Cottonwood

Science.gov (United States)

R. M. Krinard

1980-01-01

Cottonwood is pure or comprises a majority of the stocking, but it is associated with other bottomland hardwoods. Eastern, plains, and swamp cottonwood are included under the type name. The chief associates in the younger stages are black and sandbar willow. Sweetgum !s rare. White or green ash, silver maple, and American elm may occur in the northern extremities of...

Status and Trend of Cottonwood Forests Along the Missouri River

Science.gov (United States)

2010-03-03

Rhamnus davurica), green ash, chokecherry ( Prunus virginiana ), and some Russian olive (Figure 30a). Younger cottonwood (all sapling stands, and...argentea), common chokecherry ( Prunus virginiana ), service berry (Amelanchier spp.) and rarely, red-osier dogwood (Cornus stolonifera) (Figure 32). In...sagebrush (Artemisia cana), common chokecherry ( Prunus virginiana ), and rarely, red-osier dogwood (Cornus stolonifera) (Ross and Hunter 1976, Scott

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

Science.gov (United States)

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...

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

Science.gov (United States)

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.

Red Cedar Invasion Along the Missouri River, South Dakota: Cause and Consequence

Science.gov (United States)

Greene, S.; Knox, J. C.

2012-12-01

This research evaluates drivers of and ecosystem response to red cedar (Juniperus virginiana) invasion of riparian surfaces downstream of Gavin's Point Dam on the Missouri River. Gavin's Point Dam changed the downstream geomorphology and hydrology of the river and its floodplain by reducing scouring floods and flood-deposited sediment. The native cottonwood species (Populus deltoides) favors cleared surfaces with little to no competitors to establish. Now that there are infrequent erosive floods along the riparian surfaces to remove competitor seeds and seedlings, other vegetation is able to establish. Red cedar is invading the understory of established cottonwood stands and post-dam riparian surfaces. To assess reasons and spatial patterns for the recent invasion of red cedar, a stratified random sampling of soil, tree density and frequency by species, and tree age of 14 forest stands was undertaken along 59 river kilometers of riparian habitat. Soil particle size was determined using laser diffraction and tree ages were estimated from ring counts of tree cores. As an indicator of ecosystem response to invasion, we measured organic matter content in soil collected beneath red cedar and cottonwood trees at three different depths. Of 565 red cedars, only two trees were established before the dam was built. We applied a multiple regression model of red cedar density as a function of cottonwood density and percent sand (63-1000 microns in diameter) in StatPlus© statistical software. Cottonwood density and percent sand are strongly correlated with invasion of red cedar along various riparian surfaces (n = 59, R2 = 0.42, p-values cedar and cottonwood trees (p-value > 0.05 for all depths). These findings suggest that the dam's minimization of downstream high-stage flows opened up new habitat for red cedar to establish. Fluvial geomorphic surfaces reflect soil type and cottonwood density and, in turn, predict susceptibility of a surface to red cedar invasion. Nonetheless

Fourfold Diels-Alder reaction of tetraethynylsilane.

Science.gov (United States)

Geyer, Florian L; Rode, Alexander; Bunz, Uwe H F

2014-12-08

A series of ethynylated silanes, including tetraethynylsilane, was treated with tetraphenylcyclopentadienone at 300 °C under microwave irradiation to give the aromatized Diels-Alder adducts as sterically encumbered mini-dendrimers with up to 20 benzene rings. The sterically most congested adducts display red-shifted emission through intramolecular π-π interactions in the excited state. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rooting Cuttings of Cottonwood, WilIow, and Sycamore

Science.gov (United States)

Charles B. Briscoe

1963-01-01

Cuttings of cottonwood, willow, and sycamore were collectd monthly through the year and set in nursery beds. Every species yield an appreciable percentage of rooted cuttings every month. The best month was March; the worst month was June. Willow rooted more cuttings than cottonwood or sycamore, and those which rooted grew faster. Cottonwood grew faster than sycamore....

Cottonwoods of the Midwest: A Community Profile

Science.gov (United States)

2008-05-01

As a component of the floodplain forest, cottonwoods provide habitat for many species of birds to roost, nest, and feed in the branches and bole...in the western United States (Malanson 1993). Cottonwood seedlings are preferred forage for cattle , which also trample young plants. Invasive...Cooper and Van Haverbeke 1990; Taylor 2001) Common Name Scientific Name Eastern Plains Invasive Graminoids Creeping bentgrass Agrostis stolonifera

Cottonwood Tree Rings and Climate in Western North America

Science.gov (United States)

Friedman, J. M.; Edmondson, J.; Griffin, E. R.; Meko, D. M.; Merigliano, M. F.; Scott, J. A.; Scott, M. L.; Touchan, R.

2012-12-01

In dry landscapes of interior western USA, cottonwood (Populus spp.) seedling establishment often occurs only close to river channels after floods. Where winter is sufficiently cold, cottonwoods also have distinct annual rings and can live up to 370 years, allowing us to reconstruct the long-term history of river flows and channel locations. We have analyzed the annual rate of cottonwood establishment along streams in Montana, Wyoming, Colorado, North Dakota and Idaho. Because the trees germinate next to the river, establishment rates are strongly correlated with the rate of channel migration driven by floods. Along large rivers dominated by snowmelt from the mountains, interannual variation in peak flows and cottonwood establishment is small, and century-scale variation driven by climate change is apparent. The upper Snake, Yellowstone and Green rivers all show a strong decrease in cottonwood establishment beginning in the late 1800s and continuing to the present, indicating a decrease in peak flows prior to flow regulation by large dams. This is consistent with published tree-ring studies of montane conifers showing decreases in snowpack at the same time scale. In contrast, beginning in the late 1800s cottonwood ring widths along the Little Missouri River, North Dakota show an increase in annual growth that continues into the present. Because annual growth is strongly correlated with April-July flows (r=0.69) the ring-width data suggest an increase in April-July flows at the same time tree establishment dates suggest a decrease in peak flows. These results may be reconciled by the hypothesis that increases in low temperatures have decreased snowpack while lengthening the growing season.

Disrupting mycorrhizal mutualisms: a potential mechanism by which exotic tamarisk outcompetes native cottonwoods.

Science.gov (United States)

Meinhardt, Kelley A; Gehring, Catherine A

2012-03-01

The disruption of mutualisms between plants and mycorrhizal fungi is a potentially powerful mechanism by which invasives can negatively impact native species, yet our understanding of this mechanism's role in exotic species invasion is still in its infancy. Here, we provide several lines of evidence indicating that invasive tamarisk (Tamarix sp.) negatively affects native cottonwoods (Populus fremontii) by disrupting their associations with arbuscular mycorrhizal (AM) and ectomycorrhizal (EM) fungi. At a field site in the early stages of tamarisk invasion, cottonwoods with tamarisk neighbors had reduced EM colonization and altered EM fungal community composition relative to cottonwoods with native neighbors, leading to reductions in EM propagule abundance in the soil beneath tamarisk. Similarly, AM colonization of cottonwoods was reduced with a tamarisk neighbor, but there were no significant changes in AM fungal spore communities or propagule abundance. Root colonization by nonmycorrhizal fungi, including potential pathogens, was higher in cottonwoods with tamarisk neighbors. A greenhouse experiment in which AM and EM inoculation and plant neighbor were manipulated in a fully factorial design showed that cottonwoods benefited from mycorrhizas, especially EM, in terms of shoot biomass when grown with a conspecific, but shoot biomass was similar to that of nonmycorrhizal controls when cottonwoods were grown with a tamarisk neighbor. These results are partially explained by a reduction in EM but not AM colonization of cottonwoods by a tamarisk neighbor. Tamarisk neighbors negatively affected cottonwood specific leaf area, but not chlorophyll content, in the field. To pinpoint a mechanism for these changes, we measured soil chemistry in the field and the growth response of an EM fungus (Hebeloma crustuliniforme) to salt-amended media in the laboratory. Tamarisk increased both NO3- concentrations and electrical conductivity 2.5-fold beneath neighboring cottonwoods in

Evaluating the Invasion of Red Cedar (Juniperus viriginiana) Downstream of Gavins Point Dam, Missouri National Recreational River

Science.gov (United States)

Greene, S.; Knox, J. C.

2013-12-01

Gavins Point Dam, the final dam on the main-stem Missouri River, alters downstream river form and function. Throughout a 59-mile downstream reach, the dam reduces overbank flooding and lowers the water surface by 1-3 meters. Under the dam-created hydro-geomorphic conditions, native cottonwood trees are unable to regenerate. The limited regeneration of native riparian cottonwoods, the lowered water surface, and the reduced overbank flooding creates a terrace environment within the riparian habitat. Consequently, red cedars, a native upland tree, are invading this new terrace-like riparian environment. To this end, we apply Bayesian statistical models to investigate patterns of red cedar riparian invasion and assess ecosystem function patterns along this flow-regulated reach. We set up plots within cottonwood stands along a 59-km reach downstream of Gavins Point Dam. Within each plot, we collected soil samples, litter samples, stem densities of trees, and collected cores of the largest cottonwood and largest red cedar in each plot. To assess influences of red cedar on soil indicators of ecosystem function and general patterns of ecosystem function within the study area, we measured organic carbon, nitrogen, pH, electrical conductivity, and hydrophobicity. To determine drivers and patterns of invasion and ecosystem function we conducted Bayesian linear regressions and means comparison tests. Red cedars existed along the floodplain prior to regulation. However, according to our tree age data and stem density data red cedars existed at a lower population than today. We found that 2 out of 565 red cedars established before the dam was completed. Also, we found no significant difference in soil properties between soils with established red cedar and soils with established cottonwood. By studying soil texture data, and interpreting fluvial geomorphic surfaces in the field and via aerial photography, we found soil texture generally reflects the type of fluvial surface

Cottonwood Response to Nitrogen Related To Plantation Age and Site

Science.gov (United States)

B.G. Blackmon

1977-01-01

When applied at plantation age 4,336 kg N/ha increased diameter growth of cottonwood on Sharkey clay by 33 percent over unfertilized controls. Fertilizing at ages 2 and 3 resulted in no response, nor was there any benefit from applying nitrogen fertilizer to cottonwood on Commerce silt loam. On both sites, foliar N levels were increased by fertilization regardless of...

Development of a spatially-distributed hydroecological model to simulate cottonwood seedling recruitment along rivers.

Science.gov (United States)

Benjankar, Rohan; Burke, Michael; Yager, Elowyn; Tonina, Daniele; Egger, Gregory; Rood, Stewart B; Merz, Norm

2014-12-01

Dam operations have altered flood and flow patterns and prevented successful cottonwood seedling recruitment along many rivers. To guide reservoir flow releases to meet cottonwood recruitment needs, we developed a spatially-distributed, GIS-based model that analyzes the hydrophysical requirements for cottonwood recruitment. These requirements are indicated by five physical parameters: (1) annual peak flow timing relative to the interval of seed dispersal, (2) shear stress, which characterizes disturbance, (3) local stage recession after seedling recruitment, (4) recruitment elevation above base flow stage, and (5) duration of winter flooding, which may contribute to seedling mortality. The model categorizes the potential for cottonwood recruitment in four classes and attributes a suitability value at each individual spatial location. The model accuracy was estimated with an error matrix analysis by comparing simulated and field-observed recruitment success. The overall accuracies of this Spatially-Distributed Cottonwood Recruitment model were 47% for a braided reach and 68% for a meander reach along the Kootenai River in Idaho, USA. Model accuracies increased to 64% and 72%, respectively, when fewer favorability classes were considered. The model predicted areas of similarly favorable recruitment potential for 1997 and 2006, two recent years with successful cottonwood recruitment. This model should provide a useful tool to quantify impacts of human activities and climatic variability on cottonwood recruitment, and to prescribe instream flow regimes for the conservation and restoration of riparian woodlands. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Energy Technology Data Exchange (ETDEWEB)

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).

North End Runway Material Extraction and Transport Environmental Assessment

Science.gov (United States)

2006-05-01

raspberry, currant, bunchberry, horsetail, and high bush cranberry as well as willow, elderberry, rusty menzeiseia, devil’s club, and sapling cottonwood...shrubs and young trees to include paper birch, willow, aspen, cottonwood/balsam poplar, high bush cranberry , Sitka alder, and mountain ash. In winter...the southeast corner of the plot. Standing water appears in small depressions around the vegetated area as well. Vegetation: Table 1, below

Biomass productivity improvement for eastern cottonwood

Science.gov (United States)

Terry L. Robison; Randy J. Rousseau; Jianwei Zhang

2006-01-01

Eastern cottonwood ( Populus deltoides Marsh.) is grown in plantations by MeadWestvaco for use at its Wickliffe Kentucky Fine Papers Mill1. Genetic and productivity research over the past two decades have led to significant increases in biomass yield while reducing production costs.Initially, genetic research identified fast growing...

Field Guide for Evaluating Cottonwood Sites

Science.gov (United States)

W.M. Broadfoot

1960-01-01

Two field methods have been developed at the Stoneville Research Center for estimating the capability of Midsouth soils to grow eastern cottonwood (Populus deltoides Bartr.). Data for establishing the procedures were collected from 155 plots* at the locations indicated in Figure 1.The methods give site index-that is, tree-growing...

The pentadehydro-Diels-Alder reaction.

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Hydrogeochemical and stream sediment detailed geochemical survey for Thomas Range-Wasatch, Utah. Cottonwood project area

International Nuclear Information System (INIS)

Butz, T.R.; Bard, C.S.; Witt, D.A.; Helgerson, R.N.; Grimes, J.G.; Pritz, P.M.

1980-01-01

Results of Cottonwood project area of the Thomas Range-Wasatch detailed geochemical survey are reported. Field and laboratory data are presented for 15 groundwater samples, 79 stream sediment samples, and 85 radiometric readings. Statistical and areal distributions of uranium and possible uranium-related variables are given. A generalized geologic map of the project area is provided, and pertinent geologic factors which may be of significance in evaluating the potential for uranium mineralization are briefly discussed. Uranium concentrations in groundwater range from 0.25 to 3.89 ppB. The highest concentrations are from groundwaters from the Little Cottonwood and Ferguson Stocks. Variables that appear to be associated with uranium in groundwater include cobalt, iron, potassium, manganese, nickel, sulfate, and to a lesser extent, molybdenum and strontium. This association is attributed to the Monzonitic Little Cottonwood Stock, granodioritic to granitic and lamprophyric dikes, and known sulfide deposits. Soluble uranium concentrations (U-FL) in stream sediments range from 0.31 to 72.64 ppM. Total uranium concentrations (U-NT) range from 1.80 to 75.20 ppM. Thorium concentrations range from <2 to 48 ppM. Anomalous values for uranium and thorium are concentrated within the area of outcrop of the Little Cottonwood and Ferguson Stocks. Variables which are areally associated with high values of uranium, thorium, and the U-FL:U-NT ratio within the Little Cottonwood Stock are barium, copper, molybdenum, and zinc. High concentrations of these variables are located near sulfide deposits within the Little Cottonwood Stock

Genetic Variation Among Open-Pollinated Progeny of Eastern Cottonwood

Science.gov (United States)

R. E. Farmer

1970-01-01

Improvement programs in eastern cottonwood (Populus deltoides Bartr.) are most frequently designed to produce genetically superior clones for direct commercial use. This paper describes a progeny test to assess genetic variability on which selection might be based.

The potential of grey alder plantation forestry

Energy Technology Data Exchange (ETDEWEB)

Rytter, L. [Swedish Univ. of Agricultural Sciences, Uppsala (Sweden). Dept. of Short Rotation Forestry

1996-12-31

A survey concerning the potential use of grey alder (Alnus incana (L.) Moench.) in short rotation forestry is performed. The most important characters in this context are discussed. It is concluded that grey alder is an interesting contributor in plantation forestry, because it has a high woody biomass production, is more or less self-supporting with nitrogen, and is well adapted to the conditions in Fennoscandia and Balticum. 36 refs, 2 figs, 1 tab

Planting Season for Cottonwood Can Be Extended

Science.gov (United States)

Harvey E. Kennedy

1979-01-01

Cottonwood cuttings planted as early as November and as late as May survive and grow well if sufficient soil moisture is available and cuttings are properly handled. About 6 inches or more of well distributed rainfall is needed in September and October to recharge Commerce soil. If these two months are dry, planting should be delayed. In March or later, cuttings should...

