-defined concentration and thickness providing a minimum barrier to charge transfer. Here we investigate the use of anthranilic acid derivatives for grafting aryl groups to few layer graphene and pyrolyzed photoresist film (PPF). Under mild conditions, anthranilic acids generate arynes, which undergo Diels-Alder cycloadditions. Using spectroscopy, electrochemistry, and atomic force microscopy, we demonstrate that the reaction yields monolayers of aryl groups on graphene and PPF with maximum surface coverages consistent with densely packed layers. Our study confirms that anthranilic acids offer a convenient route to covalent modification of planar graphitic carbons (both basal and edge plane materials). PMID:27529723

  9. 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.

  10. Metalloporphyrin-Based Hypercrosslinked Polymers Catalyze Hetero-Diels-Alder Reactions of Unactivated Aldehydes with Simple Dienes: A Fascinating Strategy for the Construction of Heterogeneous Catalysts.

    PubMed

    Dou, Zhiyu; Xu, Li; Zhi, Yongfeng; Zhang, Yuwei; Xia, Hong; Mu, Ying; Liu, Xiaoming

    2016-07-11

    We describe a novel and intriguing strategy for the construction of efficient heterogeneous catalysts by hypercrosslinking catalyst molecules in a one-pot Friedel-Crafts alkylation reaction. The new hypercrosslinked polymers (HCPs) as porous solid catalysts exhibit the combined advantages of homogeneous and heterogeneous catalysis, owing to their high surface area, good stability, and tailoring of catalytic centers on the frameworks. Indeed, a new class of metalloporphyrin-based HCPs were successfully synthesized using modified iron(III) porphyrin complexes as building blocks, and the resulting networks were found to be excellent recyclable heterogeneous catalysts for the hetero-Diels-Alder reaction of unactivated aldehydes with 1,3-dienes. Moreover, this new strategy showed wide adaptability, and many kinds of homogeneous-like solid-based catalysts with high catalytic performance and excellent recyclability were also constructed. PMID:27147500

  11. Catalytic effect of gallium chloride in the diels-alder reaction between maleic anhydride and its derivatives and unsubstituted and substituted anthracenes

    SciTech Connect

    Kiselev, V.D.; Konovalov, A.I.; Shakirov, I.M.

    1985-11-10

    The stability of n, v complexes between gallium chloride and unsubstituted and substituted maleic anhydrides was determined in benzene by a thermochemical method; it was shown that the stability of the complexes decreases in the transition from maleic anhydrides with electron-donating substituents to maleic anhydrides with electron-withdrawing substituents. The reactivity of these dienophiles in the uncatalyzed Diels-Alder reactions with unsubstituted and substituted anthracenes in benzene and in the reactions catalyzed by gallium chloride was studied. The reactivity of the dienophiles varies similarly in the reactions with the investigated dienes, and this rules out treatment of steric hindrances as the reason for the reduced reactivity of the substituted dienophiles. A decrease in the catalytic effect was observed for the unreactive diene-dienophile pairs.

  12. Unique Steric Effect of Geminal Bis(silane) To Control the High Exo-selectivity in Intermolecular Diels-Alder Reaction.

    PubMed

    Liu, Zengjin; Lin, Xinglong; Yang, Na; Su, Zhishan; Hu, Changwei; Xiao, Peihong; He, Yanyang; Song, Zhenlei

    2016-02-17

    The unique steric effect of geminal bis(silane) [(R3Si)2CH] allows an exo-selective intermolecular Diels-Alder reaction of geminal bis(silyl) dienes with α,β-unsaturated carbonyl compounds. The approach shows good generality to form ortho-trans cyclohexenes in good yields with high exo-selectivity and high enantioselectivity in some asymmetric cases. The excellent exo-stereocontrol aptitude of (R3Si)2CH group is highlighted by comparing with R3SiCH2 and R3Si groups, which leads to endo-selectivity predominantly. The conformational analysis of dienes suggests that (R3Si)2CH group effectively shields both sides of the diene moiety, ensuring the desired exo-selectivity. Moreover, the geminal bis(silane) can be further functionalized to transform the resulting ortho-trans cycloadducts into useful synthons, which makes the approach hold great potential for organic synthesis.

  13. 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.

  14. Astragalus and Paeoniae radix rubra extract inhibits liver fibrosis by modulating the transforming growth factor‑β/Smad pathway in rats.

    PubMed

    Huang, Weijuan; Li, Lin; Tian, Xiaopeng; Yan, Jinjin; Yang, Xinzheng; Wang, Xinlong; Liao, Guozhen; Qiu, Genquan

