Science.gov

Sample records for grey alder stands

  1. 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

  2. Red alder stand development and dynamics.

    Treesearch

    R.L. Deal

    2006-01-01

    This paper synthesizes information on the development of natural pure red alder stands and dynamics of mixed alder-conifer stands. Early research on red alder growth and yield focused on developing stand volume and normal yield. tables for alder in the Pacific Northwest. Recent site-index estimation and height-growth curves were developed on a 20-year site base age....

  3. Understory plant diversity in riparian alder-conifer stands after logging in southeast Alaska.

    Treesearch

    Robert L. Deal

    1997-01-01

    Stand structure, tree height growth, and understory plant diversity were assessed in five mixed alder-conifer stands after logging in southeast Alaska. Tree species composition ranged from 7- to 91-percent alder, and basal area ranged from 30 to 55 m2/ha. The alder exhibited rapid early height growth, but recent growth has slowed considerably. Some conifers have...

  4. Stand dynamics of mixed red alder-conifer forests of southeast Alaska.

    Treesearch

    Robert L. Deal; Paul E. Hennon; Ewa H. Orlikowska; David V. D' Amore

    2004-01-01

    Stand structure and dynamics were evaluated in mixed red alder (Alnus rubra Bong.) - conifer forests of southeast Alaska. We assessed stand development, tree density, total basal area, diameter distribution of live and dead trees, height distribution of live trees, and mean diameter of all and largest conifers in 40-year-old red alder - conifer...

  5. Nitrogen isotope fractionation during N uptake via arbuscular mycorrhizal and ectomycorrhizal fungi into grey alder.

    PubMed

    Schweiger, Peter F

    2016-10-20

    Arbuscular mycorrhizal (AM) and ectomycorrhizal (ECM) fungi affect plant nitrogen (N) dynamics. Plant N isotope patterns have been used to characterise the contribution of ECM fungi to plant N uptake. By quantifying and comparing the effects of an AM and an ECM fungus on growth, N uptake and isotopic composition of one host plant grown at different relative N supply levels, the aim of this study was to improve the mechanistic understanding of natural (15)N abundance patterns in mycorrhizal plants and their underlying causes. Grey alders were inoculated with one ECM fungus or one AM fungus or left non-mycorrhizal. Plants were grown under semi-hydroponic conditions and were supplied with three rates of relative N supply ranging from deficient to luxurious. Neither mycorrhizal fungus increased plant growth or N uptake. AM root colonisation had no effect on whole plant δ(15)N and decreased foliar δ (15)N only under N deficiency. The roots of these plants were (15)N-enriched. ECM root colonisation consistently decreased foliar and whole plant δ(15)N. It is concluded, that both mycorrhizal fungi contributed to plant N uptake into the shoot. Nitrogen isotope fractionation during N assimilation and transformations in fungal mycelia is suggested to have resulted in plants receiving (15)N-depleted N via the mycorrhizal uptake pathways. Negative mycorrhizal growth effects are explained by symbiotic resource trade on carbon and N and decreased direct plant N uptake. Copyright © 2016 Elsevier GmbH. All rights reserved.

  6. Comparison of terrestrial invertebrate biomass and richness in young mixed red alder-conifer, young conifer, and old conifer stands of southeast Alaska.

    Treesearch

    Mark E. Schultz; Toni L. De Santo

    2008-01-01

    Coniferous stands that regenerate following clearcutting in southeast Alaska can be characterized by the amount of soil disturbance during logging. There are indications that red alder in mixed stands mitigates some of the negative effects of clearcutting. We compared invertebrate biomass in four stands each of (1) young conifers, (2) young mixed alder and conifer, and...

  7. Growth and development of red alder compared with conifers in 30-year-old stands.

    Treesearch

    Carl M. Berntsen

    1961-01-01

    Red alder (Alnus rubra), although a widespread tree species in Pacific coast forests, has only in recent years attained commercial importance as a source of wood material for diversified products including furniture, paneling, and paper pulp. With the rapid increase in the harvest of red alder, both public agencies and private industry are making a...

  8. A 20-year growth record for three stands of red alder.

    Treesearch

    Carl M. Berntsen

    1962-01-01

    Until very recently, only fragmentary growth information has been available for red alder (Alnus rubra). This gap has now been partially closed through the preparation of normal yield tabled based on temporary sample plot data collected in northwestern Oregon, western Washington, and southern British Columbia.

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

    PubMed

    Elo; Maunuksela; Salkinoja-Salonen; Smolander; Haahtela

    2000-02-01

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

  10. Utilization and management of alder.

    Treesearch

    David G. Briggs; Dean S. DeBell; William A. Atkinson

    1978-01-01

    In the Pacific Northwest and British Columbia, red alder often grows on forest lands following natural or man-caused disturbances. Frequently ignored as a pest or weed, many alder stands have developed to the point where important utilization and management questions are being asked. It is recognized that alder is a fast growing species, and that its rapid early growth...

  11. Description and identification of Alnus acuminata ectomycorrhizae from Argentinean alder stands.

    PubMed

    Pritsch, Karin; Becerra, Alejandra; Põlme, Sergei; Tedersoo, Leho; Schloter, Michael; Agerer, Reinhard

    2010-01-01

    The objective of this study was to describe the morphological and anatomical features of five unidentified ectomycorrhizal types of Alnus acuminata and to complement their identification based on ITS-rDNA sequence analysis. The combined approach of morphotyping and sequence analysis based on ITS sequence comparison with sequences contained in GenBank and the UNITE database let us assign three of the five field-collected ectomycorrhiza morphotypes to the tomentella-thelephora lineage that closely matched European and North American species. The sequencing results within Tomentella point toward alder specific clades within T. sublilacina, T. ellisii and T. stuposa sensu lato. The two other EcM morphotypes matched Lactarius omphaliiformis and a Russula sp. Better focused, concomitant fruit body surveys are needed for accurate identification of South American ectomycorrhizal fungi because of the evidence of cryptic speciation in both agaricoid and resupinate mycobionts.

  12. 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.

  13. Red alder harvesting opportunities in western Oregon.

    Treesearch

    Donald R. Gedney

    1990-01-01

    This report presents statistics on the present distribution and ownership of merchantable stands of red alder in western Oregon and the character of these stands as they affect harvesting opportunities.

  14. Red alder-conifer stands in Alaska: An example of mixed species management to enhance structural and biological complexity

    Treesearch

    Robert Deal; Ewa Orlikowska; David D’Amore; Paul Hennon

    2017-01-01

    There is worldwide interest in managing forests to improve biodiversity, enhance ecosystem services and assure long-term sustainability of forest resources. An increasingly important goal of forest management is to increase stand diversity and improve wildlife and aquatic habitat. Well-planned silvicultural systems containing a mixture of broadleaf-conifer species have...

  15. Alder flycatcher

    Treesearch

    Scott H. Stoleson

    2010-01-01

    The alder flycatcher is a small flycatcher in the confusing genus Empidonax. It so closely resembles its look-alike congener, the willow flycatcher (E. traillii), that until 1973 they were considered a single species, Traill's flycatcher (American Ornithologists' Union 1973). As most published studies of Traill's...

  16. Grey analysis

    SciTech Connect

    Cable, G.D.

    1996-12-01

    Grey logic is not another name for fuzzy logic. Grey logic--also called grey analysis or grey system theory--is a new technology, a group of techniques for system analysis and modeling. Like fuzzy logic, grey logic is useful in situations with incomplete and uncertain information. Grey analysis is particularly applicable in instances with very limited data and in cases with little system knowledge or understanding. In this paper, a summary of the basic concepts of grey analysis is provided, with descriptions of its application to several classes of problems. Calculations methods are provided for grey relation analysis, and for modeling and prediction using grey methods.

  17. 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.

  18. Site curves for red alder.

    Treesearch

    Daniel M. Bishop; Floyd A. Johnson

    1958-01-01

    The increasing commercial importance of red alder (Alnus rubra) in the Pacific Northwest has created a demand for research on this species. Noting the lack of information on growth of alder, the Puget Sound Research Center Advisory Committee established a subcommittee in January 1956 to undertake construction of alder yield tables. Through the...

  19. Red alder potential in Alaska

    Treesearch

    Allen Brackley; David Nicholls; Mike Hannan

    2010-01-01

    Over the past several decades, red alder has established itself as a commercially important species in the Pacific Northwest. Once considered a weed species, red alder now commands respect within many markets, including furniture, architectural millwork, and other secondary manufactured products. Although red alder's natural range extends to southeast Alaska, an...

  20. Height growth and site index curves for red alder.

    Treesearch

    Constance A. Harrington; Robert O. Curtis

    1985-01-01

    New height growth and site index curves for red alder (Alnus rubra Bong.) were developed from stem analysis data. The analyses use a reference (site index) age of 20 years and are applicable to natural stands between 5 and 50 years of age in western Washington and northwestern Oregon. The new curves are polymorphic and provide a better fit to observed patterns of...

  1. Relations between red alder composition and understory vegetation in young mixed forests of southeast Alaska.

    Treesearch

    Thomas A. Hanley; Robert L. Deal; Ewa H. Orlikowska

    2006-01-01

    Interest in mixed red alder (Alnus rubra Bong.)—conifer young-growth stands has grown in southeast Alaska, USA, because they appear to provide much more productive understory vegetation and wildlife habitat than do similar-aged pure conifer stands. We studied understory vegetation in nine even-aged young-growth stands (38-42 years old)...

  2. Volume tables for red alder.

    Treesearch

    Floyd A. Johnson; R. M. Kallander; Paul G. Lauterbach

    1949-01-01

    The increasing importance of red alder as a commercial species in the Pacific Northwest has prompted the three agencies listed above to pool their tree measurement data for the construction of standard regional red alder volume tables. The tables included here were based on trees from a variety of sites and form classes. Approximately one quarter of the total number of...

  3. Red alder, Alnus rubra, as a potential mitigating factor for wildlife habitat following clearcut logging in southeastern Alaska.

    Treesearch

    T.A. Hanley; J.C. Barnard

    1998-01-01

    Within-stand variation in understory species composition and biomass was studied in 16 even-aged stands of mixed red alder-Sitka spruce-western hemlcock (Alnus rubra-Picea sitchensis-Tsuga heterophylla) forest. The sites were upland sites, and the stands were 28-39 years old. We compared understory within...

  4. Mechanistic insights into Diels-Alder reactions in natural product biosynthesis.

    PubMed

    Hashimoto, Takuya; Kuzuyama, Tomohisa

    2016-12-01

    Natural enzymes that catalyze Diels-Alder reactions have long been sought after, yet few enzymes have been experimentally confirmed to perform this reaction. In the past five years, several stand-alone enzymes that can catalyze the Diels-Alder reaction had been identified and characterized. Among which, the crystal structures of SpnF, PyrI4 and AbyU have been determined. The structures of PyrI4 and AbyU, which are involved in spirotetronate/spirotetramate biosynthesis, are particularly informative since they shed light on how a natural catalyst captures the flexible substrate and facilitates the intramolecular Diels-Alder reaction through stabilization of the transition state in catalysis. These pioneering studies will inspire the design of artificial catalysts for Diels-Alder reactions. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    Treesearch

    Takashi Gomi; Adelaide C. Johnson; Robert L. Deal; Paul E. Hennon; Ewa H. Orlikowska; Mark S. Wipfli

    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) in southeast Alaska. More riparian red alder were found along...

  6. Red alder: a state of knowledge.

    Treesearch

    Robert L. Deal; Constance A. Harrington

    2006-01-01

    In March 23-25, 2005, an international symposium on red alder was held at the University of Washington Center for Urban Horticulture in Seattle, WA. The symposium was entitled "Red alder: A State of Knowledge" and brought together regional experts to critically examine the economic, ecological and social values of red alder. The primary goal of the symposium...

  7. Influence of red alder on chemical properties of a clay loam soil in western Washington.

    Treesearch

    D.S. DeBell; M.A. Radwan; J.M. Kraft

    1983-01-01

    Chemical characteristics of mineral soil beneath red alder (Alnus rubra Bong.) stands of various ages were studied. Total nitrogen (N) of the 0-to 20-centimeter (0- to 8-inch) soil layer increased with stand age, and pH of both the 0- to 20-centimeter and 20- to 50-centimeter (8- to 20-inch) layers decreased with stand age. Contents of some mineral...

  8. Germination of red alder seed.

    Treesearch

    M.A. Radwan; D.S. DeBell

    1981-01-01

    Red alder seeds were collected from six locations throughout the natural range of the species. Each seed lot was obtained from a single tree, and the seeds were used to determine germination with and without stratification treatment. Irrespective of treatment, germination varied significantly (P

  9. Water Relations of White Alder

    Treesearch

    Virginia I. Dains

    1989-01-01

    White alder (Alnus rhombifolia) is a potentially valuable indicator of water stress along California's waterways. Measurements of stomatal conductance, water potential and tissue water relations in conjunction with growth and morphological studies give evidence for the sensitivity of this species to changes in water availability. Potted...

  10. An Appreciation: Berni Julian Alder

    NASA Astrophysics Data System (ADS)

    Graham Hoover, William

    Berni Alder profoundly influenced my research career at Lawrence Livermore National Laboratory and the Davis Campus' Teller Tech, beginning in 1962 and lasting for over fifty years. I very much appreciate the opportunity provided by his Ninetieth Birthday Celebration to review some of the many high spots along the way.

  11. "Grey matters".

    PubMed

    Rose, Katie

    2014-01-01

    It's common in this world, for diagnoses to be confused. This grey, oblique world is the "World of Brain Tumors" from which these narratives are written, a world I entered when a tangerine-sized tumor was found on my temporal lobe. Each narrative illustrates this world in which everything is covered in a thick film rendering things once obvious, now unknown. Parents are asked to choose treatment plans for their children, plans that will inevitably alter their child's quality of life but in ways they cannot determine or even imagine. Parents are asked to play God. Most of the parents who share their stories in this collection, parents of PBT (pediatric brain tumor) patients have to walk the line of trying to not disrupt their relationships with their physicians, wanting the best for their child, and facing the decision to follow their gut or go with advised treatment plans.

  12. The reliability of determining age of red alder by ring counts

    Treesearch

    Dean S. DeBell; Boyd C. Wilson; Bernard T. Bormann

    1978-01-01

    Examination of cross-sections of 54 red alder trees from 14 stands of varying age and site conditions indicated that abnormal rings (false, partial, or missing) occur infrequently. Rings may be indistinct and ring counting must be done with great care, preferably on prepared surfaces (cross-sections or cores) and under magnification and good lighting. With such...

  13. Time and distance to clear wood in pruned red alder saplings.

    Treesearch

    Dean S. DeBell; Constance A. Harrington; Barbara L. Gartner; Ryan. Singleton

    2006-01-01

    Pruning trials in young alder stands were sampled to evaluate response to pruning. Effects of pruning (1) live branches on different dates, and (2) dead branches with or without damaging the branch collar were assessed on trees pruned in 3- and 6-year-old plantations, respectively. Six years after pruning, stem sections were collected and dissected in the longitudinal-...

  14. New Polybenzimidazole Architectures by Diels Alder Polymerization

    DTIC Science & Technology

    2012-02-14

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

  15. Control of red alder by cutting.

    Treesearch

    Dean S. DeBell; Thomas C. Turpin

    1989-01-01

    Effects of tree age, month of cut, and height and angle of cut on sprouting of red alder stumps were evaluated in a study designed to develop an effective method for controlling red alder in Douglas-fir plantations. Ninety-five percent or more of alder stumps cut in June or July died by the end of the next growing season; mortality was 88, 70, and 22 percent for stumps...

  16. Early wide spacing in red alder (Alnus rubra Bong.): effects on stem form and stem growth.

    Treesearch

    Bernard T. Bormann

    1985-01-01

    A thinning trial was established in 1962 in a 7-year-old red alder stand in northwestern Washington. Spacings were 8 x 8 ft (dense), 12 x 12 it (intermediate), and 16 x 16 ft (open). The effect of early thinning on growth and stem form was measured in 1982, 20 years after spacing treatment. There was negligible tree lean and sweep in open and intermediate stands except...

  17. Normal yield tables for red alder.

    Treesearch

    Norman P. Worthington; Floyd A. Johnson; George R. Staebler; William J. Lloyd

    1960-01-01

    Increasing interest in the management of red alder (Alnus rubra) has created a need for reliable yield information. Existing yield tables for red alder have been very useful as interim sources of information, but they are generally inadequate for current and prospective management needs. The advisory committee for the Station's Olympia...

  18. Volume and taper tables for red alder.

    Treesearch

    Robert O. Curtis; David Bruce; Caryanne. VanCoevering

    1968-01-01

    Red alder is a species of increasing importance in the Pacific Northwest. Interest in improved volume tables for the species resulted in publication of the 1949 volume tables. More recently, Browne (1962) published cubic-foot-volume tables for red alder in British Columbia, and Hoyer (1966) presented tarif access tables, based on the 1949 tables, for use with the...

  19. 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

  20. 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.

  1. 35. GREY IRON TUMBLERS, IN THE GREY IRON FOUNDRY ROTATE ...

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

    35. GREY IRON TUMBLERS, IN THE GREY IRON FOUNDRY ROTATE CASTINGS WITH SHOT TO REMOVE AND SURFACE OXIDES AND REMAINING EXCESS METALS. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  2. Gold(I)-Initiated Cycloisomerization/Diels-Alder/Retro-Diels-Alder Cascade Strategy to Biaryls.

    PubMed

    Jin, Shengfei; Niu, Yujie; Liu, Chengjun; Zhu, Lifeng; Li, Yangming; Cui, Shanshan; Xiong, Zhiling; Cheng, Maosheng; Lin, Bin; Liu, Yongxiang

    2017-09-01

    A unique approach to biaryls was developed on the basis of propargyl vinyl ethers and dienophiles substrates via a gold(I)-initiated cycloisomerization/Diels-Alder/retro-Diels-Alder cascade reaction. The scope and mechanism of the reaction were investigated on the basis of a series of synthetic substrates, control experiments, and DFT calculations.

  3. Uncertainty representation of grey numbers and grey sets.

    PubMed

    Yang, Yingjie; Liu, Sifeng; John, Robert

    2014-09-01

    In the literature, there is a presumption that a grey set and an interval-valued fuzzy set are equivalent. This presumption ignores the existence of discrete components in a grey number. In this paper, new measurements of uncertainties of grey numbers and grey sets, consisting of both absolute and relative uncertainties, are defined to give a comprehensive representation of uncertainties in a grey number and a grey set. Some simple examples are provided to illustrate that the proposed uncertainty measurement can give an effective representation of both absolute and relative uncertainties in a grey number and a grey set. The relationships between grey sets and interval-valued fuzzy sets are also analyzed from the point of view of the proposed uncertainty representation. The analysis demonstrates that grey sets and interval-valued fuzzy sets provide different but overlapping models for uncertainty representation in sets.

  4. Can Puva Darken Grey Hair.

    PubMed

    Pasricha, J S

    1987-01-01

    Grey hairs obtained from patients having premature grey hairs were exposed to UVA or UVB for 30 mmutes daily for 17 days and another group of grey hairs were first daily painted with 1% aqueous solution of psoralen and then exposed to UVA for 30 minutes for 17 days. Under neither of these conditions, the greys hairs showed any darkening.

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

    SciTech Connect

    Farnham, R.S.; Read, P.

    1981-03-01

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

  6. Welcome and Reflections on Berni Alder

    NASA Astrophysics Data System (ADS)

    Tarter, C. Bruce

    Good morning and welcome to Berni Alder's 90th Birthday Symposium. My name is Bruce Tarter and I'm representing Director Bill Goldstein, who could not be here this morning, but will be here for the afternoon session and will make comments of his own at the end of the Symposium…

  7. Red alder: A bibliography with abstracts

    Treesearch

    Charles F. Heebner; Mary Jane Bergener

    1983-01-01

    This bibliography lists 661 references to world literature through Hay 1978 containing information about red alder (Alnus rubra Bong.). Included are publications about its taxonomy, biology and silvics, chemical and physical information about its wood and fiber, studies on its nitrogen fixing properties, and reports on industrial uses and economic...

  8. Biology and ecology of red alder.

    Treesearch

    Constance A. Harrington

    2006-01-01

    Red alder is the most common hardwood in the Pacific Northwest with a range stretching from coastal southeast Alaska to southern California and east to isolated populations in Idaho. Soil moisture during the growing season influences where it grows and its growth rates; it can tolerate poor drainage but not droughty, hot sites. Due to its tolerance of wet soil...

  9. 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.

  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.

  11. Origins of Stereoselectivity in the trans-Diels-Alder Paradigm

    PubMed Central

    Paton, Robert S.; Mackey, Joel L.; Kim, Woo Han; Lee, Jun Hee; Danishefsky, Samuel J.; Houk, K. N.

    2010-01-01

    The regioselectivity and stereoselectivity aspects of the Diels-Alder/radical hydrodenitration reaction sequence leading to trans-fused ring systems have been investigated with density functional calculations. A continuum of transition structures representing Diels-Alder and hetero-Diels-Alder cycloadditions as well as a sigmatropic rearrangement have been located, and they all lie very close in energy on the potential energy surface. All three pathways are found to be important in the formation of the Diels-Alder adduct. Reported regioselectivities are reproduced by the calculations. The stereoselectivity of radical hydrodenitration of the cis-Diels-Alder adduct is found to be related to the relative conformational stabilities of bicyclic radical intermediates. Overall, the computations provide understanding of the regioselectivities and stereoselectivities of the trans-Diels-Alder paradigm. PMID:20557046

  12. Origins of stereoselectivity in the trans Diels-Alder paradigm.

    PubMed

    Paton, Robert S; Mackey, Joel L; Kim, Woo Han; Lee, Jun Hee; Danishefsky, Samuel J; Houk, K N

    2010-07-14

    The regioselectivity and stereoselectivity aspects of the Diels-Alder/radical hydrodenitration reaction sequence leading to trans-fused ring systems have been investigated with density functional calculations. A continuum of transition structures representing Diels-Alder and hetero-Diels-Alder cycloadditions as well as a sigmatropic rearrangement have been located, and they all lie very close in energy on the potential energy surface. All three pathways are found to be important in the formation of the Diels-Alder adduct. Reported regioselectivities are reproduced by the calculations. The stereoselectivity of radical hydrodenitration of the cis-Diels-Alder adduct is found to be related to the relative conformational stabilities of bicyclic radical intermediates. Overall, the computations provide understanding of the regioselectivities and stereoselectivities of the trans-Diels-Alder paradigm.

  13. Grey swan tropical cyclones

    NASA Astrophysics Data System (ADS)

    Lin, Ning; Emanuel, Kerry

    2016-01-01

    We define `grey swan’ tropical cyclones as high-impact storms that would not be predicted based on history but may be foreseeable using physical knowledge together with historical data. Here we apply a climatological-hydrodynamic method to estimate grey swan tropical cyclone storm surge threat for three highly vulnerable coastal regions. We identify a potentially large risk in the Persian Gulf, where tropical cyclones have never been recorded, and larger-than-expected threats in Cairns, Australia, and Tampa, Florida. Grey swan tropical cyclones striking Tampa, Cairns and Dubai can generate storm surges of about 6 m, 5.7 m and 4 m, respectively, with estimated annual exceedance probabilities of about 1/10,000. With climate change, these probabilities can increase significantly over the twenty-first century (to 1/3,100-1/1,100 in the middle and 1/2,500-1/700 towards the end of the century for Tampa). Worse grey swan tropical cyclones, inducing surges exceeding 11 m in Tampa and 7 m in Dubai, are also revealed with non-negligible probabilities, especially towards the end of the century.

  14. Grey water biodegradability.

    PubMed

    Ghunmi, Lina Abu; Zeeman, Grietje; Fayyad, Manar; van Lier, Jules B

    2011-02-01

    Knowing the biodegradability characteristics of grey water constituents is imperative for a proper design and operation of a biological treatment system of grey water. This study characterizes the different COD fractions of dormitory grey water and investigates the effect of applying different conditions in the biodegradation test. The maximum aerobic and anaerobic biodegradability and conversion rate for the different COD fractions is determined. The results show that, on average, dormitory grey water COD fractions are 28% suspended, 32% colloidal and 40% dissolved. The studied factors incubation time, inoculum addition and temperature are influencing the determined biodegradability. The maximum biodegradability and biodegradation rate differ between different COD fractions, viz. COD(ss), COD(col) and COD(diss). The dissolved COD fraction is characterised by the lowest degradation rate, both for anaerobic and aerobic conditions. The maximum biodegradability for aerobic and anaerobic conditions is 86 and 70% respectively, whereas the first order conversion rate constant, k₂₀, is 0.119 and 0.005 day⁻¹, respectively. The anaerobic and aerobic conversion rates in relation to temperature can be described by the Arrhenius relation, with temperature coefficients of 1.069 and 1.099, respectively.

  15. Density and rectangularity of planting influence 20-year growth and development of red alder.

    Treesearch

    Dean S. DeBell; Constance A. Harrington

    2002-01-01

    Red alder (Alnus rubra Bong.) seedlings were planted in northwestern Oregon, U.S.A., at five initial spacings: 0.6 × 1.2 m, 1.2 × 1.2 m, 1.2 × 1.8 m, 1.8 × 1.8 m, and 2.5 × 2.5 m. Up to about age 10, tree and stand characteristics were correlated primarily with initial planting density in the expected manner; through age 20, however, tree growth...

  16. Production and assessment of red alder planting stock.

    Treesearch

    M.A. Radwan; Y. Tanaka; A. Dobkowskl; W. Fangen

    1992-01-01

    A series of experiments was conducted over 4 years to test and develop methods to produce acceptable red alder planting stock and to assess quality and outplanting performance of resulting stock. Results indicated that red alder planting stock can be produced as containerized seedlings (plugs) or as bare-root nontransplant and transplant trees. In general, bare-root...

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

    PubMed

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

    1996-03-08

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

  18. Climate, canker, and alder mortality in the Southern Rockies

    Treesearch

    James J. Worrall

    2012-01-01

    An increase in dieback and mortality of thinleaf alder (Alnus incana ssp. tenuifolia) raised concern in southern Wyoming and Colorado two decades ago. In 1990, there was concern over extensive mortality of thinleaf alder along Big Laramie River near Jelm, WY, as well as in multiple locations in Colorado.2 Trees of all ages were...

  19. Potential productivity of dense, young thickets of red alder

    Treesearch

    Dean S. DeBell

    1972-01-01

    Total above-ground production was evaluated in 28 natural alder thickets, aged 1 to 14 years. On a per acre basis; mean annual production varied from 3 to more than 20 tons of green wood per acre. Such yields warrant preliminary trials of short-rotation cultural systems with red alder.

  20. Inverse electron demand Diels-Alder reactions in chemical biology.

    PubMed

    Oliveira, B L; Guo, Z; Bernardes, G J L

    2017-08-14

    The emerging inverse electron demand Diels-Alder (IEDDA) reaction stands out from other bioorthogonal reactions by virtue of its unmatchable kinetics, excellent orthogonality and biocompatibility. With the recent discovery of novel dienophiles and optimal tetrazine coupling partners, attention has now been turned to the use of IEDDA approaches in basic biology, imaging and therapeutics. Here we review this bioorthogonal reaction and its promising applications for live cell and animal studies. We first discuss the key factors that contribute to the fast IEDDA kinetics and describe the most recent advances in the synthesis of tetrazine and dienophile coupling partners. Both coupling partners have been incorporated into proteins for tracking and imaging by use of fluorogenic tetrazines that become strongly fluorescent upon reaction. Selected notable examples of such applications are presented. The exceptional fast kinetics of this catalyst-free reaction, even using low concentrations of coupling partners, make it amenable for in vivo radiolabelling using pretargeting methodologies, which are also discussed. Finally, IEDDA reactions have recently found use in bioorthogonal decaging to activate proteins or drugs in gain-of-function strategies. We conclude by showing applications of the IEDDA reaction in the construction of biomaterials that are used for drug delivery and multimodal imaging, among others. The use and utility of the IEDDA reaction is interdisciplinary and promises to revolutionize chemical biology, radiochemistry and materials science.

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  2. 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.

  3. 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.

  4. Diels–Alder reaction of maldoxin with an isopropenylallene

    PubMed Central

    Yu, Min; Snider, Barry. B.

    2011-01-01

    The Diels–Alder reaction of maldoxin with an isopropenylallene at 60-75 °C afforded an adduct closely related to chloropestolide A (24%) and a second adduct (0-11%) that underwent an ene reaction to generate the chloropupukeanolide D (11-22%) skeleton. The Diels–Alder reaction occurred with good selectively (>5:1) from a single face of maldoxin under much milder conditions than previously reported for the analogous dimethoxycyclohexadienone. Furthermore, the ene reaction took place under mild conditions whereas the analogous Diels–Alder adduct from the dimethoxycyclohexadienone did not undergo an ene reaction. PMID:22518065

  5. Accurate prediction of rate constants of Diels-Alder reactions and application to design of Diels-Alder ligation.

    PubMed

    Tang, Shi-Ya; Shi, Jing; Guo, Qing-Xiang

    2012-04-07

    Bioorthogonal reactions are useful tools to gain insights into the structure, dynamics, and function of biomolecules in the field of chemical biology. Recently, the Diels-Alder reaction has become a promising and attractive procedure for ligation in bioorthogonal chemistry because of its higher rate and selectivity in water. However, a drawback of the previous Diels-Alder ligation is that the widely used maleimide moiety as a typical Michael acceptor can readily undergo Michael addition with nucleophiles in living systems. Thus, it is important to develop a nucleophile-tolerant Diels-Alder system in order to extend the scope of the application of Diels-Alder ligation. To solve this problem, we found that the theoretical protocol M06-2X/6-31+G(d)//B3LYP/6-31G(d) can accurately predict the activation free energies of Diels-Alder reactions with a precision of 1.4 kcal mol(-1) by benchmarking the calculations against the 72 available experimental data. Subsequently, the electronic effect and ring-strain effect on the Diels-Alder reaction were studied to guide the design of the new dienophiles. The criteria of the design is that the designed Diels-Alder reaction should have a lower barrier than the Michael addition, while at the same time it should show a similar (or even higher) reactivity as compared to the maleimide-involving Diels-Alder ligation. Among the designed dienophiles, three substituted cyclopropenes (i.e. 1,2-bis(trifluoromethyl)-, 1,2-bis(hydroxylmethyl)- and 1,2-bis(hydroxylmethyl)-3-carboxylcyclopropenes) meet our requirements. These substituted cyclopropene analogs could be synthesized and they are thermodynamically stable. As a result, we propose that 1,2-bis(trifluoromethyl)-, 1,2-bis(hydroxylmethyl)- and 1,2-bis(hydroxylmethyl)-3-carboxylcyclopropenes may be potential candidates for efficient and selective Diels-Alder ligation in living systems.