Dendroclimatic potential of plains cottonwood (Populus deltoides subsp. monilifera) from the Northern Great Plains, USA

Science.gov (United States)

Edmonson, Jesse; Friedman, Jonathan; Meko, David; Touchan, Ramzi; Scott, Julian; Edmonson, Alan

2014-01-01

A new 368-year tree-ring chronology (A.D. 1643–2010) has been developed in western North Dakota using plains cottonwood (Populus deltoides subsp. monilifera) growing on the relatively undisturbed floodplain of the Little Missouri River in the North Unit of Theodore Roosevelt National Park. We document many slow-growing living trees between 150–370 years old that contradict the common understanding that cottonwoods grow fast and die young. In this northern location, cottonwood produces distinct annual rings with dramatic interannual variability that strongly crossdate. The detrended tree-ring chronology is significantly positively correlated with local growing season precipitation and soil moisture conditions (r  =  0.69). This time series shows periods of prolonged low radial tree growth during the known droughts of the instrumental record (e.g. 1931–1939 and 1980–1981) and also during prehistory (e.g. 1816–1823 and 1856–1865) when other paleoclimate studies have documented droughts in this region. Tree rings of cottonwood will be a useful tool to help reconstruct climate, streamflow, and the floodplain history of the Little Missouri River and other northern river systems.

Solvent Effects in Asymmetric Hetero Diels-Alder and Ene Reactions

DEFF Research Database (Denmark)

Johannsen, Mogens; Jørgensen, Karl Anker

1996-01-01

The use of polar solvents such as nitromethane or 2-nitropropane leads to a significant improvement of the catalytic properties of a cationic copper-Lewis acid in the hetero Diels-Alder reaction of alkyl glyoxylates with dienes; The scope of a newly developed copper(II)-bisoxazoline catalyst...... for the hetero Diels-Alder reaction is demonstrated by the reaction of different dienes with alkyl glyoxylates in nitroalkane solvents with the formation of the hetero Diels-Alder adduct in high enantiomeric excess as the major product. The synthetic application of the reaction is exemplified by an improved...

Ecophysiology of riparian cottonwood and willow before, during, and after two years of soil water removal.

Science.gov (United States)

Hultine, K R; Bush, S E; Ehleringer, J R

2010-03-01

Riparian cottonwood/willow forest assemblages are highly valued in the southwestern United States for their wildlife habitat, biodiversity, and watershed protection. Yet these forests are under considerable threat from climate change impacts on water resources and land-use activities to support human enterprise. Stream diversions, groundwater pumping, and extended drought have resulted in the decline of cottonwood/willow forests along many riparian corridors in the Southwest and, in many cases, the replacement of these forests with less desirable invasive shrubs and trees. Nevertheless, ecophysiological responses of cottonwood and willow, along with associated ecohydrological feedbacks of soil water depletion, are not well understood. Ecophysiological processes of mature Fremont cottonwood and coyote willow stands were examined over four consecutive growing seasons (2004-2007) near Salt Lake City, Utah, USA. The tree stands occurred near the inlet of a reservoir that was drained in the spring of 2005 and remained empty until mid-summer of 2006, effectively removing the primary water source for most of two growing seasons. Stem sap flux density (Js) in cottonwood was highly correlated with volumetric soil moisture (theta) in the upper 60 cm and decreased sevenfold as soil moisture dropped from 12% to 7% after the reservoir was drained. Conversely, Js in willow was marginally correlated with 0 and decreased by only 25% during the same period. Opposite patterns emerged during the following growing season: willow had a lower whole-plant conductance (kt) in June and higher leaf carbon isotope ratios (delta13C) than cottonwood in August, whereas k(t) and delta13C were otherwise similar between species. Water relations in both species recovered quickly from soil water depletion, with the exception that sapwood area to stem area (As:Ast) was significantly lower in both species after the 2007 growing season compared to 2004. Results suggest that cottonwood has a greater

The Diels Alder/retro-Diels Alder concept on solid support : a study of the scope, limitations and conceivable applications as a traceless thermocleavable linker

NARCIS (Netherlands)

Gieling, Reinerus Gerardus

2003-01-01

This thesis deals with the conceivable transfer of the Diels Alder/retro-Diels Alder concept to the solid phase in order to broaden the scope of the methodology to a combinatorial level. In addition, based on this methodology the development of a traceless thermocleavable linking system for

Stepwise radical cation Diels-Alder reaction via multiple pathways.

Science.gov (United States)

Shimizu, Ryo; Okada, Yohei; Chiba, Kazuhiro

2018-01-01

Herein we disclose the radical cation Diels-Alder reaction of aryl vinyl ethers by electrocatalysis, which is triggered by an oxidative SET process. The reaction clearly proceeds in a stepwise fashion, which is a rare mechanism in this class. We also found that two distinctive pathways, including "direct" and "indirect", are possible to construct the Diels-Alder adduct.

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

Science.gov (United States)

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...

Changes in Species Composition in Alder Swamp Forest Following Forest Dieback

Directory of Open Access Journals (Sweden)

Remigiusz Pielech

2018-06-01

Full Text Available It is generally hypothesized that forest dieback is a characteristic of alder swamp forests (alder carrs, Alnion glutinosae alliance. Different internal and external factors may trigger this process, including human disturbance, changes in river discharge, unusually severe and prolonged flooding, terminal age of an even-aged alder forest (ca. 100–150 years and others. Although forest dieback in this type of forest may cause major changes in environmental conditions, the influence of this change on the floristic composition has not been well recognized. The study aimed to detect any possible changes in floristic variation in alder swamp forest following forest dieback. Vegetation plots in alder swamp forests affected by forest dieback were resurveyed 20 years after a previous study. PERMANOVA was used to test the significance of the compositional change and nonmetric multidimensional scaling (NMDS with passively fitted means of the Ellenberg’s Indicator Values were used to interpret its ecological meaning. In addition, different structural and diversity indices were compared, including species richness, percentage cover of vegetation layers, Shannon and Simpson diversity and evenness. Finally, we analyzed changes in the frequency of vascular plant species using Chi square tests. We recorded clear and significant compositional changes following alder swamp forest dieback. This change was most related to the gradient of moisture, followed by the gradients of light and temperature. The analysis of the individual species showed that the species of hummocks declined, while the species of hollows increased. Moreover, the current communities are dominated by some hydrophytes that were not recorded 20 years ago. Forest dieback resulted in profound changes in the hydrological regime. The observed changes are consistent with a model of cyclic succession as proposed for alder swamps. In addition, we conclude that the natural forest dynamics have to be

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

Science.gov (United States)

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Cottonwood Lake study area, a long-term wetland ecosystem monitoring site

Science.gov (United States)

Mushet, David M.; Euliss, Ned H.

2012-01-01

The Cottonwood Lake study area is one of only three long-term wetland ecosystem monitoring sites in the prairie pothole region of North America; the other two are Orchid Meadows in South Dakota and St. Denis in Saskatchewan. Of the three, Cottonwood Lake has, by far, the longest continuous data-collection record. Research was initiated at the study area in 1966, and intensive investigations of the hydrology, chemistry, and biology of prairie pothole wetlands continue at the site today. This fact sheet describes the study area, provides an overview of wetland ecology research that has been conducted at the site in the past, and provides an introduction to current work being conducted at the study area by USGS scientists.

Intramolecular Diels-Alder reactions of pyrimidines, a synthetic and computational study

NARCIS (Netherlands)

Stolle, W.A.W.

1992-01-01

This thesis deals with an investigation on the ringtransformation reactions of 2and 5-(ω-alkynyl)pyrimidine derivatives, which undergo upon heating an intramolecular Diels-Alder reaction and subsequently a spontaneous retro Diels- Alder reaction. To get a better insight into the

Rooting ability of native cottonwoods depends on the clone used

Science.gov (United States)

Frank E. Cunningham

1953-01-01

Vegetative propagation of eastern cottonwood (Populus deltoides) from dormant cuttings has generally been considered rather easy. Yet test plantings of unrooted cuttings of this species on the Hopkins Memorial Experimental Forest at Williamstown, Mass., showed considerable variation in rooting ability of the clones used.

Nitrogen Fertilization Increases Cottonwood Growth on Old-Field Soil

Science.gov (United States)

B. G. Blackmon; E. H. White

1972-01-01

Nitrogen (150 lb ./acre as NH4N03 ) applied to a 6-year-old eastern cottonwood plantation in an old field on Commerce silt loam soil increased diameter, basal area, and volume growth by 200 percent over untreated controls. The plantation did not respond to 100 pounds P per acre from concentrated superphosphate.

The hexadehydro-Diels-Alder reaction.

Science.gov (United States)

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

2012-10-11

Arynes (aromatic systems containing, formally, a carbon-carbon triple bond) are among the most versatile of all reactive intermediates in organic chemistry. They can be 'trapped' to give products that are used as pharmaceuticals, agrochemicals, dyes, polymers and other fine chemicals. Here we explore a strategy that unites the de novo generation of benzynes-through a hexadehydro-Diels-Alder reaction-with their in situ elaboration into structurally complex benzenoid products. In the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'diynophile' to produce the highly reactive benzyne intermediate. The reaction conditions for this simple, thermal transformation are notable for being free of metals and reagents. 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.

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

Science.gov (United States)

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.

Asymmetric Diels-Alder reactions with 5-menthyloxy-2(5H)-furanones

NARCIS (Netherlands)

Jong, Johannes Cornelis de

2006-01-01

At the beginning of the reseach described in this thesis the catalytic asymmetric Diels-Alder reaction had scarcely been investigated. No good catalytic processes with high enantiomeric excess were known at that time. At the same time the Diels-Alder reactions with chiral dienophiles needed further

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

Science.gov (United States)

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.

Field performance of alternative landfill covers vegetated with cottonwood and eucalyptus trees.

Science.gov (United States)

Abichou, Tarek; Musagasa, Jubily; Yuan, Lei; Chanton, Jeff; Tawfiq, Kamal; Rockwood, Donald; Licht, Louis

2012-01-01

A field study was conducted to assess the ability of landfill covers to control percolation into the waste. Performance of one conventional cover was compared to that of two evapotranspiration (ET) tree covers, using large (7 x 14 m) lined lysimeters at the Leon County Solid Waste management facility in Tallahassee, Florida. Additional unlined test sections were also constructed and monitored in order to compare soil water storage, soil temperature, and tree growth inside lysimeters and in unlined test sections. The unlined test sections were in direct contact with landfill gas. Surface runoff on the ET covers was a small proportion of the water balance (1% of precipitation) as compared to 13% in the conventional cover. Percolation in the ET covers averaged 17% and 24% of precipitation as compared to 33% in the conventional cover. On average, soil water storage was higher in the lined lysimeters (429 mm) compared to unlined test sections (408 mm). The average soil temperature in the lysimeters was lower than in the unlined test sections. The average tree height inside the lysimeters was not significantly lower (8.04 mfor eucalyptus and 7.11 mfor cottonwood) than outside (8.82 m for eucalyptus and 8.01 m for cottonwood). ET tree covers vegetated with cottonwood or eucalyptus are feasible for North Florida climate as an alternative to GCL covers.

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

Science.gov (United States)

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.

Identification and Characterization of Disturbed Alder Sites on Elmendorf Air Force Base, Alaska

National Research Council Canada - National Science Library

Tande, Gerald

2001-01-01

Vegetation data were collected to identify and characterize disturbed alder (Alnus spp.) areas and provide an ArcView GIS layer for specific sites of alder encroachment likely due to human disturbance...

Comparison of Cottonwood Dendrochronology and Optically Stimulated Luminescence Geochronometers Along a High Plains Meandering River, Powder River, Montana, USA

Science.gov (United States)

Hasse, T. R.; Schook, D. M.

2017-12-01

Geochronometers at centennial scales can aid our understanding of process rates in fluvial geomorphology. Plains cottonwood trees (Populus deltoides ssp. Monilifera) in the high plains of the United States are known to germinate on freshly created deposits such as point bars adjacent to rivers. As the trees mature they may be partially buried (up to a few meters) by additional flood deposits. Cottonwood age gives a minimum age estimate of the stratigraphic surface where the tree germinated and a maximum age estimate for overlying sediments, providing quantitative data on rates of river migration and sediment accumulation. Optically Stimulated Luminescence (OSL) of sand grains can be used to estimate the time since the sand grains were last exposed to sunlight, also giving a minimum age estimate of sediment burial. Both methods have disadvantages: Browsing, partial burial, and other damage to young cottonwoods can increase the time required for the tree to reach a height where it can be sampled with a tree corer, making the germination point a few years to a few decades older than the measured tree age; fluvial OSL samples can have inherited age (when the OSL age is older than the burial age) if the sediment was not completely bleached prior to burial. We collected OSL samples at 8 eroding banks of the Powder River Montana, and tree cores at breast height (±1.2 m) from cottonwood trees growing on the floodplain adjacent to the OSL sample locations. Using the Minimum Age Model (MAM) we found that OSL ages appear to be 500 to 1,000 years older than the adjacent cottonwood trees which range in age (at breast height) from 60 to 185 years. Three explanations for this apparent anomaly in ages are explored. Samples for OSL could be below a stratigraphic unconformity relative to the cottonwood germination elevation. Shallow samples for OSL could be affected by anthropogenic mixing of sediments due to plowing and leveling of hay fields. The OSL samples could have

Diels–Alder cycloaddition of 2-methylfuran and ethylene for renewable toluene

Energy Technology Data Exchange (ETDEWEB)

Green, Sara K.; Patet, Ryan E.; Nikbin, Nima; Williams, C. Luke; Chang, Chun-Chih; Yu, Jingye; Gorte, Raymond J.; Caratzoulas, Stavros; Fan, Wei; Vlachos, Dionisios G.; Dauenhauer, Paul J.

2016-01-01

Diels–Alder cycloaddition of biomass-derived 2-methylfuran and ethylene provides a thermochemical pathway to renewable toluene. In this work, the kinetics and reaction pathways of toluene formation have been evaluated with H-BEA and Sn-BEA catalysts. Kinetic analysis of the main reaction chemistries reveals the existence of two rate-controlling reactions: (i) Diels–Alder cycloaddition of 2-methylfuran and ethylene where the production rate is independent of the Brønsted acid site concentration, and (ii) dehydration of the Diels–Alder cycloadduct where the production rate is dependent on the Brønsted acid site concentration. Application of a reduced kinetic model supports the interplay of these two regimes with the highest concentration of toluene measured at a catalyst loading equal to the transition region between the two kinetic regimes. Selectivity to toluene never exceeded 46%, as 2-methylfuran was consumed by several newly identified reactions to side products, including dimerization of 2-methylfuran, the formation of a trimer following hydrolysis and ring-opening of 2-methylfuran, and the incomplete dehydration of the Diels–Alder cycloadduct of 2-methylfuran and ethylene.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Growth and Survival of Hardwoods and Pine Interplanted with European Alder

Science.gov (United States)

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...

Niobium Pentachloride Activation of Enone Derivatives: Diels-Alder and Conjugate Addition Products

Directory of Open Access Journals (Sweden)

Gil Valdo José da Silva

2002-05-01

Full Text Available Niobium pentachloride has proven to be a powerful activating agent for Diels-Alder or conjugate addition reactions of cycloenones. The Diels-Alder product was obtained only with an unsubstituted enone (cyclohexenone and the highly reactive diene cyclopentadiene; substituents in the b-position of enones seem to prevent Diels-Alder reaction: oxygenated substituents favor the formation of vinyl chlorides (ethyl ether or dichloromethane as solvents or enol ethers (ethyl acetate as solvent, while a methyl substituent prevents any kind of transformation with NbCl5. Less reactive dienes, furan and 2-methylfuran gave the conjugate addition products of the furan ring to the enone system.

Dynamics of Plains Cottonwood ( Populus deltoides) Forests and Historical Landscape Change along Unchannelized Segments of the Missouri River, USA

Science.gov (United States)

Dixon, Mark D.; Johnson, W. Carter; Scott, Michael L.; Bowen, Daniel E.; Rabbe, Lisa A.

2012-05-01

Construction of six large dams and reservoirs on the Missouri River over the last 50-75 years has resulted in major landscape changes and alterations in flow patterns, with implications for riparian forests dominated by plains cottonwood ( Populus deltoides). We quantified changes in land cover from 1892-1950s and the 1950s-2006 and the current extent and age structure of cottonwood forests on seven segments (two reservoir and five remnant floodplain) comprising 1127 km (53 %) of the unchannelized upper two-thirds of the Missouri River. Riparian forest area declined by 49 %; grassland 61 %; shrubland 52 %; and sandbar habitat 96 %; while agricultural cropland increased six-fold and river/reservoir surface area doubled from 1892 to 2006. Net rates of erosion and accretion declined between the 1892-1950s and 1950s-2006 periods. Accretion exceeded erosion on remnant floodplain segments, resulting in declines in active channel width, particularly in 1950s-2006. Across all study segments in 2006, most cottonwood stands (67 %) were >50 years old, 22 % were 25-50 years old, and only 10 % were <25 years old. Among stands <50 years old, the higher proportion of 25-50 year old stands represents recruitment that accompanied initial post-dam channel narrowing; while declines in sandbar and shrubland area and the low proportion of stands <25 years old suggest declines in geomorphic dynamism and limited recruitment under recent river management. Future conservation and restoration efforts should focus both on limiting further loss of remnant cottonwood stands and developing approaches to restore river dynamics and cottonwood recruitment processes.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Riparian Cottonwood Ecosystems and Regulated Flows in Kootenai and Yakima Sub-Basins : Volume III (Overview and Tools).