    2015-02-01

    It has been previously demonstrated that Astragalus and Paeoniae radix rubra extract (APE) had a protective effect against liver fibrosis in mice. The present study aimed to investigate the hepatoprotective effect of APE on CCl4‑induced hepatic fibrosis in rats. Liver fibrosis was induced in male Sprague‑Dawley rats by intraperitoneal injection of 50% CCl4 twice a week for eight weeks. Organ coefficients, serum aspartate aminotransferase (AST), alanine aminotransferase (ALT), hexadecenoic acid (HA), laminin (LN), procollagen type III (PCIII), hydroxyproline (Hyp), glutathione (GSH‑Px), malondialdehyde (MDA), superoxide dismutase (SOD) and transforming growth factor β1 (TGF‑β1) levels were measured in rats with hepatic fibrosis. Histopathological changes in affected livers were studied using hematoxylin‑eosin and Masson's trichrome staining. The expression of transforming growth factor‑β/Smad pathway proteins, α‑smooth muscle actin (α‑SMA), collagen I and collagen III was observed in fibrotic livers using western blot analysis. The present study observed significant reductions in serum levels of AST, ALT, HA, LN, PCIII and Hyp in APE‑treated (2.6 and 5.2 g/kg) rats, indicating the significant hepatoprotective effects of APE. Furthermore, the depletion of GSH‑Px and SOD, in addition to the accumulation of MDA in liver tissue was suppressed by APE (2.6 and 5.2 g/kg). Pathological assessment of CCl4‑induced fibrotic livers revealed a significant reduction of liver injury and development of hepatic fibrosis in rats treated with APE (2.6 and 5.2 g/kg). Moreover, APE (2.6 and 5.2 g/kg) decreased the elevation of TGF‑β1, α‑SMA, collagen I and collagen III expression, inhibited Smad2/3 phosphorylation as well as elevated the expression of the TGF‑β1 inhibitor Smad7. These results suggested that APE may protect against liver damage and inhibit the progression of CCl4‑induced hepatic fibrosis. The mechanism of action of APE is

  15. The effect of heat waves, elevated [CO2 ] and low soil water availability on northern red oak (Quercus rubra L.) seedlings.

    PubMed

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

    2013-02-01

    The frequency and intensity of heat waves are predicted to increase. This study investigates whether heat waves would have the same impact as a constant increase in temperature with the same heat sum, and whether there would be any interactive effects of elevated [CO2 ] and soil moisture content. We grew Quercus rubra seedlings in treatment chambers maintained at either ambient or elevated [CO2 ] (380 or 700 μmol CO2 mol(-1) ) with temperature treatments of ambient, ambient +3 °C, moderate heat wave (+6 °C every other week) or severe heat wave (+12 °C every fourth week) temperatures. Averaged over a 4-week period, and the entire growing season, the three elevated temperature treatments had the same average temperature and heat sum. Half the seedlings were watered to a soil water content near field capacity, half to about 50% of this value. Foliar gas exchange measurements were performed morning and afternoon (9:00 and 15:00 hours) before, during and after an applied heat wave in August 2010. Biomass accumulation was measured after five heat wave cycles. Under ambient [CO2 ] and well-watered conditions, biomass accumulation was highest in the +3 °C treatment, intermediate in the +6 °C heat wave and lowest in the +12 °C heat wave treatment. This response was mitigated by elevated [CO2 ]. Low soil moisture significantly decreased net photosynthesis (Anet ) and biomass in all [CO2 ] and temperature treatments. The +12 °C heat wave reduced afternoon Anet by 23% in ambient [CO2 ]. Although this reduction was relatively greater under elevated [CO2 ], Anet values during this heat wave were still 34% higher than under ambient [CO2 ]. We concluded that heat waves affected biomass growth differently than the same amount of heat applied uniformly over the growing season, and that the plant response to heat waves also depends on [CO2 ] and soil moisture conditions.

  16. Structure and function of Frankia vesicles in dinitrogen fixation by actinorhizal plants. Final report, April 1, 1982-March 31, 1984

    SciTech Connect

    Torrey, J.G.

    1985-11-01

    Frankia, a filamentous bacterium which induces N/sub 2/-fixing root nodules on the roots of a wide range of woody dicotyledonous plants, is the first known actinomycete which fixes dinitrogen when growing in free-living culture. The nitrogenase enzyme is induced in many strains of this organism by withholding fixed nitrogen compounds from its nutrient medium. Terminal swellings of the bacterial filaments develop rapidly and acetylene reduction activity (= nitrogenase) increases in proportion to the number of terminal vesicles formed. The induction of vesicles and establishment of acetylene reduction occurs under aerobic conditions, and the evidence is accumulating which demonstrates the existence of a multilaminate vesicle envelope which serves as a physical barrier protecting the oxygen-labile nitrogenase from denaturation. Our studies are concerned with the physiology, biochemistry and structural development of the N/sub 2/-fixing apparatus in Frankia grown in vitro and in root nodules of host plants. Diverse strains of Frankia are under study isolated and cultured from different host plants. Two strains have been studied, especially HFPArI3, an isolate from nodules of the red alder Alnus rubra, and HFPCcI3, isolated from root nodules of the tropical tree Casuarina cunninghamiana. The goal is to understand the structure and function which leads to optimum effectiveness for dinitrogen fixation. 9 refs.

  17. 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.

  18. 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.

  19. Efficient preparation of pseudoalteromone A from marine Pseudoalteromonas rubra QD1-2 by combination of response surface methodology and high-speed counter-current chromatography: a comparison with high-performance liquid chromatography.