  6. A black alder plantation improves the greenhouse gas balance of a degraded moist peat grassland

    NASA Astrophysics Data System (ADS)

    Bereswill, Sarah; Hoffmann, Mathias; Huth, Vytas; Popova, Yulia; Zak, Dominik; Augustin, Jürgen

    2017-04-01

    Drained peatlands are among the strongest terrestrial sources of the greenhouse gases (GHG) CO2 and N2O. Therefore, activities of peatland revitalisation through rewetting, often combined with the implementation of peat forming vegetation, aim to restore the GHG sink function that is characteristic for pristine peatlands. Black alder (Alnus glutinosa) naturally occurs in temperate marshes and minerotrophic peatlands (= fens) and is also suitable for paludiculture, the cultivation of biomass on wet or rewetted peatlands. However, only little information exists, if a black alder plantation can reduce the climate impact of restored peatlands. Therefore, we investigated the effect of a newly established black alder plantation on the net GHG balance of a degraded fen in north-eastern Germany during a two-year study (August 2010 - August 2012). We compared the alder plantation (Awet) with an extensively used meadow (Mwet) both characterized by very moist soil conditions and a drier reference meadow (Mdry) characterized by moderately moist soil conditions. CO2, CH4 and N2O fluxes were measured monthly to bi-monthly with the manual closed chamber method. Fluxes were calculated using a modular R script and gap filled to obtain continuous daily fluxes. Awet was a net GHG sink of -4.8 t CO2-eq ha-1 yr-1, Mwet was climate neutral (-0.03 t CO2-eq ha-1 yr-1), and Mdry was a net GHG source of 15.7 t CO2-eq ha-1 yr-1. This was mainly caused by CO2 uptake at the two very moist sites and a high CO2 release at the drier reference site. In addition, Awet was a larger CO2 sink than Mwet, likely caused by an additional CO2 uptake of the alder stand. All sites were significant CH4 sources. Due to inundation following extraordinarily heavy precipitation in summer 2011 remarkable CH4emission peaks were found on all sites which accounted for up to 70 % of the cumulated two-year CH4emissions. However, overall Awet emitted significantly lesser CH4(4.9 g C m-2 yr-1). We assume that the black

  7. 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).

  8. 54. ALDER CREEK DIVERSION, PROJECT 1933, EXHIBIT F, SANTA ANA ...

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

    54. ALDER CREEK DIVERSION, PROJECT 1933, EXHIBIT F, SANTA ANA POWERHOUSE NO. 2 SCE drawing no. 5206858, no date (FERC no. 1933-48). - Santa Ana River Hydroelectric System, Redlands, San Bernardino County, CA

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

    PubMed Central

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

    2010-01-01

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

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

    PubMed

    Rizzacasa, Mark A; Pollex, Annett

    2009-03-21

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

  11. 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

  12. Mountain Pine Beetle Impact on Stand-level Water Balance

    NASA Astrophysics Data System (ADS)

    Reilly, J. A.; Woods, S.

    2012-12-01

    The recent mountain pine beetle (MPB) epidemic has disturbed millions of hectares throughout the Rocky Mountain West. The most persistent effects of MPB infestation on the stand-level water balance are likely concomitant with the grey stage of the disturbance cycle. The grey stage occurs within 3 to 5 years of the initial infestation after the needles of an infected tree have turned red and fallen off due to tree death. Large numbers of grey-stage trees in a stand may remain on the landscape for up to 20 years, until windthrow or another disturbance sends them to the forest floor. The greater temporal persistence of the grey stage over antecedent stages suggested that an examination of the grey stage would best capture long-term effects of MPB disturbance on the forest water balance. In this study we hypothesized that changes to the forest canopy associated with MPB disturbance may affect the stand-level water balance. The needle loss and windthrow that follows MPB disturbance is expected to increase the amount of precipitation reaching the forest floor. Additionally, overstory evapotranspiration (ET) demand is expected to decrease as MPB-induced tree mortality increases within disturbed stands. The expected cumulative effect of MPB disturbance on the stand-level water balance is an increase in soil moisture due to increased precipitation inputs and reduced overstory ET. This study was conducted in Lubrecht Experimental Forest and adjacent Bureau of Land Management areas near Missoula, Montana. Sub-canopy measurements of soil moisture, precipitation (rain and snow water equivalent), overstory transpiration and micro-meteorological data (net radiation, temperature, wind speed, etc.) were collected in three 50 x 50 meter plots. The plots consisted of a uniform stand of grey-stage lodgepole pine, a uniform stand of non-infested lodgepole pine, and a recent clear-cut stand, which served as a control unit. Water balances for each stand were constructed using a mass

  13. 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

  14. Diels-Alder reactions in high temperature fluids

    SciTech Connect

    Manka, M.J.; Jeffers, J.M.

    1988-08-01

    While free radical reactions are thought to be the primary chemical mechanism for gas phase soot formation at combustion temperatures, Deils-Alder condensation reactions may be important in the formation of cyclic hydrocarbon species leading to aromatic hydrocarbons in pyrolytic-processes at lower temperatures which suffer from carbon formation. In order to evaluate the importance of Diels-Alder reactions in the formation of carbon, accurate kinetic rate data is needed for proper chemical modeling efforts. Diels-Alder reactions have been extensively studied in the gas and liquid phases. Since the reaction is a condensation reaction, the rate constant has a significant pressure as well as a temperature dependence. We report in this paper the results of reaction rate measurements of 1,3-cyclohexadiene with itself. We also report the effect of pressure on the kinetic rate constant for the pressure range 4000-18,000 kPa and the temperature range 200-250/degree/C.

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

    PubMed Central

    Chery, Joyce

    2015-01-01

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

  16. Comparative effects of precommercial thinning, urea fertilizer, and red alder in a site II, coast Douglas-fir plantation.

    Treesearch

    Richard E. Miller; Edmund L. Obermeyer; Harry W. Anderson

    1999-01-01

    We varied the number of red alder retained with 300 Douglas-fir per acre on a high-quality site in coastal Oregon. Alder densities of 0, 20, 40, and 80 per acre were tested. Our fifth treatment eliminated nitrogen-fixing alder, but substituted nitrogen fertilizer. Treatment 6 had neither thinning nor alder control. Treatments were randomly assigned within each of three...

  17. Aminocatalytic asymmetric Diels-Alder reactions via HOMO activation.

    PubMed

    Li, Jun-Long; Liu, Tian-Yu; Chen, Ying-Chun

    2012-09-18

    In the first successful catalytic asymmetric Diels-Alder reaction in 1979, Koga and colleagues used a chiral aluminum complex as a Lewis acid catalyst, but since then, researchers have developed numerous catalytic systems for these reactions. By 2000, several chiral organic compounds, such as the salts of imidazolidinones or TADDOLs, emerged as robust catalysts in the asymmetric Diels-Alder reactions. According to frontier molecular orbital theory, most of these catalysts employ a LUMO-lowering strategy as a means of activating electron-deficient dienophiles. Only rarely do chiral catalysts take advantage of the alternative strategy of activating the HOMO. In this Account we will discuss the development of asymmetric Diels-Alder reactions based on the HOMO-raising effects of chiral amines. First, we show that enamine intermediates formed in situ between an amine catalyst and enolizable aliphatic aldehydes can act as electron-rich dienophiles in inverse-electron-demand Diels-Alder reactions. We describe the preparation of a variety of oxygen- or nitrogen-containing heterocycles with high optical purity. Then, we demonstrate that the dienamine species from α,β-unsaturated aldehydes can act either as electron-rich dienes in normal-electron-demand Diels-Alder reactions or as dienophiles in inverse-electron-demand Diels-Alder reactions. These reactions generally occur with high chemo-, regio-, and stereoselectivity. Finally, we introduce a new activation mode for Diels-Alder reactions, in which reactive trienamine intermediates derived from 2,4-dienals or even 2,4-dienones play a key role. Notably, we observe remarkable β,ε-regioselectivity and obtain excellent stereocontrol even at the very remote ε-reactive center-up to seven bonds away from the chiral center of the amine catalyst. These results demonstrate that a HOMO-activation strategy via aminocatalysis could become a significant tool in asymmetric Diels-Alder reactions. In addition, these reactions using

  18. Permuting Diels-Alder and Robinson Annulation Stereopatterns.

    PubMed

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

    2012-01-01

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

  19. Whole-brain grey matter density predicts balance stability irrespective of age and protects older adults from falling.

    PubMed

    Boisgontier, Matthieu P; Cheval, Boris; van Ruitenbeek, Peter; Levin, Oron; Renaud, Olivier; Chanal, Julien; Swinnen, Stephan P

    2016-03-01

    Functional and structural imaging studies have demonstrated the involvement of the brain in balance control. Nevertheless, how decisive grey matter density and white matter microstructural organisation are in predicting balance stability, and especially when linked to the effects of ageing, remains unclear. Standing balance was tested on a platform moving at different frequencies and amplitudes in 30 young and 30 older adults, with eyes open and with eyes closed. Centre of pressure variance was used as an indicator of balance instability. The mean density of grey matter and mean white matter microstructural organisation were measured using voxel-based morphometry and diffusion tensor imaging, respectively. Mixed-effects models were built to analyse the extent to which age, grey matter density, and white matter microstructural organisation predicted balance instability. Results showed that both grey matter density and age independently predicted balance instability. These predictions were reinforced when the level of difficulty of the conditions increased. Furthermore, grey matter predicted balance instability beyond age and at least as consistently as age across conditions. In other words, for balance stability, the level of whole-brain grey matter density is at least as decisive as being young or old. Finally, brain grey matter appeared to be protective against falls in older adults as age increased the probability of losing balance in older adults with low, but not moderate or high grey matter density. No such results were observed for white matter microstructural organisation, thereby reinforcing the specificity of our grey matter findings.

  20. Grey Literature and the Internet

    ERIC Educational Resources Information Center

    Hartman, Karen A.

    2006-01-01

    Accreditation standards for professional schools offering social work degrees mandate curriculum content that provides students with skills to analyze, formulate, and influence social policies. An important source of analytical thinking about social policy is the "grey" literature issued by public policy organizations, think tanks,…

  1. Grey Literature and the Internet

    ERIC Educational Resources Information Center

    Hartman, Karen A.

    2006-01-01

    Accreditation standards for professional schools offering social work degrees mandate curriculum content that provides students with skills to analyze, formulate, and influence social policies. An important source of analytical thinking about social policy is the "grey" literature issued by public policy organizations, think tanks,…

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

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

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

  3. Chemical composition and deer browsing of red alder foliage

    Treesearch

    M.A. Radwan; W.D. Ellis; G.L. Crouch

    1978-01-01

    Chemical factors suspected of influencing seasonal change in deer preference for red alder leaves were investigated. There were many differences in the leaves between seasons. It is postulated, however, that changes in contents of crude fat and total phenols were the important factors in increasing deer preference for the species from June to September.

  4. Diels-Alder Reactions of 1,2-Azaborines.

    PubMed

    Burford, Richard J; Li, Bo; Vasiliu, Monica; Dixon, David A; Liu, Shih-Yuan

    2015-06-26

    Diels-Alder reactions employing 1,2-azaborine heterocycles as 1,3-dienes are reported. Carbocyclic compounds with high stereochemical and functional complexity are produced, as exemplified by the straightforward two-step synthesis of an amino allyl boronic ester bearing four contiguous stereocenters as a single diastereomer. Whereas electron-deficient dienophiles undergo irreversible Diels-Alder reactions, a reversible Diels-Alder reaction with the less electron-deficient methyl acrylate is observed. Both the N and the B substituent of the 1,2-azaborine exert significant influence on the [4+2] cycloaddition reactivity as well as the aromatic character of the heterocycle. The experimentally determined thermodynamic parameters of the reversible Diels-Alder reaction between 1,2-azaborines and methyl acrylate correlate with aromaticity trends and place 1,2-azaborines approximately between furan and thiophene on the aromaticity scale. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. 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

  7. A method of site quality evaluation for red alder.

    Treesearch

    Constance A. Harrington

    1986-01-01

    A field guide to predict site index for red alder (Alnus rubra Bong.) was developed for use in western Washington and Oregon. The guide requires the user to evaluate 14 soil-site properties that are grouped into three general factors: (1) geographic and topographic position, (2) soil moisture and aeration during the growing season, and (3) soil fertility and physical...

  8. Take a Stand for Standing

    ERIC Educational Resources Information Center

    Labandz, Stephenie

    2010-01-01

    As a school-based physical therapist, the author sees children with a wide variety of diagnoses affecting their mobility and motor function. Supported standing is an important part of the routines of those who are unable to stand independently due to issues affecting the neuromuscular system. Being eye-to-eye with their peers and interacting with…

  9. Take a Stand for Standing

    ERIC Educational Resources Information Center

    Labandz, Stephenie

    2010-01-01

    As a school-based physical therapist, the author sees children with a wide variety of diagnoses affecting their mobility and motor function. Supported standing is an important part of the routines of those who are unable to stand independently due to issues affecting the neuromuscular system. Being eye-to-eye with their peers and interacting with…

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

    PubMed

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

    2017-04-11

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

  11. Multicomponent Diene-Transmissive Diels-Alder Sequences Featuring Aminodendralenes.

    PubMed

    Tan, Siu Min; Willis, Anthony C; Paddon-Row, Michael N; Sherburn, Michael S

    2016-02-24

    1-Aminodecalins were prepared from acyclic precursors by combining the powerful twofold diene-transmissive Diels-Alder chemistry of [3]dendralenes with the simplicity of enamine formation. On mixing at ambient temperature, a simple dienal condenses with a primary or secondary amine to generate the enamine, a 1-amino-[3]dendralene in situ, and this participates as a double diene in a sequence of two Diels-Alder events with separate dienophiles. Overall, four C-C bonds and one C-N bond are formed. Mechanistic insights into these reactions are provided by means of density functional theory calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. An antibody-catalyzed bimolecular Diels-Alder reaction

    SciTech Connect

    Braisted, A.C.; Schultz, P.G. )

    1990-09-26

    There exist over 1,500 known enzymes which carry out a vast array of chemical reactions with remarkable specificity and reaction rates. It is surprising then that there are no documented examples of enzyme-catalyzed pericyclic cycloaddition reactions, yet there are among the most powerful and commonly used reactions in synthetic organic chemistry. The most important of these is the Diels-Alder reaction of a diene with a dienophile, which provides a straightforward and highly stereospecific route to cyclohexene derivatives. Given the importance of this reaction in organic chemistry and its novel mechanism, it was of interest to ask whether a Diels-Alderase enzymatic catalyst could be evolved from an antibody combining site. Generation of antibodies to a structure that mimics the pericyclic transition state for a Diels-Alder reaction should result in an antibody combining site that lowers the entropy of activation {Delta}S{sup {double dagger}} by binding both the diene and the dienophile in a reactive conformation. The authors approach toward the design of a transition-state analogue involves incorporation of an ethano bridge, which locks the cyclohexene ring of hapten in a conformation that resembles the proposed pericyclic transition state for the Diels-Alder reaction of cisoid diene with dienophile. The authors now report that antibodies generated to the transition-state analogue catalyze the addition of the acyclic water-soluble diene to the maleimide derivative to give the cyclohexene product.

  13. Inverse Electron-Demand Diels-Alder Bioorthogonal Reactions.

    PubMed

    Wu, Haoxing; Devaraj, Neal K

    2016-02-01

    Bioorthogonal reactions have been widely used over the last 10 years for imaging, detection, diagnostics, drug delivery, and biomaterials. Tetrazine reactions are a recently developed class of inverse electron-demand Diels-Alder reactions used in bioorthogonal applications. Given their rapid tunable reaction rate and highly fluorogenic properties, tetrazine bioorthogonal reactions have come to be considered highly attractive tools for elucidating biological functions and messages in vitro and in vivo. In this chapter, we present recent advances expanding the scope of precursor reactivity and we introduce new biomedical methodology based on bioorthogonal tetrazine chemistry. We specifically highlight novel applications for different kinds of biomolecules, including nucleic acid, protein, antibodies, lipids, glycans, and bioactive small molecules, in the areas of imaging, detection, and diagnostics. We also briefly present other recently developed inverse electron-demand Diels-Alder bioorthogonal reactions. Lastly, we consider future directions and potential roles that inverse electron-demand Diels-Alder reactions may play in the fields of bioorthogonal and biomedical chemistry.

  14. Acquired ciliary circumscribed grey hair (ACCG).

    PubMed

    Romero, A G; Calatayud, J C

    2001-12-01

    Grey-haired areas usually occur due to aging or inheritance. A case is described of abrupt occurrence of a focal circumscribed grey-hair in the eyebrow region (a single hair) in a 27-year-old woman. The phenomenon was named acquired ciliary circumscribed grey-hair (ACCG). Qualitative and semiquantitative findings were obtained by microanalytical studies. In addition to morphological differences from control hair, the ACCG hair showed a high percentage of sulfur (99.8%) and absence of oligoelements.

  15. 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

  16. 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.

  17. Climate sensitivity of thinleaf alder growth on an interior Alaska floodplain

    Treesearch

    Dana R. Nossov; Roger W. Ruess; Teresa N. Hollingsworth

    2010-01-01

    This study examined the climate sensitivity of the growth of riparian Alnus incana ssp. tenuifolia (thinleaf alder), a keystone nitrogen-fixer, on the Tanana River floodplain of interior Alaska. We investigated correlations between alder radial growth and inter-annual variation in monthly meteorology and hydrology, spatial...

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

    PubMed

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

    2013-10-07

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

  19. Alder (Alnus crispa) effects on soils in ecosystems of the Agashashok River valley, northwest Alaska

    USGS Publications Warehouse

    Rhoades, Charles; Oskarsson, Hlynur; Binkley, Dan; Stottlemeyer, Robert

    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 occurred 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.

  20. Growth response of speckled alder and willow to depth of flooding

    Treesearch

    M. Dean Knighton

    1981-01-01

    Growth and survival of speckled alder and willow were determined for two growing seasons with continuous flooding at different depths. Growth was at least four times greater when the water table was below the root crown than when it was 15 cm above. Mortality increased with flooding depth and as greatest for alder.

  1. Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds

    DOE PAGES

    Settle, Amy E.; Berstis, Laura; Rorrer, Nicholas A.; ...

    2017-05-17

    In this tutorial review, we provide an overview of heterogeneous Diels–Alder catalysis for the production of lignocellulosic biomass-derived aromatic compounds. Diels–Alder reactions afford an extremely selective and efficient route for carbon–carbon cycloadditions to produce intermediates that can readily undergo subsequent dehydration or dehydrogenation reactions for aromatization. As a result, catalysis of Diels–Alder reactions with biomass-derived dienes and dienophiles has seen a growth of interest in recent years; however, significant opportunities remain to (i) tailor heterogeneous catalyst materials for tandem Diels–Alder and aromatization reactions, and (ii) utilize biomass-derived dienes and dienophiles to access both conventional and novel aromatic monomers. As such,more » this review discusses the mechanistic aspects of Diels–Alder reactions from both an experimental and computational perspective, as well as the synergy of Brønsted–Lewis acid catalysts to facilitate tandem Diels–Alder and aromatization reactions. Heterogeneous catalyst design strategies for Diels–Alder reactions are reviewed for two exemplary solid acid catalysts, zeolites and polyoxometalates, and recent efforts for targeting direct replacement aromatic monomers from biomass are summarized. In conclusion, we point out important research directions for progressing Diels–Alder catalysis to target novel, aromatic monomers with chemical functionality that enables new properties compared to monomers that are readily accessible from petroleum.« less

  2. Red alder kitchen cabinets—How does application of commercial stains influence customer choice?

    Treesearch

    David Nicholls; Joseph. Roos

    2007-01-01

    A better understanding of consumer reaction and preferences for red alder (Alnus rubra Bong.) secondary products will help Alaska producers in entering new markets. In this study, red alder kitchen cabinets were commercially stained to six different levels and displayed at home shows in Portland, Oregon, and Anchorage, Alaska. The stains simulated...

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

    USDA-ARS?s Scientific Manuscript database

    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 ...

  4. Interactions between white spruce and shrubby alders at three boreal forest sites in Alaska.

    Treesearch

    Tricia L. Wurtz

    2000-01-01

    To document possible soil nitrogen mosaics before timber harvesting on three boreal forest sites in Alaska, maps of the distribution of understory green (Alnus crispa (Ait.) Pursh) and Sitka alder (A. sitchensis(Reg.) Rydb.) stems were made. Understory alders were regularly distributed throughout the northernmost site (Standard...

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

    PubMed Central

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

    2012-01-01

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

  6. Growth and Survival of Hardwoods and Pine Interplanted with European Alder

    Treesearch

    William T. Plass

    1977-01-01

    European black alder is recommended for planting on many surface mine spoils in the eastern United States. It grows rapidly on a range of spoil types and contributes to soil enrichment by fixing nitrogen and providing a leaf fall rich in nutrients. This study evaluated the effect of alder on the survival and growth of five hardwood and five pine species. After 10...

  7. Locating grey literature on communication disorders.

    PubMed

    Shpilko, Inna

    2005-01-01

    This article provides an overview of selected Web-based resources containing grey literature in the area of communication disorders. It is geared to practitioners, researchers, students, and consumers seeking reliable, freely available scientific information. Grey (or gray) literature has been defined as "that which is produced on all levels of government, academics, business, and industry in print and electronic formats, but which is not controlled by commercial publishers."1 This paper reviews various general reference sources potentially containing grey literature on communication disorders. This review includes identification of the methods specialists in this field use to obtain this valuable, yet often overlooked, literature. Access points and search tools for identifying grey literature on communication disorders are recommended. Commercial databases containing grey literature are not included. Conclusions presented in this article are considered complementary to traditionally published information resources on communication disorders, such as scholarly journals, online databases, etc.

  8. Berni Alder and Phase Transitions in Two Dimensions

    NASA Astrophysics Data System (ADS)

    Kosterlitz, J. Michael

    I do not know Berni Alder as a person, but I feel that I know him well through his seminal paper "Phase Transition in Elastic Disks𠇍 by B. J. Alder and T. E. Wainwright [1962], which was essential in motivating David Thouless and myself to think about phase transitions in two dimensional systems with a continuous symmetry. In the early 1970's, the conventional wisdom was that a crystalline solid could not exist in a two dimensional world because of the rigorous Mermin-Wagner theorem prohibiting true long range translational order at any non-zero temperature. This contradiction was settled by the theory of dislocation mediated melting to an intermediate hexatic phase followed by a second transition to the isotropic fluid at a higher temperature. This scenario, with its associated sophisticated theory, seemed to settle the controversy of two dimensional melting once and for all. However, in our elation at understanding the fundamental physics and the essential excitations of melting in 2D, we had all forgotten that the early work of Berni Alder also showed that this melting involved a weak first order transition while theory now predicted melting by two successive continuous transitions with no discontinuity in area at the critical pressure. This discrepancy could be hand waved away by arguing that Berni's system was far too small and his computers far too slow so that the areal discontinuity could be due to finite size effects or to failing to equilibrate the system. Experiments were not able to resolve the order of the transitions, but seemed to agree quantitatively with theory…

  9. Diels-Alder reactions onto fluorinated and hydrogenated graphene

    NASA Astrophysics Data System (ADS)

    Denis, Pablo A.

    2017-09-01

    We studied Diels-Alder (DA) reactions onto functionalized graphene. When fluorine, hydrogen or oxygen functional groups are present on one side of the sheet, the DA cycloadditions become significantly more exergonic when performed on the opposite side. Hydrogen is more effective than fluorine and oxygen to promote these cycloadditions. In contrast with the results obtained for perfect graphene, the functionalization with H, F or O turns the DA reactions exergonic, with ΔG°298 = -127.2 kcal/mol. The reaction barriers are expected to be considerably lowered with respect to perfect graphene because the functional groups significantly reduce the distortion energy.

  10. Storing solar energy by liquid phase Diels-Alder reactions

    SciTech Connect

    Sparks, B.G.; Thompson, P.F.; Poling, B.E.

    1981-01-01

    Using chemical reactions to store energy is not a new concept. But the idea of using chemical reactions entirely in the liquid phase at low temperatures for relatively small scale storage applications, i.e., for space heating, is relatively undeveloped. In this study, the method of how chemical reactions could be used to store energy without generation and storage of new phases is described. Criteria a reaction must satisfy to successfully store energy are presented and several Diels-Alder reactions are evaluated in terms of these criteria. All this time, no reactions have been identified that meet all the criteria. 6 refs.

  11. Hetero-Diels-Alder approach to Bis(indolyl)methanes.

    PubMed

    Grosso, Carla; Cardoso, Ana L; Rodrigues, Maria João; Marques, Cátia; Barreira, Luísa; Lemos, Américo; Pinho E Melo, Teresa M D V

    2017-02-01

    A novel synthetic approach to bis(indolyl)methanes has been established. Our one-pot synthetic strategy based on two consecutive hetero-Diels-Alder cycloaddition reactions of electrophilic conjugated nitrosoalkenes with indoles was extended to a range of new 1-hydroxyiminomethyl-bis(indolyl)methanes. Furthermore, a similar and broad range approach was applied to the synthesis of previously unknown 1-hydrazonomethyl-bis(indolyl)methanes. The biological evaluation of the new bis(indolyl)methanes as anti-cancer agents was investigated. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Effect of Grey Hair Evulsion on the Response to Calcium Pantothenate in Premature Grey Hairs.

    PubMed

    Pasricha, J S

    1986-01-01

    Thirty nine girls between 12 and 31 years in age, having Premature grey hairs were, treated with calcium pantothenate 200 mg, Basiton Forte. (a vitamin B complex formulation), and/or vitamin E 200 mg a day orally, combined with grey hair evulsion which consists of pulling out all the grey hairs along with snipping the converted hairs at the grey black junction, and checking after 3-5 months, the numbers of hairs regrowing as grey hairs, new grey hairs, new converted hairs and the hairs missed during the previous check - ups. This study revealed that following evulsion of grey hairs, all such hairs do not regrow as grey hairs, the per cent rate of regrowth varied between nil and 88.23% during the first recheck, and almost similar results were obtained during further follow up. Out of 7 patients who have been followed up for almost 3 years, the total numbers of grey hairs had decreased from 109 to 15, 47 to 1, 35 to 7, and 242 to 7 in 4 cases, increased from 31 to 108 and 23 to 41 in 2 cases, and remained almost unchanged from 25 to 33 in the seventh case. This response is considered better than the effect of calcium panthothenate used without grey hair evulsion.

  13. Anion-π Catalysis of Diels-Alder Reactions.

    PubMed

    Liu, Le; Cotelle, Yoann; Bornhof, Anna-Bea; Besnard, Céline; Sakai, Naomi; Matile, Stefan

    2017-09-08

    Among concerted cycloadditions, the Diels-Alder reaction is the grand old classic, which is usually achieved with acid catalysis. In this report, hydroxypyrones, oxa-, and thiazolones are explored because they provide access to anionic dienes. Their [4+2] cycloaddition with cyclic and acyclic dienophiles, such as maleimides and fumarates, affords bicyclic products with four new stereogenic centers. Bifunctional anion-π catalysts composed of amine bases next to the π surface of naphthalenediimides (NDIs) are shown to selectively stabilize the "open", fully accessible anionic exo transition state on the π-acidic aromatic surface. Our results also include reactivities that are hard to access with conventional organocatalysts, such as the exo-specific and highly enantioselective Diels-Alder reaction of thiazolones and maleimides with complete suppression of the otherwise dominant Michael addition. With increasing π acidity of the anion-π catalysts, the rates, chemo-, diastereo-, and enantioselectivities increase consistently. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 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.

  15. Puvasol Therapy in Premature Greying of Hair.

    PubMed

    Pavithran, K

    1986-01-01

    Accidental observation of cure of premature greying in a patient who had lten on PUVASOL therapy for psoriasis made the author to try this form of therapy in 37 patients with premature greying. Majority (59.09%) of the patients were aged between 10 and 15 years. Complete repigmentation of the hairs was noted in 17 patients after treatment. Seven patients responded only partially, and in 8 there was no response at all.

  16. Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction.

    PubMed

    Siegel, Justin B; Zanghellini, Alexandre; Lovick, Helena M; Kiss, Gert; Lambert, Abigail R; St Clair, Jennifer L; Gallaher, Jasmine L; Hilvert, Donald; Gelb, Michael H; Stoddard, Barry L; Houk, Kendall N; Michael, Forrest E; Baker, David

    2010-07-16

    The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond-forming reactions should be broadly useful in synthetic chemistry.

  17. Disturbed grey matter coupling in schizophrenia.

    PubMed

    Collin, Guusje; de Reus, Marcel A; Cahn, Wiepke; Hulshoff Pol, Hilleke E; Kahn, René S; van den Heuvel, Martijn P

    2013-01-01

    In schizophrenia, grey matter deficits have been shown for many regions throughout the brain. These regions do not operate in isolation. Rather, they form a structural network of interconnected grey matter regions. To examine the mutual dependence of brain regions, this study investigated interregional coupling in lobar and regional grey matter volumes obtained from 146 schizophrenia patients and 122 healthy comparison subjects. Compared to healthy controls, schizophrenia patients showed both decreased (e.g. between left frontal and bilateral subcortical, p≤0.005) and increased (e.g. between left temporal and bilateral subcortical, p≤0.001) coupling between lobar grey matter volumes. On a regional scale, decreased coupling was most pronounced between fronto-parietal cortical regions and subcortical structures, and between frontal and occipital regions. In addition, an increased association was found among frontal and limbic regions, and for temporo-occipital connexions. Consistent with dysconnectivity theories of schizophrenia, impaired grey matter coupling may be reflective of reduced integrity of the brain's network. Furthermore, as cross-sectional volumetric coupling is indicative of maturational coupling, aberrant grey matter coupling may be a marker of neurodevelopmental abnormalities in schizophrenia.

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

    PubMed Central

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

    2009-01-01

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

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

    PubMed

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

    2012-06-07

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

  20. Mechanistic insight on the Diels-Alder reaction catalyzed by a self-assembled molecular capsule.

    PubMed

    Xu, Lina; Hua, Weijie; Hua, Shugui; Li, Jun; Li, Shuhua

    2013-04-19

    We combined Monte Carlo simulations and density functional theory calculations to study the mechanism of the Diels-Alder reaction of p-quinone and cyclohexadiene catalyzed by a self-assembled molecular capsule. Our calculations show that the encapsulation of the reactants into the cage is driven by hydrogen-bonding interactions and π-π stacking interactions between two reactants and the capsule. The encapsulated Diels-Alder reaction at different locations inside the capsule may have quite different reactivity due to different guest-host interactions. A comparison of the free energy profiles of the Diels-Alder reaction in the capsule and in the bulk solution reveals that the Diels-Alder reaction in the capsule is accelerated because the host-guest interaction leads to a relatively smaller barrier for the cycloaddition step.

  1. The asymmetric hetero-Diels-Alder reaction in the syntheses of biologically relevant compounds.

    PubMed

    Eschenbrenner-Lux, Vincent; Kumar, Kamal; Waldmann, Herbert

    2014-10-13

    The hetero-Diels-Alder reaction is one of the most powerful transformations in the chemistry toolbox for the synthesis of aza- and oxa-heterocycles embodying multiple stereogenic centers. However, as compared to other cycloadditions, in particular the dipolar cycloadditions and the Diels-Alder reaction, the hetero-Diels-Alder reaction has been much less explored and exploited in organic synthesis. Nevertheless, this powerful transformation has opened up efficient and creative routes to biologically relevant small molecules and different natural products which contain six-membered oxygen or nitrogen ring systems. Recent developments in this field, in particular in the establishment of enantioselectively catalyzed hetero-Diels-Alder cycloadditions steered by a plethora of different catalysts and the application of the resulting small molecules in chemical biology and medicinal chemistry research, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis of Polycyclic Nitrogen Heterocycles via Cascade Pd-Catalyzed Alkene Carboamination/Diels-Alder Reactions.