Energy Technology Data Exchange (ETDEWEB)

Jamieson, Bob; Braatne, Jeffrey H.

2001-10-01

Riparian vegetation and especially cottonwood and willow plant communities are dependent on normative flows and especially, spring freshette, to provide conditions for recruitment. These plant communities therefore share much in common with a range of fish species that require natural flow conditions to stimulate reproduction. We applied tools and techniques developed in other areas to assess riparian vegetation in two very different sub-basins within the Columbia Basin. Our objectives were to: Document the historic impact of human activity on alluvial floodplain areas in both sub-basins; Provide an analysis of the impacts of flow regulation on riparian vegetation in two systems with very different flow regulation systems; Demonstrate that altered spring flows will, in fact, result in recruitment to cottonwood stands, given other land uses impacts on each river and the limitations imposed by other flow requirements; and Assess the applicability of remote sensing tools for documenting the distribution and health of cottonwood stands and riparian vegetation that can be used in other sub-basins.

Genetic improvement and evaluation of black cottonwood for short- rotation biomass production. Final report, 1987--1992

Energy Technology Data Exchange (ETDEWEB)

Stettler, R.F.; Hinckley, T.M. [Washington Univ., Seattle, WA (United States). Coll. of Forest Resources; Heilman, P.E. [Washington State Univ., Puyallup, WA (United States). Research and Extension Center; Bradshaw, H.D. Jr. [Washington Univ., Seattle, WA (United States). Dept. of Biochemistry

1993-04-30

This project was initiated in 1978 to serve three objectives: (1) develop genetically improved poplar cultivars offering increased productivity under short-rotation culture; (2) identify the major components of productivity in poplar and determine ways in which they can be manipulated, genetically and culturally; and (3) engage in technology transfer to regional industry and agencies so as to make poplar culture in the Pacific Northwest economically feasible. The project is aimed at capturing natural variation in the native black cottonwood. Populus trichocarpa T & G, and enhancing it through selective breeding. Major emphasis has been placed on hybridization of black cottonwood with P deltoides and P maximowiczii, more recently with p nigra. First-generation (F{sub 1}) hybrids have consistently outperformed black cottonwood by a factor of 1.5.-2. The high yields of woody biomass obtained from these clonally propagated hybrids, in rotations of 4-7 years, have fostered the establishment of large-scale plantations by the pulp and paper industry in the region. Physiological studies have helped to elucidate hybrid superiority and several of the underlying mechanisms.

Pyrrole PMOs, incorporating new N-heterocyclic compounds on an ethene-PMO through Diels–Alder reactions

International Nuclear Information System (INIS)

Esquivel, Dolores; De Canck, Els; Jiménez-Sanchidrián, César; Romero-Salguero, Francisco J.; Van Der Voort, Pascal

2014-01-01

The ethenylene bridges on the walls of an ethenylene-bridged periodic mesoporous organosilica were successfully modified with a variety of pyrrole derivatives – pyrrole, methylpyrrole, dimethylpyrrole, trimethylpyrrole and 1-phenylpyrrole – through Diels–Alder reactions. X-ray diffraction measurements and N 2 adsorption–desorption analysis confirmed the preservation of the ordering and mesoporosity of the parent material as well as the decoration of the pores with the surface Diels–Alder adducts. Moreover, other techniques such as DRIFT, 13 C and 29 Si nuclear magnetic resonances revealed the formation of the surface N-heterocyclic compounds at the parent ethenylene sites. - Highlights: • Chemical modification of the double bonds on an ethene-PMO through the Diels–Alder reaction. • A family of pyrrole derivatives act as dienes in the Diels–Alder reaction. • Well-ordering and mesoporosity are retained after the post-functionalization. • N-containing compounds on the surface of ethene-PMO are present after the Diels–Alder reaction

Pyrrole PMOs, incorporating new N-heterocyclic compounds on an ethene-PMO through Diels–Alder reactions

Energy Technology Data Exchange (ETDEWEB)

Esquivel, Dolores; De Canck, Els [Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium); Jiménez-Sanchidrián, César [Department of Organic Chemistry, Nanochemistry and Fine Chemistry Research Institute (IUIQFN), Faculty of Sciences, University of Córdoba, Campus de Rabanales, Marie Curie Building, Ctra. Nnal. IV, km 396, 14071 Córdoba (Spain); Romero-Salguero, Francisco J., E-mail: qo2rosaf@uco.es [Department of Organic Chemistry, Nanochemistry and Fine Chemistry Research Institute (IUIQFN), Faculty of Sciences, University of Córdoba, Campus de Rabanales, Marie Curie Building, Ctra. Nnal. IV, km 396, 14071 Córdoba (Spain); Van Der Voort, Pascal, E-mail: pascal.vandervoort@ugent.be [Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium)

2014-11-14

The ethenylene bridges on the walls of an ethenylene-bridged periodic mesoporous organosilica were successfully modified with a variety of pyrrole derivatives – pyrrole, methylpyrrole, dimethylpyrrole, trimethylpyrrole and 1-phenylpyrrole – through Diels–Alder reactions. X-ray diffraction measurements and N{sub 2} adsorption–desorption analysis confirmed the preservation of the ordering and mesoporosity of the parent material as well as the decoration of the pores with the surface Diels–Alder adducts. Moreover, other techniques such as DRIFT, {sup 13}C and {sup 29}Si nuclear magnetic resonances revealed the formation of the surface N-heterocyclic compounds at the parent ethenylene sites. - Highlights: • Chemical modification of the double bonds on an ethene-PMO through the Diels–Alder reaction. • A family of pyrrole derivatives act as dienes in the Diels–Alder reaction. • Well-ordering and mesoporosity are retained after the post-functionalization. • N-containing compounds on the surface of ethene-PMO are present after the Diels–Alder reaction.

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

Science.gov (United States)

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.

DIELS-ALDER REACTIONS IN AQUEOUS-SOLUTIONS - ENFORCED HYDROPHOBIC INTERACTIONS BETWEEN DIENE AND DIENOPHILE

NARCIS (Netherlands)

BLOKZIJL, W; BLANDAMER, MJ; ENGBERTS, JBFN

1991-01-01

Second-order rate constants and isobaric activation parameters for the intermolecular Diels-Alder reactions of cyclopentadiene with alkyl vinyl ketones (2a,b) and 5-substituted-1,4-naphthoquinones (3a-c) as well as for the intramolecular Diels-Alder reaction of N-furfuryl-N-methylmaleamic acid (4)

Estimating Leaf Nitrogen of Eastern Cottonwood Trees with a Chlorophyll Meter

Science.gov (United States)

Benoit Moreau; Emile S. Gardiner; John A. Stanturf; Ronald K. Fisher

2004-01-01

The utility of the SPAD-502 chlorophyll meter for nondestructive and rapid field determination of leaf nitrogen (N) has been demonstrated in agricultural crops, but this technology has not yet been extended to woody crop applications. Upper canopy leaves from a 5-year-old plantation of two eastern cottonwood (Populus deltoides Bartr. ex Marsh.)...

The first organocatalytic, ortho-regioselective inverse-electron-demand hetero-Diels-Alder reaction.

Science.gov (United States)

Hejmanowska, Joanna; Jasiński, Marcin; Wojciechowski, Jakub; Mlostoń, Grzegorz; Albrecht, Łukasz

2017-10-17

The development of the unprecedented ortho-regioselective inverse-electron-demand hetero-Diels-Alder (IEDHDA) reaction is described. It has been demonstrated that by proper choice of reactants and reaction conditions the inverse-electron-demand hetero-Diels-Alder cycloaddition can be realized with unprecedented regioselectivity arising from the reaction between the terminal carbon atom of the dienophile and the heteroatom of the heterodiene.

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

Science.gov (United States)

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.

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

International Nuclear Information System (INIS)

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

2013-01-01

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.

Riparian Cottonwood Ecosystems and Regulated Flows in Kootenai and Yakima Sub-Basins : Volume II Yakima (Overview, Report, Appendices).

Energy Technology Data Exchange (ETDEWEB)

Jamieson, Bob; Braatne, Jeffrey H.

2001-10-01

Riparian vegetation and especially cottonwood and willow plant communities are dependent on normative flows and especially, spring freshette, to provide conditions for recruitment. These plant communities therefore share much in common with a range of fish species that require natural flow conditions to stimulate reproduction. We applied tools and techniques developed in other areas to assess riparian vegetation in two very different sub-basins within the Columbia Basin. Our objectives were to: Document the historic impact of human activity on alluvial floodplain areas in both sub-basins; Provide an analysis of the impacts of flow regulation on riparian vegetation in two systems with very different flow regulation systems; Demonstrate that altered spring flows will, in fact, result in recruitment to cottonwood stands, given other land uses impacts on each river and the limitations imposed by other flow requirements; and Assess the applicability of remote sensing tools for documenting the distribution and health of cottonwood stands and riparian vegetation that can be used in other sub-basins.

Identifying data gaps and prioritizing restoration strategies for Fremont cottonwood using linked geomorphic and population models

Science.gov (United States)

Harper, E. B.; Stella, J. C.; Fremier, A. K.

2009-12-01

Fremont cottonwood (Populus fremontii) is an important component of semi-arid riparian ecosystems throughout western North America, but its populations are in decline due to flow regulation. Achieving a balance between human resource needs and riparian ecosystem function requires a mechanistic understanding of the multiple geomorphic and biological factors affecting tree recruitment and survival, including the timing and magnitude of river flows, and the concomitant influence on suitable habitat creation and mortality from scour and sedimentation burial. Despite a great deal of empirical research on some components of the system, such as factors affecting cottonwood recruitment, other key components are less studied. Yet understanding the relative influence of the full suite of physical and life-history drivers is critical to modeling whole-population dynamics under changing environmental conditions. We addressed these issues for the Fremont cottonwood population along the Sacramento River, CA using a sensitivity analysis approach to quantify uncertainty in parameters on the outcomes of a patch-based, dynamic population model. Using a broad range of plausible values for 15 model parameters that represent key physical, biological and climatic components of the ecosystem, we ran 1,000 population simulations that consisted of a subset of 14.3 million possible combinations of parameter estimates to predict the frequency of patch colonization and total forest habitat predicted to occur under current hydrologic conditions after 175 years. Results indicate that Fremont cottonwood populations are highly sensitive to the interactions among flow regime, sedimentation rate and the depth of the capillary fringe (Fig. 1). Estimates of long-term floodplain sedimentation rate would substantially improve model accuracy. Spatial variation in sediment texture was also important to the extent that it determines the depth of the capillary fringe, which regulates the availability of

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

Science.gov (United States)

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 ...

The Diels-Alder cyclization of ketenimines.

Science.gov (United States)

Erb, Jeremy; Strull, Jessica; Miller, David; He, Jean; Lectka, Thomas

2012-04-20

A Diels-Alder reaction between cyclopentadiene and a variety of ketenimines is reported. A copper(I)-bis(phosphine complex catalyzes the cycloaddition across the C═N bond of the ketenimine in a [4 + 2] reaction to give an enamine intermediate that is hydrolyzed upon purification to generate aminoketones. © 2012 American Chemical Society

Grady Highway Extension (Ship Creek Crossing) Elmendorf Air Force Base and Fort Richardson, Alaska

Science.gov (United States)

2005-06-01

appear to have developed in depressions and floodplain channels where water is either shallow or exposed to the surface during periods of high water...Emergent, Persistent, Seasonally Flooded). A narrow depressional area with exposed water demonstration flow characteristics of the hyporheic zone...hyporheic zone. Dominant vegetation includes thin-leaf alder, cottonwood, lady fern, highbush cranberry , tuberous spring beauty and marsh

Evaluating growth effects from an imidacloprid treatment in black willow and eastern cottonwood cuttings

Science.gov (United States)

Luciano de Sene Fernandes; Ray A. Souter; Theodor D. Leininger

2015-01-01

Black willow (Salix nigra Marsh.) and eastern cottonwood (Populus deltoides Bartram ex Marsh.), two species native in the Lower Mississippi Alluvial Valley, have importance in short rotation woody crop (SRWC) systems for biomass production (Ruark 2006).

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

Science.gov (United States)

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.

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.

Science.gov (United States)

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.

Water Resources and Related Land Management, Buffalo Metropolitan Area, New York

Science.gov (United States)

1991-04-01

nettle , Queen Ann’s lace, aster (New England, bushy), beggarstick, cocklebur, chickory, tickseed-sunflower, timothy, teasel, and grasses (quake, orchard...in leaf litter and falling insects off such overhanging trees, that contribute to the fish food chain in the creek. Channelization would disrupt and...alder and eastern cottonwood. Goldenrod, stinging nettle and various grasses are abundant to common. Aquatic vegetation is limited, although spikerush

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

Directory of Open Access Journals (Sweden)

Christian H. Hornung

2017-01-01

Full Text Available 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.

Susceptibility of common alder (Alnus glutinosa) seeds and seedlings to Phytophthora alni and other Phytophthora species

Energy Technology Data Exchange (ETDEWEB)

Haque, M. M.; Diez, J. J.

2012-11-01

Phytophthora alni is a highly destructive host specific pathogen to alders (Alnus spp.) spreading all over Europe. Recently this pathogen has been reported to cause diseases in common alder (Alnus glutinosa) in Spain. Seeds and seedlings of A. glutinosa were tested in vitro for their susceptibility to alder Phytophthora and other Phytophthora species. Isolates of P. alni ssp. alni, P. cinnamomi, P. citrophthora, P. nicotianae and P. palmivora were used in the experiments. Seeds and seedlings were inoculated with a zoospore suspension and uniform mycelial blocks of agar of the Phytophthora species. Susceptibility was calculated in terms of pathogen virulence on seed germination and seedling mortality 42 and 67 days after inoculation respectively. Seed germination and seedling mortality rates varied differently among the isolates used. Results implied that common alder and its seeds and seedlings are at risk to be infected by P. alni. In addition, other Phytophthora species are able to infect this kind of material showing their relative host non-specificity. This is one important finding concerning alder regeneration in infected areas, and the possibility of disease spread on this plant material. (Author) 42 refs.

Riparian Cottonwood Ecosystems and Regulated Flows in Kootenai and Yakima Sub-Basins : Volume I Kootenai River (Overview, Report and Appendices).

Energy Technology Data Exchange (ETDEWEB)

Jamieson, Bob; Braatne, Jeffrey H.

2001-10-01

Riparian vegetation and especially cottonwood and willow plant communities are dependent on normative flows and especially, spring freshette, to provide conditions for recruitment. These plant communities therefore share much in common with a range of fish species that require natural flow conditions to stimulate reproduction. We applied tools and techniques developed in other areas to assess riparian vegetation in two very different sub-basins within the Columbia Basin. Our objectives were to: Document the historic impact of human activity on alluvial floodplain areas in both sub-basins; Provide an analysis of the impacts of flow regulation on riparian vegetation in two systems with very different flow regulation systems; Demonstrate that altered spring flows will, in fact, result in recruitment to cottonwood stands, given other land uses impacts on each river and the limitations imposed by other flow requirements; and Assess the applicability of remote sensing tools for documenting the distribution and health of cottonwood stands and riparian vegetation that can be used in other sub-basins.

Covalently crosslinked diels-alder polymer networks.

Energy Technology Data Exchange (ETDEWEB)

Bowman, Christopher (University of Colorado, Boulder, CO); Adzima, Brian J. (University of Colorado, Boulder, CO); 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.

Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

Science.gov (United States)

Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

2018-02-02

The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

Paraffin dispersant application for cleaning subsea flow lines in the deep water Gulf of Mexico cottonwood development

Energy Technology Data Exchange (ETDEWEB)

Jennings, David; White, Jake; Pogoson, Oje [Baker Hughes Inc., Houston, TX (United States); Barros, Dalmo; Ramachandran, Kartik; Bonin, George; Waltrich, Paulo; Shecaira, Farid [PETROBRAS America, Houston, TX (United States); Ziglio, Claudio [Petroleo Brasileiro S.A. (CENPES/PETROBRAS), Rio de Janeiro, RJ (Brazil). Centro de Pesquisa e Desenvolvimento

2012-07-01

This paper discusses a paraffin dispersant (in seawater) application to clean paraffin deposition from a severely restricted 17.4-mile dual subsea flow line system in the Gulf of Mexico Cottonwood development. In principle, dispersant treatments are simple processes requiring effective dispersant packages and agitation to break-up and disperse deposition. Dispersants have been used onshore for treating wax deposition for decades. Implementation of a treatment in a long deep water production system, however, poses numerous challenges. The Cottonwood application was one of the first ever deep water dispersant applications. The application was designed in four separate phases: pre-treatment displacement for hydrate protection, dispersant treatment for paraffin deposition removal, pigging sequence for final flow line cleaning, and post-treatment displacement for hydrate protection. In addition, considerable job planning was performed to ensure the application was executed in a safe and environmentally responsible manner. Two dynamically positioned marine vessels were used for pumping fluids and capturing returns. The application was extremely successful in restoring the deep water flow lines back to near pre-production state. Final pigging operations confirmed the flow lines were cleaned of all restrictions. Significant paraffin deposition was removed in the application. Approximately 900 bbls of paraffin sludge was recovered from the 4000 bbl internal volume flow line loop. Furthermore, the application was completed with zero discharge of fluids. The application provided significant value for the Cottonwood development. It allowed production from wells to be brought on-line at a higher capacity, thereby generating increased revenue. It also allowed resumption of routine pigging operations. As such, the Cottonwood dispersant application illustrates that with proper planning and execution, paraffin dispersant treatments can be highly effective solutions for cleaning

Response of the Cottonwood Leaf Beetle (Coleoptera: Chrysomelidae) to Bacillus thuringiensis var. san diego

Science.gov (United States)

Leah S. Bauer

1990-01-01

A standardized laboratory bioassay was used to quantify the lethal and sub-lethal responses of larval and adult cottonwood leaf beetles, Chrysomela scripta F., to Bacillus thuringiensis var. san diego, formulated as M-One standard powder (Mycogen Corporation, San Diego). The median lethal concentration (LC

A Ligand Structure-Activity Study of DNA-Based Catalytic Asymmetric Hydration and Diels-Alder Reactions

NARCIS (Netherlands)

Rosati, F.; Roelfes, J.G.

A structure-activity relationship study of the first generation ligands for the DNA-based asymmetric hydration of enones and Diels-Alder reaction in water is reported. The design of the ligand was optimized resulting in a maximum ee of 83% in the hydration reaction and 75% in the Diels-Alder

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

Science.gov (United States)

Zhou, Wanpeng; Zhang, Hui; Chen, Fangeng

2018-02-01

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 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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. © 2015 by The Mycological Society of America.

76 FR 34197 - Anchorage; Change to Cottonwood Island Anchorage, Columbia River, Oregon and Washington

Science.gov (United States)

2011-06-13

... Cottonwood Island in the vicinity of the spoil area to approximately the Kalama North dock and the previous... litigation, eliminate ambiguity, and reduce burden. Protection of Children We have analyzed this proposed rule under Executive Order 13045, Protection of Children from Environmental Health Risks and Safety...

The Wall-Rock Record of Incremental Emplacement in the Little Cottonwood-Alta Magmatic and Hydrothermal System, Wasatch Mountains, Utah, U.S.A.

Science.gov (United States)

Stearns, M.; Callis, S.; Beno, C.; Bowman, J. R.; Bartley, J. M.

2017-12-01

Contact aureoles record the cumulative effects on wall rocks of magma emplacement. Like the plutons they surround, contact aureoles have long been regarded to form geologically instantaneously. Protracted incremental emplacement of plutons must be reconciled with the wall-rock record of heat and mass transfer. Fundamental questions include how heat and material move from intrusions into their aureoles and how long that process takes. The Little Cottonwood stock is surrounded by a 2 km-wide contact aureole that contains prograde AFM mineral assemblages in the pelitic layers of the Proterozoic Big Cottonwood Formation. The Alta stock is surrounded by a well characterized 1 km-wide contact aureole containing both prograde AFM and CMS mineral assemblages in Ophir Shale and Mississippian dolostones, respectively. Understanding the petrogenesis of these aureoles requires the timing of magmatism and wall-rock metamorphism to be independently determined. Preliminary petrochronology (U/Th-Pb dates and trace element concentrations collected by LASS-ICP-MS) from the inner aureoles of both intrusions establishes a protracted history of monazite (re)crystallization from 35-25 Ma in the Little Cottonwood aureole and 35 Ma in the Alta aureole. Little Cottonwood aureole monazites are characterized by a positive age correlation with heavy rare earth elements (HREE) and a negative correlation with Eu/Eu*. Alta aureole monazites have a similar range of the HREE concentrations and Eu/Eu* variation. Zircon growth interpreted to record emplacement-level magmatic crystallization of the western Little Cottonwood stock ranges from 33-28 Ma near the contact. Multi-grain U-Pb zircon TIMS dates from the Alta stock range from 35-33 Ma and are interpreted to suggest the full range of emplacement-level magmatism in the Alta stock. Additionally, in situ U-Pb titanite dates from the Alta stock record intermittent high temperature hydrothermal activity in the stock margin from 35-24 Ma. These new

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

Science.gov (United States)

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?;.

Survival and Growth of Cottonwood Clones After Angle Planting and Base Angle Treatments

Science.gov (United States)

W.K. Randall; Harvey E. Kennedy

1976-01-01

Presently, commercial cottonwood plantations in the lower Mississippi Valley are established using vertically planted, unrooted cuttings with a flat (90°) base. Neither survival nor first-year growth of a group of six Stoneville clones was improved by angle planting or cutting base angles diagonally. For one clone, survival was significantly better when base angle was...

Physical properties and fiber dimension in Stem, Branch and root of Alder Wood

OpenAIRE

Moya-Roque, Roger; Kiaei, Majid

2015-01-01

The aim of this study was to determine physical properties and fiber dimensions in stem, branch and root wood for alder (Alnus glutinosa L) species. For this purpose, three normal alder trees were selected from Khanican forest in north of Iran. Disks were taken from three parts such as stem, branch and root of trees. Testing samples were randomly taken at disk surfaces to examine the physical properties (according to the ISO standard for oven-dry density and volumetric shrinkage) and fiber di...

Berni Alder and Phase Transitions in Two Dimensions

Science.gov (United States)

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…

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

Science.gov (United States)

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...

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

Science.gov (United States)

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.

Climatic data for the Cottonwood Lake area, Stutsman County, North Dakota 1982

Science.gov (United States)

Sturrock, A.M.; Hanson, B.A.; Scarborough, J.L.; Winter, T.C.

1986-01-01

Research on the hydrology of the Cottonwood Lake area, Stutsman County, North Dakota, includes study of evaporation. Presented here are those climatic data needed for energy-budget and mass-transfer evaporation studies, including: water-surface temperature, sediment temperature dry-bulb and wet-bulb air temperatures, vapor pressure at and above the water surface, wind speed, and short- and long-wave radiation. Data were collected at raft and land stations.

Climatic data for the Cottonwood Lake area, Stutsman County, North Dakota, 1983

Science.gov (United States)

Sturrock, A.M.; Hanson, B.A.; Scarborough, J.L.; Winter, T.C.

1987-01-01

Research on the hydrology of the Cottonwood Lake area, Stutsman County, North Dakota, includes study of evaporation. Climatic data needed for energy-budget and mass-transfer evaporation studies that were collected during 1983 include water-surface temperature, sediment temperature, dry-bulb and wet-bulb air temperature, vapor pressure at and above the water surface, wind speed, and short-and long-wave radiation. Data are collected at raft and land stations. (USGS)

Catalytic Asymmetric Total Synthesis of (+)- and (-)-Paeoveitol via a Hetero-Diels-Alder Reaction.

Science.gov (United States)

Li, Tian-Ze; Geng, Chang-An; Yin, Xiu-Juan; Yang, Tong-Hua; Chen, Xing-Long; Huang, Xiao-Yan; Ma, Yun-Bao; Zhang, Xue-Mei; Chen, Ji-Jun

2017-02-03

The first catalytic asymmetric total synthesis of (+)- and (-)-paeoveitol has been accomplished in 42% overall yield via a biomimetic hetero-Diels-Alder reaction. The chiral phosphoric acid catalyzed hetero-Diels-Alder reaction showed excellent diastereo- and enantioselectivity (>99:1 dr and 90% ee); two rings and three stereocenters were constructed in a single step to produce (-)-paeoveitol on a scale of 452 mg. This strategy enabled us to selectively synthesize both paeoveitol enantiomers from the same substrates by simply changing the enantiomer of the catalyst.

Elements in cottonwood trees as an indicator of ground water contaminated by landfill leachate

Science.gov (United States)

Erdman, James A.; Christenson, Scott

2000-01-01

Ground water at the Norman Landfill Research Site is contaminated by a leachate plume emanating from a closed, unlined landfill formerly operated by the city of Norman, Oklahoma, Ground water contaminated by the leachate plume is known to be elevated in the concentration of many, organic and inorganic constituents. Specific conductance, alkalinity, chloride, dissolved organic carbon, boron, sodium, strontium, and deuterium in ground water are considered to be indicators of the leachate plume at this site. Leaf samples of broad-leafed cottonwood, Populus deltoides, were collected from 57 sites around the closed landfill. Cottonwood, a phreatophyte or “well plant,” functions as a & surrogate well and serves as a ground water quality sampler. The leaf samples were combusted to ash and analyzed by instrumental neutron activation for 35 elements and by prompt-gamma instrumental neutron activation, for boron. A monitoring well was located within a few meters of a sampled cottonwood tree at 15 of the 57 sites, and ground water samples were collected from these monitoring wells simultaneously with a leaf sample. The chemical analyses of the ground water and leaf samples from these 15 sites indicated that boron, bromine, sodium, and strontium concentrations in leaves were significantly correlated with leachate indicator constituents in ground water. A point-plot map of selected percentiles indicated high concentrations of boron, bromine, and sodium in leaf ash from sites downgradient of the most recent landfill and from older landfills nearby. Data from leaf analysis greatly extended the known areal extent of the leachate plume previously determined from a network of monitoring wells and geophysical surveys. This phytosgeochemical study provided a cost-effective method for assessing the extent of a leachate plume from an old landfill. Such a method may be useful as a preliminary sampling tool to guide the design of hydrogeochemical and geophysical studies.

The Concentration of Nutrients in Tissues of Plantation-Grown Eastern Cottonwood (Populus deltoides Bart.)

Science.gov (United States)

M. G. Shelton; L. E. Nelson; G. L. Switzer; B. G. Blackmon

1981-01-01

Nutrient concentrations were determined for 10 tissues from each of 24 cottonwood trees that ranged in age from four to 16 years. Highest concentrations occurred in the most physiologically active tissues; i.e., stemtips, current branches and foliage. Tree age had little influence on the variation in nutrient concentration of tissues. Some differences in concentrations...

Seasonal N changes in alnus orientalis and populus nigra and N2 fixation by exotic alder species in Syria

International Nuclear Information System (INIS)

Kurdali, F.

2002-01-01

Two experiments were conducted.The first was to study nodulation and N 2 fixation of several introduced alder species (Alnus glutinosa, A. incana, A. rubra and A. viridis) grown in soil from beneath Alnus orientalis. The second was to determine pattern of N changes in leaves and bark of Alnus orientalis and populus nigra natural stands during two successive years. Results showed that frankia in soil from underneath Alnus orientalis nodulated and fixed nitrogen on roots of local alder as well as on roots of introduced alder species from distant and ecologically diverse localities. However, differences were found among species in the number of nodules formed and amount of nitrogen fixed. Percentages of nitrogen derived from atmosphere (%Ndfa) ranged from 5% in A.viridis to 66% in A. orientalis. Microscopic study of Alnus orientalis nodules showed the presence of vesicles, and frankia belonging to Sp-type. Foliar N concentration was higher in alder than in poplar. Total N concentration in alder leaves remained relatively constant at about 3% during summer, whereas N concentration in poplar decreased sharply in leaves and increased in bark. No substantial increase in N concentration was found in alder bark, and the fallen leaves were rich in nitrogen. During autumn, leaf N concentration in poplar decreased by 43% and 51% for the first and the second year, respectively, whereas N concentrations in bark increased by 71% and 100%. Total N concentrations in alder leaves decreased only by 8-16% while, values in the adjacent bark remained stable. In contrast to poplar, it seems that Alnus orientalis does not exhibit net leaf retranslocation to bark tissues.(author)

Intramolecular inverse electron demand Diels-Alder reactions of pyrimidines

NARCIS (Netherlands)

Frissen, A.E.

1990-01-01

This thesis deals with the intramolecular inverse electron demand Diels-Alder reaction of pyrimidines. The main objective of the study was to investigate the synthetic applicability of this reaction and to get more insight in the electronic and steric effects which determine the reactivity

Sequencing of red wine proanthocyanidins by UHPLC-ESI-Q-ToF

Directory of Open Access Journals (Sweden)

Adéline Delcambre

2015-04-01

Full Text Available Dimers of proanthocyanidins with four monomeric units and two distinct linkages are detected and tentatively identified for the first time in Merlot red wine variety without sample preparation. These compounds were characterized by electrospray ionization quadrupole time of flight mass spectrometry in negative mode. Fragments ions derived from retro-Diels Alder, heterocyclic ring fission and quinone methide were detected in targeted MS/MS mode and then assigned by using well-known theoretical fragmentation pathways. The sequencing of these compounds was correlated with the theoretical numbers of oligomers established by mathematical relationship taking in consideration the four monomeric units, the interflavan bond and the ether bond. Our analytical method allows the identification of twenty B-type dimers and twelve A-type dimers in red wine.

DFT studies for the substituent effect on the diels-alder reaction of 1,4-diaza-1,3-butadienes

International Nuclear Information System (INIS)

Lee, Gab Yong

2001-01-01

DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4-DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular orbital) energies for the optimized 1,4-disubstituted-1,4DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively

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

Energy Technology Data Exchange (ETDEWEB)

Fan, Ming; Ma, Ye; Zhang, Ziwei; Mao, Jiahui [School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing (China); Tan, Huaping, E-mail: hptan@njust.edu.cn [School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing (China); Hu, Xiaohong [School of Material Engineering, Jinling Institute of Technology, Nanjing (China)

2015-11-01

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Niobium(V) chloride as catalyst in Diels-Alder reaction of furan ring

International Nuclear Information System (INIS)

Santos, Deborah A. dos; Rodrigues, Ludmila R.; Arpini, Bruno H.; Lacerda Junior, Valdemar; Greco, Sandro J.; Santos, Reginaldo B. dos; Neto, Alvaro C.; Castro, Eustaquio V.R. de

2014-01-01

According to the relevant literature, the Diels-Alder reaction of furan without a catalyst can last several weeks and shows a low yield due to the diene’s low reactivity. The use of Lewis acid catalysts or high pressures is described as an effective method for improving the reaction yields. This paper describes our recent study on the use of niobium pentachloride as the catalyst in Diels-Alder reactions between furan and several reactive dienophiles, among which methyl acrylate showed good yields, especially at lower temperatures. Other dienophiles have shown lower yields because of problems such as byproduct formation and the high reversibility of the reaction. (author)

Niobium(V) chloride as catalyst in Diels-Alder reaction of furan ring

Energy Technology Data Exchange (ETDEWEB)

Santos, Deborah A. dos; Rodrigues, Ludmila R.; Arpini, Bruno H.; Lacerda Junior, Valdemar; Greco, Sandro J.; Santos, Reginaldo B. dos; Neto, Alvaro C.; Castro, Eustaquio V.R. de, E-mail: vljuniorqui@gmail.com [Universidade Federal do Espirito Santo (UFES), Vitoria, ES (Brazil). Dept. de Quimica; Romao, Wanderson [Instituto Federal de Educacao, Ciencia e Tecnologia (IFES), Vila Velha, ES (Brazil)

2014-05-15

According to the relevant literature, the Diels-Alder reaction of furan without a catalyst can last several weeks and shows a low yield due to the diene’s low reactivity. The use of Lewis acid catalysts or high pressures is described as an effective method for improving the reaction yields. This paper describes our recent study on the use of niobium pentachloride as the catalyst in Diels-Alder reactions between furan and several reactive dienophiles, among which methyl acrylate showed good yields, especially at lower temperatures. Other dienophiles have shown lower yields because of problems such as byproduct formation and the high reversibility of the reaction. (author)

High stereoselectivity on low temperature Diels-Alder reactions

Directory of Open Access Journals (Sweden)

Invernize Paulo

2005-12-01

Full Text Available Abstract 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.