    PubMed

    Ding, Lijian; He, Shan; Yan, Xiaojun

    2014-05-01

    Pseudoalteromone A (PA) is a cytotoxic and anti-inflammatory ubiquinone discovered recently from a marine bacterium Pseudoalteromonas sp. CGH2XX. In order to meet its sample supply for further in vivo pharmacological investigation, an efficient method was developed for the preparation of PA by combination of response surface methodology (RSM) and high-speed counter-current chromatography (HSCCC) from marine bacterium P. rubra QD1-2. First, optimization of culture conditions was studied by the RSM to enhance PA production. The results indicated that the optimal cultivation condition was peptone (2.21 g/l), yeast extract (3.125 g/l), glucose (0.125 g/l), KBr (0.02 g/l), inoculum size (6.5 %), medium volume (595 ml), initial pH value (7.0), temperature (28 °C). Under the optimized fermentation condition, PA production was 1.04 mg/l with 14.8-fold increase comparing to 0.07 mg/l under original standard fermentation condition. The PA production was further investigated using a 14-l jar fermenter. Compared to the flask culture, P. rubra QD1-2 offered 45 % increase of PA production at 1.51 mg/l. Then, a rapid and efficient method for the separation and purification of PA from crude culture extract was developed using HSCCC. The two-phase solvent system used for HSCCC separation was composed of n-hexane-ethyl acetate-methanol-water (5:5:9:5, v/v/v/v). The isolation was accomplished within 100 min, and the purity of PA was over 95 %. The recovery of the process was 93 %.

  20. 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.

  1. 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

  2. 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

  3. 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

  4. The Diels-Alder-reaction with inverse-electron-demand, a very efficient versatile click-reaction concept for proper ligation of variable molecular partners.

    PubMed

    Wiessler, Manfred; Waldeck, Waldemar; Kliem, Christian; Pipkorn, Ruediger; Braun, Klaus

    2009-12-05

    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 (DAR(inv)) turns out to be an appropriate candidate. The DAR(inv) 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 DAR(inv) 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 DAR(inv).We report here that the DAR(inv) 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 DAR(inv) 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 DAR(inv) 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 DAR(inv) 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

  5. The Diels-Alder-reaction with inverse-electron-demand, a very efficient versatile click-reaction concept for proper ligation of variable molecular partners.

    PubMed

    Wiessler, Manfred; Waldeck, Waldemar; Kliem, Christian; Pipkorn, Ruediger; Braun, Klaus

    2009-01-01

    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 (DAR(inv)) turns out to be an appropriate candidate. The DAR(inv) 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 DAR(inv) 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 DAR(inv).We report here that the DAR(inv) 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 DAR(inv) 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 DAR(inv) 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 DAR(inv) 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

  6. Testing the link between community structure and function for ectomycorrhizal fungi involved in a global tripartite symbiosis.

    PubMed

    Walker, Jennifer K M; Cohen, Hannah; Higgins, Logan M; Kennedy, Peter G

    2014-04-01

    Alnus trees associate with ectomycorrhizal (ECM) fungi and nitrogen-fixing Frankia bacteria and, although their ECM fungal communities are uncommonly host specific and species poor, it is unclear whether the functioning of Alnus ECM fungal symbionts differs from that of other ECM hosts. We used exoenzyme root tip assays and molecular identification to test whether ECM fungi on Alnus rubra differed in their ability to access organic phosphorus (P) and nitrogen (N) when compared with ECM fungi on the non-Frankia host Pseudotsuga menziesii. At the community level, potential acid phosphatase (AP) activity of ECM fungal root tips from A. rubra was significantly higher than that from P. menziesii, whereas potential leucine aminopeptidase (LA) activity was significantly lower for A. rubra root tips at one of the two sites. At the individual species level, there was no clear relationship between ECM fungal relative root tip abundance and relative AP or LA enzyme activities on either host. Our results are consistent with the hypothesis that ECM fungal communities associated with Alnus trees have enhanced organic P acquisition abilities relative to non-Frankia ECM hosts. This shift, in combination with the chemical conditions present in Alnus forest soils, may drive the atypical structure of Alnus ECM fungal communities. PMID:24320607

  7. Taxonomy and evolution of bacteriochlorophyll a-containing members of the OM60/NOR5 clade of marine gammaproteobacteria: description of Luminiphilus syltensis gen. nov., sp. nov., reclassification of Haliea rubra as Pseudohaliea rubra gen. nov., comb. nov., and emendation of Chromatocurvus halotolerans