    PubMed

    White, Derick R; Wolfe, John P

    2015-05-15

    Cascade Pd-catalyzed alkene carboamination/Diels-Alder reactions between bromodienes and amines bearing two pendant alkenes are described. These transformations generate 4 bonds, 3 rings, and 3-5 stereocenters to afford polycyclic nitrogen heterocycles with high diastereoselectivity.

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

    PubMed

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

    2011-01-01

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

  4. Research and Application for Grey Relational Analysis in Multigranularity Based on Normality Grey Number

    PubMed Central

    Liu, Xin; Hu, Feng

    2014-01-01

    Grey theory is an essential uncertain knowledge acquisition method for small sample, poor information. The classic grey theory does not adequately take into account the distribution of data set and lacks the effective methods to analyze and mine big sample in multigranularity. In view of the universality of the normal distribution, the normality grey number is proposed. Then, the corresponding definition and calculation method of the relational degree between the normality grey numbers are constructed. On this basis, the grey relational analytical method in multigranularity is put forward to realize the automatic clustering in the specified granularity without any experience knowledge. Finally, experiments fully prove that it is an effective knowledge acquisition method for big data or multigranularity sample. PMID:24701157

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

    NASA Astrophysics Data System (ADS)

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

    2001-09-01

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

  6. Early survival and growth of planted Douglas-fir with red alder in four mixed regimes.

    Treesearch

    Marshall D. Murray; Richard E. Miller

    1986-01-01

    To quantify between-species interactions, we measured and compared survival and growth of planted Douglas-fir and associated planted and volunteer red alder at a location on the west side of the Cascade Range in Washington. The planted alder were wildlings dug either from a nearby area or from a distant, coastal site and interplanted into a 3-year-old Douglas-fir...

  7. Enantioselective and regioselective pyrone Diels-Alder reactions of vinyl sulfones: total synthesis of (+)-cavicularin.

    PubMed

    Zhao, Peng; Beaudry, Christopher M

    2014-09-22

    The total synthesis of (+)-cavicularin is described. The synthesis features an enantio- and regioselective pyrone Diels-Alder reaction of a vinyl sulfone to construct the cyclophane architecture of the natural product. The Diels-Alder substrate was prepared by a regioselective one-pot three-component Suzuki reaction of a non-symmetric dibromoarene. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A preliminary study of the deterioration of alder and Douglas-fir chips in outdoor piles.

    Treesearch

    Ernest. Wright

    1954-01-01

    In the fall of 1952, E. E. Matson of the Pacific Northwest Forest and Range Experiment Station learned that the Fir-Tex Insulating Board Company bf St. Helens, Oregon was considering mixing alder with Douglas-fir chips for outside storage. Since alder heartwood i s more susceptible to decay than that of Douglas-fir, the question arose whether mixing the two might...

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

    PubMed

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

    2011-05-07

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

  10. Spinal cord grey matter segmentation challenge.

    PubMed

    Prados, Ferran; Ashburner, John; Blaiotta, Claudia; Brosch, Tom; Carballido-Gamio, Julio; Cardoso, Manuel Jorge; Conrad, Benjamin N; Datta, Esha; Dávid, Gergely; Leener, Benjamin De; Dupont, Sara M; Freund, Patrick; Wheeler-Kingshott, Claudia A M Gandini; Grussu, Francesco; Henry, Roland; Landman, Bennett A; Ljungberg, Emil; Lyttle, Bailey; Ourselin, Sebastien; Papinutto, Nico; Saporito, Salvatore; Schlaeger, Regina; Smith, Seth A; Summers, Paul; Tam, Roger; Yiannakas, Marios C; Zhu, Alyssa; Cohen-Adad, Julien

    2017-03-07

    An important image processing step in spinal cord magnetic resonance imaging is the ability to reliably and accurately segment grey and white matter for tissue specific analysis. There are several semi- or fully-automated segmentation methods for cervical cord cross-sectional area measurement with an excellent performance close or equal to the manual segmentation. However, grey matter segmentation is still challenging due to small cross-sectional size and shape, and active research is being conducted by several groups around the world in this field. Therefore a grey matter spinal cord segmentation challenge was organised to test different capabilities of various methods using the same multi-centre and multi-vendor dataset acquired with distinct 3D gradient-echo sequences. This challenge aimed to characterize the state-of-the-art in the field as well as identifying new opportunities for future improvements. Six different spinal cord grey matter segmentation methods developed independently by various research groups across the world and their performance were compared to manual segmentation outcomes, the present gold-standard. All algorithms provided good overall results for detecting the grey matter butterfly, albeit with variable performance in certain quality-of-segmentation metrics. The data have been made publicly available and the challenge web site remains open to new submissions. No modifications were introduced to any of the presented methods as a result of this challenge for the purposes of this publication.

  11. 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.

  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. 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.

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

    PubMed

    Cantín, Ángel; Gomez, M Victoria; de la Hoz, Antonio

    2016-01-01

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

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

    PubMed Central

    Cantín, Ángel

    2016-01-01

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

  16. ELECTROMAGNETISM, OPTICS, ACOUSTICS, HEAT TRANSFER, CLASSICAL MECHANICS, AND FLUID DYNAMICS: Incoherently Coupled Grey-Grey Spatial Soliton Pairs in Biased Two-Photon Photovoltaic Photorefractive Crystals

    NASA Astrophysics Data System (ADS)

    Su, Yan-Li; Jiang, Qi-Chang; Ji, Xuan-Mang

    2010-05-01

    The incoherently coupled grey-grey screening-photovoltaic spatial soliton pairs are predicted in biased two-photon photovoltaic photorefractive crystals under steady-state conditions. These grey-grey screening-photovoltaic soliton pairs can be established provided that the incident beams have the same polarization, wavelength, and are mutually incoherent. The grey-grey screening-photovoltaic soliton pairs can be considered as the united form of grey-grey screening soliton pairs and open or closed-circuit grey-grey photovoltaic soliton pairs.

  17. Tularemia without lesions in grey tree squirrels: A diagnostic challenge

    USDA-ARS?s Scientific Manuscript database

    Fifteen cases of Francisella tularenesis infection (tularemia) were identified in western grey (Sciurus griseus) and eastern grey (Sciurus carolinesis) squirrels submitted to the Washington Animal Disease Diagnostic Laboratory between 2008 and 2011. All of the squirrels originated in Washington stat...

  18. 36. LARGE MOLD MAKING MACHINE, GREY IRON UNIT #4 SHOWING ...

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

    36. LARGE MOLD MAKING MACHINE, GREY IRON UNIT #4 SHOWING PATTERNS THAT FLASKS FIT OVER PRIOR TO BEING FILLED WITH SAND AND COMPRESSED. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  19. 40. THIS TUMBLING MILL IN THE GREY IRON FOUNDRY IS ...

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

    40. THIS TUMBLING MILL IN THE GREY IRON FOUNDRY IS USED TO TUMBLE CASTINGS OVER EACH OTHER TO BREAK OFF RUNNERS AND SPRUES. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  20. 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. © 2014 John Wiley & Sons Ltd.

  1. Diels-Alder mediated controlled release from a poly(ethylene glycol) based hydrogel.

    PubMed

    Koehler, Kenneth Christopher; Anseth, Kristi S; Bowman, Christopher N

    2013-02-11

    A synthetic amino acid bearing a furan functionality was developed and incorporated into peptide sequences using solid phase synthesis. Peptides expressing the furan moiety were attached to poly(ethylene glycol) (PEG) hydrogels through a thermally reversible covalent bond formed by a Diels-Alder reaction. Reactions of thiol and maleimide PEG macromers in an off-stoichiometric Michael addition were performed, such that the maleimide moiety was in excess, to create hydrogel networks with pendant Diels-Alder compatible tethering sites, that is, the maleimide. By making use of the Diels-Alder reaction, it was possible to control the release rate of reversibly bound moieties from the hydrogel by changing the temperature; higher temperatures favor a faster retro-Diels-Alder reaction and, therefore, a faster release from the polymer network. This concept was demonstrated by incorporating a fluorescently labeled furan-RGDS sequence into a hydrogel possessing excess maleimide functionalities and monitoring the subsequent liberation of RGDS at various temperatures, illustrating a Diels-Alder mediated release mechanism. The release profile was quantified at temperatures ranging from physiological (37 °C) to 80 °C. By changing the temperature, varying extents of release were attained over the time course of several days, ranging from 40% release for lower temperatures to complete release for the highest temperature considered. Further confirmation of a reaction-diffusion controlled release mechanism was obtained through comparison of experimental release data to a reaction-diffusion model of the release. In addition to thermal modulation, tuning of the release rate was accomplished by altering the number of possible Diels-Alder tethering sites present in the hydrogel. Increasing the amount of free maleimide and, therefore, the number of potential Diels-Alder reaction sites, effectively slowed the release of peptide from the polymer. For instance, doubling the amount of

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

    PubMed

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

    2016-11-01

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

  3. Grey matter atrophy in patients suffering from multiple sclerosis.

    PubMed

    Kincses, Zsigmond Tamás; Tóth, Eszter; Bankó, Nóra; Veréb, Dániel; Szabó, Nikoletta; Csete, Gergő; Faragó, Péter; Király, András; Bencsik, Krisztina; Vécsei, László

    2014-09-30

    White matter lesions are defining characteristics of multiple sclerosis (MS), whereas grey matter involvement is a less recognised attribute. Recent investigations using dedicated imaging approaches have made it possible to depict cortical lesions. Additionally, grey matter atrophy may be estimated using various methods. Several studies have suggested that grey matter atrophy closely correlates to clinical disability. In this review we have collected information on grey matter atrophy in MS and the effect of disease modifying therapies upon brain atrophy.

  4. Searching for Grey Literature for Systematic Reviews: Challenges and Benefits

    ERIC Educational Resources Information Center

    Mahood, Quenby; Van Eerd, Dwayne; Irvin, Emma

    2014-01-01

    There is ongoing interest in including grey literature in systematic reviews. Including grey literature can broaden the scope to more relevant studies, thereby providing a more complete view of available evidence. Searching for grey literature can be challenging despite greater access through the Internet, search engines and online bibliographic…

  5. 23. INTERIOR VIEW WITH UNIT NO. 2 GREY IRON DISAMATIC ...

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

    23. INTERIOR VIEW WITH UNIT NO. 2 GREY IRON DISAMATIC SETTING A 1 X 1/2 INCH ELBOW PIPE FITTING, A 'GREY IRON EL'. THIS MACHINE SETS CORES THROUGH AN AUTOMATED PROCESS. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  6. NORTHEAST VIEW OF FOUNDRY FROM TOP OF GREY IRON CUPOLA ...

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

    NORTHEAST VIEW OF FOUNDRY FROM TOP OF GREY IRON CUPOLA SHOWING CORE ROOM ROOF DIRECTLY NORTHEAST, GREY IRON FOUNDRY TO THE RIGHT, MALLEABLE IRON CUPOLAS AND FOUNDRY NORTHEAST OF GREY IRON FOUNDRY WITH THE BRASS FOUNDRY IN THE REAR. - Stockham Pipe & Fittings Company, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  7. 24. INTERIOR VIEW WITH UNIT NO. 2 GREY IRON DISAMATIC ...

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

    24. INTERIOR VIEW WITH UNIT NO. 2 GREY IRON DISAMATIC SETTING A 1 X 1/2 INCH ELBOW PIPE FITTING, A 'GREY IRON EL', THROUGH AN AUTOMATED PROCESS. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  8. Grey Documentation as a Knowledge Base in Social Work.

    ERIC Educational Resources Information Center

    Berman, Yitzhak

    1994-01-01

    Defines grey documentation as documents issued informally and not available through normal channels and discusses the role that grey documentation can play in the social work knowledge base. Topics addressed include grey documentation and science; social work and the empirical approach in knowledge development; and dissemination of grey…

  9. 78 FR 17183 - Information Collection: Grey Towers Visitor Comment Card

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-03-20

    ... Forest Service Information Collection: Grey Towers Visitor Comment Card AGENCY: Forest Service, USDA... collection 0596- 0222, ``Grey Towers Visitor Comment Card'' with 0596-0226, ``Forest Service Generic... addressed to Nicole Bernarsky, USDA Forest Service, Grey Towers National Historic Site, P.O. Box...

  10. Searching for Grey Literature for Systematic Reviews: Challenges and Benefits

    ERIC Educational Resources Information Center

    Mahood, Quenby; Van Eerd, Dwayne; Irvin, Emma

    2014-01-01

    There is ongoing interest in including grey literature in systematic reviews. Including grey literature can broaden the scope to more relevant studies, thereby providing a more complete view of available evidence. Searching for grey literature can be challenging despite greater access through the Internet, search engines and online bibliographic…

  11. Knowledge Transfer in Social Work: The Role of Grey Documentation.

    ERIC Educational Resources Information Center

    Berman, Yitzhak

    1995-01-01

    Discusses scholarly journals in the field of social work, information sources for social work practitioners versus researchers, and grey documentation as an alternative means of knowledge transfer. Highlights include research versus practice; grey documentation and scientific credibility; and dissemination of grey literature. (LRW)

  12. Quantifying Possible Routes for SpnF-Catalyzed Formal Diels-Alder Cycloaddition.

    PubMed

    Medvedev, Michael G; Zeifman, Alexey A; Novikov, Fedor N; Bushmarinov, Ivan S; Stroganov, Oleg V; Titov, Ilya Yu; Chilov, Ghermes G; Svitanko, Igor V

    2017-03-22

    The Diels-Alder reaction is a cornerstone of modern organic synthesis. Despite this, it remains essentially inaccessible to biosynthetic approaches. Only a few natural enzymes catalyze even a formal [4 + 2] cycloaddition, and it remains uncertain if any of them proceed via the Diels-Alder mechanism. In this study, we focus on the [4 + 2] cycloaddition step in the biosynthesis of spinosyn A, a reaction catalyzed by SpnF enzyme, one of the most promising "true Diels-Alderase" candidates. The four currently proposed mechanisms (including the Diels-Alder one) for this reaction in water (as a first-order approximation of the enzymatic reaction) are evaluated by an exhaustive quantum mechanical search for possible transition states (728 were found in total). We find that the line between the recently proposed bis-pericyclic [J. Am. Chem. Soc. 2016, 138 (11), 3631] and Diels-Alder routes is blurred, and favorable transition states of both types may coexist. Application of the Curtin-Hammett principle, however, reveals that the bis-pericyclic mechanism accounts for ∼83% of the reaction flow in water, while the classical Diels-Alder mechanism contributes only ∼17%. The current findings provide a route for modeling this reaction inside the SpnF active site and inferring the catalytic architecture of possible Diels-Alderases.

  13. Diels-Alder reactions of inert aromatic compounds within a self-assembled coordination cage.

    PubMed

    Horiuchi, Shinnosuke; Murase, Takashi; Fujita, Makoto

    2011-07-04

    A self-assembled coordination cage serves as a nanometer-sized molecular flask to promote the Diels-Alder reactions of aromatic hydrocarbons with N-cyclohexylmaleimide. The coordination cage accelerated the Diels-Alder reaction of anthracene at the electronically unfavorable, terminal benzene ring to give a compact, cavity-restrained syn-adduct. Activation-parameter measurements for the reactions revealed considerable reduction in the entropy cost, and preorganization of the substrates is a dominant factor in the enhanced reactivity. Owing to this entropy-cost reduction, otherwise-unreactive aromatic compounds, such as naphthalenes or triphenylene, also underwent Diels-Alder reactions in a regio- and stereocontrolled fashion. In the naphthalene Diels-Alder reaction, X-ray crystallographic analysis of the guest-inclusion complex clarified the reinforced orientation and proximity of the substrate pairs before the reaction. A perylene Diels-Alder adduct was stabilized inside the cage and protected from aerial oxidation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Reaction energetics on long-range corrected density functional theory: Diels-Alder reactions.

    PubMed

    Singh, Raman K; Tsuneda, Takao

    2013-02-15

    The possibility of quantitative reaction analysis on the orbital energies of long-range corrected density functional theory (LC-DFT) is presented. First, we calculated the Diels-Alder reaction enthalpies that have been poorly given by conventional functionals including B3LYP functional. As a result, it is found that the long-range correction drastically improves the reaction enthalpies. The barrier height energies were also computed for these reactions. Consequently, we found that dispersion correlation correction is also crucial to give accurate barrier height energies. It is, therefore, concluded that both long-range exchange interactions and dispersion correlations are essentially required in conventional functionals to investigate Diels-Alder reactions quantitatively. After confirming that LC-DFT accurately reproduces the orbital energies of the reactant and product molecules of the Diels-Alder reactions, the global hardness responses, the halves of highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, along the intrinsic reaction coordinates of two Diels-Alder reactions were computed. We noticed that LC-DFT results satisfy the maximum hardness rule for overall reaction paths while conventional functionals violate this rule on the reaction pathways. Furthermore, our results also show that the HOMO-LUMO gap variations are close to the reaction enthalpies for these Diels-Alder reactions. Based on these results, we foresee quantitative reaction analysis on the orbital energies. Copyright © 2012 Wiley Periodicals, Inc.

  15. Standing footprint diagnostic method

    NASA Astrophysics Data System (ADS)

    Fan, Y. F.; Fan, Y. B.; Li, Z. Y.; Newman, T.; Lv, C. S.; Fan, Y. Z.

    2013-10-01

    Center of pressure is commonly used to evaluate standing balance. Even though it is incomplete, no better evaluation method has been presented. We designed our experiment with three standing postures: standing with feet together, standing with feet shoulder width apart, and standing with feet slightly wider than shoulder width. Our platform-based pressure system collected the instantaneous plantar pressure (standing footprint). A physical quantity of instantaneous standing footprint principal axis was defined, and it was used to construct an index to evaluate standing balance. Comparison between results from our newly established index and those from the center of pressure index to evaluate the stability of different standing postures revealed that the standing footprint principal axis index could better respond to the standing posture change than the existing one. Analysis indicated that the insensitive response to the relative position between feet and to the standing posture change from the center of pressure could be better detected by the standing footprint principal axis index. This predicts a wide application of standing footprint principal axis index when evaluating standing balance.

  16. Grey matter heterotopia: an unusual association of intractable epilepsy.

    PubMed

    Stafford Johnson, D B; Brennan, P; Dwyer, A J; Toland, J

    1997-01-01

    Heterotopic grey matter is an abnormality of neuronal migration that has been reported in association with refractory epilepsy. In this study we reviewed the magnetic resonance (MR) imaging records of all patients undergoing MR scanning for evaluation of intractable epilepsy and identified sixteen patients who had grey matter heterotopia. The distribution of the grey matter heterotopia was periventricular in 9 patients, laminar in 3 and was in a "band" form in 4 patients. Congenital anomalies associated with grey matter heterotopia in this study included polymicrogyria in one patient and absence of the corpus callosum in 2 patients. Grey matter heterotopia is an important MR finding in patients with intractable epilepsy.

  17. Evaluation of appropriate technologies for grey water treatments and reuses.

    PubMed

    Li, Fangyue; Wichmann, Knut; Otterpohl, Ralf

    2009-01-01

    As water is becoming a rare resource, the onsite reuse and recycling of grey water is practiced in many countries as a sustainable solution to reduce the overall urban water demand. However, the lack of appropriate water quality standards or guidelines has hampered the appropriate grey water reuses. Based on literature review, a non-potable urban grey water treatment and reuse scheme is proposed and the treatment alternatives for grey water reuse are evaluated according to the grey water characteristics, the proposed standards and economical feasibility.

  18. Character-marked furniture made from red alder harvested in southeast Alaska: product perspectives from consumers and retailers

    Treesearch

    Matthew Bumgardner; David Nicholls; Valerie Barber

    2009-01-01

    In recent decades. red alder (Alnus rubra Bong.) has become an important Pacific Northwest hardwood in appearance-grade lumber markets, such as exports, furniture, and cabinets. However, red alder generally is a short-lived pioneer species, and small logs can result in proportionally large volumes of lower grade lumber containing numerous visual...

  19. Character-marked furniture made from red alder harvested in southeast Alaska: product perspectives from consumers and retailers

    Treesearch

    Matthew Bumgardner; Nicholls David; Valerie Barber

    2009-01-01

    In recent decades, red alder (Alnus rubra Bong.) has become an important Pacific Northwest hardwood in appearance-grade lumber markets, such as exports, furniture, and cabinets. However, red alder generally is a short-lived pioneer species, and small logs can result in proportionally large volumes of lower grade...

  20. 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 ...

  1. 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 ...

  2. Bioinspired intramolecular Diels-Alder reaction: a rapid access to the highly-strained cyclopropane-fused polycyclic skeleton.

    PubMed

    Zhu, Shifa; Guo, Zhengjiang; Huang, Zhipeng; Jiang, Huanfeng

    2014-02-24

    A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0(2,7) ]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Allelopathic effects of black walnut on european black alder coplanted as a nurse species.

    PubMed

    Rietveld, W J; Schlesinger, R C; Kessler, K J

    1983-08-01

    Black alder trees were interplanted with black walnut on a 2.4 × 3.7-m spacing at four locations in Illinois and Missouri. In every plantation, the alders suddenly declined and died after 8-13 years. Alternative causes for the mortality were investigated-competition from walnut, adverse soil properties, frost, insects, disease, unsuitable seed source, and allelopathy-but only allelopathy could be substantiated. The decline in alder survival and diameter growth was strongly related to walnut above-ground dry biomass and walnut crown competition factor. We propose that the black walnut allelopathy most likely results from a combination of (1) sufficient walnut biomass to contribute substantial amounts of juglone to the environment, and (2) wet soil that greatly restricts aerobic metabolism by soil microorganisms, allowing juglone to build up to toxic levels.

  4. Enantioselective Diels-Alder-lactamization organocascades employing a furan-based diene.

    PubMed

    Abbasov, Mikail E; Hudson, Brandi M; Kong, Weixu; Tantillo, Dean J; Romo, Daniel

    2017-04-11

    α,β-Unsaturated acylammonium salts are useful dienophiles enabling highly enantioselective and stereodivergent Diels-Alder-initiated organocascades with furan-based dienes. Complex polycyclic systems can thus be obtained from readily prepared dienes, commodity acid chlorides, and a chiral isothiourea organocatalyst under mild conditions. We describe the use of furan-based dienes bearing pendant sulfonamides leading to the generation of oxa-bridged, trans-fused tricyclic γ-lactams. This process constitutes the first highly enantio- and diastereoselective, organocatalytic Diels-Alder cycloadditions with these typically problematic dienes due to their reversibility. Computational studies suggest that the high diastereoselectivity with these furan dienes may be due to a reversible Diels-Alder cycloaddition for the endo adducts. In addition, the utility of this methodology is demonstrated through a concise approach to a core structure with similarity to the natural product isatisine A and a nonpeptidyl ghrelin-receptor inverse agonist.

  5. Theoretical study of the Diels-Alder reaction between o-benzoquinone and norbornadiene

    NASA Astrophysics Data System (ADS)

    Quijano-Quiñones, Ramiro F.; Quesadas-Rojas, M.; Cuevas, Gabriel; Mena-Rejón, Gonzalo J.

    2013-06-01

    The reaction between norbornadiene and o-benzoquinone is an important step in polyalicyclic rigid structures synthesis. It has been considered that this reaction is an example of Diels-Alder (DA) and hetero-Diels-Alder (HDA) cycloadditions with o-benzoquinone acting as diene (forming C-C bonds) and heterodiene (forming O-C bonds). We have performed a Density Functional Theory study of this reaction, employing B3LYP, mPW1PW91, and B1B95 functionals and 6-31G(d,p) and 6-31+G(d,p) Gaussian type basis sets. The results indicate that Diels-Alder is a feasible mechanism for both reactions, but should not be the main route to the formation of products with C-C bonds.

  6. Modified lignin: Preparation and use in reversible gel via Diels-Alder reaction.

    PubMed

    Zhou, Wanpeng; Zhang, Hui; Chen, Fangeng

    2017-09-18

    In this study, popular soda lignin was modified with either furan or maleimide ring, and the modified lignins were subjected to reversible Diels-Alder reaction. A new process was proposed to prepare the functionalized lignin. A long chain was introduced to the hydroxyl groups of lignin, and then either the furan or maleimide ring was added to the other end of the chain. The test results confirmed that either the furan ring or the maleimide ring was bound to lignin. Furan- and maleimide-functionalized lignins were also combined to generate crosslinking via Diels-Alder [4+2] cycloaddition reaction. Under appropriate conditions, the formation of a gel was identified, which reverted to liquid state after retro Diels-Alder reaction upon heating at 120°C. This study reveals the significant versatility and potential of the developed strategy for the utilization of lignin-based recyclable networks. Copyright © 2017. Published by Elsevier B.V.

  7. Quinones as dienophiles in the Diels-Alder reaction: history and applications in total synthesis.

    PubMed

    Nawrat, Christopher C; Moody, Christopher J

    2014-02-17

    In the canon of reactions available to the organic chemist engaged in total synthesis, the Diels-Alder reaction is among the most powerful and well understood. Its ability to rapidly generate molecular complexity through the simultaneous formation of two carbon-carbon bonds is almost unrivalled, and this is reflected in the great number of reported applications of this reaction. Historically, the use of quinones as dienophiles is highly significant, being the very first example investigated by Diels and Alder. Herein, we review the application of the Diels-Alder reaction of quinones in the total synthesis of natural products. The highlighted examples span some 60 years from the landmark syntheses of morphine (1952) and reserpine (1956) by Gates and Woodward, respectively, through to the present day examples, such as the tetracyclines. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. Standing Tall: The Benefits of Standing Devices

    ERIC Educational Resources Information Center

    Warner, Mark P.

    2007-01-01

    In the author's opinion as a pediatric physical therapist, with the exception of a wheelchair, there is no other piece of assistive technology that is more beneficial to children and adults with special needs than a standing device. Postural symmetry during standing and walking activities is extremely important for everyone. Very few children…

  10. Standing Tall: The Benefits of Standing Devices

    ERIC Educational Resources Information Center

    Warner, Mark P.

    2007-01-01

    In the author's opinion as a pediatric physical therapist, with the exception of a wheelchair, there is no other piece of assistive technology that is more beneficial to children and adults with special needs than a standing device. Postural symmetry during standing and walking activities is extremely important for everyone. Very few children…

  11. Glacier Grey view from Lago Grey (Grey Lake), photographed during NASA's AirSAR 2004 campaign in Chile

    NASA Image and Video Library

    2004-03-11

    Glacier Grey view from Lago Grey (Grey Lake), photographed during NASA's AirSAR 2004 campaign in Chile. Land visible in this photo was covered by glacier just 6 years earlier. AirSAR 2004 is a three-week expedition in Central and South America by an international team of scientists that is using an all-weather imaging tool, called the Airborne Synthetic Aperture Radar (AirSAR), located onboard NASA's DC-8 airborne laboratory. Scientists from many parts of the world are combining ground research with NASA's AirSAR technology to improve and expand on the quality of research they are able to conduct. Founded in 1959, Torres del Paine National Park encompasses 450,000 acres in the Patagonia region of Chile. This region is being studied by NASA using a DC-8 equipped with an Airborne Synthetic Aperture Radar (AirSAR) developed by scientists from NASA’s Jet Propulsion Laboratory. This is a very sensitive region that is important to scientists because the temperature has been consistently rising causing a subsequent melting of the region’s glaciers. AirSAR will provide a baseline model and unprecedented mapping of the region. This data will make it possible to determine whether the warming trend is slowing, continuing or accelerating. AirSAR will also provide reliable information on ice shelf thickness to measure the contribution of the glaciers to sea level.

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

    PubMed

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

    2012-08-01

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

  13. Field reflectance calibration with grey standard reflectors

    NASA Astrophysics Data System (ADS)

    Philipson, Warren R.; Gordon, Daniel K.; Philpot, William D.; Duggin, Michael J.

    1989-06-01

    Spectral reflectances of natural targets are measured in comparison with white standards, even when target reflectances are substantially different from those of the white standards. With some targets, the differences are sufficient to require a change in radiometer gain settings. Under these circumstances, measurement errors could likely be reduced if calibration were with standards whose reflectances were closer to those of the targets. This paper describes field testing that compared a black and a grey standard with a white barium sulphate standard. Variations in the reflectance properties of the black and grey standards, although higher than variations in the white standard, were less than 6 percent. The availability and use of such standards would simplify and increase the accuracy of field measurements.

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

    PubMed Central

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

    2017-01-01

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

  15. Chiral Dawson-Type Hybrid Polyoxometalate Catalyzes Enantioselective Diels-Alder Reactions.

    PubMed

    Xuan, Wen-Jing; Botuha, Candice; Hasenknopf, Bernold; Thorimbert, Serge

    2015-11-09

    Can achiral organocatalysts linked to chiral polyanionic metal oxide clusters provide good selectivity in enantioselective C-C bond formations? The answer to this question is investigated by developing a new active hybrid polyoxometalate-based catalyst for asymmetric Diels-Alder reaction. Chirality transfer from the chiral anionic polyoxometalate to the covalently linked achiral imidazolidinone allows Diels-Alder cycloaddition products to be obtained with good yields and high enantioselectivities when using cyclopentadiene and acrylaldehydes as partners. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.

    PubMed

    Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

    2015-04-07

    The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Schleyer hyperconjugative aromaticity and Diels-Alder reactivity of 5-substituted cyclopentadienes.

    PubMed

    Levandowski, Brian J; Zou, Lufeng; Houk, K N

    2016-01-05

    Schleyer's discovery of hyperconjugative aromaticity and antiaromaticity in 5-substituted cyclopentadienes further expanded our understanding of the pervasive influence of aromaticity. Acceptors induce antiaromatic character by Schleyer's negative hyperconjugative aromaticity, and donors have the opposite effect. We computationally explored the Diels-Alder reactivity of 5-substituted cyclopentadienes with ethylene and maleic anhydride. The predicted billionfold difference in the computed gas phase rate constants at room temperature for the Diels-Alder reactions of 5-substituted cyclopentadienes with ethylene or maleic anhydride results from differences in the transition state distortion energies, which are directly related to the hyperconjugative aromaticity of these molecules. © 2015 Wiley Periodicals, Inc.

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

    PubMed

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

    2015-06-03

    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.

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

    USGS Publications Warehouse

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

    1979-01-01

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

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

    PubMed

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

    2016-07-01

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

  1. 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

  2. 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.

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

    PubMed

    Tuvi-Arad, Inbal; Avnir, David

    2012-08-06

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

  4. Electrostatic catalysis of a Diels-Alder reaction

    NASA Astrophysics Data System (ADS)

    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.

  5. Electrostatic catalysis of a Diels-Alder reaction.

    PubMed

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

    2016-03-03

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

  6. 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

  7. Silvery grey hair: clue to diagnose immunodeficiency.

    PubMed

    Sahana, Ms; Sacchidanand, S; Hiremagalore, R; Asha, Gs

    2012-04-01

    Silvery hair is a common presentation of rare group of autosomal recessive disorders called Silvery hair syndromes including Griscelli syndrome (GS), Chediak-Higashi syndrome, and Elejalde syndrome. GS is characterized by a silvery grey sheen to hair, large clumped melanosomes in hair shaft, partial albinism, and variable cellular immunodeficiency. We report two cases of GS with classical clinical features and confirmatory findings by microscopic skin and hair examination.