Characterization and kinetic study of Diels-Alder reaction: Detailed study on N-phenylmaleimide and furan based benzoxazine with potential self-healing application

Directory of Open Access Journals (Sweden)

Z. Stirn

2016-07-01

Full Text Available The Diels-Alder reaction between N-phenylmaleimide and benzoxazine bearing furan group was investigated for the purpose of successful appliance of self-healing in benzoxazine polymer networks. The reaction as a function of temperature/time was performed in molten state and in a solution, where also the kinetic study was performed. The Diels-Alder reaction leads to a mixture of two diastereomers: endo presented at lower cyclo-reversion temperature and exo at higher. Therefore, the conversion rates and exo/endo ratio were studied in detail for both systems. For instance, in molten state the Diels-Alder reaction was triggered by the temperature of the melting point at 60 °C with exo/endo ratio preferable to the endo adduct. The study of the kinetics in a solution revealed that the Diels-Alder reaction followed typical bimolecular reversible second-order reaction. The activation energies were close to the previous literature data; 48.4 and 51.9 kJ·mol–1 for Diels-Alder reaction, and 91.0 and 102.3 kJ·mol–1 for retro-Diels-Alder reaction, in acetonitrile and chloroform, respectively. The reaction equilibrium in a solution is much more affected by the retro-Diels-Alder reaction than in a molten state. This study shows detailed investigation of DA reaction and provides beneficial knowledge for further use in self-healing polymer networks.

Thermoplastic-thermosetting merged polyimides via furan-maleimide Diels–Alder polymerization

Directory of Open Access Journals (Sweden)

Yogesh S. Patel

2017-02-01

Full Text Available Novel thermoplastic-thermosetting merged polyimide system has been developed via Diels–Alder intermolecular polymerization of bisfuran namely, 2,5-bis(furan-2-ylmethylcarbamoyl terephthalic acid A with a series of bismaleimides B1–4. Thus obtained intermediate Diels–Alder adducts C1–4 were aromatized and imidized (i.e. cyclized through carboxylic and amide groups to afford thermoplastic-thermosetting merged polyimides D1–4. Bisfuran A was prepared by the condensation of pyromellitic dianhydride with furan-2-ylmethanamine and characterized by elemental, spectral, thermal and LCMS analyses. Synthesized Diels–Alder adducts C1–4 and polyimides D1–4 were characterized by elemental analysis, spectral features, number average molecular weight (Mn‾, degree of polymerization (DP and thermal analysis. To facilitate the correct structural assessment and to be able to verify the occurrence of the DA adducts and PIs, a model compound 4 was prepared from phthalic anhydride and furan-2-ylmethanamine in a similar way. FTIR spectral features of polyimides D1–4 were compared with model compound 4 and they were found to be quite identical. The ‘in situ' void-free glass fiber reinforced composites GFRC1–4 were prepared from the produced system and characterized by chemical, mechanical and electrical analyses. All the composites showed good mechanical, electrical and thermal properties and good resistance to organic solvents and mineral acids.

Coupling legacy geomorphic surface facies to riparian vegetation: Assessing red cedar invasion along the Missouri River downstream of Gavins Point dam, South Dakota

Science.gov (United States)

Greene, Samantha L.; Knox, James C.

2014-01-01

Floods increase fluvial complexity by eroding established surfaces and creating new alluvial surfaces. As dams regulate channel flow, fluvial complexity often decreases and the hydro-eco-geomorphology of the riparian habitat changes. Along the Missouri River, flow regulation resulted in channel incision of 1-3 m within the study area and disconnected the pre-dam floodplain from the channel. Evidence of fluvial complexity along the pre-dam Missouri River floodplain can be observed through the diverse depositional environments represented by areas of varying soil texture. This study evaluates the role of flow regulation and depositional environment along the Missouri River in the riparian invasion of red cedar downstream of Gavins Point dam, the final dam on the Missouri River. We determine whether invasion began before or after flow regulation, determine patterns of invasion using Bayesian t-tests, and construct a Bayesian multivariate linear model of invaded surfaces. We surveyed 59 plots from 14 riparian cottonwood stands for tree age, plot composition, plot stem density, and soil texture. Red cedars existed along the floodplain prior to regulation, but at a much lower density than today. We found 2 out of 565 red cedars established prior to regulation. Our interpretation of depositional environments shows that the coarser, sandy soils reflect higher energy depositional pre-dam surfaces that were geomorphically active islands and point bars prior to flow regulation and channel incision. The finer, clayey soils represent lower energy depositional pre-dam surfaces, such as swales or oxbow depressions. When determining patterns of invasion for use in a predictive statistical model, we found that red cedar primarily establishes on the higher energy depositional pre-dam surfaces. In addition, as cottonwood age and density decrease, red cedar density tends to increase. Our findings indicate that flow regulation caused hydrogeomorphic changes within the study area that

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

Science.gov (United States)

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.

Unsaturated aldehydes as alkene equivalents in the Diels-Alder reaction

DEFF Research Database (Denmark)

Taarning, Esben; Madsen, Robert

2008-01-01

A one-pot procedure is described for using alpha,beta-unsaturated aldehydes as olefin equivalents in the Diels-Alder reaction. The method combines the normal electron demand cycloaddition with aldehyde dienophiles and the rhodium-catalyzed decarbonylation of aldehydes to afford cyclohexenes...

Intramolecular Diels-Alder Reactions in Organic Synthesis

OpenAIRE

Sizemore, Nicholas Blandford Luke

2014-01-01

Intramolecular Diels-Alder (IMDA) reactions are an important class of reactions in synthetic organic chemistry for the rapid construction of polycyclic frameworks. Three classes of IMDA reactions were investigated synthetically and computationally: 1) all-carbon type 1 IMDA reactions, 2) N-acylnitroso type 2 IMDA reactions, and 3) cyano-azadiene IMDA reactions. The first class was implemented in research toward the total synthesis of maoecrystal Z and isopalhinine A. The second class was stud...

Quinine-Promoted, Enantioselective Boron-Tethered Diels-Alder Reaction by Anomeric Control of Transition State Conformation.

Science.gov (United States)

Scholl, Katie; Dillashaw, John; Timpy, Evan; Lam, Yu-Hong; DeRatt, Lindsey; Benton, Tyler R; Powell, Jacqueline P; Houk, Kendall N; Morgan, Jeremy B

2018-05-01

Diels-Alder reactions of tethered vinyl-metal species offer the opportunity to fashion highly functionalized diol intermediates for synthesis. We have developed the first enantioselective boron-tethered Diels-Alder reaction using quinine as a chiral promoter. Quinine recovery, enantioselectivity enhancement, and manipulation of the cyclohexene core are also investigated. DFT modeling calculations confirm the role of quinine as a bidentate ligand enhancing reaction rates. The enantioselectivity of the cycloaddition is proposed to originate from a boron-centered anomeric effect.

Well-defined Polymethylene-Based Co/Terpolymers by Combining Anthracene/Maleimide Diels-Alder Reaction with Polyhomologation

KAUST Repository

Hadjichristidis, Nikolaos

2015-05-26

A novel strategy towards well-defined polymethylene-based co/terpolymers, by combining anthracene/maleimide Diels-Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: a) synthesis of α-anthracene-ω-hydroxy- polymethylene by polyhomologation using tri (9-anthracene-methyl propyl ether) borane as initiator, b) synthesis of furan-protected-maleimide-terminated poly (ε-caprolactone) or polyethylene glycol and c). Diels-Alder reaction between the anthracene and maleimide-terminated polymers. In the case of triblock terpolymers the α-anthracene-ω-hydroxy-polymethylene was used as macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by Diels-Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. All intermediate and final products were characterized by SEC, 1H NMR, UV-VIS spectroscopy and DSC.

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

Science.gov (United States)

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

2015-12-23

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

Synthesis of a Phlorin from a Meso-Fused Anthriporphyrin by a Diels-Alder Strategy.

Science.gov (United States)

Aslam, Adil S; Hong, Jung-Ho; Shin, June-Ho; Cho, Dong-Gyu

2017-12-18

An anthracene-containing meso-fused carbaporphyrin, which has extended π-conjugation pathways as compared to the corresponding naphthalene-containing carbaporphyrin, has been synthesized. The weak global aromaticity of the anthriporphyrin also allowed its use as the diene for a Diels-Alder reaction with dimethyl acetylenedicarboxylate (DMAD). The resulting phlorin contains an interesting bicyclic structure. Moreover, to the best of our knowledge, this phlorin is the first Diels-Alder adduct of a diene forming part of the global π-conjugation pathway of an aromatic porphyrinoid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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.

Reclamation of a lignite combustion waste disposal site with alders (Alnus sp.): assessment of tree growth and nutrient status within 10 years of the experiment.

Science.gov (United States)

Pietrzykowski, Marcin; Woś, Bartłomiej; Pająk, Marek; Wanic, Tomasz; Krzaklewski, Wojciech; Chodak, Marcin

2018-06-01

Combustion wastes are characterised by extremely low N contents. Therefore, introduction of nitrogen-fixing species at the first stage of their biological reclamation is required. This paper presents an assessment of the growth parameters of alders (Alnus sp.) 10 years after their introduction to a disposal site of lignite combustion waste in Central Poland. Black (Alnus glutinosa) and grey alders (Alnus incana) were planted directly in the combustion waste. The soil amendment included three variants: control with pure combustion waste, admixture of lignite culm and addition of acid sand. Both alder species displayed good growth parameters comparable to those of alders in natural habitats. However, black alder had better growth parameters, such as stand density index (SDI), diameter at breast height (DBH) and height (H) than grey alder. The lignite amendment exerted a positive effect on tree growth, reflected in a higher SDI and H, whereas the acid sand amendment did not affect any of the growth parameters of the studied alder species. Despite the good growth parameters, the measured N:P and N:K ratios in the alder leaves largely differed from the optimal values indicating insufficient P and K supply at the combustion waste disposal site. This may pose a threat to further development of the introduced tree plantings. The introduction of alders along with the lignite addition into the planting holes seems to be a successful method of combustion waste revegetation.

Inheritance of compartmentalization of wounds in sweetgum (Liquidambar styraciflua L.) and eastern cottonwood (Populus deltoides Bartr.)

Science.gov (United States)

P. W. Garrett; W. K. Randall; A. L. Shigo; W. C. Shortle

1979-01-01

Studies of half-sib progeny tests of sweetgum (Liquidambar styraciflua) and clonal plantings of eastern cottonwood (Populus deltoides) in Mississippi indicate that rate of wound closure and size of discolored columns associated with the wounds are both heritable traits. Both are independent of stem diameter, which was used as a...

Technological and Thermal Properties of Thermoplastic Composites Filled with Heat-treated Alder Wood

Directory of Open Access Journals (Sweden)

Mürşit Tufan

2016-02-01

Full Text Available This study investigated the effect of heat-treated wood content on the water absorption, mechanical, and thermal properties of wood plastic composites (WPCs. The WPCs were produced from various loadings (30, 40, and 50 wt% of heat-treated and untreated alder wood flours (Alnus glutinosa L. using high-density polyethylene (HDPE with 3 wt% maleated polyethylene (MAPE coupling agent. All WPC formulations were compression molded into a hot press for 3 min at 170 ºC. The WPCs were evaluated using mechanical testing, Fourier transform infrared spectroscopy (FTIR, thermogravimetric analysis (TGA, and differential scanning calorimetry (DSC. The mechanical property values of the WPC specimens decreased with increasing amounts of the heat-treated wood flour, except for the tensile modulus values. The heat treatment of alder wood slightly increased the thermal stability of the WPCs compared with the reference WPCs. The crystallization degree (Xc and the enthalpy of crystallization of the WPCs slightly decreased with increasing content of the heat-treated wood flour. However, all WPCs containing the heat-treated alder wood flour showed a higher crystallinity degree than that of the virgin HDPE.

Thermally reversible rubber-toughened thermoset networks via Diels-Alder chemistry

NARCIS (Netherlands)

Araya-Hermosilla, R.; Fortunato, G.; Pucci, A.; Raffa, P.; Polgar, L.; Broekhuis, A. A.; Pourhossein, P.; Lima, G. M. R.; Beljaars, M.; Picchioni, F.

In this work we present a reversible and toughened thermoset system based on the covalent incorporation of a furane functionalized ethylene-propylene rubber (EPM-Fu) into a thermoset furane functionalized polyketone (PK-Fu) via Diels-Alder (DA) reversible cross-linking with bismaleimide (b-MA).

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

Science.gov (United States)

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.

A Diels-Alder Reaction Conducted Within the Parameters of Aqueous Organocatalysis: Still Just Smoke and Mirrors

Science.gov (United States)

Stowe, G. Neil

2010-01-01

Conducting reactions using water as solvent is a highly prized goal for the organic chemist. Based upon recent literature and our continuing interest in the field of aqueous organocatalysis, we tested the scope of an enamine based Diels-Alder reaction using (±)-nornicotine, proline and a proline derivative as aqueous organocatalysts. Unfortunately, none of the examined catalysts under aqueous conditions proved useful, leaving the aqueous Diels-Alder reaction as an elusive goal. PMID:21516231

Efficient Diels-Alder reaction of 1,2-benzoquinones with arynes and its utility in one-pot reactions.

Science.gov (United States)

Kaicharla, Trinadh; Bhojgude, Sachin Suresh; Biju, Akkattu T

2012-12-21

A new protocol for the efficient Diels-Alder reaction of 1,2-benzoquinones with arynes is reported. The aryne generated by the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates undergoes a facile Diels-Alder reaction with 1,2-benzoquinones, affording the dioxobenzobicyclooctadienes in moderate to excellent yields. In addition, this methodology has been applied to the one-pot synthesis of benzoquinoxalinobarrelene and naphthalene derivatives.

Oldman river dam mitigation program downstream vegetation project report, Volume II: The potential effects of an operating plan for the Oldman River dam on Riparian cottonwood forests

Energy Technology Data Exchange (ETDEWEB)

Mahoney, J.M.

1993-01-01

Extensive cottonwood (poplar) forests exist in the Oldman River valley downstream of the Oldman River dam. Studies of similar forests in nearby river valleys and elsewhere on the western prairies have found significant declines of some riparian forests following river damming. This investigation was initiated to determine the causes of cottonwood forest decline downstream from existing dams in southern Alberta; inventory the existing river valley forests in the Oldman Basin; establish study sites in the Oldman River forests to monitor changes in forest status following commissioning of the Oldman River dam, and evaluate the probable impact of proposed operating plans for the Oldman River dam and associated water control structures on downstream forests. This report summarizes the progress made in the analyses of the probable effects on the survival of the forests, including a discussion of the hydrological conditions essential for cottonwood forest regeneration and an explanation of the effects of altering these characteristics on riparian forests; the hydrological alterations expected along various river reaches in the Oldman Basin with the implementation of the proposed OD05 Oldman Dam operating plan; and preliminary analyses of the problem impacts of the OD05 operating plan on the cottonwood forests along these reaches.

Diels-Alder reactions of anthracenes with C-sulfonyldithioformates

DEFF Research Database (Denmark)

El-Sayed, I.; Ali, O.M.; Fischer, A.

2003-01-01

C-Sulfonyldithioformates (2) (R-1 = ArSO2, R 2 = ArS) readily add to anthracene and 9-methylanthracene (1) in a Diels-Alder fashion with formation of 9,10-dihydro-10,9-(epithiomethano)anthracenes (3) which in turn may suffer thermally induced elimination of arenesulfinic acid to yield the 9......-anthracenedithiocarboxylic esters (4). The reactions with the unsymmetrical diene 9-methylanthracene take place in a highly stereoselective fashion....

Mechanisms of Cottonwood Establishment in Gravel-Bed Rivers, across Scales from the Bar to the Reach

Science.gov (United States)

Meier, C. I.

2017-12-01

Riparian cottonwoods are pioneer trees adapted to colonizing fluvial corridors, with strong effects on ecosystem structure and function. As their populations are being affected by flow alterations and invasive species, their recruitment mechanisms need to be understood, to support scientifically-based restoration efforts. I propose new concepts for cottonwood establishment in gravelly streams, from the local to the reach scale. These notions complement the currently-accepted ideas, which apply only to the landscape scale, and whose basic assumptions (existence of an alluvial water table, which is planar, almost horizontal, and linked to the river stage, with a parallel, spatially-uniform capillary fringe) seem to be based on a physical template that is only valid in the case of sand-bed streams. At the local, within-the-bar scale, two concepts drive establishment success. First, a finer matrix material helps retain more capillary water after the yearly snowmelt flood or a precipitation event. Second, the coarse surface layer of clean gravel and cobble acts as rock mulch, strongly decreasing evaporative losses. At the reach scale, we find that the commonly reported arcuate bands of cottonwoods do not depend on groundwater, but are caused by water dispersal (hydrochory). Wind-dispersed seeds fall into the river, are entrained into the drift, and start germinating as they travel under water. Some of the seeds and germinants find their way into the shallow, high relative roughness flow along the cobble shoreline. They are able to deposit in this environment, where they start growing, also under water. As waters recede, during the period of seed availability in the drift, the river seeds its banks and bars. Thus, the boundaries of observed bands and patches with successful seedling recruitment correspond to the location of flow profiles at different dates during the flood recession.

Medium-Ring Effects on the Endo/Exo Selectivity of the Organocatalytic Intramolecular Diels-Alder Reaction.