    PubMed Central

    2013-01-01

    Background Aerobic gammaproteobacteria affiliated to the OM60/NOR5 clade are widespread in saline environments and of ecological importance in several marine ecosystems, especially the euphotic zone of coastal areas. Within this group a close relationship between aerobic anoxygenic photoheterotrophs and non-phototrophic members has been found. Results Several strains of aerobic red-pigmented bacteria affiliated to the OM60/NOR5 clade were obtained from tidal flat sediment samples at the island of Sylt (North Sea, Germany). Two of the novel isolates, Rap1red and Ivo14T, were chosen for an analysis in detail. Strain Rap1red shared a 16S rRNA sequence identity of 99% with the type strain of Congregibacter litoralis and was genome-sequenced to reveal the extent of genetic microheterogeneity among closely related strains within this clade. In addition, a draft genome sequence was obtained from the isolate Ivo14T, which belongs to the environmental important NOR5-1 lineage that contains so far no cultured representative with a comprehensive description. Strain Ivo14T was characterized using a polyphasic approach and compared with other red-pigmented members of the OM60/NOR5 clade, including Congregibacter litoralis DSM 17192T, Haliea rubra DSM 19751T and Chromatocurvus halotolerans DSM 23344T. All analyzed strains contained bacteriochlorophyll a and spirilloxanthin as photosynthetic pigments. Besides a detailed phenotypic characterization including physiological and chemotaxonomic traits, sequence information based on protein-coding genes and a comparison of draft genome data sets were used to identify possible features characteristic for distinct taxa within this clade. Conclusions Comparative sequence analyses of the pufLM genes of genome-sequenced representatives of the OM60/NOR5 clade indicated that the photosynthetic apparatus of these species was derived from a common ancestor and not acquired by multiple horizontal gene transfer from phylogenetically distant

  8. A Near-Infrared Photothermal Effect-Responsive Drug Delivery System Based on Indocyanine Green and Doxorubicin-Loaded Polymeric Micelles Mediated by Reversible Diels-Alder Reaction.

    PubMed

    Li, Hui; Li, Junjie; Ke, Wendong; Ge, Zhishen

    2015-10-01

    Near-infrared light (NIR) possesses great advantages for light-responsive controllable drug release, such as deep tissue penetration and low damage to healthy tissues. Herein, a NIR-responsive drug delivery system is developed based on a NIR dye, indocyanine green (ICG), and anticancer drug, doxorubicin (DOX)-loaded thermoresponsive block copolymer micelles, in which the drug release can be controlled via NIR irradiation. First, block copolymers, poly(oligo(ethylene glycol) methacrylate)-block-poly(furfuryl methacrylate) (POEGMA-b-PFMA), are synthesized by sequential reversible addition-fragmentation chain-transfer (RAFT) polymerization, followed by modification with N-octyl maleimide through Diels-Alder (DA) reaction to produce POEGMA-b-POMFMA. The self-assembly of POEGMA-b-POMFMA by nano-precipitation in aqueous solution affords the polymeric micelles which are used to simultaneously encapsulate ICG and DOX. Upon irradiation by NIR light (805 nm), the loaded DOX is released rapidly from the micelles due to partial retro DA reaction and local temperature increase-induced faster drug diffusion by the photothermal effect. Cytotoxicity evaluation and intracellular distribution observation demonstrate significant synergistic effects of NIR-triggered drug release, photothermal, and chemotherapy toward cancer cells under NIR irradiation.

  9. 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.

  10. 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. PMID:27085663

  11. 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.

  12. Lewis Acids as Activators in CBS-Catalysed Diels-Alder Reactions: Distortion Induced Lewis Acidity Enhancement of SnCl4.

    PubMed

    Nödling, Alexander R; Möckel, Robert; Tonner, Ralf; Hilt, Gerhard

    2016-09-01

    The effect of several Lewis acids on the CBS catalyst (named after Corey, Bakshi and Shibata) was investigated in this study. While (2) H NMR spectroscopic measurements served as gauge for the activation capability of the Lewis acids, in situ FT-IR spectroscopy was employed to assess the catalytic activity of the Lewis acid oxazaborolidine complexes. A correlation was found between the Δδ((2) H) values and rate constants kDA , which indicates a direct translation of Lewis acidity into reactivity of the Lewis acid-CBS complexes. Unexpectedly, a significant deviation was found for SnCl4 as Lewis acid. The SnCl4 -CBS adduct was much more reactive than the Δδ((2) H) values predicted and gave similar reaction rates to those observed for the prominent AlBr3 -CBS adduct. To rationalize these results, quantum mechanical calculations were performed. The frontier molecular orbital approach was applied and a good correlation between the LUMO energies of the Lewis acid-CBS-naphthoquinone adducts and kDA could be found. For the SnCl4 -CBS-naphthoquinone adduct an unusual distortion was observed leading to an enhanced Lewis acidity. Energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV) calculations revealed the relevant interactions and activation mode of SnCl4 as Lewis acid in Diels-Alder reactions. PMID:27492791

  13. Origin of the synchronicity in bond formation in polar Diels-Alder reactions: an ELF analysis of the reaction between cyclopentadiene and tetracyanoethylene.

    PubMed

    Domingo, Luis R; Pérez, Patricia; Sáez, Jose A

    2012-05-21

    The origin of the synchronicity in C-C bond formation in polar Diels-Alder (P-DA) reactions involving symmetrically substituted electrophilic ethylenes has been studied by an ELF analysis of the electron reorganization along the P-DA reaction of cyclopentadiene (Cp) with tetracyanoethylene (TCE) at the B3LYP/6-31G* level. The present study makes it possible to establish that the synchronicity in C-C bond formation in P-DA reactions is controlled by the symmetric distribution of the electron-density excess reached in the electrophile through the charge transfer process, which can be anticipated by an analysis of the spin electron-density at the corresponding radical anion. The ELF comparative analysis of bonding along the DA reactions of Cp with ethylene and with TCE asserts that these DA reactions, which have a symmetric electron reorganization, do not have a cyclic electron reorganization as the pericyclic mechanism states. Due to the very limited number of cases of symmetrically substituted ethylenes, we can conclude that the synchronous mechanism is an exception of DA reactions. PMID:22527420

  14. A Near-Infrared Photothermal Effect-Responsive Drug Delivery System Based on Indocyanine Green and Doxorubicin-Loaded Polymeric Micelles Mediated by Reversible Diels-Alder Reaction.