  8. Searching and synthesising 'grey literature' and 'grey information' in public health: critical reflections on three case studies.

    PubMed

    Adams, Jean; Hillier-Brown, Frances C; Moore, Helen J; Lake, Amelia A; Araujo-Soares, Vera; White, Martin; Summerbell, Carolyn

    2016-09-29

    Grey literature includes a range of documents not controlled by commercial publishing organisations. This means that grey literature can be difficult to search and retrieve for evidence synthesis. Much knowledge and evidence in public health, and other fields, accumulates from innovation in practice. This knowledge may not even be of sufficient formality to meet the definition of grey literature. We term this knowledge 'grey information'. Grey information may be even harder to search for and retrieve than grey literature. On three previous occasions, we have attempted to systematically search for and synthesise public health grey literature and information-both to summarise the extent and nature of particular classes of interventions and to synthesise results of evaluations. Here, we briefly describe these three 'case studies' but focus on our post hoc critical reflections on searching for and synthesising grey literature and information garnered from our experiences of these case studies. We believe these reflections will be useful to future researchers working in this area. Issues discussed include search methods, searching efficiency, replicability of searches, data management, data extraction, assessing study 'quality', data synthesis, time and resources, and differentiating evidence synthesis from primary research. Information on applied public health research questions relating to the nature and range of public health interventions, as well as many evaluations of these interventions, may be predominantly, or only, held in grey literature and grey information. Evidence syntheses on these topics need, therefore, to embrace grey literature and information. Many typical systematic review methods for searching, appraising, managing, and synthesising the evidence base can be adapted for use with grey literature and information. Evidence synthesisers should carefully consider the opportunities and problems offered by including grey literature and information

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

    PubMed Central

    2011-01-01

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

  10. In vitro toxicity of formocresol, ferric sulphate, and grey MTA on human periodontal ligament fibroblasts.

    PubMed

    Al-Haj Ali, S N; Al-Jundi, S H; Ditto, D J

    2015-02-01

    This was to assess and compare the in vitro toxicity of formocresol, ferric sulphate and MTA on cultured human periodontal ligament (PDL) fibroblasts. PDL cells were obtained from sound first permanent molars and cultured in Dulbecco's modified Eagle's medium. PDL cells were subjected to different concentrations of formocresol, ferric sulphate, and grey MTA for 24, 48, and 72 h at 37 °C. Cells that were not exposed to the tested materials served as the negative control. In vitro toxicity was assessed using MTT assay. Statistical analysis of data was accomplished using ANOVA and Tukey statistical tests (p<0.05). The overall toxicity ranking of the tested materials was as follows: formocresol>ferric sulphate>grey MTA. Only grey MTA had comparable cell viability to the negative control, the other tested materials were significantly inferior at the three exposure periods (p<0.05). Regarding the viability of PDL fibroblasts, MTA stands as the most promising substitute to formocresol. However, considering MTA's unavailability and high price in Jordan, ferric sulphate may be the best alternative to formocresol in pulpotomy of primary teeth.

  11. Phylogeny and vicariant speciation of the Grey Rhebok, Pelea capreolus

    PubMed Central

    Robinson, T J; Cernohorska, H; Diedericks, G; Cabelova, K; Duran, A; Matthee, C A

    2014-01-01

    A South African endemic antelope, the Grey Rhebok (Pelea capreolus), has long been an evolutionary enigma in bovid systematics—its phylogenetic intractability attributed to its curious combination of derived and primitive morphological attributes and the consequences of a rapid radiation. By using a combination of DNA sequences, chromosomal characteristics and quantitative and qualitative morphological features we show that the species is a sister taxon to a clade that comprises the waterbuck, reedbuck and allies. Our finding of few unambiguous synapomorphies reinforces suggestions of a rapid radiation and highlights the effects of incomplete lineage sorting, including the hemiplasic nature of several chromosomal rearrangements. We investigate these data to address the general question of what may have led to Pelea being both genetically and ecologically distinct from the Reduncini. We argue that its adaptation to exposed habitats, free of standing water, arose by vicariance prompted by increasing aridity of the extreme south/southwestern region of the African continent in the Miocene. Ancestral lineages leading to the extant Redunca and Kobus, on the other hand, retreated to water-abundant refugia in the north during these mostly globally cool phases. The mosaic of water-rich environments provided by the Okavango and the drainage systems in the southwestern extension of the East African Rift system are considered to have facilitated speciation and chromosomal evolution within these antelope. PMID:24281547

  12. Test Stand Construction

    NASA Technical Reports Server (NTRS)

    1964-01-01

    Construction crews install steel reinforcing rods at the base of what became the A-2 test stand. The excavation for the stand went down 50 feet with steel H-beams driven 100 feet deeper to form a foundation for the huge piers of the test stand.

  13. A-3 Test Stand

    NASA Image and Video Library

    2012-06-08

    A tethered Stennis Space Center employee climbs an A-3 Test Stand ladded June 8, 2012, against the backdrop of the A-2 and B-1/B-2 stands. The new A-3 Test Stand will enable simulated high-altitude testing of next-generation rocket engines.

  14. A-3 Test Stand

    NASA Image and Video Library

    2012-06-08

    A tethered Stennis Space Center employee climbs an A-3 Test Stand ladder June 8, 2012, against the backdrop of the A-2 and B-1/B-2 stands. The new A-3 Test Stand will enable simulated high-altitude testing of next-generation rocket engines.

  15. Stand density relationships

    Treesearch

    John C. Tappeiner

    2013-01-01

    Th inning stands (managing their densities) aff ects the development of trees and understory plants as individuals, as well as stand-level characteristics like structure, microclimate, and stand growth, habitat for various species, and fuel and potential fi re severity. Th ese characteristics and the rate of changes are aff ected by thinning severity—the reduction in...

  16. Test Stand Construction

    NASA Technical Reports Server (NTRS)

    1964-01-01

    Construction crews install steel reinforcing rods at the base of what became the A-2 test stand. The excavation for the stand went down 50 feet with steel H-beams driven 100 feet deeper to form a foundation for the huge piers of the test stand.

  17. 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.

  18. Previous herbivore attack of red alder may improve food quality for fall webworm larvae.

    PubMed

    Williams, Kathy S; Myers, Judith H

    1984-08-01

    Three hypotheses of insect-plant interactions were tested by rearing fall webworm larvae in the laboratory on foliage from red alder trees with different histories of western tent caterpillar herbivory. Fall webworm larvae raised on foliage from trees which had been attacked previously for two summers by moderate densities of western tent caterpillars grew faster and attained heavier pupal weights than did those fed foliage from unattacked trees. This contradicts the hypothesis that moderate levels of previous herbivory induces the production of plant defensive chemicals in red alders. Growth of webworms, when fed foliage from unattacked trees adjacent to alders that were attacked by fall webworm larvae, was the same as when fed foliage from trees isolated by distance from attacked trees. This contradicts the hypothesis that attacked trees stimulate the production of defensive chemicals in neigh-boring trees. Young and mature alder foliage was equally good for fall webworm growth and survival, and foliage from trees heavily attacked by both fall webworm and western tent caterpillars for three years produced slow growth rates and small pupal sizes. This supports the hypothesis that continued heavy insect attack can cause the deterioration of the food quality of attacked trees.

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    PubMed

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

    2011-12-16

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

  1. Influence of flooding duration on the biomass growth of alder and willow.

    Treesearch

    Lewis F. Ohmann; M. Dean Knighton; Ronald McRoberts

    1990-01-01

    Simple second-order (quadratic) polynomials were used to model the relationship between 3-year biomass increase (net ovendry weight in grams) and flooding duration (days) for four combinations of shrub type (alder, willow) and soils type (fine-sand, clay-loam).

  2. 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...

  3. ROLE OF RED ALDER IN NITROGEN LOSSES FROM FORESTED WATERSHEDS IN THE OREGON COAST RANGE

    EPA Science Inventory

    Variations in plant community composition across the landscape may have strong impacts on nutrient losses from small forested watersheds. One extreme example of this impact is the role of the nitrogen-fixing tree, red alder, in the biogeochemistry of forested watersheds in the P...

  4. Developing Biomass Equations for Western Hemlock and Red Alder Trees in Western Oregon Forests

    Treesearch

    Krishna Poudel; Hailemariam Temesgen

    2016-01-01

    Biomass estimates are required for reporting carbon, assessing feedstock availability, and assessing forest fire threat. We developed diameter- and height-based biomass equations for Western hemlock (Tsuga heterophylla (Raf.) Sarg.) and red alder (Alnus rubra Bong.) trees in Western Oregon. A system of component biomass...

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

    PubMed Central

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

    2009-01-01

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

  6. 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…

  7. Limited evaluation of physical and mechanical properties of Nepal alder grown in Hawaii

    Treesearch

    C. C. Gerhards

    1964-01-01

    Nepal alder (Alnus nepalensis ) grown in Hawaii was evaluated for shrinkage, strength in bending, and hardness. This Hawaii-grown wood was comparable in bending strength to wood of the same species grown in Bengal, India, but was lower in modulus of elasticity and exhibited greater hardness and shrinkage. It was also harder than such Mainland species as aspen (Populus...

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

    PubMed

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

    2009-08-11

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

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

    PubMed

    Alberti, Mariza N; Orfanopoulos, Michael

    2009-04-02

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

  10. Greenhouse germination trials of pelletized western redcedar and red alder seeds

    Treesearch

    Nabil Khadduri

    2007-01-01

    Pelletized western redcedar (Thuja plicata Donn ex D. Don) and red alder (Alnus rubra Bong.) seeds exhibited lower total germination and delayed germination speed (G50 or days to 50% germination) when compared to non-pelletized “raw” seeds in greenhouse trials. Averaged across two lots of western redcedar, pelletizing decreased...

  11. Solar-chemical energy conversion via reversible liquid phase Diels-Alder reactions. Final technical report

    SciTech Connect

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

    1983-05-01

    Thermochemical energy conversion at moderate or low temperature (< about 400/sup 0/C) employing liquid phase components throughout a cycle is suggested as a promising concept for high-efficiency conversion of solar energy to a convenient chemical form. In particular, we propose liquid phase Diels-Alder cycloaddition chemistry as an important class of reversible reactions for such low or moderate temperature thermochemical energy conversion systems. One of the important attributes of thermally driven Diels-Alder reactions is their concerted mechanism, with consequent high yields and efficiencies relative to liquid photochemical systems. Since the systems we propose involve organic species, with thermal stability concerns about 400/sup 0/C, it is important to demonstrate equilibrium shift capability for the highly energetic reactions sought. We have therefore carried out experimental studies with model liquid Diels-Alder systems that clearly demonstrate the degree of control over equilibrium available through substituent entropy effects. These results are of importance as regards subsequent systematic identification of Diels-Alder reactions having ideal thermochemical and physical properties.

  12. Microbial diversification of Diels-Alder cycloadducts by whole cells of Penicillium brasilianum.

    PubMed

    Din, Zia Ud; Fill, Taicia P; Donatoni, M Carolina; Dos Santos, Carolina A A; Brocksom, Timothy J; Rodrigues-Filho, E

    2016-11-01

    Functionalizations of cycloadducts are important steps for the use of Diels-Alder reactions in the construction of complex cyclic or polycyclic molecules from relatively simple starting materials. In the present work, we studied the ability of Penicillium brasilianum to perform microbial transformations of racemic Diels-Alder endo-cycloadducts. Thus, Diels-Alder products, obtained from reacting cyclopentadiene or 2,3-dimethylbutadiene with alkylated para-benzoquinones, were transformed by the resting cells of P. brasilianum producing new functionalized polycyclic compounds. These biotransformations yielded novel products of oxidation and ring closure, reduction of the C=C or C=O in [Formula: see text]-unsaturated system, and allylic hydroxylations. The reduction products (conjugated double bond and carbonyl group) were also synthesized, and the enantioselectivity of both in vitro and in vivo processes was evaluated. In all cases, the microbiological transformations were enantioselective. In silico docking studies of the Diels-Alder cycloadducts with P. brasilianum oxidoreductase "old yellow enzymes" shed more light on these transformations.

  13. Occurrence, structure, and nitrogen-fixation of root nodules of actinorhizal Arizona alder

    Treesearch

    J. O. Dawson; Gerald J. Gottfried; D. Hahn

    2005-01-01

    Actinorhizal plants are nodulated by the symbiotic, nitrogen-fixing actinomycete Frankia. The genus Alnus in the family Betulaceae is one of the 24 genera in 8 families of angiospermous plants that are actinorhizal. Arizona alder (Alnus oblongifolia Torr.) occurs in isolated populations associated with the watersheds of Madrean Sky Islands in the...

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

    PubMed

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

    2006-11-23

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

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

    PubMed Central

    2010-01-01

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

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

    PubMed Central

    Anderson, Erin D.; Boger, Dale L.

    2011-01-01

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

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

    PubMed

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

    2016-02-07

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

  18. 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...

  19. Taper equation and volume tables for plantation-grown red alder.

    Treesearch

    Andrew A. Bluhm; Sean M. Garber; David E. Hibbs

    2007-01-01

    A taper equation and associated tables are presented for red alder (Alnus rubra Bong.) trees grown in plantations. The data were gathered from variable-density experimental plantations throughout the Pacific Northwest. Diameter inside bark along the stem was fitted to a variable exponent model form by using generalized nonlinear least squares and a...

  20. 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…

  1. Consumer preferences for kitchen cabinets made from red alder: a comparison to other hardwoods.

    Treesearch

    David L. Nicholls; Geoffrey H. Donovan; Joseph. Roos

    2004-01-01

    In Alaska, red alder (Alnus rubra Bong.) is an abundant but commercially underutilized species despite having properties suitable for higher value products, including furniture and cabinetry. However, it laces the name recognition of mote traditional hardwoods. Our research measured the effect of this lack of familiarity on consumer preferences...

  2. Variation in damage from growing-season frosts among open-pollinated families of red alder.

    Treesearch

    Kevin C. Peeler; Dean S. DeBell

    1987-01-01

    Repeated growing-season frosts during late April and early May 1985 caused extensive damage to red alder (Alnus rubra Bong.) seedlings in a newly planted research trial in western Washington. About two-thirds of the seedlings were severely damaged (entire stem damaged or necrotic). Such damage varied by family, from 50 percent of seedlings in the...

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

    PubMed

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

    2013-02-01

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

  4. 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.

  5. Chiral Boron Complex-Promoted Asymmetric Diels-Alder Cycloaddition and Its Application in Natural Product Synthesis.

    PubMed

    Li, Xia; Han, Jianguang; Jones, Alexander X; Lei, Xiaoguang

    2016-01-15

    An efficient method for the asymmetric Diels-Alder cycloaddition of 2'-hydroxychalcones with acyclic or cyclic dienes has been successfully developed. The Diels-Alder cycloaddition is mediated by a chiral boron complex with VANOL, affording the corresponding products in high yields and with excellent diastereo- and enantioselectivities. This reaction enabled the enantioselective construction of cyclohexene skeletons crucial for the total synthesis of a number of Diels-Alder-type natural products (-)-nicolaioidesin C, (-)-panduratine A, (-)-kuwanon I, (+)-kuwanon J, and (-)-brosimones A and B.

  6. Searching for grey literature for systematic reviews: challenges and benefits.

    PubMed

    Mahood, Quenby; Van Eerd, Dwayne; Irvin, Emma

    2014-09-01

    There is ongoing interest in including grey literature in systematic reviews. Including grey literature can broaden the scope to more relevant studies, thereby providing a more complete view of available evidence. Searching for grey literature can be challenging despite greater access through the Internet, search engines and online bibliographic databases. There are a number of publications that list sources for finding grey literature in systematic reviews. However, there is scant information about how searches for grey literature are executed and how it is included in the review process. This level of detail is important to ensure that reviews follow explicit methodology to be systematic, transparent and reproducible. The purpose of this paper is to provide a detailed account of one systematic review team's experience in searching for grey literature and including it throughout the review. We provide a brief overview of grey literature before describing our search and review approach. We also discuss the benefits and challenges of including grey literature in our systematic review, as well as the strengths and limitations to our approach. Detailed information about incorporating grey literature in reviews is important in advancing methodology as review teams adapt and build upon the approaches described.

  7. Exploring the origins of grey matter damage in multiple sclerosis.

    PubMed

    Calabrese, Massimiliano; Magliozzi, Roberta; Ciccarelli, Olga; Geurts, Jeroen J G; Reynolds, Richard; Martin, Roland

    2015-03-01

    Multiple sclerosis is characterized at the gross pathological level by the presence of widespread focal demyelinating lesions of the myelin-rich white matter. However, it is becoming clear that grey matter is not spared, even during the earliest phases of the disease. Furthermore, grey matter damage may have an important role both in physical and cognitive disability. Grey matter pathology involves both inflammatory and neurodegenerative mechanisms, but the relationship between the two is unclear. Histological, immunological and neuroimaging studies have provided new insight in this rapidly expanding field, and form the basis of the most recent hypotheses on the pathogenesis of grey matter damage.

  8. Grey Hair Evlsion Technique For Evaluating the Effect of Drugs For the Treatment of Premature Grey Hairs.

    PubMed

    Pasricha, J S

    1985-01-01

    An improved method for evaluating the effect of treatment for premature grey hairs is described. The method consists of pulling out all the grey hairs in a patient and counting the number removed. Simultaneously, the converted hairs are also snipped at the grey-black junction and counted. After a gap of 3 months, the survey is repeated to count the number of hairs which have regrowing as grey hairs, the hairs which have become grey and also the hairs which have got converted into black during this period. Such surveys are repeated at 3 months intervals over a period of several years to see the progress of greying of hair in an individual and to evaluate the effect of various therapeutic procedures.

  9. Grey('s) Identity: Complications of Learning and Becoming in a Popular Television Show

    ERIC Educational Resources Information Center

    Jubas, Kaela

    2013-01-01

    In this article, the author outlines an analysis of the American show "Grey's Anatomy" as an example of how popular culture represents identity and the process of professional identity construction in a medical workplace, particularly the surgical service of a large urban hospital. In discussing identity, she connects professional identity to…

  10. Grey('s) Identity: Complications of Learning and Becoming in a Popular Television Show

    ERIC Educational Resources Information Center

    Jubas, Kaela

    2013-01-01

    In this article, the author outlines an analysis of the American show "Grey's Anatomy" as an example of how popular culture represents identity and the process of professional identity construction in a medical workplace, particularly the surgical service of a large urban hospital. In discussing identity, she connects professional identity to…

  11. On grey levels in random CAPTCHA generation

    NASA Astrophysics Data System (ADS)

    Newton, Fraser; Kouritzin, Michael A.

    2011-06-01

    A CAPTCHA is an automatically generated test designed to distinguish between humans and computer programs; specifically, they are designed to be easy for humans but difficult for computer programs to pass in order to prevent the abuse of resources by automated bots. They are commonly seen guarding webmail registration forms, online auction sites, and preventing brute force attacks on passwords. In the following, we address the question: How does adding a grey level to random CAPTCHA generation affect the utility of the CAPTCHA? We treat the problem of generating the random CAPTCHA as one of random field simulation: An initial state of background noise is evolved over time using Gibbs sampling and an efficient algorithm for generating correlated random variables. This approach has already been found to yield highly-readable yet difficult-to-crack CAPTCHAs. We detail how the requisite parameters for introducing grey levels are estimated and how we generate the random CAPTCHA. The resulting CAPTCHA will be evaluated in terms of human readability as well as its resistance to automated attacks in the forms of character segmentation and optical character recognition.

  12. Diels-Alder adduct of C{sub 60} and 4-carboxy-o-quinodimethane: Synthesis and chemical transformations

    SciTech Connect

    Belik, P.; Guegel, A.; Kraus, A.; Walter, M.; Muellen, K.

    1995-06-02

    Diels-Alder reaction of C{sub 60} with o-quinodimethanes results in stable fullerene derivatives. Further reactions of these adducts give the corresponding esters and amines. A number of these produccts were separated and characterized.

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

    PubMed Central

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

    2012-01-01

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

  14. 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.

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

    PubMed

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

    2013-02-13

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

  16. 11. INTERIOR VIEW WITH JAMES WILLIAMS INSIDE GREY IRON UNIT ...

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

    11. INTERIOR VIEW WITH JAMES WILLIAMS INSIDE GREY IRON UNIT NO. 1 MOLDING CONVEYOR, AIR CLEANING A PATTERN AS IT SITS WITHIN A FLASK ON A MOLDING MACHINE PRIOR TO BEING FILLED WITH SAND FROM THE OVERHEAD CONVEYOR. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  17. 8. INTERIOR VIEW, LOOKING WEST, WITH GREY IRON HOLDING FURNACES ...

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

    8. INTERIOR VIEW, LOOKING WEST, WITH GREY IRON HOLDING FURNACES AND AN IRON POUR IN PROCESS, CUPOLA TENDER RICHARD SLAUGHTER SUPERVISING THE POUR. MOLTEN DUCTILE IRON IS POURED FROM THIS 25-TON HOLDING FURNACE INTO LADLES FOR TRANSPORT TO CASTING STATIONS. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  18. 7. INTERIOR VIEW, LOOKING WEST, WITH GREY IRON HOLDING FURNACE ...

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

    7. INTERIOR VIEW, LOOKING WEST, WITH GREY IRON HOLDING FURNACE AND AN IRON POUR IN PROCESS. MOLTEN DUCTILE IRON IS POURED FROM THIS 25-TON HOLDING FURNACE INTO LADLES FOR TRANSPORT TO CASTING STATIONS. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  19. 34. DESPATCH CORE OVENS, GREY IRON FOUNDRY CORE ROOM, BAKES ...

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

    34. DESPATCH CORE OVENS, GREY IRON FOUNDRY CORE ROOM, BAKES CORES THAT ARE NOT MADE ON HEATED OR COLD BOX CORE MACHINES, TO SET BINDING AGENTS MIXED WITH THE SAND CREATING CORES HARD ENOUGH TO WITHSTAND THE FLOW OF MOLTEN IRON INSIDE A MOLD. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  20. 42. INTERIOR VIEW, LOOKING WEST, WITH GREY IRON HOLDING FURNACE ...

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

    42. INTERIOR VIEW, LOOKING WEST, WITH GREY IRON HOLDING FURNACE AND AN IRON POUR IN PROCESS. MOLTEN DUCTILE IRON IS POURED FROM THIS 25-TON HOLDING FURNACE INTO LADLES FOR TRANSPORT TO CASTING STATIONS - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  1. 32. LARGE LADLE, BOX FLOOR, GREY IRON FOUNDRY IS USED ...

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

    32. LARGE LADLE, BOX FLOOR, GREY IRON FOUNDRY IS USED TO CARRY LARGE BATCHES OF IRON FROM THE CUPOLA AREAS TO THE LARGE MOLDS MADE ON BOX FLOOR AREA. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  2. 41. INTERIOR VIEW, LOOKING WEST, WITH GREY IRON HOLDING FURNACE ...

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

    41. INTERIOR VIEW, LOOKING WEST, WITH GREY IRON HOLDING FURNACE AND AN IRON POUR IN PROCESS. MOLTEN DUCTILE IRON IS POURED FROM THIS 25-TON HOLDING FURNACE INTO LADLES FOR TRANSPORT TO CASTING STATIONS - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  3. 30. NATIONAL SHELL CORE MACHINE IN THE GREY IRON FOUNDRY ...

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

    30. NATIONAL SHELL CORE MACHINE IN THE GREY IRON FOUNDRY AUTOMATICALLY INJECTS SAND INTO CLOSED, HEATED CORE BOXES THAT SET THE RESINS AND PERMIT A HARDENED CORE TO BE REMOVED BY THE OPERATOR. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  4. 31. PETIBONE SAND THROWING MACHINE BOX FLOOR GREY IRON FOUNDRY ...

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

    31. PETIBONE SAND THROWING MACHINE BOX FLOOR GREY IRON FOUNDRY FORCES CONDITIONED MOLDING SAND, AT HIGH VELOCITY, INTO MOLDS TOO BIG TO BE MADE ON ONE OF THE CONVEYOR SYSTEMS. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  5. 28. CORE STORAGE AREA OF THE GREY IRON FOUNDRY SHOWING ...

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

    28. CORE STORAGE AREA OF THE GREY IRON FOUNDRY SHOWING CORES THAT WILL BE USED TO CREATE INTERIOR WALLS OF SMALL BALL VALVES, FOREGROUND, AND LARGE GATE VALVES, BACKGROUND. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  6. 17. INTERIOR VIEW WITH GREY UNIT NO. 1 MOLD CONVEYOR ...

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

    17. INTERIOR VIEW WITH GREY UNIT NO. 1 MOLD CONVEYOR SHOWING CHAIN HELD WEIGHTS THAT TRAVEL AT THE SAME SPEED AS THE CONVEYOR AND REST ON COMPLETED MOLDS TO HOLD THE SAND SEAMS TOGETHER AS MOLTED IRON IS POURED INTO THE MOLD CAVITY. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  7. A High Precision Prediction Model Using Hybrid Grey Dynamic Model

    ERIC Educational Resources Information Center

    Li, Guo-Dong; Yamaguchi, Daisuke; Nagai, Masatake; Masuda, Shiro

    2008-01-01

    In this paper, we propose a new prediction analysis model which combines the first order one variable Grey differential equation Model (abbreviated as GM(1,1) model) from grey system theory and time series Autoregressive Integrated Moving Average (ARIMA) model from statistics theory. We abbreviate the combined GM(1,1) ARIMA model as ARGM(1,1)…

  8. A High Precision Prediction Model Using Hybrid Grey Dynamic Model

    ERIC Educational Resources Information Center

    Li, Guo-Dong; Yamaguchi, Daisuke; Nagai, Masatake; Masuda, Shiro

    2008-01-01

    In this paper, we propose a new prediction analysis model which combines the first order one variable Grey differential equation Model (abbreviated as GM(1,1) model) from grey system theory and time series Autoregressive Integrated Moving Average (ARIMA) model from statistics theory. We abbreviate the combined GM(1,1) ARIMA model as ARGM(1,1)…

  9. 33. BENCH CORE STATION, GREY IRON FOUNDRY CORE ROOM WHERE ...

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

    33. BENCH CORE STATION, GREY IRON FOUNDRY CORE ROOM WHERE CORE MOLDS WERE HAND FILLED AND OFTEN PNEUMATICALLY COMPRESSED WITH A HAND-HELD RAMMER BEFORE THEY WERE BAKED. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  10. 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

  11. Planter unit test stand

    USDA-ARS?s Scientific Manuscript database

    A planter test stand was developed to evaluate individual row-crop metering units in early 2013. This test stand provided the ability to quantify actual seed metering in terms of population, seed spacing, skips, and multiples over a range of meter RPMs and vacuum pressures. Preliminary data has been...

  12. Saw gin stands

    USDA-ARS?s Scientific Manuscript database

    The saw gin stand is the heart of the saw ginning system. Almost from the initial filing of patents for the spiked tooth gin and the saw gin in 1794 and 1796 by Whitney and then Holmes respectively (Hughs and Holt, 2015), the saw gin stand has predominated over early roller-type gins in the U.S. co...

  13. Limbic grey matter changes in early Parkinson's disease.

    PubMed

    Li, Xingfeng; Xing, Yue; Schwarz, Stefan T; Auer, Dorothee P

    2017-05-02

    The purpose of this study was to investigate local and network-related changes of limbic grey matter in early Parkinson's disease (PD) and their inter-relation with non-motor symptom severity. We applied voxel-based morphometric methods in 538 T1 MRI images retrieved from the Parkinson's Progression Markers Initiative website. Grey matter densities and cross-sectional estimates of age-related grey matter change were compared between subjects with early PD (n = 366) and age-matched healthy controls (n = 172) within a regression model, and associations of grey matter density with symptoms were investigated. Structural brain networks were obtained using covariance analysis seeded in regions showing grey matter abnormalities in PD subject group. Patients displayed focally reduced grey matter density in the right amygdala, which was present from the earliest stages of the disease without further advance in mild-moderate disease stages. Right amygdala grey matter density showed negative correlation with autonomic dysfunction and positive with cognitive performance in patients, but no significant interrelations were found with anxiety scores. Patients with PD also demonstrated right amygdala structural disconnection with less structural connectivity of the right amygdala with the cerebellum and thalamus but increased covariance with bilateral temporal cortices compared with controls. Age-related grey matter change was also increased in PD preferentially in the limbic system. In conclusion, detailed brain morphometry in a large group of early PD highlights predominant limbic grey matter deficits with stronger age associations compared with controls and associated altered structural connectivity pattern. This provides in vivo evidence for early limbic grey matter pathology and structural network changes that may reflect extranigral disease spread in PD. Hum Brain Mapp, 2017. © 2017 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc. © 2017 The

  14. Stand density index in uneven-aged ponderosa pine stands

    Treesearch

    C.W. Woodall; C.E. Fiedler; K.S. Milner

    2003-01-01

    Stand density index (SDI) was developed to quantify relative stand density in even-aged stands. Application of SDI in uneven-aged stands has been described mathematically but not justified biologically. Diameter-class trends in SDI and sapwood area across 14 uneven-aged ponderosa pine (Pinus ponderosa Dougl. ex P. & C. Laws.) stands in eastern...

  15. Color and Grey Scale in Sonar Displays

    NASA Technical Reports Server (NTRS)

    Kraiss, K. F.; Kuettelwesch, K. H.

    1984-01-01

    In spite of numerous publications 1 it is still rather unclear, whether color is of any help in sonar displays. The work presented here deals with a particular type of sonar data, i.e., LOFAR-grams (low frequency analysing and recording) where acoustic sensor data are continuously written as a time-frequency plot. The question to be answered quantitatively is, whether color coding does improve target detection when compared with a grey scale code. The data show significant differences in receiver-operating characteristics performance for the selected codes. In addition it turned out, that the background noise level affects the performance dramatically for some color codes, while others remain stable or even improve. Generally valid rules are presented on how to generate useful color scales for this particular application.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  17. Comparative ability to detoxify alder leaf litter in field larval mosquito collections.

    PubMed

    David, J P; Rey, D; Cuany, A; Amichot, M; Meyran, J C

    2000-08-01

    The larvicidal effects of polyphenols from dietary alder leaf litter were investigated in different field collections of three detritivorous Aedes taxa (Ae. detritus, Ae. cataphylla, Ae. rusticus) and compared to the cytochrome P450 monooxygenase, glutathione S-transferase, and esterase activities. Larvae from polyphenol-rich habitats had a higher tolerance for polyphenols and higher midgut cytochrome P450 and esterase activities than larvae from polyphenol-poor habitats. Furthermore, the role of P450 enzymes in the mechanism of resistance to alder polyphenols was suggested by the synergistic effect in vivo of piperonyl butoxide in the resistant Ae. rusticus. This confirms the importance of polyphenols to larval mosquito performance, and provides evidence for the importance of specific detoxification mechanisms for tolerance to dietary polyphenols. Arch. Copyright 2000 Wiley-Liss, Inc.