Science.gov (United States)

Hooper, Joel F; James, Natalie C; Bozkurt, Esra; Aviyente, Viktorya; White, Jonathan M; Holland, Mareike C; Gilmour, Ryan; Holmes, Andrew B; Houk, K N

2015-12-18

The intramolecular Diels-Alder reaction has been used as a powerful method to access the tricyclic core of the eunicellin natural products from a number of 9-membered-ring precursors. The endo/exo selectivity of this reaction can be controlled through a remarkable organocatalytic approach, employing MacMillan's imidazolidinone catalysts, although the mechanistic origin of this selectivity remains unclear. We present a combined experimental and density functional theory investigation, providing insight into the effects of medium-ring constraints on the organocatalyzed intramolecular Diels-Alder reaction to form the isobenzofuran core of the eunicellins.

Asymmetric Catalytic Aza-Diels-Alder/Ring-Closing Cascade Reaction Forming Bicyclic Azaheterocycles by Trienamine Catalysis.

Science.gov (United States)

Li, Yang; Barløse, Casper; Jørgensen, Julie; Carlsen, Bjørn Dreiø; Jørgensen, Karl Anker

2017-01-01

An asymmetric catalytic aza-Diels-Alder/ring-closing cascade reaction between acylhydrazones and in situ formed trienamines is presented. The reaction proceeds through a formal aza-Diels-Alder cycloaddition, followed by a ring-closing reaction forming the hemiaminal ring leading to chiral bicyclic azaheterocycles in moderate to good yield (up to 71 %), good enantio- (up to 92 % ee) and diastereoselectivity (up to >20:1 d.r.). Furthermore, transformations are presented to show the potential application of the formed product. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Asymmetric Formal Aza-Diels-Alder Reaction of Trifluoromethyl Hemiaminals with Enones Catalyzed by Primary Amines.

Science.gov (United States)

Zhang, Sheng; Cha, Lide; Li, Lijun; Hu, Yanbin; Li, Yanan; Zha, Zhenggen; Wang, Zhiyong

2016-04-15

A primary amine-catalyzed asymmetric formal aza-Diels-Alder reaction of trifluoromethyl hemiaminals with enones was developed via a chiral gem-diamine intermediate. This novel protocol allowed facile access to structurally diverse trifluoromethyl-substituted piperidine scaffolds with high stereoselectivity. The utility of this method was further demonstrated through a concise approach to biologically active 4-hydroxypiperidine. More importantly, a stepwise mechanism involving an asymmetric induction process was proposed to rationalize the positive correlation between the chirality of the gem-diamine intermediate and the formal aza-Diels-Alder product.

A comparative study on plant diversity in alder (Alnus subcordata stands of natural and plantation areas

Directory of Open Access Journals (Sweden)

SEYED ALIAKBAR REZAEI TALESHI

2014-04-01

Full Text Available Rezaei-Taleshi SA. 2014. A comparative study on plant diversity in alder (Alnus subcordata stands of natural and plantation areas. Biodiversitas 15: 37-45. Diversity index is the useful criteria for evaluating sustainability of forest ecosystems. Current study carried out in Alder (Alnus subcordata C.A. Meyer stands that located in north forests of Iran. The aim of the study is express the plant diversity indices and positive role of the trees both natural and plantation forms. Data of Alder trees and associated species were recorded in sample plots which lay down in study area randomly. The abundance, density, percentage of frequency of each species was calculated by standard methods. The results of analysis revealed that, 47 species (21 trees and shrubs species and 26 herbaceous species were abundant in 80 sample plots both in natural and plantations Alder stands. Whilst the results showed that the number of species in natural area (44 species was more than plantation stands (37 species. Comparison of species distribution in different physiographical situation showed that some species such as Alnus subcordata, Parrotia persica, Rubus hyrcanus and Prunus sp. recorded in spread rang of physiographic variables as elevation, slopes and aspects. The biodiversity criteria as Shannon H’ and Simpsons D and 1/D indexes showed that they were more in natural stands than plantation areas.

Influence of water table decline on growth allocation and endogenous gibberellins in black cottonwood

Energy Technology Data Exchange (ETDEWEB)

Rood, S.B.; Zanewich, K.; Stefura, C. [Lethbridge Univ., Lethbridge, AB (Canada). Dept. of Biological Sciences; Mahoney, J.M. [Alberta Environmental Protection, Lethbridge, AB (Canada)

2000-06-01

Cottonwoods have shown an adaptation to the riparian zone by coordinating root elongation to maintain contact with the water table, whose depth varies with the elevation of the adjacent river. The rate of water decline on growth allocation and concentrations of endogenous gibberellins (GAs) in black cottonwood saplings were studied at the University of Lethbridge, Alberta. Water declines were achieved by using rhizopods, and root elongation approximately doubled in response whereas leaf area was reduced. At some point, a greater water decline rate led to water stress resulting in reduced growth, increased leaf diffusive resistance, decreased water potential, and leaf senescence and abscission. After extraction of endogenous GAs, they were purified and analysed by gas chromatography-selected ion monitoring with internal ({sup 2}H{sub 2})GA standards. The results showed that GAs were higher in shoot tips and sequentially lower in basal stems, root tips, leaves and upper roots. Noticeable relationships did not appear between GA concentration and growth allocation across the water decline treatments. Only GA{sub 8} showed a consistent reduction in plants experiencing water table decline. This research did not permit the authors to conclude whether endogenous GAs play a primary role in the regulation of root elongation in response to water table decline. 7 figs., 25 refs.

Italian alder (Alnus cordata/Loisel./Desf. - new species for Allochtonous dendroflora of Serbia

Directory of Open Access Journals (Sweden)

Bobinac Martin

2015-01-01

Full Text Available The foreign tree species, Alnus cordata/Loisel./Desf. (Italian alder, (Betulaceae/Loisel./Duby, not previously recorded in the dendroflora of Serbia, is described in this paper. Italian alder trees in an experimental plot in the area of Erdevik, aged 11 years, show good vitality and fast growth, and bear fruits since their 10th year. Tree heights are in range from 10.4 to 16.2 m, and diameters at the breast height range from14.6 to 34.9 cm. The morphological properties of leaves, fruiting organs (“cones” and male catkins are in concordance with the values in literature sources, although they show great variability. Since the time of plantation establishment, the absolute minimum air temperature in the nearby meteorological station of Sremska Mitrovica was -26.50C, so it can be assumed that the species is frost hardy. On the basis of the researched properties of Italian alder, it can be concluded that this species can be cultivated in Serbia as an ornamental in urban areas and as a fast growing species in forest plantations for biomass production. [Projekat Ministarstva nauke Republike Srbije, br. 31041: Šumski zasadi u funkciji povećanja pošumljenosti Srbije

Synthesis and Diels–Alder cycloaddition reaction of norbornadiene and benzonorbornadiene dimers

Directory of Open Access Journals (Sweden)

Bilal Nişancı

2009-08-01

Full Text Available 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.

Recent applications of intramolecular Diels-Alder reactions to natural product synthesis

DEFF Research Database (Denmark)

Juhl, M.; Tanner, David Ackland

2009-01-01

This tutorial review presents some recent examples of intramolecular Diels-Alder (IMDA) reactions as key complexity-generating steps in the total synthesis of structurally intricate natural products. The opportunities afforded by transannular (TADA) versions of the IMDA reaction in complex molecu...... comprehensive, reviews....

Diels-Alder reactions in water : Enforced hydrophobic interaction and hydrogen bonding

NARCIS (Netherlands)

Engberts, Jan B.F.N.

1995-01-01

Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of

DIELS-ALDER REACTIONS IN WATER - ENFORCED HYDROPHOBIC INTERACTION AND HYDROGEN-BONDING

NARCIS (Netherlands)

Engberts, J.B.F.N.

Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of

Vertebrate Herbivore Browsing on Neighboring Forage Species Increases the Growth and Dominance of Siberian Alder Across a Latitudinal Transect in Northern Alaska.

Science.gov (United States)

McNeill, E. M.; Ruess, R. W.

2017-12-01

Vertebrate herbivores strongly influence plant growth and architecture, biogeochemical cycling, and successional dynamics in boreal and arctic ecosystems. One of the most notable impacts of vertebrate herbivory is on the growth and spread of alder, a chemically-defended, N-fixing shrub whose distribution in the Alaskan arctic has expanded dramatically over the past 60 years. Although herbivore effects on thin-leaf alder are well described for interior Alaskan floodplains, no work has been conducted on the effects of herbivores on Siberian alder (Alnus viridis spp fruticosa), despite the increasing importance of this species to high latitude ecosystems. We characterized browsing by snowshoe hares, moose, and willow ptarmigan on dominant shrub species across topo-edaphic sequences within 5 ecoregions along a 600 km latitudinal transect extending from interior Alaska to the North Slope. Ptarmigan browsed wind-blown lowland and alpine sites devoid of trees in all regions; moose browsed predominantly willow species in hardwood and mixed forests and were absent north of the Brooks Range; snowshoe hares selected habitats and forage based on their local density and vulnerability to predators. Browsing intensity on Siberian alder was either undetectable or low, limited primarily to hare browsing on young ramets in the northern boreal forest where hare density relative to forage availability is highest. Overall, alder height growth was positively correlated with levels of herbivory on competing shrub species. Our data support the hypothesis that vertebrate herbivore browsing is indirectly augmenting the growth, dominance, and possible spread of Siberian alder throughout its northern Alaskan range. Given the potential high rates of N-fixation inputs by Siberian alder, we believe herbivores are also having strong indirect effects on biogeochemical cycling and possibly C storage in these landscapes.

Lewis acid catalysis of a Diels-Alder reaction in water

NARCIS (Netherlands)

Otto, S; Bertoncin, F; Engberts, JBFN

1996-01-01

Here we report the first detailed study of a Diels-Alder (DA) reaction that is catalyzed by Lewis acids in water. The effect of Co2+, Ni2+, Cu2+ and Zn2+ ions as Lewis acid catalysts on the rate and endo-exo selectivity of the DA reaction between the bidentate dienophiles

On the irrigation requirements of cottonwood (Populus fremontii and Populus deltoides var. wislizenii) and willow (Salix gooddingii) grown in a desert environment

Science.gov (United States)

Hartwell, S.; Morino, K.; Nagler, P.L.; Glenn, E.P.

2010-01-01

Native tree plots have been established in river irrigation districts in the western U.S. to provide habitat for threatened and endangered birds. Information is needed on the effective irrigation requirements of the target species. Cottonwood (Populus spp.) and willow (Salix gooddingii) trees were grown for seven years in an outdoor plot in a desert environment in Tucson, Arizona. Plants were allowed to achieve a nearly complete canopy cover over the first four years, then were subjected to three daily summer irrigation schedules of 6.20??mm??d-1; 8.26??mm??d-1 and 15.7??mm??d-1. The lowest irrigation rate was sufficient to maintain growth and high leaf area index for cottonwoods over three years, while willows suffered considerable die-back on this rate in years six and seven. These irrigation rates were applied April 15-September 15, but only 0.88??mm??d-1 was applied during the dormant period of the year. Expressed as a fraction of reference crop evapotranspiration (ETo), recommended annual water applications plus precipitation (and including some deep drainage) were 0.83 ETo for cottonwood and 1.01 ETo for willow. Current practices tend to over-irrigate restoration plots, and this study can provide guidelines for more efficient water use. ?? 2010 Elsevier Ltd.

Chiral Pyridinium Phosphoramide as a Dual Brønsted Acid Catalyst for Enantioselective Diels-Alder Reaction.

Science.gov (United States)

Nishikawa, Yasuhiro; Nakano, Saki; Tahira, Yuu; Terazawa, Kanako; Yamazaki, Ken; Kitamura, Chitoshi; Hara, Osamu

2016-05-06

Chiral pyridinium phosphoramide 1·HX was designed to be a new class of chiral Brønsted acid catalyst in which both the pyridinium proton and the adjacent imide-like proton activated by the electron-withdrawing pyridinium moiety could work cooperatively as strong dual proton donors. The potential of 1·HX was shown in the enantioselective Diels-Alder reactions of 1-amino dienes with various dienophiles including N-unsubstituted maleimide, which has yet to be successfully used in an asymmetric Diels-Alder reaction.

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

Science.gov (United States)

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.

Diels-Alder Reactions in Water. Effects of Hydrophobicity and Hydrogen Bonding

NARCIS (Netherlands)

Otto, Sijbren; Blokzijl, Wilfried; Engberts, Jan B.F.N.

1994-01-01

In order to check whether the activated complex for the Diels-Alder reactions of 5-substituted 1,4-naphthoquinones with cyclopentadiene is more polar in water than in other solvents, we have determined the substituent effects in seven different solvents. The substituent effects gradually decrease

Micellar Catalysis of Diels-Alder Reactions : Substrate Positioning in the Micelle

NARCIS (Netherlands)

Rispens, Theo; Engberts, Jan B.F.N.

2002-01-01

We have studied the kinetics of the Diels-Alder reactions of cyclopentadiene, sorbyl alcohol, and sorbyltrimethylammonium bromide with a series of N-substituted maleimides in micellar media. Micellar rate constants have been determined and were found to be 20-40 times lower than the respective

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

Science.gov (United States)

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Edge-glued panels from Alaska hardwoods: retail manager perspectives

Science.gov (United States)

David Nicholls; Matthew Bumgardner; Valerie Barber

2010-01-01

In Alaska, red alder (Alnus rubra Bong.) and paper birch (Betula papyrifera Marsh.) are both lesser-known hardwoods grown, harvested, and manufactured into appearance products, with potential for increased utilization. The production of edgeglued panels from red alder and paper birch offers one expansion opportunity for wood...

Comparative phytosociological investigation of subalpine alder thickets in southwestern Alaska and the North Pacific

Science.gov (United States)

Talbot, Stephen S.; Talbot, Sandra L.; Daniëls, F. J. A.

2005-01-01

We present the first vegetation analysis of subalpine alder (Alnus viridis) thickets in southwestern Alaska. The data are primarily from mesic, hilly and mountainous sites ranging from the westernmost tip of the Alaska Peninsula to the northern Kenai Peninsula, spanning 1,000 km on an E–W gradient and 700 km on a N–S gradient. 127 relevés from 18 sites represent the range of structural and compositional variation in the matrix of vegetation and landform diversity. Data were analyzed by multivariate and traditional Braun-Blanquet methods. One association is distinguished, Sambuco racemosi-Alnetum viridis ass. nov. with three new subassociations, oplopanacetosum horridi, typicum, and rubetosum spectabilis with the latter subdivided into four variants. These phytocoena are well-differentiated, although they form a syntaxonomical continuum. The composition and structure of these communities are described and interpreted in relation to complex environmental factors; these are analyzed using Jancey's ranking on F-values. Community composition is primarily related to elevation, longitude, soil moisture, and latitude. Phytogeographic comparison of southwestern Alaska alder communities with those elsewhere in the North Pacific suggests a close floristic relationship to those of southcentral, southeastern Alaska and coastal British Columbia, Canada. All these communities belong to the same association, while those of the eastern and southern parts of the Kamchatka Peninsula, Russia belong to a different association. Syntaxonomy of the 4 major communities is discussed. Within the Northern Hemisphere, vascular plant species of southwestern Alaska alder thickets primarily occur in East Asia and North America, 36 %; while 26 % are circumpolar, and 22 % are restricted to North America. From a latitudinal perspective, the distribution of vascular plant species within these alder thickets peaks in the high-subarctic, low-subarctic, and temperate latitudinal zones, with low

Diels-Alder cycloaddition strategy for kinetic resolution of chiral pyrazolidinones.

Science.gov (United States)

Sibi, Mukund P; Kawashima, Keisuke; Stanley, Levi M

2009-09-03

A rare example of the application of a catalytic, enantioselective Diels-Alder cycloaddition to affect a kinetic resolution has been developed. Chiral pyrazolidinones are resolved with high selectivity through a process that utilizes a relay of stereochemical information from a permanent chiral center to a fluxional chiral center to enhance the inherent selectivity of the chiral Lewis acid catalyst.

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

NARCIS (Netherlands)

Fernandez, I.; Bickelhaupt, F.M.

2016-01-01

The Diels–Alder (DA) cycloaddition reaction has the ability to significantly increase molecular complexity regioselectively and stereospecifically in a single synthetic step. In this review it is discussed how the activation strain model of chemical reactivity reveals the physical factors that

Metal-catalyzed Asymmetric Hetero-Diels-Alder Reactions of Unactivated Dienes with Glyoxylates

DEFF Research Database (Denmark)

Johannsen, Mogens; Yao, Sulan; Graven, Anette

1998-01-01

The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo...