    PubMed

    Li, Hui; Li, Junjie; Ke, Wendong; Ge, Zhishen

    2015-10-01

    Near-infrared light (NIR) possesses great advantages for light-responsive controllable drug release, such as deep tissue penetration and low damage to healthy tissues. Herein, a NIR-responsive drug delivery system is developed based on a NIR dye, indocyanine green (ICG), and anticancer drug, doxorubicin (DOX)-loaded thermoresponsive block copolymer micelles, in which the drug release can be controlled via NIR irradiation. First, block copolymers, poly(oligo(ethylene glycol) methacrylate)-block-poly(furfuryl methacrylate) (POEGMA-b-PFMA), are synthesized by sequential reversible addition-fragmentation chain-transfer (RAFT) polymerization, followed by modification with N-octyl maleimide through Diels-Alder (DA) reaction to produce POEGMA-b-POMFMA. The self-assembly of POEGMA-b-POMFMA by nano-precipitation in aqueous solution affords the polymeric micelles which are used to simultaneously encapsulate ICG and DOX. Upon irradiation by NIR light (805 nm), the loaded DOX is released rapidly from the micelles due to partial retro DA reaction and local temperature increase-induced faster drug diffusion by the photothermal effect. Cytotoxicity evaluation and intracellular distribution observation demonstrate significant synergistic effects of NIR-triggered drug release, photothermal, and chemotherapy toward cancer cells under NIR irradiation. PMID:26274805

  15. 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

    2015-01-01

    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.

  16. Kinetic and spectrophotometric investigation of the diels-alder reaction between maleic anhydride derivatives and substituted anthracenes in the presence of gallium and aluminum chlorides

    SciTech Connect

    Kiselev, V.D.; Konovalov, A.I.; Shakirov, I.M.

    1986-10-01

    A comparison was made of the kinetic data for the normal Diels-Alder reaction of para-substituted N-arylmaleimides and substituted maleic anhydrides with meso-substituted anthracenes and of the reaction catalyzed by gallium and aluminum chlorides. The largely constant effects of gallium chloride (10/sup 4/) and aluminum chloride (10/sup 5/) in the acceleration of the reactions between the various pairs were demonstrated. The energies of charge transfer in the complexes between hexamethylbenzene and the dienophiles in the presence and absence of Lewis acids were determined by spectrophotometry. A significant decrease (to 1.2 eV) of the charge-transfer energy was found in the ..pi.., ..pi..-complexes and was attributed to the stabilization of the LUMO of the dienophile. From analysis of the obtained data it was concluded that the observed catalytic effect in the presence of Lewis acids can be explained by the approach of the frontier orbital levels and by a favorable change in the coefficients at the atomic orbitals responsible for the reaction.

  17. Determination of the energy storage capacity of the Diels-Alder reaction between methylfuran and maleic anhydride as applied to storing solar energy

    SciTech Connect

    Sparks, B.G.

    1981-01-01

    The heat storage capacity of the Diels-Alder reaction between 2-methylfuran and maleic anhydride is calculated using reaction parameters obtained from solution calorimetry. An equilibrium constant of .614 1/mol and a heat of reaction of 14.33 kcal/mole were obtained from experiments at 45/sup 0/C. A reaction ..delta..C/sub p/ of -21.8 cal/mole was calculated from heat capacity information at 25/sup 0/C. From these parameters, a solution initially seven molar in methylfuran and maleic anhydride was found to have a maximum apparent volumetric heat capacity of about 1.85 times that of water. This maximum occurs at about 335/sup 0/K. Typical active solar energy schemes operate between 300 and 400/sup 0/K. When cycled between these temperatures, this system has an overall apparent heat capacity about 1.5 times that of water. The apparent heat capacity increases as the temperature range is narrowed.

  18. Enhancing reactivity of carbonyl compounds via hydrogen-bond formation. A DFT study of the hetero-Diels-Alder reaction between butadiene derivative and acetone in chloroform.