  18. Structural basis for Diels-Alder ribozyme-catalyzed carbon-carbon bond formation

    PubMed Central

    Serganov, Alexander; Keiper, Sonja; Malinina, Lucy; Tereshko, Valentina; Skripkin, Eugene; Höbartner, Claudia; Polonskaia, Anna; Phan, Anh Tuân; Wombacher, Richard; Micura, Ronald; Dauter, Zbigniew; Jäschke, Andres; Patel, Dinshaw J

    2015-01-01

    The majority of structural efforts addressing RNA’s catalytic function have focused on natural ribozymes, which catalyze phosphodiester transfer reactions. By contrast, little is known about how RNA catalyzes other types of chemical reactions. We report here the crystal structures of a ribozyme that catalyzes enantioselective carbon-carbon bond formation by the Diels-Alder reaction in the unbound state and in complex with a reaction product. The RNA adopts a λ-shaped nested pseudoknot architecture whose preformed hydrophobic pocket is precisely complementary in shape to the reaction product. RNA folding and product binding are dictated by extensive stacking and hydrogen bonding, whereas stereoselection is governed by the shape of the catalytic pocket. Catalysis is apparently achieved by a combination of proximity, complementarity and electronic effects. We observe structural parallels in the independently evolved catalytic pocket architectures for ribozyme- and antibody-catalyzed Diels-Alder carbon-carbon bond-forming reactions. PMID:15723077

  19. Cyclodextrin-promoted Diels Alder reactions of a polycyclic aromatic hydrocarbon under mild reaction conditions.

    PubMed

    Chaudhuri, Sauradip; Phelan, Tyler; Levine, Mindy

    2015-03-01

    Reported herein is the effect of cyclodextrins on the rates of aqueous Diels Alder reactions of 9-anthracenemethanol with a variety of N-substituted maleimides. These reactions occurred under mild reaction conditions (aqueous solvent, 40 °C), and were most efficient for the reaction of N-cyclohexylmaleimide with a methyl-β-cyclodextrin additive (94% conversion in 24 hours). These results can be explained on the basis of a model wherein the cyclodextrins bind the hydrophobic substituents on the maleimides and activate the dienophile via electronic modulation of the maleimide double bond. The results reported herein represent a new mechanism for cyclodextrin-promoted Diels Alder reactions, and have significant potential applications in the development of other cyclodextrin-promoted organic transformations. Moreover, the ability to deplanarize polycyclic aromatic hydrocarbons (PAHs) under mild conditions, as demonstrated herein, has significant applications for PAH detoxification.

  20. Enantioselective Organocatalytic Diels-Alder Trapping of Photochemically Generated Hydroxy-o-Quinodimethanes.

    PubMed

    Dell'Amico, Luca; Vega-Peñaloza, Alberto; Cuadros, Sara; Melchiorre, Paolo

    2016-03-01

    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. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  1. Diels-Alder Cycloaddition of Cyclopentadiene and C60 at the Extreme High Pressure.

    PubMed

    Yang, Tao; Fukuda, Ryoichi; Cammi, Roberto; Ehara, Masahiro

    2017-06-08

    High-pressure Diels-Alder cycloaddition reaction of fullerenes is an important synthetic method for the thermally stable cycloadducts. The effects of high pressure on the potential energy surfaces of Diels-Alder cycloaddition of cyclopentadiene and C60 were studied with a recently developed approach, the polarizable continuum model for extreme pressure (XP-PCM). It is revealed that the high pressure reduces the activation energies and increases reaction energies drastically, making the DA reaction more favorable. The pressure effects on the reaction energetics can be divided into the cavitation and electronic contributions. For the activation energy, the cavitation contribution is significant in comparison with the electronic contribution. To assist future experiments, the activation volume and reaction volume were computed on the basis of the relationship between activation energy or reaction energy with the pressure as a consequence of the fitting linear correlation between activation energy or reaction energy with the pressure.

  2. Microbiological quality of grey-mullet roe.

    PubMed

    Voidarou, C; Alexopoulos, A; Plessas, S; Noussias, H; Stavropoulou, E; Fotou, K; Tzora, A; Skoufos, I; Bezirtzoglou, E; Demertzi-Akrida, K

    2011-12-01

    The Greek grey-mullet roe is produced from the fully developed gonads of the female mullet (Mugil cephalus) couth in lagoons during their reproductive migration. The traditional processing method of the roe includes, air drying, salting, shape formation and covering with multiple layers of natural beeswax for preservation and distribution. Fish Roe brands have been a staple in local diet and is increasingly becoming popular in the international market. As a ready-to-eat food it's microbial quality should be of concern for the protection of consumers health. In this study, 48 samples of fish roe, just before waxing, were collected from various local processors for microbiological examination by using selective media and incubated under aerobic and anaerobic conditions. The identification of the bacteria was carried out according to the Bergey's manual. Microscopic examination of Gram stained cells, catalase, oxidase and biochemical tests were performed when necessary to further identify. V. parahaemolyticus, Vibrio spp., Salmonella spp., and Aeromonas hydrophila were detected in one sample (2%). Shigella spp., and Flavobacterium spp. in two samples (4%), Clotriduim perfringens (vegetative forms), E. coli, and spores of Bacillus spp., were detected in three samples (6%), Staphylococcus aureus in four samples (8%). Various Micrococcus spp., and spores of C. perfringens in 16% and 35% of the samples respectively. From the Listeria genus, only the species Listeria innocua, Listeria welshimeri, Listeria seeligeri Listeria ivanovii and Listeria grayi were recovered from 2 to 10% of the samples. Microbiological analyses revealed the presence of a small number of pathogens in grey-mullet roe samples which are in accordance with the findings of similar studies. Traditional processing of the fish roe, seems inadequate to ensure the food safety and even waxing isn't expected to fully protect them against facultative anaerobes with salt tolerance. Therefore, additional measures

  3. Phylogeographic history of grey wolves in Europe.

    PubMed

    Pilot, Małgorzata; Branicki, Wojciech; Jedrzejewski, Włodzimierz; Goszczyński, Jacek; Jedrzejewska, Bogumiła; Dykyy, Ihor; Shkvyrya, Maryna; Tsingarska, Elena

    2010-04-21

    While it is generally accepted that patterns of intra-specific genetic differentiation are substantially affected by glacial history, population genetic processes occurring during Pleistocene glaciations are still poorly understood. In this study, we address the question of the genetic consequences of Pleistocene glaciations for European grey wolves. Combining our data with data from published studies, we analysed phylogenetic relationships and geographic distribution of mitochondrial DNA haplotypes for 947 contemporary European wolves. We also compared the contemporary wolf sequences with published sequences of 24 ancient European wolves. We found that haplotypes representing two haplogroups, 1 and 2, overlap geographically, but substantially differ in frequency between populations from south-western and eastern Europe. A comparison between haplotypes from Europe and other continents showed that both haplogroups are spread throughout Eurasia, while only haplogroup 1 occurs in contemporary North American wolves. All ancient wolf samples from western Europe that dated from between 44,000 and 1,200 years B.P. belonged to haplogroup 2, suggesting the long-term predominance of this haplogroup in this region. Moreover, a comparison of current and past frequencies and distributions of the two haplogroups in Europe suggested that haplogroup 2 became outnumbered by haplogroup 1 during the last several thousand years. Parallel haplogroup replacement, with haplogroup 2 being totally replaced by haplogroup 1, has been reported for North American grey wolves. Taking into account the similarity of diets reported for the late Pleistocene wolves from Europe and North America, the correspondence between these haplogroup frequency changes may suggest that they were associated with ecological changes occurring after the Last Glacial Maximum.

  4. Phylogeographic history of grey wolves in Europe

    PubMed Central

    2010-01-01

    Background While it is generally accepted that patterns of intra-specific genetic differentiation are substantially affected by glacial history, population genetic processes occurring during Pleistocene glaciations are still poorly understood. In this study, we address the question of the genetic consequences of Pleistocene glaciations for European grey wolves. Combining our data with data from published studies, we analysed phylogenetic relationships and geographic distribution of mitochondrial DNA haplotypes for 947 contemporary European wolves. We also compared the contemporary wolf sequences with published sequences of 24 ancient European wolves. Results We found that haplotypes representing two haplogroups, 1 and 2, overlap geographically, but substantially differ in frequency between populations from south-western and eastern Europe. A comparison between haplotypes from Europe and other continents showed that both haplogroups are spread throughout Eurasia, while only haplogroup 1 occurs in contemporary North American wolves. All ancient wolf samples from western Europe that dated from between 44,000 and 1,200 years B.P. belonged to haplogroup 2, suggesting the long-term predominance of this haplogroup in this region. Moreover, a comparison of current and past frequencies and distributions of the two haplogroups in Europe suggested that haplogroup 2 became outnumbered by haplogroup 1 during the last several thousand years. Conclusions Parallel haplogroup replacement, with haplogroup 2 being totally replaced by haplogroup 1, has been reported for North American grey wolves. Taking into account the similarity of diets reported for the late Pleistocene wolves from Europe and North America, the correspondence between these haplogroup frequency changes may suggest that they were associated with ecological changes occurring after the Last Glacial Maximum. PMID:20409299

  5. Development of annualized diameter and height growth equations for red alder: preliminary results.

    Treesearch

    Aaron Weiskittel; Sean M. Garber; Greg Johnson; Doug Maguire; Robert A. Monserud

    2006-01-01

    Most individual-tree based growth and yield models use a 5- to 10-year time step, which can make projections for a fast-growing species like red alder quite difficult. Further, it is rather cumbersome to simulate the effects of intensive silvicultural treatments such as thinning or pruning on a time step longer than one year given the highly dynamic nature of growth...

  6. Visible Light Photocatalysis of Radical Anion Hetero-Diels–Alder Cycloadditions

    PubMed Central

    Hurtley, Anna E.; Cismesia, Megan A.; Ischay, Michael A.

    2011-01-01

    We have discovered a photocatalytic intramolecular hetero-Diels–Alder reaction of tethered bis(enones). This transformation involves the intermediacy of an enone radical anion and constitutes the formal coupling of an electron-deficient heterodiene with an electronically mismatched enone dienophile. The diastereoselectivity and regioselectivity of the process are high, and the dihydropyran products are amenable to a variety of synthetically useful transformations. PMID:21666769

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

    PubMed

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

    2011-05-18

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

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

    PubMed

    Yuan, Yu; Li, Xin; Ding, Kuiling

    2002-09-19

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

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

    PubMed Central

    2015-01-01

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

  10. Preparation and biological evaluation of novel leucomycin analogs derived from nitroso Diels–Alder reactions†

    PubMed Central

    Yang, Baiyuan; Zollner, Tina; Gebhardt, Peter; Mollmann, Ute; Miller, Marvin J.

    2014-01-01

    A series of 10,13-disubstituted 16-membered macrolides was synthesized using nitroso Diels–Alder reactions of leucomycin A7. Despite the extensive constituent functionalities in leucomycin, the hetero cycloaddition reactions proceeded in a highly regio- and stereoselective fashion. Subsequent chemical modifications of the nitroso cycloadducts, including N–O bond reduction, were also conducted. Most leucomycin derivatives retained antibiotic profiles similar to leucomycin A7, and, in contrast to leucomycin itself, several exhibited moderate antiproliferative and cytotoxic activity. PMID:20090988

  11. 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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  13. Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels-Alder Reaction.

    PubMed

    Kumatabara, Yusuke; Kaneko, Shiho; Nakata, Satoshi; Shirakawa, Seiji; Maruoka, Keiji

    2016-08-05

    A piperidine-derived tetraalkylammonium salt with a non-coordinating counteranion worked as an effective hydrogen-bonding catalyst in an aza-Diels-Alder reaction of imines and a Danishefsky diene. The hydrogen-bonding interaction between the ammonium salt and an imine was observed as part of a (1) H NMR titration study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Diels-Alder cycloaddition of chiral nonracemic 2,5-diketopiperazine dienes.

    PubMed

    Morris, Erin N; Nenninger, E Katherine; Pike, Robert D; Scheerer, Jonathan R

    2011-08-19

    Preparation of a chiral, nonracemic 2,5-diketopiperazine diene has enabled the investigation of intermolecular hetero-Diels-Alder cycloadditions. The diketopiperazine diene is reactive with both electron-rich and -deficient alkene substrates. Diastereofacial control in the cycloaddition is enforced with a removable aminal substituent. This study partly illuminates the regiochemical, stereoelectronic, and reactivity preferences of the diketopiperazine cycloaddition as well as provides a direct diastereoselective synthetic route to bicyclo[2.2.2]diazaoctane structures. © 2011 American Chemical Society

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

  16. Effects of fertilization on growth and foliar nutrients of red alder seedlings.

    Treesearch

    M.A. Radwan

    1987-01-01

    Effects of P, K, Ca, Mg, S, Co, and Mo fertilizers on growth and foliar nutrients of red alder seedlings potted in Grove, Bunker, and Wishkah forest soils were determined. Growth in Grove soil was stimulated most by P, Ca, and P + Ca + Mg + K + S. Growth in Bunker soil was improved only by P. In Wishkah soil, best growth was obtained when P was used alone; all...

  17. Indole synthesis by palladium-catalyzed tandem allylic isomerization - furan Diels-Alder reaction.

    PubMed

    Xu, Jie; Wipf, Peter

    2017-08-30

    A Pd(0)-catalyzed elimination of an allylic acetate generates a π-allyl complex that is postulated to initiate a novel intramolecular Diels-Alder cycloaddition to a tethered furan (IMDAF). Under the reaction conditions, this convergent, microwave-accelerated cascade process provides substituted indoles in moderate to good yields after Pd-hydride elimination, aromatization by dehydration, and in situ N-Boc cleavage.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    PubMed

    Arumugam, Selvanathan; Popik, Vladimir V

    2011-04-13

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

  20. Silica-promoted Diels-Alder reactions in carbon dioxide from gaseous to supercritical conditions

    SciTech Connect

    Weinstein, R.D.; Renslo, A.R.; Danheiser, R.L.; Tester, J.W.

    1999-04-15

    Amorphous fumed silica (SiO{sub 2}) was shown to increase yields and selectivities of several Diels-Alder reactions in gaseous and supercritical CO{sub 2}. Pressure effects on the Diels-Alder reaction were explored using methyl vinyl ketone and penta-1,3-diene at 80 C. The selectivity of the reaction was not affected by pressure/density. As pressure was increased, the yield decreased. At the reaction temperature, adsorption isotherms at various pressures were obtained for the reactants and the Diels-Alder adduct. As expected when pressure is increased, the ratio of the amount of reactants adsorbed to the amount of reactants in the fluid phase decreases, thus causing the yield to decrease. The Langmuir adsorption model fit the adsorption data. The Langmuir equilibrium partitioning constants all decreased with increasing pressure. The effect of temperature on adsorption was experimentally determined and traditional heats of adsorption were calculated. However, since supercritical CO{sub 2} is a highly compressible fluid, it is logical to examine the effect of temperature at constant density. In this case, entropies of adsorption were obtained. The thermodynamic properties that influence the real enthalpy and entropy of adsorption were derived. Methods of doping the silica and improving yields and selectivities were also explored.

  1. Diene-modified nucleotides for the Diels–Alder-mediated functional tagging of DNA

    PubMed Central

    Borsenberger, Vinciane; Howorka, Stefan

    2009-01-01

    We explore the potential of the Diels–Alder cycloaddition for the functional tagging of DNA strands. A deoxyuridine triphosphate derivative carrying a diene at position 5 of the pyrimidine base was synthesized using a two-step procedure. The derivative was efficiently accepted as substrate in enzymatic polymerization assays. Diene carrying strands underwent successful cycloaddition with maleimide-terminated fluorescence dyes and a polymeric reagent. Furthermore, a nucleotide carrying a peptide via a Diels–Alder cyclohexene linkage was prepared and sequence-specifically incorporated into DNA. The Diels–Alder reaction presents a number of positive attributes such as good chemoselectivity, water compatibility, high-yield under mild conditions and no additional reagents apart from a diene and a dienophile. Furthermore, suitable dienophiles are commercially available in the form of maleimide-derivatives of fluorescent dyes and bioaffinity tags. Based on these advantages, diene- and cyclohexene-based nucleotide triphosphates are expected to find wider use in the area of nucleic acid chemistry. PMID:19139071

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

    PubMed

    Durkaya, Ali; Durkaya, Birsen

    2009-07-01

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

  3. Using atmospheric pressure plasma treatment for treating grey cotton fabric.

    PubMed

    Kan, Chi-Wai; Lam, Chui-Fung; Chan, Chee-Kooi; Ng, Sun-Pui

    2014-02-15

    Conventional wet treatment, desizing, scouring and bleaching, for grey cotton fabric involves the use of high water, chemical and energy consumption which may not be considered as a clean process. This study aims to investigate the efficiency of the atmospheric pressure plasma (APP) treatment on treating grey cotton fabric when compared with the conventional wet treatment. Grey cotton fabrics were treated with different combinations of plasma parameters with helium and oxygen gases and also through conventional desizing, scouring and bleaching processes in order to obtain comparable results. The results obtained from wicking and water drop tests showed that wettability of grey cotton fabrics was greatly improved after plasma treatment and yielded better results than conventional desizing and scouring. The weight reduction of plasma treated grey cotton fabrics revealed that plasma treatment can help remove sizing materials and impurities. Chemical and morphological changes in plasma treated samples were analysed by FTIR and SEM, respectively. Finally, dyeability of the plasma treated and conventional wet treated grey cotton fabrics was compared and the results showed that similar dyeing results were obtained. This can prove that plasma treatment would be another choice for treating grey cotton fabrics.

  4. Bibliometric study of grey literature in core veterinary medical journals

    PubMed Central

    Pelzer, Nancy L.; Wiese, William H.

    2003-01-01

    Objectives: Grey literature has been perceived by many as belonging to the primary sources of information and has become an accepted method of nonconventional communication in the sciences and medicine. Since little is known about the use and nature of grey literature in veterinary medicine, a systematic study was done to analyze and characterize the bibliographic citations appearing in twelve core veterinary journals. Methods: Citations from 2,159 articles published in twelve core veterinary journals in 2000 were analyzed to determine the portion of citations from grey literature. Those citations were further analyzed and categorized according to the type of publication. Results: Citation analysis yielded 55,823 citations, of which 3,564 (6.38%) were considered to be grey literature. Four veterinary specialties, internal medicine, pathology, theriogenology, and microbiology, accounted for 70% of the total number of articles. Three small-animal clinical practice journals cited about 2.5–3% grey literature, less than half that of journals with basic research orientations, where results ranged from almost 6% to approximately 10% grey literature. Nearly 90% of the grey literature appeared as conferences, government publications, and corporate organization literature. Conclusions: The results corroborate other reported research that the incidence of grey literature is lower in medicine and biology than in some other fields, such as aeronautics and agriculture. As in other fields, use of the Internet and the Web has greatly expanded the communication process among veterinary professionals. The appearance of closed community email forums and specialized discussion groups within the veterinary profession is an example of what could become a new kind of grey literature. PMID:14566374

  5. Phagocytosis in pup and adult harbour, grey and harp seals.

    PubMed

    Frouin, Héloïse; Lebeuf, Michel; Hammill, Mike; Fournier, Michel

    2010-04-15

    Knowledge on pinniped immunology is still in its infancy. For instance, age-related and developmental aspects of the immune system in pinnipeds need to be better described. The present study examined the phagocytic activity and efficiency of harbour, grey and harp seal leukocytes. In the first part of the study, peripheral blood was collected from captive female harbour seals of various ages. Data showed an age-related decrease in phagocytosis in female harbour seals from sub-adult to adulthood. In the second part of the study, changes in phagocytosis were quantified during lactation in wild newborn harbour, grey and harp seals and in their mothers (harp and grey seals). In newborns of the same age, leukocytes of harbour and harp seals phagocytosed less than those of grey seal pups. The phagocytic activity and efficiency increased significantly from early to mid-lactation in newborn harbour seals, and from early to late lactation in newborn grey seals, which could suggest that the transfer of phagocytosis-promoting factor(s) in colostrum is an important feature of temporary protection for pups. In contrast, no changes in phagocytic activity and efficiency were observed in lactating females of the two seal species, harp and grey, examined. At late lactation, phagocytic activity in both grey and harp seal pups and phagocytic efficiency in grey seal pups were significantly higher than in their mothers. These results could reflect either the capacity of phagocytes of the newborn harp and grey seals to respond to pathogens. Results from this study suggest that the phagocytosis of the seal species examined is not fully developed at birth as it generally increases in pups during lactation. Thereafter, the phagocytic activity of seals appears to decrease throughout adulthood.

  6. TEST STAND 4697 CONSTRUCTION

    NASA Image and Video Library

    2016-01-06

    A CRANE MOVES THE FIRST STEEL TIER TO BE BOLTED INTO PLACE ON JAN. 6, FOR WELDING OF A SECOND NEW STRUCTURAL TEST STAND AT NASA'S MARSHALL SPACE FLIGHT CENTER IN HUNTSVILLE, ALABAMA -- CRITICAL TO DEVELOPMENT OF NASA'S SPACE LAUNCH SYSTEM. WHEN COMPLETED THIS SUMMER, THE 85-FOOT-TALL TEST STAND 4697 WILL USE HYDRAULIC CYLINDERS TO SUBJECT THE LIQUID OXYGEN TANK AND HARDWARE OF THE MASSIVE SLS CORE STAGE TO THE SAME LOADS AND STRESSES IT WILL ENDURE DURING A LAUNCH. THE STAND IS RISING IN MARSHALL'S WEST TEST AREA, WHERE WORK IS ALSO UNDERWAY ON THE 215-FOOT-TALL TOWERS OF TEST STAND 4693, WHICH WILL CONDUCT SIMILAR STRUCTURAL TESTS ON THE SLS CORE STAGE'S LIQUID HYDROGEN TANK. SLS, THE MOST POWERFUL ROCKET EVER BUILT, WILL CARRY ASTRONAUTS IN NASA'S ORION SPACECRAFT ON DEEP SPACE MISSIONS, INCLUDING THE JOURNEY TO MARS.

  7. A-3 Test Stand

    NASA Image and Video Library

    2011-08-19

    The A-3 Test Stand under construction at Stennis Space Center is set for completion and activation in 2013. It will allow operators to conduct simulated high-altitude testing on the next-generation J-2X rocket engine.

  8. NEO Test Stand Analysis

    NASA Technical Reports Server (NTRS)

    Pike, Cody J.

    2015-01-01

    A project within SwampWorks is building a test stand to hold regolith to study how dust is ejected when exposed to the hot exhaust plume of a rocket engine. The test stand needs to be analyzed, finalized, and fabrication drawings generated to move forward. Modifications of the test stand assembly were made with Creo 2 modeling software. Structural analysis calculations were developed by hand to confirm if the structure will hold the expected loads while optimizing support positions. These calculations when iterated through MatLab demonstrated the optimized position of the vertical support to be 98'' from the far end of the stand. All remaining deflections were shown to be under the 0.6'' requirement and internal stresses to meet NASA Ground Support Equipment (GSE) Safety Standards. Though at the time of writing, fabrication drawings have yet to be generated, but are expected shortly after.

  9. The Stimulus test stand

    SciTech Connect

    Christofek, L.; Rapidis, P.; Reinhard, A.; /Fermilab

    2005-06-01

    The Stimulus Test Stand was originally constructed and assembled for testing the SVX2 ASIC readout and then upgraded for SVX3 ASIC prototyping and testing. We have modified this system for SVX4 ASIC [1] prototype testing. We described the individual components below. Additional details for other hardware for SVX4 testing can be found in reference [2]. We provide a description of the Stimulus Test Stand used for prototype testing of the SVX4 chip.

  10. Grey Relational Evaluation on Road Project Delivery Models

    NASA Astrophysics Data System (ADS)

    Lo, Shih-Ching; Chao, Yu; Lee, Gin-Yuan

    2009-08-01

    In this study, four road delivery project models are analyzed by grey relational evaluation. The four models are design-bid-build (DBB), design-build (DB), construction management (CM) and design-build-maintenance (DBM). Evaluating road project delivery models is difficult because the projects differ from road to road, state to state and country to country. Thus, the evaluation data of project delivery systems are poor and lacking. Grey theory is an effective mathematical method, which is a multidisciplinary and generic theory dealing with systems characterized by poor information and/or for which information is lacking. Therefore, grey relational analysis and grey model are employed to compare the efficiency of the four road project delivery models. According to the result, DBM is the best model. DBB is the worst one and DB is better than CM. The results may provide public sectors to employ an adequate model so as to proceed with road construction project.

  11. 4. General view of road with grey birch trees looking ...

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

    4. General view of road with grey birch trees looking E. - Great Smoky Mountains National Park Roads & Bridges, Heintooga Round Bottom Road & Balsam Mountain Road, Between Blue Ridge Parkway & Big Cove Road, Gatlinburg, Sevier County, TN

  12. Wick type SDEs driven by grey Brownian motion

    NASA Astrophysics Data System (ADS)

    Bock, Wolfgang; da Silva, José Luís

    2017-08-01

    We derive solutions of the Ornstein-Uhlenbeck and of a linear Wick-type stochastic differential equation (SDE) driven by grey Brownian motion. The solutions are characterized to be in a suitable distribution space.

  13. How to search for and use 'grey literature' in research.

    PubMed

    Coad, Jane; Hardicre, Jayne; Devitt, Patric

    An ever-growing amount of grey literature is available to nurses, including oral presentations, personal communication, leaflets, newspapers and magazines, unpublished research, internal reports and minutes of meetings. It can be an invaluable research resource.

  14. 29. DEPENDABLE FORDATHSHELL CORE MACHINES IN THE GREY IRON FOUNDRY ...

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

    29. DEPENDABLE FORDATH-SHELL CORE MACHINES IN THE GREY IRON FOUNDRY INJECTS SAND INTO A CLOSED CORE BOX. SOME OF THE UNITS HEAT THE CORE BOX TO FIX THE RESINS AS THE CORE REMAINS IN THE BOX, OTHERS MERELY SHAPED THE CORE SAND REQUIRING BAKING OF THE CORES TO HARDEN THEM. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  15. Brain grey matter volume alterations in late-life depression.

    PubMed

    Du, Mingying; Liu, Jia; Chen, Ziqi; Huang, Xiaoqi; Li, Jing; Kuang, Weihong; Yang, Yanchun; Zhang, Wei; Zhou, Dong; Bi, Feng; Kendrick, Keith M; Gong, Qiyong

    2014-11-01

    Voxel-based morphometry (VBM) studies have demonstrated that grey matter abnormalities are involved in the pathophysiology of late-life depression (LLD), but the findings are inconsistent and have not been quantitatively reviewed. The aim of the present study was to conduct a meta-analysis that integrated the reported VBM studies, to determine consistent grey matter alterations in individuals with LLD. A systematic search was conducted to identify VBM studies that compared patients with LLD and healthy controls. We performed a meta-analysis using the effect size signed differential mapping method to quantitatively estimate regional grey matter abnormalities in patients with LLD. We included 9 studies with 11 data sets comprising 292 patients with LLD and 278 healthy controls in our meta-analysis. The pooled and subgroup meta-analyses showed robust grey matter reductions in the right lentiform nucleus extending into the parahippocampus, the hippocampus and the amygdala, the bilateral medial frontal gyrus and the right subcallosal gyrus as well as a grey matter increase in the right lingual gyrus. Meta-regression analyses showed that mean age and the percentage of female patients with LLD were not significantly related to grey matter changes. The analysis techniques, patient characteristics and clinical variables of the studies included were heterogeneous, and most participants were medicated. The present meta-analysis is, to our knowledge, the first to overcome previous inconsistencies in the VBM studies of LLD and provide robust evidence for grey matter alterations within fronto-striatal-limbic networks, thereby implicating them in the pathophysiology of LLD. The mean age and the percentage of female patients with LLD did not appear to have a measurable impact on grey matter changes, although we cannot rule out the contributory effects of medication.

  16. The Diels-Alder reaction: A powerful tool for the design of drug delivery systems and biomaterials.

    PubMed

    Gregoritza, Manuel; Brandl, Ferdinand P

    2015-11-01

    Click reactions have the potential to greatly facilitate the development of drug delivery systems and biomaterials. These reactions proceed under mild conditions, give high yields, and form only inoffensive by-products. The Diels-Alder cycloaddition is one of the click reactions that do not require any metal catalyst; it is one of the most useful reactions in synthetic organic chemistry and material design. Herein, we highlight possible applications of the Diels-Alder reaction in pharmaceutics and biomedical engineering. Particular focus is placed on the synthesis of polymers and dendrimers for drug delivery, the preparation of functionalized surfaces, bioconjugation techniques, and applications of the Diels-Alder reaction in nanotechnology. Moreover, applications of the reaction for the preparation of hydrogels for drug delivery and tissue engineering are reviewed. A general introduction to the Diels-Alder reaction is presented, along with a discussion of potential pitfalls and challenges. At the end of the article, we provide a set of tools that may facilitate the application of the Diels-Alder reaction to solve important pharmaceutical or biomedical problems. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. 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.

  18. Benefit to N2-fixing alder of extending growth period at the cost of leaf nitrogen loss without resorption.

    PubMed

    Tateno, Masaki

    2003-11-01

    This study examines the adaptive role of not resorbing N in N(2)-fixing deciduous trees in terms of their energy balance. The autumnal growth of N(2)-fixing Alnus firma Sieb. et Zucc. (alder) was compared with that of the non-N(2)-fixing Morus bombycis Koizumi (mulberry), which resorbs leaf N. The freezing resistance of leaves of both species was -2 degrees C. Mulberry seedlings lost their photosynthetic ability in mid-October, although the minimum temperature was still above 0 degrees C. Thereafter, their leaves turned yellow and were gradually shed. In contrast, seedlings of the alder maintained their photosynthetic ability until mid-November, when the minimum temperature fell to the freezing resistance limit. Thereafter, their leaves were shed quickly without an autumn tint. The mulberry resorbed 48.9% of leaf N, whereas the alder resorbed hardly any. These results show that, compared with the mulberry tree, the alder extended its growth period for 1 month in return for losing leaf N without resorption. The amount of energy assimilated by the alder in the extended growth period was about six times that required for compensating for the nitrogen loss, if the compensation is dependent only on the tree's own nitrogen fixation. This surplus energy balance has probably allowed N(2)-fixing deciduous trees to evolve their non-N-resorbing trait.

  19. Looking northeast from Test Stand 'A' superstructure towards Test Stand ...

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

    Looking northeast from Test Stand 'A' superstructure towards Test Stand 'D' tower (4223/E-24, left background), Test Stand 'C' tower (4217/E-18, center), and Test Stand 'B' (4215/E-16, right foreground). - Jet Propulsion Laboratory Edwards Facility, Edwards Air Force Base, Boron, Kern County, CA

  20. PPT Thrust Stand

    NASA Technical Reports Server (NTRS)

    Haag, Thomas W.

    1995-01-01

    A torsional-type thrust stand has been designed and built to test Pulsed Plasma Thrusters (PPT's) in both single shot and repetitive operating modes. Using this stand, momentum per pulse was determined strictly as a function of thrust stand deflection, spring constant, and natural frequency. No empirical corrections were required. The accuracy of the method was verified using a swinging impact pendulum. Momentum transfer data between the thrust stand and the pendulum were consistent to within 1%. Following initial calibrations, the stand was used to test a Lincoln Experimental Satellite (LES-8/9) thruster. The LES-8/9 system had a mass of approximately 7.5 kg, with a nominal thrust to weight ratio of 1.3 x 10(exp -5). A total of 34 single shot thruster pulses were individually measured. The average impulse bit per pulse was 266 microN-s, which was slightly less than the value of 300 microN-s published in previous reports on this device. Repetitive pulse measurements were performed similar to ordinary steady-state thrust measurements. The thruster was operated for 30 minutes at a repetition rate of 132 pulses per minute and yielded an average thrust of 573 microN. Using average thrust, the average impulse bit per pulse was estimated to be 260 microN-s, which was in agreement with the single shot data. Zero drift during the repetitive pulse test was found to be approximately 1% of the measured thrust.