Synthesis of 3-Alkenyl-1-azaanthraquinones via Diels-Alder and Electron Transfer Reactions

Directory of Open Access Journals (Sweden)

Patrice Vanelle

2002-12-01

Full Text Available A convenient route to 3-alkenyl-1-azaanthraquinones via a hetero Diels-Alder reaction between an azadiene and naphthoquinone, a free radical chlorination and an electron transfer reaction is reported.

The climate warming effect of a fen peat meadow with fluctuating water table is reduced by young alder trees

Directory of Open Access Journals (Sweden)

V. Huth

2018-03-01

Full Text Available Black alder (Alnus glutinosa (L. Gaertn. occurs naturally in temperate marshes and in minerotrophic peatlands and is also suitable for paludiculture - the cultivation of biomass on wet or rewetted peatland. We investigated the effect of a newly established black alder plantation on the greenhouse gas (GHG balance of a degraded fen in north-eastern Germany over a two-year period (August 2010–August 2012. We compared the alder plantation (Awet with an extensively used meadow (Mwet and a drier reference meadow (Mmoist. GHG fluxes were measured monthly to bi-monthly using the closed chamber method. Our results show that Awet was a slight net GHG (in CO2-eq sink of 3.4 ± 1.7 t ha-1 yr-1, Mwet was a moderate net GHG source of 9.6 ± 1.2 t ha 1 yr-1, and Mmoist was a strong net GHG source of 24.5 ± 1.6 t ha-1 yr-1. This was mainly driven by CO2 uptake at the two very moist (wet sites and by high CO2 release at the drier reference site. Awet was a larger CO2 sink than Mwet, probably due to additional CO2 uptake by the alder stand at Awet and carbon export in plant material harvested from Mwet. All sites were significant CH4 sources. Substantial CH4 emission peaks were observed at all sites following extraordinarily heavy precipitation during the summer of 2011, which accounted for up to 70 % of the accumulated two-year CH4 emissions. However, the Awet site generally emitted less CH4, possibly due to the effective oxygen transport mechanism in black alders. N2O emissions were negligible at all three sites. Our results indicate that the GHG balances of formerly drained fens benefit in the short term from planting of black alders, mostly due to reduced CH4 emissions. This study highlights the importance of acknowledging extreme precipitation events and groundwater fluctuations for the derivation of reliable GHG emission factors.

Effects of light regime and IBA concentration on adventitious rooting of an eastern cottonwood (Populus deltoides) clone

Science.gov (United States)

Alexander P. Hoffman; Joshua P. Adams; Andrew Nelson

2016-01-01

Eastern cottonwood (Populus deltoides) has received a substantial amount of interest from invitro studies within the past decade. The ability to efficiently multiply the stock of established clones such as clone 110412 is a valuable asset for forest endeavors. However, a common problem encountered is initiating adventitious rooting in new micropropagation protocols....

Biotransformation of a cage-like diels-alder adduct and derivatives by Mucor ramosissimus samutsevitsch Biotransformação de um aduto de diels-alder cage-like e derivados por Mucor ramosissimus samutsevitsch

Directory of Open Access Journals (Sweden)

Felicia Megumi Ito

2009-09-01

Full Text Available The present study aimed to evaluate the ability for biotransformation of the Diels-Alder adduct tricyclo[6.2.1.0(2,7]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.Neste trabalho avaliou-se a capacidade de biotransformação do aduto de Diels-Alder triciclo[6.2.1.0(2-7]undeca-4,9-dien-3,6-diona (1 e dois derivados sintéticos pelo fungo sapróbio Mucor ramosissimus Samutsevitsch. Produtos de oxidação, isomerização e redução regiosseletiva e enantiosseletiva foram obtidos.

Photoreactive polymer brushes for high-density patterned surface derivatization using a Diels-Alder photoclick reaction.

Science.gov (United States)

Arumugam, Selvanathan; Orski, Sara V; Locklin, Jason; Popik, Vladimir V

2012-01-11

Reactive polymer brushes grown on silicon oxide surfaces were derivatized with photoreactive 3-(hydroxymethyl)naphthalene-2-ol (NQMP) moieties. Upon 300 or 350 nm irradiation, NQMP efficiently produces o-naphthoquinone methide (oNQM), which in turn undergoes very rapid Diels-Alder addition to vinyl ether groups attached to a substrate, resulting in the covalent immobilization of the latter. Any unreacted oNQM groups rapidly add water to regenerate NQMP. High-resolution surface patterning is achieved by irradiating NQMP-derivatized surfaces using photolithographic methods. The Diels-Alder photoclick reaction is orthogonal to azide-alkyne click chemistry, enabling sequential photoclick/azide-click derivatizations to generate complex surface functionalities. © 2011 American Chemical Society

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

Science.gov (United States)

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.

Enantio- and Stereoselective Construction of Atisane Scaffold via Organocatalytic Intramolecular Michael Reaction and Diels-Alder Reaction.

Science.gov (United States)

Sekita, Hiroko; Adachi, Kyohei; Kobayashi, Ippei; Sato, Yusuke; Nakada, Masahisa

2017-05-05

An enantio- and stereoselective construction of the atisane scaffold via organocatalytic intramolecular Michael reaction and Diels-Alder reaction is described. The organocatalytic intramolecular Michael reaction has been found to stereoselectively generate a trans-stereodiad comprising an all-carbon quaternary and a tertiary stereogenic centers. Use of the chiral secondary amine bearing thiourea with benzoic acid as additive is the key to obtaining the desired product with excellent ee in synthetically acceptable yield. The prepared chiral building block has been successfully converted to the compound including the atisane scaffold via the highly stereoselective intramolecular Diels-Alder reaction.

Tandem Mannich/Diels–Alder reactions for the synthesis of indole compound libraries

DEFF Research Database (Denmark)

Wu, Peng; Petersen, Michael Åxman; Petersen, Rico

2016-01-01

A tandem Mannich/Diels–Alder sequence for the synthesis of small-molecule libraries with an indolyl-octahydro-3a,6-epoxy-isoindole core structure is demonstrated in this study. Representative diversification examples based on this scaffold were performed, and a library is being produced within...

Using chiral ionic liquid additives to enhance asymmetric induction in a Diels-Alder reaction.

Science.gov (United States)

Goodrich, P; Nimal Gunaratne, H Q; Hall, L; Wang, Y; Jin, L; Muldoon, M J; Ribeiro, A P C; Pombeiro, A J L; Pârvulescu, V I; Davey, P; Hardacre, C

2017-01-31

A bis-oxazoline ligand has been complexed using Cu(ii) and Zn(ii) trifluoromethanesulfonate and a range of chiral ionic liquid (CIL) additives based on natural products were used as a co-catalyst for a Diels-Alder reaction. The catalytic performance of these systems was compared for the asymmetric Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene with and without the presence of a CIL additive. In the absence of the CIL, both catalysts resulted in low enantioselectivities in conventional solvents and ionic liquids. However, whilst only a minor effect of the CIL was observed for the Cu based catalyst, in the case of the Zn based catalyst, significant enhancements in endo enantioselectivity of up to 50% were found on the addition of a CIL.

Application of Carbohydrate-Templated Asymmetric Diels-Alder Reaction to the Syntheses of ent-Penicillones A and B.

Science.gov (United States)

Weng, Chia-Hao; Hsu, Day-Shin; Liao, Chun-Chen

2016-11-18

Total syntheses of ent-penicillones A (ent-1) and B (ent-2) from 3,5-dimethylcatechol (3) were accomplished in 10 and 9 synthetic steps, respectively. A carbohydrate-templated asymmetric intramolecular Diels-Alder reaction of a masked o-benzoquinone (MOB) 9 and an aqueous acid-catalyzed intramolecular aldol reaction are the key synthetic steps. In addition, the absolute configurations of the bicyclo[2.2.2]oct-5-en-2-one core obtained from the per-O-benzylated α-d-glucopyranosyl as a carbohydrate template in the intramolecular Diels-Alder reaction of MOBs were revised.

alpha,beta-unsaturated 2-acyl imidazoles as a practical class of dienophiles for the DNA-Based catalytic asymmetric diels-alder reaction in water

NARCIS (Netherlands)

Boersma, A.J.; Feringa, B.L.; Roelfes, G.

2007-01-01

alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic

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

NARCIS (Netherlands)

Fernandez, Israel; Bickelhaupt, F. Matthias

2016-01-01

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

Mechanistic Insight into the Dehydro-Diels-Alder Reaction of Styrene-Ynes.

Science.gov (United States)

Kocsis, Laura S; Kagalwala, Husain N; Mutto, Sharlene; Godugu, Bhaskar; Bernhard, Stefan; Tantillo, Dean J; Brummond, Kay M

2015-12-04

The Diels-Alder reaction represents one of the most thoroughly studied and well-understood synthetic transformations for the assembly of six-membered rings. Although intramolecular dehydro-Diels-Alder (IMDDA) reactions have previously been employed for the preparation of naphthalene and dihydronaphthalene substrates, low yields and product mixtures have reduced the impact and scope of this reaction. Through the mechanistic studies described within, we have confirmed that the thermal IMDDA reaction of styrene-ynes produces a naphthalene product via loss of hydrogen gas from the initially formed cycloadduct, a tetraenyl intermediate. Alternatively, the dihydronaphthalene product is afforded from the same tetraenyl intermediate via a radical isomerization process. Moreover, we have identified conditions that can be used to achieve efficient, high-yielding, and selective IMDDA reactions of styrene-ynes to form either naphthalene or dihydronaphthalene products. The operational simplicity and retrosynthetic orthogonality of this method for the preparation of naphthalenes and dihydronaphthalenes makes this transformation appealing for the synthesis of medicinal and material targets. The mechanistic studies within may impact the development of other thermal transformations.

The Hexadehydro-Diels-Alder Cycloisomerization Reaction Proceeds by a Stepwise Mechanism.

Science.gov (United States)

Wang, Tao; Niu, Dawen; Hoye, Thomas R

2016-06-29

We report here experiments showing that the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction proceeds in a stepwise manner-i.e., via a diradical intermediate. Judicious use of substituent effects was decisive. We prepared (i) a series of triyne HDDA substrates that differed only in the R group present on the remote terminus of the diynophilic alkyne and (ii) an analogous series of dienophilic alkynes (n-C7H15COC≡CR) for use in classical Diels-Alder (DA) reactions (with 1,3-cyclopentadiene). The R groups were CF3, CHO, COMe/Et, CO2Me, CONMe2/Et2, H, and 1-propynyl. The relative rates of both the HDDA cyclization reactions and the simple DA cycloadditions were measured. The reactivity trends revealed a dramatic difference in the behaviors of the CF3 (slowest HDDA and nearly fastest DA) and 1-propynyl (fastest HDDA and slowest DA) containing members of each series. These differences can be explained by invoking radical-stabilizing energies rather than electron-withdrawing effects as the dominating feature of the HDDA reaction.

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

Science.gov (United States)

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.

A comparative study on plant diversity in alder (Alnus subcordata stands of natural and plantation areas

Directory of Open Access Journals (Sweden)

SEYED ALIAKBAR REZAEI TALESHI

2014-11-01

Full Text Available Diversity index is the useful criteria for evaluating sustainability of forest ecosystems. Current study carried out in Alder (Alnus subcordata C.A. Meyer stands that located in north forests of Iran. The aim of the study is express the plant diversity indices and positive role of the trees both natural and plantation forms. Data of Alder trees and associated species were recorded in sample plots which lay down in study area randomly. The abundance, density, percentage of frequency of each species was calculated by standard methods. The results of analysis revealed that, 47 species (21 trees and shrubs species and 26 herbaceous species were abundant in 80 sample plots both in natural and plantations Alder stands. Whilst the results showed that the number of species in natural area (44 species was more than plantation stands (37 species. Comparison of species distribution in different physiographical situation showed that some species such as Alnus subcordata, Parrotia persica, Rubus hyrcanus and Prunus sp. recorded in spread rang of physiographic variables as elevation, slopes and aspects. The biodiversity criteria as Shannon H’ and Simpsons D and 1/D indexes showed that they were more in natural stands than plantation areas.

Growth of Fullerene Fragments Using the Diels-Alder Cycloaddition Reaction: First Step towards a C60 Synthesis by Dimerization

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Julio A. Alonso

2013-02-01

Full Text Available 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.

Nitropyrroles, Diels-Alder reactions assisted by microwave irradiation and solvent effect. An experimental and theoretical study

Science.gov (United States)

Mancini, Pedro M. E.; Kneeteman, María N.; Cainelli, Mauro; Ormachea, Carla M.; Domingo, Luis R.

2017-11-01

The behaviors of N-tosylnitropyrroles acting as electrophilic dienophiles in polar Diels-Alder reactions joint to different dienes of increeased nucleophilicity are analyzed. The reactions were developed under microwave irradiation using toluene or protic ionic liquids (PILs) as solvents and in free solvent conditions. In all the cases explored we observed good yields in short reaction times. For these reactions, the free solvent condition and the use of protic ionic liquids as solvents offer similar results. However, the free solvent conditions favor environmental sustainability. The role of PILs in these polar Diels-Alder reactions has been theoretically studied within the Molecular Electron Density Theory.

On a conjecture of Alley and Alder for fluids and Lorentz models

NARCIS (Netherlands)

Ernst, M.H.; Beijeren, H. van

1981-01-01

We discuss a conjecture of Alley and Alder predicting a relation between the four-point and the two-point velocity autocorrelation functions for fluids and Lorentz models at sufficiently long times. If the conjecture is correct a modified Burnett coefficient can be defined, which has a finite value,

Wood Colorization through Pressure Treating: The Potential of Extracted Colorants from Spalting Fungi as a Replacement for Woodworkers’ Aniline Dyes

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Sara C. Robinson

2014-07-01

Full Text Available The extracellular colorants produced by Chlorociboria aeruginosa, Scytalidium cuboideum, and Scytalidium ganodermophthorum, three commonly utilized spalting fungi, were tested against a standard woodworker’s aniline dye to determine if the fungal colorants could be utilized in an effort to find a naturally occurring replacement for the synthetic dye. Fungal colorants were delivered in two methods within a pressure treater—the first through solubilization of extracted colorants in dichloromethane, and the second via liquid culture consisting of water, malt, and the actively growing fungus. Visual external evaluation of the wood test blocks showed complete surface coloration of all wood species with all colorants, with the exception of the green colorant (xylindein from C. aeruginosa in liquid culture, which did not produce a visible surface color change. The highest changes in external color came from noble fir, lodgepole pine, port orford cedar and sugar maple with aniline dye, cottonwood with the yellow colorant in liquid culture, lodgepole pine with the red colorant in liquid culture, red alder and Oregon maple with the green colorant in dichloromethane, and sugar maple and port orford cedar with the yellow colorant in dichloromethane. The aniline dye was superior to the fungal colorants in terms of internal coloration, although none of the tested compounds were able to completely visually color the inside of the test blocks.

Sequential aminodiene Diels-Alder approach to the ergoline skeleton.

Science.gov (United States)

Padwa, Albert; Bur, Scott K; Zhang, Hongjun

2005-08-19

Through a novel sequence of aminodiene Diels-Alder reactions, several substituted amidofurans were readily converted to tricyclic ketones in good yield. The formation of the tricyclic ketone system is the result of a ring opening and dehydration of a transient oxabicyclic adduct formed by an intramolecular Diels-Alder cycloaddition of an amidofuran with a cyclohexenone moiety tethered such that it participates in the cycloaddition as the 2pi component. A convenient way to construct the cyclohexenone is to make use of some aminodiene chemistry developed by Rawal. An angular carbomethoxy group is required in order to activate the olefin toward cycloaddition with Rawal's diene. The presence of this activating group not only prevents the isomerization of the advanced ergoline intermediate to a naphthalene but can also be leveraged for an oxidation to provide Uhle's ketone (13). The easily formed Kornfeld ketone analogue 25 was readily transformed into the corresponding triflate 41 by the action of triflic anhydride and a base. Oxidative addition of vinyl triflate 41 to Pd(0) and the ability of the resulting vinyl palladium species to undergo cross-coupling with terminal alkynes prompted us to devise an expeditious route to lysergic acid. Unfortunately, our inability to carry out a regioselective Heck reaction using vinyl triflate 41 and the methylene amino acrylate ester 48 thwarted the completion of the synthesis of lysergic acid.

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

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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.

Theoretical study on the Diels-Alder reaction of bromo-substituted 2H-pyrane-2-ones and some substituent vinyls

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Haghdadi Mina

2015-01-01

Full Text Available A DFT study of the reactivity, regio- and stereoselectivity of Diels-Alder reaction between 3-bromo, 5-bromo, and 3,5-dibromo-2(H-pyran-2-ones and some weakly activated and unactivated alkenes has been carried out using density functional theory (DFT. Four possible reaction channels, which are related to the formation of meta- and para- and endo- and exo-cycloadducts have been explored and characterized. The energy and natural bond orbital analysis shows that the meta-regioselectivity on the exo pathway is preferred and follows an asynchronous concerted mechanism with a polar nature in all Diels-Alder cycloadditions. Moreover, the activation free energies of Diels-Alder cycloadditions of 3,5-dibromo-2(H-pyran-2one are lower than 3- bromo-2(H-pyran-2one and 5-bromo-2(H-pyran-2one, which are in line with experimental observation. DFT-based reactivity indices clearly predict the regiochemistry of the isolated cycloadducts.