    PubMed

    Domingo, Luis R; Andrés, Juan

    2003-10-31

    To examine how hydrogen-bond (HB) formation involving chloroform solvent molecules influences the chemical reactivity of ketones, the hetero-Diels-Alder reaction of N,N-dimethyl-1-amino-3-methoxy-1,3-butadiene and acetone has been studied by using density functional theory (DFT) at the B3LYP/6-31G level. The effects of the chloroform on the activation energies have been modeled by means of discrete-continuum models. In the gas phase, the formation of specific HB between acetone and one and two chloroform molecules decreases the activation barriers from 19.3 to 13.6 and 8.5 kcal/mol, respectively. Inclusion of solvent effects by means of combined discrete and polarizable continuum models yields a change of molecular mechanism from a concerted to a two-step mechanism, and the first nucleophilic step is the rate-limiting step. The corresponding values of activation barriers in chloroform are 18.6 kcal/ mol (no HB), 13.5 kcal/mol (one HB), and 9.6 kcal/mol (two HBs). These theoretical results account for the experimental observation that chloroform accelerates the reaction more markedly than more polar aprotic solvent such as acetonitrile. A DFT analysis of the global electrophilicity power of the reagents provides a sound explanation about the catalytic effects of chloroform.

  19. Origin of the synchronicity in bond formation in polar Diels-Alder reactions: an ELF analysis of the reaction between cyclopentadiene and tetracyanoethylene.

    PubMed

    Domingo, Luis R; Pérez, Patricia; Sáez, Jose A

    2012-05-21

    The origin of the synchronicity in C-C bond formation in polar Diels-Alder (P-DA) reactions involving symmetrically substituted electrophilic ethylenes has been studied by an ELF analysis of the electron reorganization along the P-DA reaction of cyclopentadiene (Cp) with tetracyanoethylene (TCE) at the B3LYP/6-31G* level. The present study makes it possible to establish that the synchronicity in C-C bond formation in P-DA reactions is controlled by the symmetric distribution of the electron-density excess reached in the electrophile through the charge transfer process, which can be anticipated by an analysis of the spin electron-density at the corresponding radical anion. The ELF comparative analysis of bonding along the DA reactions of Cp with ethylene and with TCE asserts that these DA reactions, which have a symmetric electron reorganization, do not have a cyclic electron reorganization as the pericyclic mechanism states. Due to the very limited number of cases of symmetrically substituted ethylenes, we can conclude that the synchronous mechanism is an exception of DA reactions.

  20. Catalytic Activity of Cationic and Neutral Silver(I)-XPhos Complexes with Nitrogen Ligands or Tolylsulfonate for Mannich and Aza-Diels-Alder Coupling Reactions.

    PubMed

    Grirrane, Abdessamad; Álvarez, Eleuterio; García, Hermenegildo; Corma, Avelino

    2016-01-01

    Cationic and neutral silver(I)-L complexes (L=Buchwald-type biaryl phosphanes) with nitrogen co-ligands or organosulfonate counter ions have been synthesised and characterised through their structural and spectroscopic properties. At room temperature, both cationic and neutral silver(I)-L complexes are extremely active catalysts in the promotion of the single and double A(3) coupling of terminal (di)alkynes, pyrrolidine and formaldehyde. In addition, the aza-Diels-Alder two- and three-component coupling reactions of Danishefsky's diene with an imine or amine and aldehyde are efficiently catalysed by these cationic or neutral silver(I)-L complexes. The solvent influences the catalytic performance due to limited complex solubility or solvent decomposition and reactivity. The isolation of new silver(I)-L complexes with reagents as ligands lends support to mechanistic proposals for such catalytic processes. The activity, stability and metal-distal arene interaction of these silver(I)-L catalysts have been compared with those of analogous cationic gold(I) and copper(I) complexes. PMID:26598792

  1. 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.

  2. QM/MM Protocol for Direct Molecular Dynamics of Chemical Reactions in Solution: The Water-Accelerated Diels-Alder Reaction.

    PubMed

    Yang, Zhongyue; Doubleday, Charles; Houk, K N

    2015-12-01

    We describe a solvent-perturbed transition state (SPTS) sampling scheme for simulating chemical reaction dynamics in condensed phase. The method, adapted from Truhlar and Gao's ensemble-averaged variational transition state theory, includes the effect of instantaneous solvent configuration on the potential energy surface of the reacting system (RS) and allows initial conditions for the RS to be sampled quasiclassically by TS normal mode sampling. We use a QM/MM model with direct dynamics, in which QM forces of the RS are computed at each trajectory point. The SPTS scheme is applied to the acceleration of the Diels-Alder reaction of cyclopentadiene (CP) + methyl vinyl ketone (MVK) in water. We explored the effect of the number of SPTS and of solvent box size on the distribution of bond lengths in the TS. Statistical sampling of the sampling was achieved when distribution of forming bond lengths converged. We describe the region enclosing the partial bond lengths as the transition zone. Transition zones in the gas phase, SMD implicit solvent, QM/MM, and QM/MM+QM (3 water molecules treated by QM) vary according to the ability of the medium to stabilize zwitterionic structures. Mean time gaps between formation of C-C bonds vary from 11 fs for gas phase to 25 fs for QM/MM+QM. Mean H-bond lengths to O(carbonyl) in QM/MM+QM are 0.14 Å smaller at the TS than in MVK reactant, and the mean O(carbonyl)-H(water)-O(water) angle of H-bonds at the TS is 10° larger than in MVK reactant.