  1. PPT thrust stand

    NASA Astrophysics Data System (ADS)

    Haag, Thomas W.

    1995-11-01

    A torsional-type thrust stand has been designed and built to test Pulsed Plasma Thrusters (PPT's) in both single shot and repetitive operating modes. Using this stand, momentum per pulse was determined strictly as a function of thrust stand deflection, spring constant, and natural frequency. No empirical corrections were required. The accuracy of the method was verified using a swinging impact pendulum. Momentum transfer data between the thrust stand and the pendulum were consistent to within 1%. Following initial calibrations, the stand was used to test a Lincoln Experimental Satellite (LES-8/9) thruster. The LES-8/9 system had a mass of approximately 7.5 kg, with a nominal thrust to weight ratio of 1.3 x 10(exp -5). A total of 34 single shot thruster pulses were individually measured. The average impulse bit per pulse was 266 microN-s, which was slightly less than the value of 300 microN-s published in previous reports on this device. Repetitive pulse measurements were performed similar to ordinary steady-state thrust measurements. The thruster was operated for 30 minutes at a repetition rate of 132 pulses per minute and yielded an average thrust of 573 microN. Using average thrust, the average impulse bit per pulse was estimated to be 260 microN-s, which was in agreement with the single shot data. Zero drift during the repetitive pulse test was found to be approximately 1% of the measured thrust.

  2. Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies.

    PubMed

    Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu

    2017-03-03

    Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.

  3. Comparative effects of urea fertilizer and red alder in a site III, coast Douglas-fir plantation in the Washington Cascade Range.

    Treesearch

    Richard E. Miller; Harry W. Anderson; Marshall Murray; Rick. Leon

    2005-01-01

    Five randomly assigned treatments were used to quantify effects of adding varying numbers of red alder (Alnus rubra Bong.) or nitrogen (N) fertilization on growth of a 10-year-old conifer plantation at a medium quality site in the western Washington Cascade Range. Zero, 20, 40, and 80 alder trees per acre were retained along with about 300 conifers...

  4. Domino Aza-Michael-ih-Diels-Alder Reaction to Various 3-Vinyl-1,2,4-triazines: Access to Polysubstituted Tetrahydro-1,6-naphthyridines.

    PubMed

    Jouha, Jabrane; Buttard, Floris; Lorion, Magali; Berthonneau, Clément; Khouili, Mostafa; Hiebel, Marie-Aude; Guillaumet, Gérald; Brière, Jean-François; Suzenet, Franck

    2017-09-15

    A straightforward domino aza-Michael-inverse-electron-demand-hetero-Diels-Alder/retro-Diels-Alder reaction between primary and secondary propargylamine derivatives and 3-vinyl-1,2,4-triazines is developed highlighting not only the uniqueness of this dual-heterocyclic platform but also a novel and unprecedented path to polysubstituted tetrahydro-1,6-naphthyridine scaffolds.

  5. Standing wave compressor

    DOEpatents

    Lucas, Timothy S.

    1991-01-01

    A compressor for compression-evaporation cooling systems, which requires no moving parts. A gaseous refrigerant inside a chamber is acoustically compressed and conveyed by means of a standing acoustic wave which is set up in the gaseous refrigerant. This standing acoustic wave can be driven either by a transducer, or by direct exposure of the gas to microwave and infrared sources, including solar energy. Input and output ports arranged along the chamber provide for the intake and discharge of the gaseous refrigerant. These ports can be provided with optional valve arrangements, so as to increase the compressor's pressure differential. The performance of the compressor in either of its transducer or electromagnetically driven configurations, can be optimized by a controlling circuit. This controlling circuit holds the wavelength of the standing acoustical wave constant, by changing the driving frequency in response to varying operating conditions.

  6. Treating mature stands for wildlife

    Treesearch

    William H. Healy; Gary F. Houf

    1989-01-01

    Stands older than 60 years or that are medium to large sawtimber size generally provide good wildlife habitat. Mature trees usually produce abundant mast and provide den sites (see fig. 1 in Note 9.04 Treating Immature Stands). The undergrowth in these stands produces moderate amounts of browse and herbage. Mature stands also provide opportunities for management...

  7. Treating immature stands for wildlife

    Treesearch

    William M. Healy; Garry F. Houf

    1989-01-01

    Immature stands include those up to 60 years old or in the sapling, pole, and small sawtimber size-class. Immature stands, particularly in the sapling or pole stage, present a challenge to the wildlife manager. Compared to either younger regenerating stands or more mature stands, pole-size trees do not provide much mast or forage beneficial for wildlife (fig. 1).

  8. Aerial shows Stennis test stands

    NASA Image and Video Library

    2004-04-16

    An aerial photo shows the B-1/B-2 Test Stand (foreground), A-2 Test Stand (middle) and A-1 Test Stand (back). The historic stands have been used to test engines used on every manned Apollo and space shuttle mission.

  9. Standing equine sinus surgery.

    PubMed

    Barakzai, Safia Z; Dixon, Padraic M

    2014-04-01

    Trephination of the equine sinuses is a common surgical procedure in sedated standing horses. Standing sinus flap surgery has become increasingly popular in equine referral hospitals and offers several advantages over sinusotomy performed under general anesthesia, including reduced patient-associated risks and costs; less intraoperative hemorrhage, allowing better visualization of the operative site; and allows surgeons to take their time. Other minimally invasive surgical procedures include sinoscopic surgery, balloon sinuplasty, and transnasal laser sinonasal fenestration. Despite the procedure used, appropriate indications for surgery, good patient selection, and familiarity with regional anatomy and surgical techniques are imperative for good results. Copyright © 2014 Elsevier Inc. All rights reserved.

  10. 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

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

    SciTech Connect

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

    1993-06-30

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

  12. Synthesis of the AB ring system of clifednamide utilizing Claisen rearrangement and Diels-Alder reaction as key steps.

    PubMed

    Loke, Inga; Bentzinger, Guillaume; Holz, Julia; Raja, Aruna; Bhasin, Aman; Sasse, Florenz; Köhn, Andreas; Schobert, Rainer; Laschat, Sabine

    2016-01-21

    In order to construct the functionalized AB ring system of clifednamide, member of the class of macrocyclic tetramic acid lactams, a synthesis was developed which utilized an Ireland-Claisen rearrangement and an intramolecular Diels-Alder reaction. Starting from di-O-isopropylidene-d-mannitol the allyl carboxylate precursor for the sigmatropic rearrangement was prepared. This rearrangement proceeded diastereoselectively only in the presence of an allyl silyl ether instead of the parent enone in the side chain, as suggested by deuteration experiments. A subsequent Diels-Alder reaction yielded the target ethyl hexahydro-1H-indene-carboxylate with high diastereoselectivity. Quantum-chemical investigations of this intramolecular Diels-Alder reaction support the proposed configuration of the final product.

  13. 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

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

    NASA Astrophysics Data System (ADS)

    Inagaki, Yusuke; Nakamoto, Masaaki; Sekiguchi, Akira

    2014-01-01

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

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

    PubMed

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

    2015-09-02

    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.

  16. 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.

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

    SciTech Connect

    Zhu, Z.; Espenson, J.H.

    1997-04-16

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

  18. Assessment of global grey water footprint of major food crops

    NASA Astrophysics Data System (ADS)

    Yang, Hong; Liu, Wenfeng; Antonelli, Marta

    2016-04-01

    Agricultural production is one of the major sources of water pollution in the world. This is closely related to the excess application of fertilizers. Leaching of N and P to water bodies has caused serious degradation of water quality in many places. With the persistent increase in the demand for agricultural products, agricultural intensification evident during the past decades will continue in the future. This will lead to further increase in fertilizer application and consequently water pollution. Grey water footprint is a measure of the intensity of water pollution caused by water use for human activities. It is defined as the volume of water that is required to assimilate a load of pollutants to a freshwater body, based on natural background concentrations and water quality standards. This study conducts a global assessment of grey water footprint for major cereal crops, wheat, maize and rice. A crop model, Python-based EPIC (PEPIT), is applied to quantify the leaching of N and P from the fertilizer application in the three crops on a global scale with 0.5 degree spatial resolution. The hotspots of leaching are identified. The results suggest that, based on the definition and method of grey water footprint proposed by the World Water Footprint Network, the grey water footprint in many parts of the world has exceeded their total water resources availability. This indicates the seriousness of water pollution caused by agricultural production. However, the situation may also call for the development of a realistic measurement of grey water footprint which is more pertinent to water resources management. This paper proposes some alternatives in measuring grey water footprint and also discusses incorporation of grey water footprint assessment into water policy formulation and river basins plan development.

  19. Relationship between grey matter integrity and executive abilities in aging.

    PubMed

    Manard, Marine; Bahri, Mohamed Ali; Salmon, Eric; Collette, Fabienne

    2016-07-01

    This cross-sectional study was designed to investigate grey matter changes that occur in healthy aging and the relationship between grey matter characteristics and executive functioning. Thirty-six young adults (18-30 years old) and 43 seniors (60-75 years old) were included. A general executive score was derived from a large battery of neuropsychological tests assessing three major aspects of executive functioning (inhibition, updating and shifting). Age-related grey matter changes were investigated by comparing young and older adults using voxel-based morphometry and voxel-based cortical thickness methods. A widespread difference in grey matter volume was found across many brain regions, whereas cortical thinning was mainly restricted to central areas. Multivariate analyses showed age-related changes in relatively similar brain regions to the respective univariate analyses but appeared more limited. Finally, in the older adult sample, a significant relationship between global executive performance and decreased grey matter volume in anterior (i.e. frontal, insular and cingulate cortex) but also some posterior brain areas (i.e. temporal and parietal cortices) as well as subcortical structures was observed. Results of this study highlight the distribution of age-related effects on grey matter volume and show that cortical atrophy does not appear primarily in "frontal" brain regions. From a cognitive viewpoint, age-related executive functioning seems to be related to grey matter volume but not to cortical thickness. Therefore, our results also highlight the influence of methodological aspects (from preprocessing to statistical analysis) on the pattern of results, which could explain the lack of consensus in literature.

  20. Diels-Alder cycloaddition in the synthesis of 1-azafagomine, analogs, and derivatives as glycosidase inhibitors.

    PubMed

    Salgueiro, Daniela A L; Sousa, Cristina E A; Fortes, A Gil; Alves, M José

    2012-12-01

    This comprehensive review deals with the synthesis of 1-azafagomine, analogs, and derivatives having the Diels-Alder cycloaddition as the key step. Most of the compounds referred are racemic or have been resolved by lipase transesterification. There are two asymmetric cycloadditions leading to 1-azafagomine or to an analog. In one case both enantiomers of 1-azafagomine were prepared together with a pair of derivatives. The study comprises glycosidase inhibition studies of the target compounds to a set of glycosidic enzymes, and evidenced molecular features that enhance or diminish their activity as glycosidase inhibitors.

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

    SciTech Connect

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

    1999-12-08

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

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

    PubMed

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

    2012-01-06

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

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

    PubMed

    Brulíková, Lucie; Harrison, Aidan; Miller, Marvin J; Hlaváč, Jan

    2016-01-01

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

  4. Rate variations of a hetero-Diels--Alder reaction in supercritical fluid CO{sub 2}

    SciTech Connect

    Thompson, R.L.; Glaeser, R.; Bush, D.; Liotta, C.L.; Eckert, C.A.

    1999-11-01

    The hetero-Diels-Alder reaction between anthracene and excess 4-phenyl-1,2,4-triazoline-3,5-dione has been investigated in supercritical CO{sub 2} at 40 C and pressures between 75 and 216 bar. Biomolecular reaction rate constants have been measured via fluorescence spectroscopy by following the decrease in anthracene concentration with reaction time. The reaction rate is elevated in the vicinity of the critical pressure. This difference is consistent with local composition enhancement and can be modeled with the Peng-Robinson equation of state.

  5. Deeper Insight into the Diels-Alder Reaction through the Activation Strain Model.

    PubMed

    Fernández, Israel; Bickelhaupt, F Matthias

    2016-12-06

    In this Focus Review, we present the application of the so-called Activation Strain Model of chemical reactivity to the Diels-Alder cycloaddition reaction. To this end, representative recent examples have been selected to illustrate the power of this new computational approach to gain a deeper quantitative understanding of this fundamental process in chemistry. We cover a wide range of issues, such as, the "endo-rule", reactivity trends emerging from systematic variation in the reactants' strain, and cycloaddition reactions involving relevant species in material science, that is, fullerenes, polycyclic aromatic hydrocarbons and nanotubes. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Approach Matters: The Kinetics of Interfacial Inverse-Electron Demand Diels-Alder Reactions.

    PubMed

    Sen, Rickdeb; Gahtory, Digvijay; Escorihuela, Jorge; Firet, Judith; Pujari, Sidharam P; Zuilhof, Han

    2017-09-21

    Rapid and quantitative click functionalization of surfaces remains an interesting challenge in surface chemistry. In this regard, inverse electron demand Diels-Alder (IEDDA) reactions represent a promising metal-free candidate. Herein, we reveal quantitative surface functionalization within 15 min. Furthermore, we report the comprehensive effects of substrate stereochemistry, surrounding microenvironment and substrate order on the reaction kinetics as obtained by surface-bound mass spectrometry (DART-HRMS). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  7. Catalytic Asymmetric Inverse-Electron-Demand Hetero-Diels-Alder Reactions.

    PubMed

    Xie, Mingsheng; Lin, Lili; Feng, Xiaoming

    2017-05-16

    In this review, the recent developments in catalytic asymmetric inverse-electron-demand hetero-Diels-Alder reaction, which is recognized as one of the most powerful routes to construct highly functionalized and enantioenriched six-membered heterocycles, are described. The article is organized on the basis of different kinds of electron-deficient heterodienes, including α,β-unsaturated ketones/aldehydes, o-benzoquinones, α,β-unsaturated imines, N-aryl imines, o-benzoqinone imides, and other aza-olefins. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Energy storage capacity of reversible liquid phase Diels-Alder reactions as determined by drop calorimetry

    SciTech Connect

    Chung, C.P.

    1983-01-01

    Several Diels-Alder reactions were evaluated as possible candidates for energy storage. The goal was to use simple drop calorimetry to screen reactions and to identify those with high energy storage capacities. The dienes used were furan and substituted furans. The dienophiles used were maleic anhydride and substituted maleic anhydrides. Sixteen reactions have been examined. Three had energy storage capacities that were increased due to reaction (maleic anhydride and 2-methyl furan, maleic anhydride and 2-ethyl furan, maleic anhydride and 2,5-dimethyl furan). The remaining thirteen showed no increase in apparent heat capacity due to reaction.

  9. 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.

  10. Kinetic stability of the C[sub 60]-cyclopentadiene diels-alder adduct

    SciTech Connect

    Giovane, L.M.; Barco, J.W.; Yadav, T.; Lafleur, A.L.; Marr, J.A.; Howard, J.B.; Rotello, V.M. )

    1993-08-19

    Buckminsterfullerene (C[sub 60]) reacts with cyclopentadiene to produce the Diels-Alder adduct C[sub 60]C[sub 5]H[sub 6] (1). To determine the thermal stability of adduct 1, we have determined the rates of decomposition in the temperature range 80-95[degree]C. Fitting this data to the Arrhenius form of the rate expression gives a pre-exponential factor of log A = 12.59 [plus minus] 0.4 and an activation energy of 26.7 [plus minus] 2.2 kcal/mol. 14 refs., 3 figs., 1 tab.

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

    PubMed Central

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

    2016-01-01

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

  12. 1-Azadienes as regio- and chemoselective dienophiles in aminocatalytic asymmetric Diels-Alder reaction.

    PubMed

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

    2013-12-20

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

  13. 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

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

    PubMed

    Pham, Hung V; Houk, K N

    2014-10-03

    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.

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

    PubMed

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

    2014-12-17

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

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

    PubMed Central

    Volz, Nicole; Gläser, Franziska; Nieger, Martin

    2012-01-01

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

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

    PubMed

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

    2012-01-01

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

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

    PubMed

    Kramer, Carsten S; Bräse, Stefan

    2013-01-01

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

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

    PubMed Central

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

    2006-01-01

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

  20. β-Silyl-Assisted Tandem Diels-Alder/Nazarov Reaction of 1-Aryl-3-(trimethylsilyl) Ynones.

    PubMed

    Carmichael, Rachael A; Sophanpanichkul, Punyanuch; Chalifoux, Wesley A

    2017-05-19

    A one-pot tandem Diels-Alder/Nazarov reaction of 1-aryl-3-(trimethylsilyl) ynones has been achieved to generate carbo- and heterocyclic fused ring systems in good to excellent yields. The β-silyl effect is instrumental in accessing this otherwise challenging cascade annulation reaction. The tandem reaction proceeds in the presence of BCl3 to generate three new carbon-carbon bonds, a quaternary carbon, and two stereogenic centers with excellent diastereocontrol. A variety of substituted arenes, and even heteroaromatics, are tolerated to provide tricyclic products that are of interest as advanced intermediates toward biologically relevant compounds.

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

    PubMed Central

    Miller, Marvin J

    2016-01-01

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

  2. Free-Standing Canes.

    ERIC Educational Resources Information Center

    Ehresman, Paul

    1995-01-01

    A precane device, called the "free-standing cane," was developed to help children with blindness along with other disabilities. The cane detects obstacles; guides the user's hands into a relaxed, static position in front of the hips; facilitates postural security and control; and offers tactile and kinesthetic feedback. (JDD)

  3. Free-Standing Canes.

    ERIC Educational Resources Information Center

    Ehresman, Paul

    1995-01-01

    A precane device, called the "free-standing cane," was developed to help children with blindness along with other disabilities. The cane detects obstacles; guides the user's hands into a relaxed, static position in front of the hips; facilitates postural security and control; and offers tactile and kinesthetic feedback. (JDD)

  4. Principles of managing stands

    Treesearch

    David A. Marquis; Rodney Jacobs

    1989-01-01

    Forest stands are managed to achieve some combination of desired products or values. These products or values may include income and tangible benefits from timber production or fees for hunting rights and other recreational activities. The values may be intangible, such as the enjoyment of seeing wildlife or flowering plants, or the simple satisfaction of knowing that...

  5. Fertilizing natural stands

    Treesearch

    L. R. Auchmoody

    1989-01-01

    Given our present knowledge, and under current costs and returns, there appears to be little reason to fertilize natural stands of central hardwoods. Yet, some of the numerous fertilizer tests conducted with hardwoods over the past 50 years have shown very positive--but short-lived-growth responses. One "operational" (nonexperimental) use of nitrogen and...

  6. Economics of stand management

    Treesearch

    David K. Lewis

    1986-01-01

    This paper sets out to demonstrate the importance of considering the wealth represented by the growing stock in economic analyses of stand management alternatives, and to demonstrate the role of thinning in the manipulation of the efficiency of growing stock in the management of shortleaf pine (Pinus echinata Mill.). These goals are achieved through a demonstration of...

  7. Grey relational clustering associated with CAPRI applied to FPGA placement

    NASA Astrophysics Data System (ADS)

    Wu, Jan-Ou; Fan, Yang-Hsin; Wang, San-Fu

    2016-04-01

    Grey relational clustering is used to minimise wire length during field programmable gate arrays (FPGA) placement and routing. The proposed Grey Relational Clustering Apply to Placement (GRAP) algorithm combines grey relational clustering and convex assigned placement for regular ICs method to construct a placement netlist, which was successfully used to solve the problem of minimising wire length in an FPGA placement. Upon calculating the grey relational grade, GRAP can rank the sequence and analyse the minimal distance in configuration logic blocks based on the grey relational sequence and combined connection-based approaches. The experimental results demonstrate that the GRAP effectively compares the Hibert, Z and Snake with bounding box (BB) cost function in the space-filling curve. The GRAP improved BB cost by 0.753%, 0.324% and 0.096% for the Hilbert, Z and Snake, respectively. This study also compares the critical path with the space-filling curve. The GRAP approach improved the critical path for Snake by 1.3% in the space-filling curve; however, the GRAP increased critical path wire by 1.38% and 0.03% over that of the Hilbert and Z of space-filling curve, respectively.

  8. Fluorescence and coloration of grey hair.

    PubMed

    Daly, S; Bianchini, R; Polefka, T; Jumbelic, L; Jachowicz, J

    2009-10-01

    Grey hair samples were collected from 11 individuals and separated into un-pigmented and pigmented fibres (International Hair Importers). Fluorescence measurements were obtained by using a double-grating fluorescence spectrophotometer and a bifurcated fibre optics accessory to measure the spectra directly from the surface of hair at various distances from the fibre root. Colour measurements were carried out by using a Hunter colorimeter. The fluorescence spectra of un-pigmented hair obtained by the excitation at 290 nm show a peak at 356 nm [tryptophan (Trp)], and multi-peak emissions in the range from 395 to 500 nm. A significant variation in the Trp emission intensity at 356 nm vs. the intensity of emission in the 395-500 nm range was observed for hair collected from various individuals with yellow coloured hair producing stronger relative emission in 395-500 nm range. Quantitative measurements of coloration and the calculation of the Yellowness Index (YI) showed linear correlation between YI and the ratio of fluorescence intensities I(440)/I(356) The spectra obtained by excitation at 320 nm showed the emission peaks at 395 nm (unidentified), 420 nm (N-formylkynurenine), 460 nm (kynurenine), and 495 nm (3-hydroxykynurenine), which are the products of oxidative or metabolic conversion of tryptophan. Un-pigmented, yellow hair showed a build-up of the fluorescence band corresponding to 3-hydroxykynurenine at 495 nm. The data also showed the fluorescence quenching effect of melanin resulting in the lowering of the fluorescence intensity of pigmented hair. The spectra obtained at various positions along the fibres demonstrated gradual photo-decomposition of hair chromophores during their lifetimes. This was indicated by a decrease of Trp fluorescence intensity, which was relatively fast (8.10(-4)-1.5.10(-3) [day(-1)] as calculated for hair obtained from various individuals) for un-pigmented hair and slower for pigmented hair. A decrease in Trp emission was accompanied

  9. 20. Building 202, detail of stand A, rocket test stand ...

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

    20. Building 202, detail of stand A, rocket test stand in test cell. View looking southeast. - Rocket Engine Testing Facility, GRC Building No. 202, NASA Glenn Research Center, Cleveland, Cuyahoga County, OH

  10. 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

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

    PubMed

    Ninh, Chi; Bettinger, Christopher J

    2013-07-08

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

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

    PubMed

    Linder, Mats; Brinck, Tore

    2012-08-03

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

  13. Reactivity of End-functionalized Polymers Containing Diels-Alder Functional Groups

    NASA Astrophysics Data System (ADS)

    Meng, Yuan; Zhang, Yuan; Anthamatten, Mitchell

    2013-03-01

    Incorporation of reversible covalent bond into macromolecular systems has proven useful in engineering novel responsive architectures, and Diels-Alder bonding in this context is now well established. However, efficient synthesis of end-functionalized polymers is a major obstacle hindering further development of responsive and modular polymer architectures. In this current research, two immiscible polymers, poly(methyl methacrylate) (PMMA) and poly(benzyl methacrylate) (PBzMA) with controlled molecular weight, bearing terminal furan-maleimide groups, are prepared via Reversible Addition-Fragmentation chain transfer (RAFT) polymerization. The reactivity of such end-functionalized polymers is explored to expose the relationship between chain composition and their ability to undergo modular cross-coupling to form monodisperse block copolymers. To elucidate how reaction conditions affect the efficiency of the Diels-Alder reaction, Hydrogen Nuclear Magnetic Resonance (H-NMR) and Size Exclusion Chromatography (SEC) techniques are actively applied. Experimental results will be interpreted on the basis of dissimilarity between interaction energies of polymer segments and the concentration of reactive groups.

  14. 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.

  15. 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.

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

    PubMed

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

    2016-04-18

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-01-01

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

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

    PubMed

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

    2014-08-14

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

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

    NASA Astrophysics Data System (ADS)

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

    1982-12-01

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

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

    PubMed

    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

    2016-10-12

    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.

  1. 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.

  2. A grey {gamma}-ray transfer procedure for supernovae

    SciTech Connect

    Jeffery, D.J.

    1997-12-01

    The {gamma}-ray transfer in supernovae for the purposes of energy deposition in the ejecta can be approximated as grey radiative transfer using mean opacities. In past work there is a single pure absorption mean opacity which is a free parameter. Accurate results can be obtained by varying this mean opacity to fit the results of more accurate procedures. In this paper, the authors present a grey {gamma}-ray transfer procedure for energy deposition in which there are multiple mean opacities that are not free parameters and that have both absorption and scattering components. This procedure is based on a local-state (LS) approximation, and so they call it the LS grey {gamma}-ray transfer procedure or LS procedure for short.

  3. Efficiency of searching the grey literature in palliative care.

    PubMed

    Cook, A M; Finlay, I G; Edwards, A G; Hood, K; Higginson, I J; Goodwin, D M; Normand, C E; Douglas, H R

    2001-09-01

    A systematic review into palliative care team effectiveness was undertaken which has, inherent in its methodology, grey literature searching. Over 100 letters were written to a systematically chosen range of service providers, commissioners, and experts in combination with requests for information in six UK national cancer/palliative care organization newsletters. In addition, the System for Information on Grey Literature (SIGLE ) database was searched. As a result, 25 document hard copies were received. The documents were, in all but one case (this one study was also highlighted by the SIGLE search), not relevant as they were predominated by annual reports, service descriptions, and needs assessments. In terms of obtaining unpublished studies for possible inclusion in the review, this comprehensive search was unsuccessful and, therefore, it would appear that grey literature searching is not a useful tool in palliative care systematic reviews.

  4. Inbreeding and relatedness in Scandinavian grey wolves Canis lupus.

    PubMed

    Ellegren, H

    1999-01-01

    Management of small and threatened populations may require detailed knowledge about the genetic status of individuals and the genetic relatedness between individuals. I show here that individual heterozygosity at a set of 29 microsatellite loci correlates closely to the degree of inbreeding in a captive grey wolf population. Microsatellite allele sharing similarly correlates closely to known relatedness between pairs of individuals. Genotyping the same markers in a small (60-70 individuals) natural population of grey wolves in Sweden, low individual heterozygosities and high values of allele sharing between some animals were found. Since inbreeding depression has been documented in a captive grey wolf population of Scandinavian origin, the results point out an additional risk for the small Swedish wild population.

  5. Get up, Stand up

    ERIC Educational Resources Information Center

    Melia, Ed

    2009-01-01

    Ignorance about dyslexia meant a miserable school experience for Barrie Hughes. He was in his 50s when he found the courage to stand up in front of a classroom of learners and admit he couldn't read. Barrie, who is now 59 and works for the parks department of Brighton and Hove Council, only began to learn how to read words in the last three years…

  6. Get up, Stand up

    ERIC Educational Resources Information Center

    Melia, Ed

    2009-01-01

    Ignorance about dyslexia meant a miserable school experience for Barrie Hughes. He was in his 50s when he found the courage to stand up in front of a classroom of learners and admit he couldn't read. Barrie, who is now 59 and works for the parks department of Brighton and Hove Council, only began to learn how to read words in the last three years…

  7. Beam optics test stand

    NASA Astrophysics Data System (ADS)

    Humphries, S., Jr.; Hess, G.

    1988-04-01

    The design and construction of the Beam Optics Test Stand (BOTS) is presented. A variety of computer compatible diagnostics has been developed to facilitate experiments. Extensive theoretical work is presented leading to the identification of two potential methods to correct aberrations in magnetic optics: biased grid arrays and space charge corrected solenoidal lenses. A series of experiments is presented which demonstrates, for the first time, the feasibility of space charge corrected optics.

  8. Environmental vulnerability assessment using Grey Analytic Hierarchy Process based model

    SciTech Connect

    Sahoo, Satiprasad; Dhar, Anirban; Kar, Amlanjyoti

    2016-01-15

    Environmental management of an area describes a policy for its systematic and sustainable environmental protection. In the present study, regional environmental vulnerability assessment in Hirakud command area of Odisha, India is envisaged based on Grey Analytic Hierarchy Process method (Grey–AHP) using integrated remote sensing (RS) and geographic information system (GIS) techniques. Grey–AHP combines the advantages of classical analytic hierarchy process (AHP) and grey clustering method for accurate estimation of weight coefficients. It is a new method for environmental vulnerability assessment. Environmental vulnerability index (EVI) uses natural, environmental and human impact related factors, e.g., soil, geology, elevation, slope, rainfall, temperature, wind speed, normalized difference vegetation index, drainage density, crop intensity, agricultural DRASTIC value, population density and road density. EVI map has been classified into four environmental vulnerability zones (EVZs) namely: ‘low’, ‘moderate’ ‘high’, and ‘extreme’ encompassing 17.87%, 44.44%, 27.81% and 9.88% of the study area, respectively. EVI map indicates that the northern part of the study area is more vulnerable from an environmental point of view. EVI map shows close correlation with elevation. Effectiveness of the zone classification is evaluated by using grey clustering method. General effectiveness is in between “better” and “common classes”. This analysis demonstrates the potential applicability of the methodology. - Highlights: • Environmental vulnerability zone identification based on Grey Analytic Hierarchy Process (AHP) • The effectiveness evaluation by means of a grey clustering method with support from AHP • Use of grey approach eliminates the excessive dependency on the experience of experts.

  9. Occurrence, structure, and function of the nitrogen-fixing microsymbiont Frankia from nodules of Arizona alder [Abstract

    Treesearch

    J. O. Dawson; G. J. Gottfried; D. Hahn

    2005-01-01

    Actinorhizal plants are nodulated by the symbiotic, nitrogen-fixing actinomycete Frankia. The genus Alnus in the family Betulaceae is one of the 25 genera in 8 families of angiospermous plants that are actinorhizal. Arizona alder (Alnus oblongifolia Torr.) occurs in isolated populations associated with the...

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

    PubMed Central

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

    2016-01-01

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

  11. 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…

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

    PubMed

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

    2017-01-12

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

  14. 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...

  15. Juvenile wood effect in red alder : analysis of physical and mechanical data to delineate juvenile and mature wood zones

    Treesearch

    Joel W. Evans; John F. Senft; David W. Green

    2000-01-01

    The objective of this study was to investigate the influence of juvenile wood on the mechanical and physical properties of red alder. Tree growth in the first 10 to 20 years, usually referred to as juvenile wood, often influences wood quality by adversely affecting mechanical strength properties. Strength can be reduced up to 50 percent by the presence of juvenile wood...

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

    PubMed

    Hara, Kenji; Akiyama, Ryuto; Sawamura, Masaya

    2005-12-08

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

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

    PubMed

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

    2011-11-04

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

  18. Asymmetric Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene

    PubMed Central

    Raja, Sadiya

    2012-01-01

    Summary A new chiral Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene has been developed. The reaction provides optically active aza-tetracycles in good yields with high diastereo- and enantioselectivities under mild reaction conditions. PMID:23209517

  19. A Kinetic Study of the Diels-Alder Reaction. An Experiment Illustrating Simple Second-Order Reaction Kinetics.

    ERIC Educational Resources Information Center

    Silvestri, Michael G.; Dills, Charles E.