  3. Osmotic adjustment in five tree species under elevated CO sub 2 and water stress. [Platanus occidentalis L. ; Liquidambar styraciflua L. ; Quercus rubra L. ; Acer saccharum Marsh; Liriodendron tulipifera L

    SciTech Connect

    Tschaplinski, T.J.; Hanson, P.J.; Norby, R.J. ); Stewart, D.B. )

    1991-05-01

    Since osmotic adjustment to water stress requires carbon assimilation during stress, the stimulation of photosynthesis by elevated CO{sub 2} may enhance osmotic adjustment. Osmotic adjustment of American sycamore (Platanus occidentalis L.), sweetgum (Liquidambar styraciflua L.), sugar maple (Acer saccharum Marsh.), yellow-poplar (Liriodendron tulipifera L.), and northern red oak (Quercus rubra L.) to water stress was assessed under ambient and elevated CO{sub 2} (ambient +300 {mu}L L{sup {minus}1}), with seedlings grown in 8-L pots in four open-top chambers, fitted with rain exclusion canopies. Trees were subjected to repeated water stress cycles over a six-week period. Well-watered trees were watered daily to maintain a soil matric potential > {minus}0.3 MPa, whereas stressed trees were watered when soil matric potential declined to < {minus}0.9 MPa. Gas exchange and water relations were monitored at the depth of stress and after rewatering. All species displayed an increase in leaf-level water-use efficiency (net photosynthesis/transpiration). Leaves of sycamore and sweetgum displayed an adjustment in osmotic potential at saturation (pressure-volume analysis) of 0.3 MPa and 0.6 MPa, respectively. Elevated CO{sub 2} did not enhance osmotic adjustment in leaves of any of the species studied. Studies to characterize organic solute concentrations in roots are ongoing to determine if osmotic adjustment occurred in the roots.

  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. The role of motivation in the performance of conditioned reflex switching of a maze skill in response to substitution of food reward quality in ants of the species Myrmica rubra.

    PubMed

    Udalova, G P; Karas', A Ya

    2006-11-01

    The characteristics of learning in ants - active Myrmica rubra foragers - were studied in a maze at different levels of colony carbohydrate food need with reinforcement consisting of carbohydrate (sugar syrup) or protein (pupae of Lasius niger ants). Measures of the maze skill during learning reinforced with syrup were somewhat worse than those during learning reinforced with pupae, especially in terms of time-based measures. Ants were able to modify the acquired conditioned reflex reaction when the quality of reinforcement changed. At high levels of food need (" hungry" colony), substitution of syrup with larvae and vice versa was followed by transformation of the previously formed skill; this occurred at both experimental periods (training and testing). At low levels of motivation ("sated colony"), the optimized maze habit formed with protein reinforcement was replaced in the test with carbohydrate reinforcement by a "stochastic," unoptimized behavior with a dominance of investigative activity. These experiments demonstrated that conditioned reflex switching can occur in higher social insects - ants - in which the different forms depend on the level of colony need for food and, respectively, on the level of social food-related motivation of forager ants. The special importance of using the switch activating the corresponding motivational system before changing the reinforcement food quality is emphasized.

  6. 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...

  7. Four mechanisms in the reactions of 3-aminopyrrole with 1,3,5-triazines: inverse electron demand Diels-Alder cycloadditions vs S(N)Ar reactions via uncatalyzed and acid-catalyzed pathways.

    PubMed

    De Rosa, Michael; Arnold, David; Hartline, Douglas

    2013-09-01

    Reaction of 3-aminopyrrole with seven 1,3,5-triazines was studied in a one-step reaction (in situ formation of 3-aminopyrrole) and a two-step reaction (using the tetraphenylborate salt and an amine base). An inverse-electron demand Diels-Alder reaction (IEDDA) was observed with R1 = CF3, CO2Et, and H with the formation of 5H-pyrrolo[3,2-d]pyrimidine derivatives. S(N)Ar was observed when 2,4,6-trifluoro- or 2,4,6-trichloro-1,3,5-triazine were used--1,3,5-triazines that had leaving groups. If excess 1,3,5-triazine was present the initial S(N)Ar product reacted further, in the presence of acid and water, with another equivalent of 1,3,5-triazine to give compounds containing three linked heterocyclic rings. No reaction was observed with R1 = C6H5 and OCH3. Four mechanisms are proposed to explain the experimental results: uncatalyzed and acid catalyzed inverse electron demand Diels-Alder cascades leading to cycloaddition, and uncatalyzed and acid-catalyzed S(N)Ar reactions leading, respectively, to single and double substitution products. Acid catalysis was a factor when there was reduced reactivity in either reactant.

  8. 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

  9. Dehydrogenative Diels-Alder reaction.

    PubMed

    Ozawa, Takuya; Kurahashi, Takuya; Matsubara, Seijiro

    2011-10-01

    The dehydrogenative cycloaddition of dieneynes, which possess a diene in the form of a styrene moiety and a dienophile in the form of an alkyne moiety, produces naphthalene derivatives when heated. It was found that a key requirement of this process is the presence of a silyl group attached to the alkyne moiety, which forces a dehydrogenation reaction to occur. PMID:21905638

  10. 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.

  11. Pressure Dependent Mass Fraction in Noble Gas Mass Spectrometers: A Possible Explanation for the Excessive Dispersion in the EARTHTIME Fish Canyon/Alder Creek Inter-Calibration Experiment

    NASA Astrophysics Data System (ADS)

    Turrin, B. D.; Swisher, C. C.; Mana, S.

    2011-12-01

    Mass spectrometer fractionation bias (mass discrimination) is a ubiquitous phenomenon in noble gas mass spectroscopy and must be corrected for in order to obtain accurate-high precision isotopic ratios that are used in isotopic age calculations. Temporal variations in mass fractionation are well known phenomena and have been reported in several studies (eg. Turrin et al., 2010 and references therein). Here we report on the pressure dependency on mass spectrometer fractionation bias. In our experiment, we varied by a factor of five the signal size of aliquots of atmospheric argon delivered from an automated air pipette system. The measured mass discrimination difference (MD) as determined by the 40Ar/36Ar ratio between the 1-fold and 5-fold air pipette shots is ~5%. The air 40Ar/36Ar aliquots were measured using a MAP 215-50 operating in pulse counting mode. The air measurements were interspersed with measurements of Alder Creek (AC) sanidine and Fish Canyon (FC) sanidine that were co-irradiated for 0.75 hours. The grain sizes for the two mineral standards were chosen such that the AC sample yielded 40Ar signals of about 50 kcps, similar to that delivered by a single aliquot delivered by the air pipette. The FC grains were about 5-10 times greater (150-600 kcps) than the single air aliquot. Following the analyses, we applied the MD correction to both the FC and AC analyses. When the MD as determined from the single pipette data (which matches 40Ar beam intensity of the AC sample) is applied to both the AC and FC data a "J" of 1.579±0.001x10-4 is obtained from the FC data and an age of 1183 ±4 ka for AC. However, when the MD as determined from the multiple aliquot pipette data (with an 40Ar beam similar to that of the FC analyses) is applied to the FC data a "J" of 1.588±0.001x10-4 is obtained and an AC age of 1189 ±4 ka the same age at the 95% confidence level, the reported age for AC. We conclude that variation in MD over signal sizes typically analyzed in 40Ar

  12. Gold-Catalyzed Cycloisomerization and Diels-Alder Reaction of 1,4,9-Dienyne Esters to 3 a,6-Methanoisoindole Esters with Pro-Inflammatory Cytokine Antagonist Activity.

    PubMed

    Susanti, Dewi; Liu, Li-Juan; Rao, Weidong; Lin, Sheng; Ma, Dik-Lung; Leung, Chung-Hang; Chan, Philip Wai Hong

    2015-06-15

    A synthetic method to prepare 3a,6-methanoisoindole esters efficiently by gold(I)-catalyzed tandem 1,2-acyloxy migration/Nazarov cyclization followed by Diels-Alder reaction of 1,4,9-dienyne esters is described. We also report the ability of one example to inhibit binding of tumor necrosis factor-α (TNF-α) to the tumor necrosis factor receptor 1 (TNFR1) site and TNF-α-induced nuclear factor κ-light-chain-enhancer of activated B cells (NF-κB) activation in cell at a half-maximal inhibitory concentration (IC50 ) value of 6.6 μM. Along with this is a study showing the isoindolyl derivative to exhibit low toxicity toward human hepatocellular liver carcinoma (HepG2) cells and its possible mode of activity based on molecular modeling analysis. PMID:25982956

  13. Why Nature Eschews the Concerted [2 + 2 + 2] Cycloaddition of a Nonconjugated Cyanodiyne. Computational Study of a Pyridine Synthesis Involving an Ene – Diels-Alder – Bimolecular Hydrogen Transfer Mechanism

    PubMed Central

    Lan, Yu; Danheiser, Rick L.; Houk, K. N.

    2012-01-01

    An intramolecular formal metal-free intramolecular [2 + 2 + 2] cycloaddition for the formation of pyridines has been investigated with M06-2X and B3LYP density functional theory, and compared to the experimentally established three-step mechanism that involves ene reaction - Diels-Alder reaction -hydrogen transfer. The ene reaction of two alkynes is the rate-determining step. This is considerably easier than other possible mechanisms, such as those involving an ene reaction of an alkyne with a nitrile, a concerted [2 + 2 + 2] cycloaddition, or a 1,4-diradical mechanism. The relative facilities of these processes are analyzed with the distortion-interaction model. A bimolecular hydrogen transfer mechanism involving a radical pair intermediate is proposed rather than a concerted intramolecular 1,5-hydrogen shift for the last step in the mechanism. PMID:22188179

  14. 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.

  15. 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 ...

  16. 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

  17. 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. PMID:25788602

  18. 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.

  19. Heat Rash or Prickly Heat (Miliaria Rubra)

    MedlinePlus

    ... which can be a causative agent in the development of the rash. Remove any occlusive clothing, limit activity, and seek air conditioning or any cooler environment. Cool compresses can also help with the discomfort. ...

  20. Heat Rash or Prickly Heat (Miliaria Rubra)

    MedlinePlus

    ... 2006-2013 Logical Images, Inc. All rights reserved. Advertising Notice This Site and third parties who place ... would like to obtain more information about these advertising practices and to make choices about online behavioral ...