    1989-01-01

    Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)

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

    USDA-ARS?s Scientific Manuscript database

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

  1. The confined space inside carbon nanotubes can dictate the stereo- and regioselectivity of Diels-Alder reactions.

    PubMed

    Smith, Nicole M; Iyer, K Swaminathan; Corry, Ben

    2014-04-21

    Chemical reactions inside carbon nanotubes can yield unusual outcomes. Molecular dynamics simulations show that within the confined space of carbon nanotubes, the 1,4-exo adduct of a Diels-Alder cycloaddition may be produced instead of the 9,10-adduct, which is favoured in bulk. The likely product is highly dependent on the nanotube radius and reactant size.

  2. Improving germination of red elm (Ulmus rubra), gray alder (Alnus incana), and buffaloberry (Shepherdia canadensis) seeds with gibberellic acid

    Treesearch

    Brenda Morales; Charles Barden; Cheryl Boyer; Jason Griffin; Lillian Fisher; Joni Thompson

    2012-01-01

    Red elm (Ulmus rubra), gray alder (Alnus incana), and buffaloberry (Shepherdia canadensis) are considered important plants for many Native American tribes in the United States. Native Americans use these 3 species for a variety of traditional and medicinal purposes. For example, red elm is still the preferred firewood for the cultural ceremonies of several tribes....

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

    PubMed

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

    2002-08-21

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

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed

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

    2013-10-11

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

  6. 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.

  7. 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?".

  8. Venture Capital Investment Base on Grey Relational Theory

    NASA Astrophysics Data System (ADS)

    Zhang, Xubo

    This paper builds a venture capital investment projects selection evaluation model base on risk-weight investment return using grey relational analysis. The risk and return in venture capital investment projects selection process is analyses. These risk and return mainly constricted in management ability, operation ability, market ability, exit obtain and investment cost. The 18 sub-indicators are the impact factors contributed to these five evaluation aspects. Grey relation analysis is use to evaluate the venture capital investment selection. Get the optimal solution of risk-weight double objective investment selection evaluation model. An example is used to demonstrate the model in this paper.

  9. Case Report of dirofilariasis in grey wolf in Serbia.

    PubMed

    Gavrilović, Pavle; Blitva-Robertson, Gordana; Özvegy, József; Kiskároly, Ferenc; Becskei, Zsolt

    2014-03-01

    This paper describes a case of dirofilariasis in a two-year old, female grey wolf (Canis lupus lupus). The autopsy revealed the presence of 42 adult forms of Dirofilaria immitis in the pulmonary artery, right ventricle and right atrium, varying in length from 9.5 to 30 cm. This is, to the best of our knowledge, the second report of D. immitis in grey wolves in Serbia. Our finding confirms that the wolf, as a subspecies distinct from the dog, should also be considered as a very suitable definitive host for dirofilariasis.

  10. Tree species effects on stand transpiration in northern Wisconsin

    NASA Astrophysics Data System (ADS)

    Ewers, B. E.; Mackay, D. S.; Gower, S. T.; Ahl, D. E.; Burrows, S. N.; Samanta, S. S.

    2002-07-01

    We quantified canopy transpiration (EC) using sap flux measurements representing the four major forest types (northern hardwoods, conifer, aspen/fir, and forested wetland) around the WLEF-TV tall tower in northern Wisconsin. In order to scale individual sap flux measurements to EC, we quantified the amount of sapwood area per unit ground area and the spatial distribution of sap flux within trees. Contrary to our hypothesis that all tree species would have the same positive relationship between tree diameter and sapwood depth, white cedar and speckled alder, both wetland species, showed no relationship. We also hypothesized that the conifer trees would have a lower whole tree hydraulic conductance than deciduous trees. We actually discovered that white cedar had the highest hydraulic conductance. Our third hypothesis, that sapwood area per unit ground area would determine stand EC, was not rejected. The resulting average daily EC values over 53 days (23 June to 16 August 2000) from combining sap flux and sapwood area per unit ground area were 1.4, 0.8, 2.1, and 1.4 mm d-1 for conifer, northern hardwoods, aspen/fir, and forested wetland cover types, respectively. Average daily EC was only explained by an exponential saturation with daily average vapor pressure deficit.

  11. 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.

  12. Catalytic enantioselective aza-Diels-Alder reactions of unactivated acyclic 1,3-dienes with aryl-, alkenyl-, and alkyl-substituted imines.

    PubMed

    Hatanaka, Yasuo; Nantaku, Shuuto; Nishimura, Yuhki; Otsuka, Tomoyuki; Sekikaw, Tohru

    2017-08-08

    A catalytic enantioselective aza-Diels-Alder reaction of unactivated acyclic dienes with aryl-, alkenyl-, and alkyl-substituted imines is described. With 5-10 mol% loadings of a new Brønsted acid catalyst, the aza-Diels-Alder reaction of unactivated acyclic dienes proceeded to give the corresponding aza-Diels-Alder adducts in high yields (up to 98%) with excellent enantioselectivity (up to 98% ee). Preliminary DFT calculations suggest that the reaction proceeds through a chiral ion pair intermediate.

  13. Double-Diels-Alder Approach to Maoecrystal V. Unexpected C-C Bond-Forming Fragmentations of the [2.2.2]-Bicyclic Core.

    PubMed

    Smith, Brandon R; Njardarson, Jon T

    2017-09-14

    Synthetic studies toward maoecrystal V are reported. An oxidative dearomatization/Diels-Alder cascade to assemble the natural product carbocyclic core in one step is proposed. A facile electrocyclization is shown to suppress the intramolecular allene Diels-Alder pathway. This obstacle is alleviated via a stepwise approach with an allene equivalent to access the key cyclopentadiene-fused [2.2.2]-bicyclic core. Upon treatment with Lewis acid, the proposed intramolecular hetero-Diels-Alder reaction is cleanly and unexpectedly diverted either via C-C bond-forming fragmentation to the spiro-indene product (when R = OMe) or via elimination (when R = H).

  14. Managing uneven-aged stands

    Treesearch

    Jay R. Law; Craig G. Lorimer

    1989-01-01

    Maintaining uneven-aged stands involves cutting trees from a range of diameter classes in such a way that the residual stand has a balanced, steeply descending diameter distribution curve (fig. 1). The objective is to distribute trees by diameter classes so that over time the stand contains trees of different ages and sizes.

  15. A-3 Test Stand work

    NASA Image and Video Library

    2011-07-29

    Stennis Space Center employees have installed liquid oxygen and liquid hydrogen tanks atop the A-3 Test Stand, raising the structure to its full 300-foot height. The stand is being built to test next-generation rocket engines that could carry humans beyond low-Earth orbit into deep space. The A-3 Test Stand is scheduled for completion and activation in 2013.

  16. Stand Density and Canopy Gaps

    Treesearch

    Boris Zeide

    2004-01-01

    Estimation of stand density is based on a relationship between number of trees and their average diameter in fully stocked stands. Popular measures of density (Reineke’s stand density index and basal area) assume that number of trees decreases as a power function of diameter. Actually, number of trees drops faster than predicted by the power function because the number...

  17. Silvicultural treatments in sapling stands

    Treesearch

    Neil I. Lamson

    1989-01-01

    Sapling stands are those in which codominant trees average less than 5 inches d.b.h. Silvicultural treatments in sapling stands can be summed up in two words: CROP TREES. Any silvicultural treatment must help crop trees if the investment in sapling stands is going to pay off. Just cutting "bad" or "undesirable" trees does not insure that crop trees...

  18. A-3 Test Stand work

    NASA Image and Video Library

    2011-07-29

    Work continues on the A-3 Test Stand at Stennis Space Center. The new stand will allow operators to test next-generation rocket engines at simulated altitudes up to 100,000 feet. The test stand is scheduled for completion and activation in 2013.

  19. Measurement and clinical effect of grey matter pathology in multiple sclerosis.

    PubMed

    Geurts, Jeroen J G; Calabrese, Massimiliano; Fisher, Elizabeth; Rudick, Richard A

    2012-12-01

    During the past 10 years, the intense involvement of the grey matter of the CNS in the pathology of multiple sclerosis has become evident. On gross inspection, demyelination in the grey matter is rather inconspicuous, and lesions in the grey matter are mostly undetectable with traditional MRI sequences. However, the results of immunohistochemical studies have shown extensive involvement of grey matter, and researchers have developed and applied new MRI acquisition methods as a result. Imaging techniques specifically developed to visualise grey matter lesions indicate early involvement, and image analysis techniques designed to measure the volume of grey matter show progressive loss. Together, these techniques have shown that grey matter pathology is associated with neurological and neuropsychological disability, and the strength of this association exceeds that related to white matter lesions or whole brain atrophy. By focusing on the latest insights into the in-vivo measurement of grey matter lesions and atrophy, we can assess their clinical effects.

  20. Review of the technological approaches for grey water treatment and reuses.

    PubMed

    Li, Fangyue; Wichmann, Knut; Otterpohl, Ralf

    2009-05-15

    Based on literature review, a non-potable urban grey water reuse standard is proposed and the treatment alternatives and reuse scheme for grey water reuses are evaluated according to grey water characteristics and the proposed standard. The literature review shows that all types of grey water have good biodegradability. The bathroom and the laundry grey water are deficient in both nitrogen and phosphors. The kitchen grey water has a balanced COD: N: P ratio. The review also reveals that physical processes alone are not sufficient to guarantee an adequate reduction of the organics, nutrients and surfactants. The chemical processes can efficiently remove the suspended solids, organic materials and surfactants in the low strength grey water. The combination of aerobic biological process with physical filtration and disinfection is considered to be the most economical and feasible solution for grey water recycling. The MBR appears to be a very attractive solution in collective urban residential buildings.

  1. 76 FR 41753 - Sierra National Forest, Bass Lake Ranger District, California, Grey's Mountain Ecosystem...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-15

    ... Forest Service Sierra National Forest, Bass Lake Ranger District, California, Grey's Mountain Ecosystem... Friday. SUPPLEMENTARY INFORMATION: Background Information: The Grey's Mountain Ecosystem Restoration... Ecosystem Restoration Project has changed from one where frequent, low intensity fires occurred to one with...

  2. 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.

  3. Comparison of grey matter volume and thickness for analysing cortical changes in chronic schizophrenia: a matter of surface area, grey/white matter intensity contrast, and curvature.

    PubMed

    Kong, Li; Herold, Christina J; Zöllner, Frank; Salat, David H; Lässer, Marc M; Schmid, Lena A; Fellhauer, Iven; Thomann, Philipp A; Essig, Marco; Schad, Lothar R; Erickson, Kirk I; Schröder, Johannes

    2015-02-28

    Grey matter volume and cortical thickness are the two most widely used measures for detecting grey matter morphometric changes in various diseases such as schizophrenia. However, these two measures only share partial overlapping regions in identifying morphometric changes. Few studies have investigated the contributions of the potential factors to the differences of grey matter volume and cortical thickness. To investigate this question, 3T magnetic resonance images from 22 patients with schizophrenia and 20 well-matched healthy controls were chosen for analyses. Grey matter volume and cortical thickness were measured by VBM and Freesurfer. Grey matter volume results were then rendered onto the surface template of Freesurfer to compare the differences from cortical thickness in anatomical locations. Discrepancy regions of the grey matter volume and thickness where grey matter volume significantly decreased but without corresponding evidence of cortical thinning involved the rostral middle frontal, precentral, lateral occipital and superior frontal gyri. Subsequent region-of-interest analysis demonstrated that changes in surface area, grey/white matter intensity contrast and curvature accounted for the discrepancies. Our results suggest that the differences between grey matter volume and thickness could be jointly driven by surface area, grey/white matter intensity contrast and curvature.

  4. Study on tunnel settlement prediction method based on parallel grey neural network model

    NASA Astrophysics Data System (ADS)

    Zhu, Lei; Huang, Teng; Shen, Yue-qian; Zeng, Xian-min

    2015-12-01

    In this paper, according to the characteristics of the grey forecast method and the neural network, constructed the parallel grey neural network model(PGNN) and apply to forecast a tunnel monitoring point's settlement displacement data based on Nanjing metro. The results showed that the prediction accuracy of PGNN is significantly higher than that of unitary grey and neural forecast method. proves that the effectiveness of PGNN in the tunnel settlement prediction. Keywords: Tunnel settlement, grey model, neural network model, prediction

  5. A-3 Test Stand construction

    NASA Image and Video Library

    2010-09-24

    A 35,000-gallon liquid oxygen tank is placed at the A-3 Test Stand construction site on Sept. 24, 2010. The tank will provide propellant for tests of next-generation rocket engines at the stand. It will be placed upright on top of the stand, helping to increase the overall height to 300 feet. Once completed, the A-3 Test Stand will enable operators to test rocket engines at simulated altitudes of up to 100,000 feet. The A-3 stand is the first large rocket engine test structure to be built at Stennis Space Center since the 1960s.

  6. A-3 Test Stand construction

    NASA Image and Video Library

    2010-10-01

    An 80,000-gallon liquid hydrogen tank is placed at the A-3 Test Stand construction site on Sept. 24, 2010. The tank will provide propellant for tests of next-generation rocket engines at the stand. It will be placed upright on top of the stand, helping to increase the overall height to 300 feet. Once completed, the A-3 Test Stand will enable operators to test rocket engines at simulated altitudes of up to 100,000 feet. The A-3 stand is the first large rocket engine test structure to be built at Stennis Space Center since the 1960s.

  7. Multi-parametric structural magnetic resonance imaging in relation to cognitive dysfunction in long-standing multiple sclerosis.

    PubMed

    Daams, Marita; Steenwijk, Martijn D; Schoonheim, Menno M; Wattjes, Mike P; Balk, Lisanne J; Tewarie, Prejaas K; Killestein, Joep; Uitdehaag, Bernard M J; Geurts, Jeroen J G; Barkhof, Frederik

    2016-04-01

    Cognitive deficits are common in multiple sclerosis. Most previous studies investigating the imaging substrate of cognitive deficits in multiple sclerosis included patients with relatively short disease durations and were limited to one modality/brain region. To identify the strongest neuroimaging predictors for cognitive dysfunction in a large cohort of patients with long-standing multiple sclerosis. Extensive neuropsychological testing and multimodal 3.0T MRI was performed in 202 patients with multiple sclerosis and 52 controls. Cognitive scores were compared between groups using Z-scores. Whole-brain, white matter, grey matter, deep grey matter and lesion volumes; cortical thickness, (juxta)cortical and cerebellar lesions; and extent and severity of diffuse white matter damage were measured. Stepwise linear regression was used to identify the strongest predictors for cognitive dysfunction. All cognitive domains were affected in patients. Patients showed extensive atrophy, focal pathology and damage in up to 75% of the investigated white matter. Associations between imaging markers and average cognition were two times stronger in cognitively impaired patients than in cognitively preserved patients. The final model for average cognition consisted of deep grey matter DGMV volume and fractional anisotropy severity (adjusted R²=0.490; p<0.001). From all imaging markers, deep grey matter atrophy and diffuse white matter damage emerged as the strongest predictors for cognitive dysfunction in long-standing multiple sclerosis. © The Author(s), 2015.

  8. View of Glacier Grey from Lago Grey (Grey Lake), with the Cuernos del Paine mountains in the background, seen during NASA's AirSAR 2004 campaign in Chile

    NASA Image and Video Library

    2004-03-11

    View of Glacier Grey from Lago Grey (Grey Lake), with the Cuernos del Paine mountains in the background, seen during NASA's AirSAR 2004 campaign in Chile. AirSAR 2004 is a three-week expedition in Central and South America by an international team of scientists that is using an all-weather imaging tool, called the Airborne Synthetic Aperture Radar (AirSAR), located onboard NASA's DC-8 airborne laboratory. Scientists from many parts of the world are combining ground research with NASA's AirSAR technology to improve and expand on the quality of research they are able to conduct. Founded in 1959, Torres del Paine National Park encompasses 450,000 acres in the Patagonia region of Chile. This region is being studied by NASA using a DC-8 equipped with an Airborne Synthetic Aperture Radar (AirSAR) developed by scientists from NASA’s Jet Propulsion Laboratory. This is a very sensitive region that is important to scientists because the temperature has been consistently rising causing a subsequent melting of the region’s glaciers. AirSAR will provide a baseline model and unprecedented mapping of the region. This data will make it possible to determine whether the warming trend is slowing, continuing or accelerating. AirSAR will also provide reliable information on ice shelf thickness to measure the contribution of the glaciers to sea level.

  9. Glacier Grey in front of The Cuernos del Paine mountains, photographed from Lago Grey (Grey Lake) during NASA's AirSAR 2004 campaign in Chile

    NASA Image and Video Library

    2004-03-11

    Glacier Grey in front of the Cuernos del Paine mountains, photographed from Lago Grey (Grey Lake) during NASA's AirSAR 2004 campaign in Chile. AirSAR 2004 is a three-week expedition in Central and South America by an international team of scientists that is using an all-weather imaging tool, called the Airborne Synthetic Aperture Radar (AirSAR), located onboard NASA's DC-8 airborne laboratory. Scientists from many parts of the world are combining ground research with NASA's AirSAR technology to improve and expand on the quality of research they are able to conduct. Founded in 1959, Torres del Paine National Park encompasses 450,000 acres in the Patagonia region of Chile. This region is being studied by NASA using a DC-8 equipped with an Airborne Synthetic Aperture Radar (AirSAR) developed by scientists from NASA’s Jet Propulsion Laboratory. This is a very sensitive region that is important to scientists because the temperature has been consistently rising causing a subsequent melting of the region’s glaciers. AirSAR will provide a baseline model and unprecedented mapping of the region. This data will make it possible to determine whether the warming trend is slowing, continuing or accelerating. AirSAR will also provide reliable information on ice shelf thickness to measure the contribution of the glaciers to sea level.

  10. Close-up view of Grey Glacier from Lago Grey (Grey Lake), taken during NASA's AirSAR 2004 campaign in Chile

    NASA Image and Video Library

    2004-03-11

    Close-up view of Grey Glacier from Lago Grey (Grey Lake), taken during NASA's AirSAR 2004 campaign in Chile. AirSAR 2004 is a three-week expedition in Central and South America by an international team of scientists that is using an all-weather imaging tool, called the Airborne Synthetic Aperture Radar (AirSAR), located onboard NASA's DC-8 airborne laboratory. Scientists from many parts of the world are combining ground research with NASA's AirSAR technology to improve and expand on the quality of research they are able to conduct. Founded in 1959, Torres del Paine National Park encompasses 450,000 acres in the Patagonia region of Chile. This region is being studied by NASA using a DC-8 equipped with an Airborne Synthetic Aperture Radar (AirSAR) developed by scientists from NASA’s Jet Propulsion Laboratory. This is a very sensitive region that is important to scientists because the temperature has been consistently rising causing a subsequent melting of the region’s glaciers. AirSAR will provide a baseline model and unprecedented mapping of the region. This data will make it possible to determine whether the warming trend is slowing, continuing or accelerating. AirSAR will also provide reliable information on ice shelf thickness to measure the contribution of the glaciers to sea level.

  11. Standing equine dental surgery.

    PubMed

    Menzies, Robert A; Easley, Jack

    2014-04-01

    Dental surgeries refer to procedures that affect the dental tissues or their supporting structures. With the development of specific, efficacious, and conservative treatments, morbidity risks have been lowered and chances of benefiting the health of equids improved. Advances in quality of sedation, analgesia, and locoregional anesthesia allow a majority of dental surgeries to be performed in the standing patient. This update focuses on an orthograde endodontic technique, a minimally invasive buccotomy technique, with the potential to combine it with a transbuccal screw extraction technique, and revisits the AO pinless external fixator for fractures of the body of the mandible.

  12. Salmonberry and salal annual aerial stem production: The maintenance of shrub cover in forest stands

    USGS Publications Warehouse

    Tappeiner, J. C.; Zasada, J.; Huffman, D.; Ganio, L.

    2001-01-01

    Annual sprouting of aerial stems and ramets enables populations of salmonberry (Rubus spectabilis Pursh), salal (Gaultheria shallon Pursh), and probably other forest shrubs to maintain dense covers (>20 000 stems/ha). We studied annual stem production of salmonberry on cut (all stems cut within 15 cm of the ground) and uncut (stems were not treated) plots for 8 years and salal for 5 years in the understories of Douglas-fir (Pseudotsuga menziesii (Mirb.) Franco), alder, and riparian stands, as well as clearcuts, which are all common stand types in western Oregon. Mean salmonberry stem production on uncut plots ranged from 4.7 stemsA?ma??2A?yeara??1 (95% CI 2.9a??7.4) in alder stands and clearcuts to 1.6 stemsA?ma??2A?yeara??1 (95% CI 1.0a??2.6) in conifer stands. Mean salal production was greater, ranging from 58 stemsA?ma??2A?yeara??1 (95% CI 25a??135) to 8.6 stemsA?ma??2A?yeara??1 (95% CI 3.7a??20.1) on uncut plots in clearcuts and unthinned Douglas-fir stands, respectively. Annual production of both species was somewhat greater on cut plots. Most stems produced in early spring die by December, but enough are recruited to replace mortality of older stems. Stem density was maintained for 8 years for salmonberry and 5 years for salal on both cut and uncut plots. Based on length of rhizomes and bud density we estimate that only 1a??5% of the buds in the rhizomes are needed to support this annual stem production. Although these species sprout vigorously after their aerial stems are killed, disturbance is not necessary for maintaining a dense cover. It appears that, once established, salal, salmonberry, and probably other clonal forest shrubs can maintain a dense cover that can interfere with establishment of trees and other shrubs in canopy gaps or other openings.

  13. The Grey Nomad Phenomenon: Changing the Script of Aging

    ERIC Educational Resources Information Center

    Onyx, Jenny; Leonard, Rosemary

    2007-01-01

    This article explores a relatively new and little understood phenomenon, that of the Australian Grey Nomads. Every year increasing numbers of older Australians take to the road. This article explores the phenomenon both empirically and theoretically. A grounded approach is used by which the experience is explored from an ethnographic account…

  14. Persistent organic pollutant patterns in grey seals (Halichoerus grypus).

    PubMed

    Roots, O; Zitko, V; Roose, A

    2005-08-01

    The aim of this paper is to examine the patterns of polychlorinated biphenyls (PCB) in the grey seals (Halichoerus grypus) from the Baltic, Northeast and Eastern England, and the St. Lawrence Estuary (Canada). In fact, the feeding habits of the ringed seal (Phoca hispida) include ingestion of major quantities of benthic crustaceans that might cause observed differences obtained in PCBs, whereas the grey seal feed mainly on fish. The profile (percent in mixture) of polychlorinated biphenyls (PCB) 101, 118, 138, 153, and 180, and the total of their concentrations in mg/kg lipid in grey seals from the Baltic, from Northeast and Eastern England, and from the St. Lawrence estuary (Canada), were examined by principal component analysis (PCA). When considering the possible effects of consuming seafood by the grey seal, it is necessary to characterize populations and individuals according to the amounts they consume, since populations in different parts of the world are likely to show big differences in their consumption of seafood. The patterns differ between juveniles and adult animals, but the gender of adults and geography do not appear to play a role.

  15. The Grey Nomad Phenomenon: Changing the Script of Aging

    ERIC Educational Resources Information Center

    Onyx, Jenny; Leonard, Rosemary

    2007-01-01

    This article explores a relatively new and little understood phenomenon, that of the Australian Grey Nomads. Every year increasing numbers of older Australians take to the road. This article explores the phenomenon both empirically and theoretically. A grounded approach is used by which the experience is explored from an ethnographic account…

  16. SOUTHWEST VIEW OF FOUNDRY FROM TOP OF GREY IRON CUPOLA ...

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

    SOUTHWEST VIEW OF FOUNDRY FROM TOP OF GREY IRON CUPOLA SHOWING OPENED TOP OF CUPOLA WITH EMISSION RECOVERY DUCT COMING OFF. TO THE RIGHT IS THE STORAGE AND SHIPPING BUILDING. - Stockham Pipe & Fittings Company, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  17. 20. SIMILAR TO THE SYSTEM INSTALLED IN THE GREY IRON ...

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

    20. SIMILAR TO THE SYSTEM INSTALLED IN THE GREY IRON FOUNDRY, MALLEABLE WORKERS FILLED MOLDS TRAVELING ON A CONVEYOR FROM LADLES ATTACHED TO OVERHEAD RAILS WHILE THEY STOOD ON A PLATFORM MOVING AT THE SAME SPEED AS THE CONVEYOR, CA. 1950 - Stockham Pipe & Fittings Company, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  18. Non-grey thermal effects in irradiated planets atmospheres

    NASA Astrophysics Data System (ADS)

    Parmentier, Vivien; Guillot, Tristan; Fortney, Jonathan J.; Marley, Mark S.

    2016-01-01

    The large diversity of exoplanets in terms of irradiation temperature, gravity and chemical composition discovered around stars with different properties call for the development of fast, accurate and versatile atmospheric models. We derive a new, non-grey analytical model for the thermal structure of irradiated exoplanets. Using two different opacity bands in the thermal frequency range, we highlight the dual role of thermal non-grey opacities in shaping the temperature profile of the atmosphere. Opacities dominated by lines enable the upper atmosphere to cool down significantly compared to a grey atmosphere whereas opacities dominated by bands lead both to a significant cooling of the upper atmosphere and a significant heating of the deep atmosphere.We compare our analytical model to a grid of temperature-pressure profiles for solar composition atmospheres obtained with a state-of-the-art numerical model taking into account the full wavelength, temperature and pressure dependence of the opacities. We demonstrate the importance of thermal non-grey opacities in setting the deep temperature of irradiated giant planets atmospheres. In the particular case of highly irradiated planets we show that the presence of TiO in their atmospheres alters both the optical and the thermal opacities. The greenhouse effect - a semi-grey effect - and the "blanketing effect" - an intrisically non-grey effect - contribute equally to set the deep temperature profile of the planet atmosphere. We conclude that non-grey thermal effects are fundamental to understand the deep temperature profile of hot Jupiters.Our calibrated analytical model matches the numerical model within 10% over a wide range of effective temperature, internal temperature and gravities and properly predict the depth of the radiative/convective boundary, an important quantity to understand the cooling history of a giant planet. Such a fast and accurate model can be of great use when numerous temperature profiles need to

  19. Environmental Systems Test Stand

    NASA Astrophysics Data System (ADS)

    Barta, D.; Young, J.; Ewert, M.; Lee, S.; Wells, P.; Fortson, R.; Castillo, J.

    A test stand has been developed for the evaluation of prototype lighting, environmental control and crop cultivation technologies for plant production within an advanced life support system. Design of the test stand was based on preliminary designs of the center growth bay of the Biomass Production Chamber, one of several modules of the Bioregenerative Planetary Life Support Systems Test Complex (BIO- Plex). It consists of two controlled-environment shelves, each with 4.7 m2 of area for crop growth (150 cm width, 315 cm length). There are two chilled water loops, one for operation at conventional temperatures (5-10C) for air temperature and humidity control and one for operation at higher temperatures (15-50C) for waste heat acquisition and heating. Modular light boxes, utilizing either air-cooled or water- jacketed HPS lamps, have been developed. This modular design will allow for easy replacement of new lighting technologies within the light banks. An advanced data acquisition and control system has been developed utilizing localized, networked- based data acquisition modules and programmed with object-based control software.

  20. Blue and grey water footprint of textile industry in China.

    PubMed

    Wang, Laili; Ding, Xuemei; Wu, Xiongying

    2013-01-01

    Water footprint (WF) is a newly developed idea that indicates impacts of freshwater appropriation and wastewater discharge. The textile industry is one of the oldest, longest and most complicated industrial chains in the world's manufacturing industries. However, the textile industry is also water intensive. In this paper, we applied a bottom-up approach to estimate the direct blue water footprint (WFdir,blue) and direct grey water footprint (WFdir,grey) of China's textile industry at sector level based on WF methodology. The results showed that WFdir,blue of China's textile industry had an increasing trend from 2001 to 2010. The annual WFdir,blue surpassed 0.92 Gm(3)/yr (giga cubic meter a year) since 2004 and rose to peak value of 1.09 Gm(3)/yr in 2007. The original and residuary WFdir,grey (both were calculated based on the concentration of chemical oxygen demand (CODCr)) of China's textile industry had a similar variation trend with that of WFdir,blue. Among the three sub-sectors of China's textile industry, the manufacture of textiles sector's annual WFdir,blue and WFdir,grey were much larger than those of the manufacture of textile wearing apparel, footware and caps sector and the manufacture of chemical fibers sector. The intensities of WFdir,blue and WF(res)dir,grey of China's textile industry were year by year decreasing through the efforts of issuing restriction policies on freshwater use and wastewater generation and discharge, and popularization of water saving and wastewater treatment technologies.

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

    PubMed

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

    2009-01-01

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

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

    DOE PAGES

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

    2015-11-28

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

  3. 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.

  4. Bio-orthogonal Fluorescent Labelling of Biopolymers through Inverse-Electron-Demand Diels-Alder Reactions.

    PubMed

    Kozma, Eszter; Demeter, Orsolya; Kele, Péter

    2017-03-16

    Bio-orthogonal labelling schemes based on inverse-electron-demand Diels-Alder (IEDDA) cycloaddition have attracted much attention in chemical biology recently. The appealing features of this reaction, such as the fast reaction kinetics, fully bio-orthogonal nature and high selectivity, have helped chemical biologists gain deeper understanding of biochemical processes at the molecular level. Listing the components and discussing the possibilities and limitations of these reagents, we provide a recent snapshot of the field of IEDDA-based biomolecular manipulation with special focus on fluorescent modulation approaches through the use of bio-orthogonalized building blocks. At the end, we discuss challenges that need to be addressed for further developments in order to overcome recent limitations and to enable researchers to answer biomolecular questions in more detail. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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

    PubMed Central

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

    2015-01-01

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

  6. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

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

  8. Asymmetric Diels-Alder Cycloadditions of Trifluoromethylated Dienophiles Under Trienamine Catalysis.

    PubMed

    Yuan, Xin; Zhang, Shan-Jun; Du, Wei; Chen, Ying-Chun

    2016-07-25

    β-Trifluoromethyl (CF3 ) enones were proved to act as good dienophiles in asymmetric normal-electron-demand Diels-Alder cycloadditions with 2,4-dienals under trienamine catalysis with a chiral secondary amine. The sequential reductive amination transformations with benzylamine produced cis- and trans-fused chiral trifluoromethylated octahydroisoquinolines in a diastereodivergent manner by using NaBH(OAc)3 and NaBH3 CN as the reductants, respectively. Moreover, other types of activated alkenes that bear a CF3 group have also been successfully utilized to construct a diverse range of chiral cyclic frameworks in high stereoselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Cyclones in the Diels-Alder reaction catalyzed by aluminum chloride

    SciTech Connect

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

    1986-07-10

    A comparison was made of the kinetic parameters for the uncatalyzed and catalyzed (with aluminum chloride) Diels-Alder reaction between N-arylmaleimides and acrylic, methacrylic, and fumaric esters as dienophiles and phencyclone and tetracyclone as dienes. By thermochemical and spectrophotometric experiments it was shown that the aluminum chloride coordinates with the dienophile in a ratio of 1:1. With a larger concentration of the catalyst coordination also takes place at the carbonyl of the diene. For the complexes of N-arylmaleimides the rate constants for the reaction with free tetracyclone and phencyclone increase by not more than 60 times, those for the esters of the unsaturated acids increase by 300-600 times, whereas those in the reaction with anthracene increase by 10/sup 5/ times. The results are discussed form the standpoint of the change in the energy of the molecular orbitals of the reagents.

  10. 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.

  11. Theoretical study of the Diels-Alder reactions of zirconium dimer with ethylene and butadiene

    SciTech Connect

    Roszak, S.; Balasubramanian, K.

    1995-03-16

    A theoretical study of the symmetry concerted Diels-Alder analogue reactions of Zr{sub 2} with ethylene and 1,3-butadiene is carried out. The optimized structures of the complexes indicate breaking of one of the multiple bonds in Zr{sub 2} and 1,3-butadiene and the formation of a six-membered ring in agreement with symmetry concerted models. Thus the reaction of ethylene with Zr{sub 2} is thermally forbidden, while it is allowed for the butadiene case. This is explained based on the natural orbitals picture. The presented potential energy surfaces are useful for the interpretation of possible reactions in both ground and excited states. 26 refs., 7 figs., 3 tabs.

  12. Organometallic analogues of the Diels-Alder reaction: Molybdenum dimer + ethylene; molybdenum dimer + butadiene

    SciTech Connect

    Roszak, S.; Balasubramanian, K.

    1994-08-31

    A theoretical study of the symmetry-concerted Diels-Alder analogue reactions of Mo{sub 2} with 1,3-butadiene and ethylene is presented. Structure optimizations indicated elongation of the Mo-Mo and C{double_bond}C bonds in the complexes. The optimized bond distances were found to be close to one known in organomolybdenum complexes. The presented potential surfaces indicated, in agreement with symmetry-concerted models, that the Mo{sub 2}-Eth complex formation is thermally forbidden, as the reaction has to proceed in the excited state, but the Mo{sub 2}-But complex may be formed in the ground state with addition of thermal energy.

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

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

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

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

    PubMed

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

    2008-10-09

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

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

    PubMed Central

    Kozma, Eszter; Demeter, Orsolya

    2017-01-01

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

  16. 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.

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

    PubMed

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

    2016-10-12

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

  18. Diels-Alder addition to H2O@C60 an electronic and structural study

    NASA Astrophysics Data System (ADS)

    Reveles, J. Ulises; Govinda, K. C.; Baruah, Tunna; Zope, Rajendra R.

    2017-10-01

    Exohedral reactivity of endohedral fullerenes has aroused a significant interest because of its potential applications. The present letter examines the effect of an entrapped single water molecule on the reactivity of C60. We study the thermodynamics and kinetics of a Diels-Alder reaction occurring at all non-identical bonds of free C60 and H2O@C60. Our calculations show that encapsulation of water does not have a significant effect on H2O@C60 reactivity compared to C60, as attested by the investigation of the reaction under several orientations of H2O inside C60. Reaction and activation energies indicate that [6,6] bonds are the most reactive sites.

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

    PubMed

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

    2016-06-22

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

  20. Factors Governing the Diels-Alder Reactivity of (2,7)Pyrenophanes.

    PubMed

    García-Rodeja, Yago; Fernández, Israel

    2017-08-04

    The physical factors governing the Diels-Alder reactivity of (2,7)pyrenophanes have been computationally explored using state-of-the-art Density Functional Theory calculations. It is found that the [4 + 2]-cycloaddition reactions between these cyclophanes and tetracyanoethylene, which occur concertedly through highly asynchronous transition states, proceed with lower activation barriers and are more exothermic than the analogous process involving the parent planar pyrene. The influence of the bent equilibrium geometry of the pyrenophane as a function of the length of the bridge as well as the nature of the tether on the transformation are analyzed in detail. By means of the Activation Strain Model of reactivity and the Energy Decomposition Analysis methods, a detailed quantitative understanding of the reactivity of this particular family of cyclophanes is presented.

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

    PubMed

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

    2016-02-17

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

  2. 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

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

    SciTech Connect

    Westermann, P.; Ahring, B.K.

    1987-10-01

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

  4. 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

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

    PubMed

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

    2010-12-15

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

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

    PubMed

    Reiner, Thomas; Zeglis, Brian M

    2014-04-01

    The inverse electron-demand Diels-Alder (IEDDA) cycloaddition between 1,2,4,5-tetrazines and strained alkene dienophiles is an emergent variety of catalyst-free 'click' chemistry that has the potential to have a transformational impact on the synthesis and development of radiopharmaceuticals. The ligation is selective, rapid, high-yielding, clean, and bioorthogonal and, since its advent in 2008, has been employed in a wide variety of chemical settings. In radiochemistry, the reaction has proven particularly useful with (18)  F and has already been utilized to create a number of (18)  F-labeled agents, including the PARP1-targeting small molecule (18)  F-AZD2281, the αv β3 integrin-targeting peptide (18)  F-RGD, and the GLP-1-targeting peptide (18)  F-exendin. The inherent flexibility of the ligation has also been applied to the construction of radiometal-based probes, specifically the development of a modular strategy for the synthesis of radioimmunoconjugates that effectively eliminates variability in the construction of these agents. Further, the exceptional speed and biorthogonality of the reaction have made it especially promising in the realm of in vivo pretargeted imaging and therapy, and pretargeted imaging strategies based on the isotopes (111) In, (18)  F, and (64) Cu have already proven capable of producing images with high tumor contrast and low levels of uptake in background, nontarget organs. Ultimately, the characteristics of inverse electron-demand Diels-Alder click chemistry make it almost uniquely well-suited for radiochemistry, and although the field is young, this ligation has the potential to make a tremendous impact on the synthesis, development, and study of novel radiopharmaceuticals. Copyright © 2013 John Wiley & Sons, Ltd.

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

    NASA Astrophysics Data System (ADS)

    Cong, Huan

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

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

    PubMed

    Lee, Jihoon; Panek, James S

    2014-06-20

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

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

    PubMed

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

    2007-01-05

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

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

    PubMed Central

    2015-01-01

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

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

    PubMed

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

    2015-09-23

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

  12. Theoretical elucidation of the origins of substituent and strain effects on the rates of Diels-Alder reactions of 1,2,4,5-tetrazines.

    PubMed

    Liu, Fang; Liang, Yong; Houk, K N

    2014-08-13

    The Diels-Alder reactions of seven 1,2,4,5-tetrazines with unstrained and strained alkenes and alkynes were studied with quantum mechanical calculations (M06-2X density functional theory) and analyzed with the distortion/interaction model. The higher reactivities of alkenes compared to alkynes in the Diels-Alder reactions with tetrazines arise from the differences in both interaction and distortion energies. Alkenes have HOMO energies higher than those of alkynes and therefore stronger interaction energies in inverse-electron-demand Diels-Alder reactions with tetrazines. We have also found that the energies to distort alkenes into the Diels-Alder transition-state geometries are smaller than for alkynes in these reactions. The strained dienophiles, trans-cyclooctene and cyclooctyne, are much more reactive than unstrained trans-2-butene and 2-butyne, because they are predistorted toward the Diels-Alder transition structures. The reactivities of substituted tetrazines correlate with the electron-withdrawing abilities of the substituents. Electron-withdrawing groups lower the LUMO+1 of tetrazines, resulting in stronger interactions with the HOMO of dienophiles. Moreover, electron-withdrawing substituents destabilize the tetrazines, and this leads to smaller distortion energies in the Diels-Alder transition states.

  13. Greying with age in mice: relation to expression of murine leukemia viruses.

    PubMed

    Morse, H C; Yetter, R A; Stimpfling, J H; Pitts, O M; Fredrickson, T N; Hartley, J W

    1985-06-01

    Some strains of C57BL/10 H-2-congenic mice were found to exhibit greying with age, whereas others did not. Two patterns of greying were observed, diffuse greying beginning at 4 to 6 months of age and patterned greying beginning at 4 to 6 weeks. Strains exhibiting either greying pattern expressed high levels of infectious ecotropic and mink cell focus-inducing murine leukemia viruses (MuLV) in tests of thymus and spleen and in cultures from skin or tail biopsies, whereas nongreying strains expressed little virus until late in life. Electron microscopy demonstrated large accumulations of MuLV in grey, but not in black areas, of skin from a mouse with patterned greying. Infectious MuLV was produced spontaneously by embryos of greying, but not of nongreying, mice and pups of nongreying strains fostered on greying mothers turned grey after 3 months. These results suggest that greying with age results from melanocyte dysfunction that occurs subsequent to pre- or early postnatal infection with MuLV.

  14. Clinical nursing and midwifery research: grey literature in African countries.

    PubMed

    Sun, C; Dohrn, J; Omoni, G; Malata, A; Klopper, H; Larson, E

    2016-03-01

    This study reviewed grey literature to assess clinical nursing and midwifery research conducted in southern and eastern African countries over the past decade. The shortage of published nursing research from African countries severely limits the ability of practicing nurses and midwives to base clinical decisions on solid evidence. However, little is known regarding unpublished or unindexed clinical research ('grey literature'), a potentially rich source of information. Identifying these sources may reveal resources to assist nurses in providing evidence-based care. This scoping review of grey literature on clinical nursing and midwifery research in southern and eastern African countries helped to identify gaps in research and assess whether these gaps differ from published research. Systematic searches of grey literature were performed. Research was included if it was conducted by nurses in 1 of 25 southern or eastern African countries, between 2004 and 2014 and included patient outcomes. Data were extracted on location, institution, research topic, institutional connections and author information. Chi-square tests were performed to compare differences between indexed and non-indexed literature. We found 262 studies by 287 authors from 17 southern and eastern African countries covering 13 topics. Although all topics were also found in indexed literature and there were statistically significant differences between the number of times, fewer topics were covered in grey literature vs. indexed. Patient satisfaction and experience and traditional health practices were more likely to be published, whereas chronic disease, assault and paediatric-related research were less often published. Generally, there is a paucity of clinical nursing research in this region. This could reflect the shortage of nurses prepared to conduct research in this region. Nurses may find additional resources for evidence in the grey literature. A complete understanding of the state of nursing

  15. A-1 Test Stand modifications

    NASA Image and Video Library

    2011-09-14

    Team members check the progress of a liquid nitrogen cold shock test on the A-1 Test Stand at Stennis Space Center on Sept. 15. The cold shock test is used to confirm the test stand's support system can withstand test conditions, when super-cold rocket engine propellant is piped. The A-1 Test Stand is preparing to conduct tests on the powerpack component of the J-2X rocket engine, beginning in early 2012.

  16. Stand size, stand distribution, and rotation lengths for forest wildlife

    Treesearch

    Steven E. Backs; Russel R. Titus

    1989-01-01

    The key to managing forest wildlife is providing diverse habitats. Stand size, stand distribution, and rotation length determine how diverse habitats will be. Since the tenure of private forest owners is generally shorter than prescribed rotations, rotation recommendations serve more as guides to the amount and intensity of cutting needed to maintain desired habitat....

  17. 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.

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

    PubMed Central

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

    2014-01-01

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

  19. 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.

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

    PubMed

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

    2014-01-01

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

  1. A Well-Defined Aluminum-Based Lewis Acid as an Effective Catalyst for Diels-Alder Transformations.

    PubMed

    Liu, Zhizhou; Lee, Jazreen Hui Qi; Ganguly, Rakesh; Vidović, Dragoslav

    2015-08-03

    A catalytically active aluminum-based system for Diels-Alder transformations is reported. The system was generated by mixing a β-diketiminate-stabilized aluminum bistriflate compound with Na[BAr(Cl) 4 (Ar(Cl) =3,5-Cl2 C6 H3). Solid-state analysis of the catalytic system reveals a unique structure incorporating a two-dimensional coordination polymer. According to the experimental results obtained from several Diels-Alder transformations, the aluminum-based system appears to be a more practical and more robust alternative to the recently reported compounds based on carbon and silicon cations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Improvement of CCME WQI using grey relational method

    NASA Astrophysics Data System (ADS)

    Yan, Feng; Qiao, Danying; Qian, Bao; Ma, Lin; Xing, Xigang; Zhang, You; Wang, Xiaogang

    2016-12-01

    The conventional CCME WQI ignores the uncertainties in aquatic environment, which may lead to biases and abrupt changes in evaluation results. To overcome this shortcoming, this study improves the calculation of CCME WQI using trapezoid grey relational degree method, a model dealing with uncertainties introduced by incomplete information. Compared with the conventional CCME WQI, the grey CCME WQI has a stricter calculation method in synthetic evaluation and a better capacity in water quality warning. The water quality of New Tongyang Canal is evaluated and the result shows that its environment deteriorates with the increasing rainfall and improves with the decreasing precipitation. To decrease its environmental risk, it is suggested to reduce the nutrients in agricultural runoff and the oxygen-consuming pollutants in urban runoff in the rainy season.

  3. Sensor for Distance Measurement Using Pixel Grey-Level Information

    PubMed Central

    Lázaro, José L.; Cano, Angel E.; Fernández, Pedro R.; Pompa, Yamilet

    2009-01-01

    An alternative method for distance measurement is presented, based on a radiometric approach to the image formation process. The proposed methodology uses images from an infrared emitting diode (IRED) to estimate the distance between the camera and the IRED. Camera output grey-level intensities are a function of the accumulated image irradiance, which is also related by inverse distance square law to the distance between the camera and the IRED. Analyzing camera-IRED distance, magnitudes that affected image grey-level intensities, and therefore accumulated image irradiance, were integrated into a differential model which was calibrated and used for distance estimation over a 200 to 600 cm range. In a preliminary model, the camera and the emitter were aligned. PMID:22291543

  4. Morphology of the lingual papillae in the eastern grey kangaroo.

    PubMed

    Emura, Shoichi

    2016-01-01

    We examined the dorsal lingual surface of an adult eastern grey kangaroo (Macropus gigantues) by scanning electron microscopy. The filiform papillae on the lingual apex and anterior body consisted of a main papilla and secondary papillae. The connective tissue core of the filiform papillae on the lingual apex had several processes. The filiform papillae on the lingual posterior body were thread-like in shape. The connective tissue core of the filiform papillae on the lingual posterior body consisted of many slender processes. The fungiform papillae were round in shape. Three vallate papillae with the apex of the triangle directed posteriorly consisted of a groove and pad. Several conical papillae derived from the posterolateral margin of the tongue where foliate papillae have been shown to be distributed in many other animal species. The surface structure of the tongue in the eastern grey kangaroo resembles that of the red kangaroo.

  5. 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

    2015-06-05

    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.

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

    PubMed

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

    2017-02-21

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

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

    SciTech Connect

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

    1995-05-19

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

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

    PubMed

    Nandi, Sisir; Monesi, Alessandro; Drgan, Viktor; Merzel, Franci; Novič, Marjana

    2013-10-30

    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. 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. 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.

  9. 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

  10. 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.

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

    PubMed

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

    2012-01-18

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

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

    PubMed

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

    2014-10-17

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

  13. Parapox infection in grey seals (Halichoerus grypus) in Cornwall.

    PubMed

    Simpson, V R; Stuart, N C; Stack, M J; Ross, H A; Head, J C

    1994-03-19

    In the winter of 1991/92 there was an outbreak of parapox infection in grey seals (Halichoerus grypus) around the coast of Cornwall. Pups were cared for at a seal rehabilitation centre and the infection occurred in most of them. The presence of parapox virus was confirmed by electron microscopy. The clinical and pathological findings, together with details of the morphology of the virus, are compared with those in previous outbreaks in North America.

  14. Hybrid nuclear reactor grey rod to obtain required reactivity worth

    DOEpatents

    Miller, John V.; Carlson, William R.; Yarbrough, Michael B.

    1991-01-01

    Hybrid nuclear reactor grey rods are described, wherein geometric combinations of relatively weak neutron absorber materials such as stainless steel, zirconium or INCONEL, and relatively strong neutron absorber materials, such as hafnium, silver-indium cadmium and boron carbide, are used to obtain the reactivity worths required to reach zero boron change load follow. One embodiment includes a grey rod which has combinations of weak and strong neutron absorber pellets in a stainless steel cladding. The respective pellets can be of differing heights. A second embodiment includes a grey rod with a relatively thick stainless steel cladding receiving relatively strong neutron absorber pellets only. A third embodiment includes annular relatively weak netron absorber pellets with a smaller diameter pellet of relatively strong absorber material contained within the aperture of each relatively weak absorber pellet. The fourth embodiment includes pellets made of a homogeneous alloy of hafnium and a relatively weak absorber material, with the percentage of hafnium chosen to obtain the desired reactivity worth.

  15. A novel kernel regularized nonhomogeneous grey model and its applications

    NASA Astrophysics Data System (ADS)

    Ma, Xin; Hu, Yi-sheng; Liu, Zhi-bin

    2017-07-01

    The nonhomogeneous grey model (NGM) is a novel tool for time series forecasting, which has attracted considerable interest of research. However, the existing nonhomogeneous grey models may be inefficient to predict the complex nonlinear time series sometimes due to the linearity of the differential or difference equations based on which these models are developed. In order to enhance the accuracy and applicability of the NGM model, the kernel method in the statistical learning theory has been utilized to build a novel kernel regularized nonhomogeneous grey model, which is abbreviated as the KRNGM model. The KRNGM model is represented by a differential equation which contains a nonlinear function of t. By constructing the regularized problem and using the kernel function which satisfies the Mercer's condition, the parameters estimation of KRNGM model only involves in solving a set of linear equations, and the nonlinear function in the KRNGM model can be expressed as a linear combination of the Lagrangian multipliers and the selected kernel function, and then the KRNGM model can be solved numerically. Two case studies of petroleum production forecasting are carried to illustrate the effectiveness of the KRNGM model, comparing to the existing nonhomogeneous models. The results show that the KRNGM model outperforms the existing NGM, ONGM, NDGM model significantly.

  16. Grey water on three agricultural catchments in the Czech Republic

    NASA Astrophysics Data System (ADS)

    Blazkova, Sarka D.; Kulasova, Alena

    2014-05-01

    The COST project EU EURO-AGRIWAT focuses apart from other problems on the assessment of water footprint (WF). WF is defined as the quantity of water used to produce some goods or a service. In particular, the WF of an agricultural product is the volume of water used during the crop growing period. It has three components: the green water which is rain or soil moisture transpired by a crop, the blue water which is the amount of irrigation water transpired and the grey water which is the volume of water required to dilute pollutants and to restore the quality standards of the water body. We have been observing three different agricultural catchments. The first of them is Smrzovka Brook, located in the protected nature area in the south part of the Jizerske Mountains. An ecological farming has been carried out there. The second agricultural catchment area is the Kralovsky Creek, which lies in the foothills of the Krkonose Mountains and is a part of an agricultural cooperative. The last agricultural catchment is the Klejnarka stream, located on the outskirts of the fertile Elbe lowlands near Caslav. Catchments Kralovsky Brook and Klejnarka carry out usual agricultural activities. On all three catchments, however, recreational cottages or houses not connected to the sewerage system and/or with inefficient septic tanks occur. The contribution shows our approach to trying to quantify the real grey water from agriculture, i.e. the grey water caused by nutrients not utilised by the crops.

  17. The trajectory prediction of spacecraft by grey method

    NASA Astrophysics Data System (ADS)

    Wang, Qiyue; Zhang, Zili; Wang, Zhongyu; Wang, Yanqing; Zhou, Weihu

    2016-08-01

    The real-time and high-precision trajectory prediction of a moving object is a core technology in the field of aerospace engineering. The real-time monitoring and tracking technology are also significant guarantees of aerospace equipment. A dynamic trajectory prediction method called grey dynamic filter (GDF) which combines the dynamic measurement theory and grey system theory is proposed. GDF can use coordinates of the current period to extrapolate coordinates of the following period. At meantime, GDF can also keep the instantaneity of measured coordinates by the metabolism model. In this paper the optimal model length of GDF is firstly selected to improve the prediction accuracy. Then the simulation for uniformly accelerated motion and variably accelerated motion is conducted. The simulation results indicate that the mean composite position error of GDF prediction is one-fifth to that of Kalman filter (KF). By using a spacecraft landing experiment, the prediction accuracy of GDF is compared with the KF method and the primitive grey method (GM). The results show that the motion trajectory of spacecraft predicted by GDF is much closer to actual trajectory than the other two methods. The mean composite position error calculated by GDF is one-eighth to KF and one-fifth to GM respectively.

  18. Reduced Regional Grey Matter Volumes in Pediatric Obstructive Sleep Apnea

    PubMed Central

    Philby, Mona F.; Macey, Paul M.; Ma, Richard A.; Kumar, Rajesh; Gozal, David; Kheirandish-Gozal, Leila

    2017-01-01

    Pediatric OSA is associated with cognitive risk. Since adult OSA manifests MRI evidence of brain injury, and animal models lead to regional neuronal losses, pediatric OSA patients may also be affected. We assessed the presence of neuronal injury, measured as regional grey matter volume, in 16 OSA children (8 male, 8.1 ± 2.2 years, AHI:11.1 ± 5.9 events/hr), and 200 control subjects (84 male, 8.2 ± 2.0 years), 191 of whom were from the NIH-Pediatric MRI database. High resolution T1-weighted whole-brain images were assessed between groups with voxel-based morphometry, using ANCOVA (covariates, age and gender; family-wise error correction, P < 0.01). Significant grey matter volume reductions appeared in OSA throughout areas of the superior frontal and prefrontal, and superior and lateral parietal cortices. Other affected sites included the brainstem, ventral medial prefrontal cortex, and superior temporal lobe, mostly on the left side. Thus, pediatric OSA subjects show extensive regionally-demarcated grey matter volume reductions in areas that control cognition and mood functions, even if such losses are apparently independent of cognitive deficits. Since OSA disease duration in our subjects is unknown, these findings may result from either delayed neuronal development, neuronal damaging processes, or a combination thereof, and could either reflect neuronal atrophy or reductions in cellular volume (neurons and glia). PMID:28303917

  19. Magnesium therapy in a hypocalcemic African grey parrot (Psittacus erithacus).

    PubMed

    Kirchgessner, Megan S; Tully, Thomas N; Nevarez, Javier; Sanchez-Migallon Guzman, David; Acierno, Mark J

    2012-03-01

    Hypocalcemic-induced seizure activity is a clinical entity that is commonly diagnosed in neurologic African grey parrots (Psittacus erithacus). Plasma calcium levels are typically less than 6.0 mg/dL at the time of seizure activity, and although the underlying cause of the hypocalcemia has not yet been determined, many theories have been proposed. An African grey parrot that had been fed a seed diet for 8 years was presented with hypocalcemia and seizures and exhibited precipitously declining plasma calcium levels, despite aggressive calcium and vitamin A, D, and E supplementation for 4 days. Baseline magnesium levels in this parrot were determined to be 1.9 mg/dL; therefore, magnesium sulfate was administered at a dose of 20 mg/kg IM once. Twenty-four hours after supplementation, the plasma magnesium level was 3.3 mg/dL, and no further seizure activity was observed. We believe that a primary dietary magnesium deficiency may have been present in this African grey parrot, similar to a syndrome in leghorn chicks, which is frequently characterized by progressive hypocalcemia that is unable to be corrected by calcium supplementation alone.

  20. 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.

  1. 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.

  2. 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.

  3. Diels-Alder Reactivities of Benzene, Pyridine, and Di-, Tri-, and Tetrazines: The Roles of Geometrical Distortions and Orbital Interactions.

    PubMed

    Yang, Yun-Fang; Liang, Yong; Liu, Fang; Houk, K N

    2016-02-10

    The cycloadditions of benzene and ten different azabenzenes (pyridine, three diazines, three triazines, and three tetrazines) with the ethylene dienophile have been explored with density functional theory (M06-2X) and analyzed with the distortion/interaction model. Activation barriers correlate closely with both distortion energies and interaction energies over an activation energy range of 45 kcal/mol. The replacement of CH with N increases Diels-Alder reactivity due not only to the more favorable orbital interaction, but also to a decrease in distortion energy. The rates of reactions are greatly influenced by the nature of the bonds being formed: two C-C bonds > one C-C bond, and one C-N bond > two C-N bonds. The activation energy of Diels-Alder reactions correlates very well with reaction energies and with the NICS(0) values of the aromatic dienes. The distortion energy of the Diels-Alder reaction transition states mostly arises from the diene out-of-plane distortion energy.

  4. 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.

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

    PubMed

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

    2016-07-06

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

  6. Where we stand.

    PubMed

    1973-12-01

    To serve the interests of members and to function in the public interest, the California Medical Association must set policies and take positions on current issues affecting the health care of Californians. These policies then guide the activities of the Association in fulfilling its leadership role and its responsibility to the public.Delegates, elected by the membership of CMA's component medical societies, meet annually to deliberate and determine the policies and courses of action for the Association. Between meetings of these Delegates, the CMA Councilors, elected by their district membership, implement the directives of the Delegates and set interim policies. By this democratic process, the membership governs the CMA. Association members must be informed if they are to participate effectively in the affairs of their medical organizations. To disseminate better understanding of CMA's activities, position papers on current issues have been developed. They are based on House of Delegates resolutions and Council actions. Entitled "Where We Stand on Medical and Health Issues," these papers represent the current policy positions of CMA. Each paper is annotated to give the reference source of the policy actions. As with any organization, CMA policies are subject to timely revision. When policies are amended or new policies are adopted, new papers will be developed.

  7. EUV Engineering Test Stand

    SciTech Connect

    Tichenor, D.A.; Kubiak, G.D.; Replogle, W.C.; Klebanoff, L.E.; Wronosky, J.B.; Hale, L.C.; Chapman, H.N.; Taylor, J.S.; Folta, J.A.; Montcalm, C.; Hudyma, R.M.

    2000-02-14

    The Engineering Test Stand (ETS) is an EUV laboratory lithography tool. The purpose of the ETS is to demonstrate EUV full-field imaging and provide data required to support production-tool development. The ETS is configured to separate the imaging system and stages from the illumination system. Environmental conditions can be controlled independently in the two modules to maximize EUV throughput and environmental control. A source of 13.4 nm radiation is provided by a laser plasma source in which a YAG laser beam is focused onto a xenon-cluster target. A condenser system, comprised of multilayer-coated mirrors and grazing-incidence mirrors, collects the EUV radiation and directs it onto a-reflecting reticle. A four-mirror, ring-field optical system, having a numerical aperture of 0.1, projects a 4x-reduction image onto the wafer plane. This design corresponds to a resolution of 70nm at a k{sub 1} of 0.52. The ETS is designed to produce full-field images in step: and-scan mode using vacuum-compatible, one-dimension-long-travel magnetically levitated stages for both reticle and wafer. Reticle protection is incorporated into the ETS design. This paper provides a system overview of the ETS design and specifications.

  8. OH Module Assembly Stand

    SciTech Connect

    Bolan, P.J.; /Fermilab

    1990-10-16

    There is an OR module assembly stand in use at IB4. This design has been approved by safety, as presented by Mike Foley, and has been successfully used. Another one is needed at the D-zero assembly building, but some modifications need to be made. This report will show that the new modified design is at least as strong, if not stronger, than the older IB4 design in every aspect. Since the weight distribution of the OR modules on the sling is indeterminate, this report compares three cases of support for the entire assembly: the lowest two beams only, the lowest four beams only, and all six beams. In each of these cases, the new design is stronger than the old design in maximum allowable weight. The ability of the the cradle to support the weight is also shown. For all of the failure conditions except for two, the cradle is stronger than the beams that it supports. In the two excepted situations, the calculated limit of the cradle is less than the beams it supports. This is because no credit is taken for the sling and strongback, which in reality will relieve much of the horizontal load.

  9. [Chile: Standing up again].

    PubMed

    Reyes B, Humberto

    2010-03-01

    One of the biggest earthquakes recorded in human history has recently devastated a large part of the Chilean territory and, followed by a Tsunami, destroyed cities, seaports, fishermen's coves, bridges, and countryside houses. This cataclysm affected a large proportion of our population, leaving homeless families, no working tools for work places, hospitals, schools, public buildings, museums. However, the loss of human Uves was small compared to similar disasters. It destroyed part of the national heritage as well as damaged people's living conditions. A national movement started immediately to help and recover, and international resources, both human and technological were also set in motion. As after previous earthquakes in Chile, young M.D.'s and medical students were organized in voluntary groups backed by institutions or by their own organizations and went from large cities as Santiago and others to provide medical and psychological care to those in most need. Young members and students of other health professions (nurses, physical therapists, etc.) were included in these groups or worked in their own ones. National and international experience indicates that the forthcoming months require special care of psychological reactions and sequel (posttraumatic stress symptoms) and health consequences after water pollution, restrictions in housing and deteriorated sanitary conditions. Nevertheless, our country will stand up once more.

  10. Economic considerations of managing stands

    Treesearch

    Gary W. Miller

    1989-01-01

    Managing central hardwood stands involves making choices. Each year landowners face at least three alternatives for managing a stand: (1) allow it to grow undisturbed, (2) undertake a partial or complete commercial harvest, or (3) culture the timber crop through a precommercial investment. Each activity affects long-term monetary returns. The "best" choice in...

  11. Dynamics of Connecticut hemlock stands

    Treesearch

    Jeffrey S. Ward; David M. Smith

    2000-01-01

    The stand dynamics and production of two one-acre plots of eastern hemlock (Tsuga canadensis L) in Connecticut have been followed for more than six decades. Data were recorded for all individual trees. One plot (Saltonstall) was established in 1924 after the removal of a hardwood overstory. This stand had a nearly pure, almost fully closed understory...

  12. A-3 Test Stand work

    NASA Image and Video Library

    2011-07-29

    Rocket engine propellant tanks and cell dome top the A-3 Test Stand under construction at Stennis Space Center. The stand will test next-generation rocket engines that could carry humans beyond low-Earth orbit into deep space once more.

  13. A-1 Test Stand work

    NASA Image and Video Library

    2010-01-13

    Employees at NASA's John C. Stennis Space Center work to maneuver a structural steam beam into place on the A-1 Test Stand on Jan. 13. The beam was one of several needed to form the thrust takeout structure that will support a new thrust measurement system being installed on the stand for future rocket engine testing. Once lifted onto the stand, the beams had to be hoisted into place through the center of the test stand, with only two inches of clearance on each side. The new thrust measurement system represents a state-of-the-art upgrade from the equipment installed more than 40 years ago when the test stand was first constructed.

  14. 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

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

    PubMed

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

    2012-03-07

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

  16. Stand density, stand structure, and species composition in transition oak stands of northwestern Pennsylvania

    Treesearch

    S.L. Stout

    1991-01-01

    Transition stands, those containing species associated with both the northern hardwood and oak-hickory forest types, are important to forest diversity in northwestern Pennsylvania. These stands have high value for a variety of forest uses, including timber production, wildlife habitat, and aesthetics. Diameter distributions are characteristically stratified by species...

  17. Projecting a Stand Table Through Time

    Treesearch

    Quang V. Cao; V. Clark Baldwin

    1999-01-01

    Stand tables provide number of trees per acre for each diameter class. This paper presents a general technique to predict a future stand table, based on the current stand table and future stand summary statistics such as trees and basal area per acre, and average diameter. The stand projection technique involves (a) predicting surviving trees for each class, and (b)...

  18. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.

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

    PubMed

    Dewar, S; Boddington, P

    2004-10-01

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