Hourly pattern of allergenic alder and birch pollen concentrations in the air: Spatial differentiation and the effect of meteorological conditions

Science.gov (United States)

Borycka, K.; Kasprzyk, I.

2018-06-01

In temperate climate widespread alder and birch are an important source of strong aeroallergens. The diurnal pattern of airborne pollen concentrations depends on the rhythm of pollen release from anthers as well as weather conditions, convection air currents, long-distance transport, pollen trap location and local vegetation. The aim of the study was to present a diurnal pattern of Alnus (alder) and Betula (birch) pollen concentrations in the air in a horizontal and vertical gradient and examine the weather parameters that had the greatest impact on the pattern. The study was conducted in Rzeszów City, southeast Poland over three years. Pollen grains were collected using a Hirst volumetric spore trap at three sampling points: two at 12 m the agl, and one at 1.5 m agl. Data were analysed using circular statistics and a nonlinear function. For alder, three models of hourly patterns were elaborated and the most common presented early morning minimum and early afternoon maximum. For birch, the most common model has one peak at night and a marked decrease in concentrations in early morning, although a second model has peak during early afternoon. A model with 3 peaks is much less common. These models are characteristic for warm temperate climate regions, where alders and birches are common. The diurnal patterns did not depend on the localization of traps or proximity of the pollen source, although these factors influenced the hourly concentrations, with higher values observed at roof level. Significant relationships between the hourly pollen counts and meteorological parameters were observed only for alder. Three incidents of increasing birch pollen concentrations were observed during the first two hours of precipitation and linked to a convection effect. Unstable weather conditions caused by air convection might strongly modify the circadian pattern and cause the nightly peaks concentrations. The general results are that people suffering from allergies may be exposed

Intramolecular and Transannular Diels-Alder Reactions

DEFF Research Database (Denmark)

Tanner, David Ackland; Ascic, Erhad

2014-01-01

Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...

Diels-Alder reactions onto fluorinated and hydrogenated graphene

Science.gov (United States)

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.

Well-defined Polymethylene-Based Co/Terpolymers by Combining Anthracene/Maleimide Diels-Alder Reaction with Polyhomologation

KAUST Repository

Hadjichristidis, Nikolaos; Alkayal, Nazeeha

2015-01-01

A novel strategy towards well-defined polymethylene-based co/terpolymers, by combining anthracene/maleimide Diels-Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: a

The Inverse Demand Oxa-Diels-Alder Reaction of Resorcinarenes: An Experimental and Theoretical Analysis of Regioselectivity and Diastereoselectivity.

Science.gov (United States)

Stefańska, Karolina; Jędrzejewska, Hanna; Wierzbicki, Michał; Szumna, Agnieszka; Iwanek, Waldemar

2016-07-15

The Diels-Alder reaction enables introduction of new functionalities onto the resorcinarene skeleton with simultaneous generation of new stereogenic centers and expansion of the internal cavity. We present highly regio- and diastereoselective inverse electron demand oxa-Diels-Alder reactions of resorcinarene ortho-quinone methide with benzofuran and indene, each generating 12 new stereogenic centers. The mechanism and reasons for regioselectivity and diastereoselectivity were analyzed using theoretical calculations (NBO charges, Fukui functions, transition state energies, and thermodynamic stability of the products). Enantiomers were separated, and their configurations were determined by comparison of experimental and theoretical electronic circular dichroism spectra.

Flow regime effects on mature Populus fremontii (Fremont cottonwood) productivity on two contrasting dryland river floodplains

Science.gov (United States)

Andersen, Douglas C.

2016-01-01

I compared riparian cottonwood (Populus fremontii) productivity-discharge relationships in a relictual stand along the highly regulated Green River and in a naturally functioning stand along the unregulated Yampa River in semiarid northwest Colorado. I used multiple regression to model flow effects on annual basal area increment (BAI) from 1982 to 2011, after removing any autocorrelation present. Each BAI series was developed from 20 trees whose mean size (67 cm diameter at breast height [DBH]) was equivalent in the two stands. BAI was larger in the Yampa River stand except in 2 y when defoliating leaf beetles were present there. I found no evidence for a Yampa flood-magnitude threshold above which BAI declined. Flow variables explained ∼45% of residual BAI variability, with most explained by current-year maximum 90-d discharge (QM90) in the Yampa River stand and by a measure of the year-to-year change in QM90 in the Green River stand. The latter reflects a management-imposed ceiling on flood magnitude—Flaming Gorge Dam power plant capacity—infrequently exceeded during the study period. BAI in the relictual stand began to trend upward in 1992 when flows started to mimic a natural flow regime. Mature Fremont cottonwoods appear to be ecologically resilient. Their productivity along regulated rivers might be optimized using multiyear environmental flow designs.

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

Science.gov (United States)

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.

Origin of Exo/Endo Selectivity in the Intramolecular Diels-Alder Reaction

International Nuclear Information System (INIS)

Yan, Shihai; Ryu, Do Hyun; Lee, Jin Yong

2010-01-01

The stereoselectivity of the intramolecular Diels-Alder reactions of 1 and its derivatives were investigated by ab initio calculations. The stereoselectivity mainly originates from the steric repulsion and the orbital interactions. The additional s-cis and s-trans conformations by introducing the carbonyl group at the neighbor of diene or dienophile may change the stereoselectivity, hence this kind of substitution can be utilized for stereoselective asymmetric synthesis

Effects of the Hydrophobicity of the Reactants on Diels-Alder Reactions in Water

NARCIS (Netherlands)

Meijer, Ale; Otto, Sijbren; Engberts, Jan B.F.N.

1998-01-01

To assess the importance of the hydrophobicity of different parts of diene and dienophile on the aqueous acceleration of Diels-Alder reactions, second-order rate constants have been determined for the reactions of cyclopentadiene (1), 2,3-dimethyl-1,3-butadiene (4), and 1,3-cyclohexadiene (6) with

Stereo-controlled synthesis of polyheterocycles via the diene-transmissive hetero-Diels-Alder reaction of β,γ-unsaturated α-keto esters.

Science.gov (United States)

Otani, Takashi; Tamai, Yumiko; Seki, Kazunori; Kikuchi, Tomohiro; Miyazawa, Taiichiro; Saito, Takao

2015-06-07

We describe the stereoselective synthesis of polyring-fused heterocyclic compounds based on diene-transmissive hetero-Diels-Alder reactions utilizing β,γ-unsaturated α-keto esters. This protocol involves the initial endo- or exo-selective Diels-Alder (DA) reactions with electron-rich dienophiles, methylenation of the ester carbonyl groups with the Tebbe reagent, and a stereoselective second DA reaction with electron-deficient dienophiles. The use of enantioselective DA reactions in the initial reaction enables access to chiral polyring-fused heterocyclic compounds with multiple chiral centres.

Role of river flow and sediment mobilization in riparian alder establishment along a bedrock-gravel river, South Fork Eel River, California

Science.gov (United States)

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

2017-10-01

Climatic, hydraulics, hydrologic, and fluvial geomorphic processes are the main drivers of riparian white alder (Alnus rhombifolia Nutt.) distribution in northern California. The Mediterranean climate and canyon bound, bedrock-gravel morphology of the South Fork Eel have a distinct effect on these processes. White alder seeds are preferentially deposited on river bars where river hydraulics create eddies coinciding with the downstream part of riffles and the upstream part of pools. Seeds are generally deposited below bankfull elevations by the descending hydrograph during the spring season in this Mediterranean climate. For successful germination and establishment, the seeds must be deposited at a location such that they are not remobilized by late spring flows. The summer establishment period is defined from the date of seed deposition and germination to the fall/winter date of river sediment mobilization. Seedling root growth rate decreases exponentially with decreasing water potential. However, seedlings are shown not to be generally limited by water availability at the elevations they are most commonly deposited. The establishment of white alder seedlings following the first summer will therefore depend on their ability to resist fall/winter high flows. The method proposed here compares the predicted rooting depth to predicted sediment scour rates. The length of the establishment period rather than water availability determines final seedling rooting depth. Over the past 40 years, very few years had establishment periods that were long enough or had fast enough alder growth rates to survive winter floods that often scour deeper than the total root length. The low survival of seedlings in the first autumn season following germination is believed to be a principal reason for the missing age classes often found in alder distributions along rivers.

Domino Wittig Diels-Alder reaction: An expeditious entry into the AB ring system of furanosesquiterpenes

Digital Repository Service at National Institute of Oceanography (India)

Patre, R.E.; Gawas, S.; Sen, S.; Parameswaran, P.S.; Tilve, S.G.

A domino Wittig Diels - Alder reaction has been employed in delineating a short and flexible synthetic stratagem for ready access to the AB ring system and the tricyclic framework of furanosesquiterpenes, such as the bioactive natural products...

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

NARCIS (Netherlands)

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

2016-01-01

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified

The influence of alternative plant propagation and stand establishment techniques on survival and growth of eastern cottonwood (Populus deltoids Bartr.) clones

Science.gov (United States)

Donald J. Kaczmarek; Randall Rousseau; Jeff A. Wright; Brian Wachelka

2014-01-01

Four eastern cottonwood clones, including standard operational clone ST66 and three advanced clonal selections were produced and included in a test utilizing five different plant propagation methods. Despite relatively large first-year growth differences among clones, all clones demonstrated similar responses to the treatments and clone × cutting treatment interactions...

Soil acid phosphomonoesterase activity and phosphorus forms in ancient and post-agricultural black alder [Alnus glutinosa (L. Gaertn.] woodlands

Directory of Open Access Journals (Sweden)

Anna Orczewska

2012-06-01

Full Text Available Black alder, an N-fixing tree is considered to accelerate the availability of phosphorus in soils due to the increased production of phosphatase enzymes, which are responsible for the P release from the litter. Acid phosphatase activity plays a pivotal role in organic P mineralization in forest soils and in making P available to plants. In order to check whether Alnus glutinosa stimulates acid phosphomonoesterase (PHACID activity, we compared enzyme activities, total P concentration (PTOT, plant-available P (PAVAIL, organic P (PORG and inorganic P (PINORG, and organic matter content in 27 ancient and 27 post-agricultural alder woods (the latter ones representing different age classes: 11-20, 21-40 and 41-60 years of soil samples taken from the litter and the mineral layers. Phosphomonoesterase activity, organic matter, PTOT, PINORG and PORG concentrations were significantly higher in ancient alder woods than in the soils of post-agricultural forests. Significant differences in the acid phosphatase activity, organic matter and PAVAIL concentration were noted between the litter and mineral layers within the same forest type. In recent stands the amount of organic matter and phosphatase activity increased significantly with the age of alder stands, although only in the mineral layer of their soils. Phosphomonoesterase activity, organic matter and PAVAIL content were higher in a litter layer and decreased significantly at a mineral depth of the soil. The acid phosphatase activity was significantly correlated with organic matter content in both ancient and recent stands. There was no significant relationship between PHACID activity and any P forms.

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

Science.gov (United States)

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.

A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride

Science.gov (United States)

Rivero, Uxía; Meuwly, Markus; Willitsch, Stefan

2017-09-01

The neutral and cationic Diels-Alder-type reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride have been computationally explored as the first step of a combined experimental and theoretical study. Density functional theory calculations show that the neutral reaction is concerted while the cationic reaction can be either concerted or stepwise. Further isomerizations of the Diels-Alder products have been studied in order to predict possible fragmentation pathways in gas-phase experiments. Rice-Ramsperger-Kassel-Marcus (RRKM) calculations suggest that under single-collision experimental conditions the neutral product may reform the reactants and the cationic product will most likely eliminate CO2.

Sara Wasson and Emily Alder, Gothic Science Fiction 1980-2010

OpenAIRE

Beaulé, Sophie

2014-01-01

With their collection of essays Gothic Science Fiction 1980-2010, Sara Wasson and Emily Alder illustrate the richness of gothic tropes in contemporary forms, from novels and movies to card games. More than cliché, melodrama, or gore, the “gothick” (to borrow Adam Roberts’s term, xi) allows for the hybridity in contemporary production, especially in science fiction, that the collected articles examine. The book is divided into three parts, “Redefining Genres”, “Biopower and Capital”, and “Gend...

Flooding Regime Impacts on Radiation, Evapotranspiration, and Latent Energy Fluxes over Groundwater-Dependent Riparian Cottonwood and Saltcedar Forests

Directory of Open Access Journals (Sweden)

James Cleverly

2015-01-01

Full Text Available Radiation and energy balances are key drivers of ecosystem water and carbon cycling. This study reports on ten years of eddy covariance measurements over groundwater-dependent ecosystems (GDEs in New Mexico, USA, to compare the role of drought and flooding on radiation, water, and energy budgets of forests differing in species composition (native cottonwood versus nonnative saltcedar and flooding regime. After net radiation (700–800 W m−2, latent heat flux was the largest energy flux, with annual values of evapotranspiration exceeding annual precipitation by 250–600%. Evaporative cooling dominated the energy fluxes of both forest types, although cottonwood generated much lower daily values of sensible heat flux (<−5 MJ m−2 d−1. Drought caused a reduction in evaporative cooling, especially in the saltcedar sites where evapotranspiration was also reduced, but without a substantial decline in depth-to-groundwater. Our findings have broad implications on water security and the management of native and nonnative vegetation within semiarid southwestern North America. Specifically, consideration of the energy budgets of GDEs as they respond to fluctuations in climatic conditions can inform the management options for reducing evapotranspiration and maintaining in-stream flow, which is legally mandated as part of interstate and international water resources agreements.

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

Science.gov (United States)

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.

Cultural Resources Investigation of a Proposed Flood Control Project along the Sheyenne River, at West Fargo, Cass County, North Dakota. Phase I.

Science.gov (United States)

1988-01-15

cottonwood (Po2ulus salrgenti), sumac (Ehus sp.), peach and sandbar willows (Salix amvdaloides; . terio), and slippery elm (Ulmus rubra). 3.4.2 Bluestem...forest of elm , oak, ash, hackberry, cottonwood, and aspen along the major streams. Archaeological evidence indicates that prehistoric people along the...black willow (Salix nifra), and American elm (Ulmus amicnan). Other components include: boxelder (Acer neaundo), red maple (A. Subrum), silver maple (A

Specific acid catalysis and Lewis acid catalysis of Diels–Alder reactions in aqueous media

NARCIS (Netherlands)

Mubofu, Egid B.; Engberts, Jan B.F.N.

2004-01-01

A comparative study of specific acid catalysis and Lewis acid catalysis of Diels–Alder reactions between dienophiles (1, 4 and 6) and cyclopentadiene (2) in water and mixed aqueous media is reported. The reactions were performed in water with copper(II) nitrate as the Lewis acid catalyst whereas

Specific acid catalysis and Lewis acid catalysis of Diels-Alder reactions in aqueous media

NARCIS (Netherlands)

Mubofu, E.B.; Engberts, J.B.F.N.

A comparative study of specific acid catalysis and Lewis acid catalysis of Diells-Alder reactions between dienophiles (1, 4 and 6) and cyclopentadiene (2) in water and mixed aqueous media is reported. The reactions were performed in water with copper(II) nitrate as the Lewis acid catalyst whereas

Kinetic and thermodynamic measurements for the facile property prediction of diels-alder-conjugated material behavior

Czech Academy of Sciences Publication Activity Database

Koehler, K. C.; Ďuračková, Andrea; Kloxin, C. J.; Bowman, C. N.

2012-01-01

Roč. 58, č. 11 (2012), s. 3545-3552 ISSN 0001-1541 Institutional research plan: CEZ:AV0Z40500505 Keywords : Diels - Alder reaction s * self-healing polymer networks * thermoreversible reaction s Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.493, year: 2012

Revisiting the stability of endo/exo Diels-Alder adducts between cyclopentadiene and 1,4-benzoquinone

International Nuclear Information System (INIS)

Tormena, Claudio F.; Lacerda Junior, Valdemar; Oliveira, Kleber T. de

2010-01-01

In this work it is presented a detailed theoretical analysis of the relative stability of endo/exo Diels-Alder adducts formed by the reaction between cyclopentadiene (1) and 1,4-benzoquinone (2). The intrinsic reaction coordinate (IRC) showed the existence of only one transition state for the reaction studied, for both endo 3 and exo 4 adducts. The energies of both adducts were obtained at high level of theory (CBS-Q) confirming that the endo adduct is more stable than exo, which is in the opposite way to the observed in reactions that usually follow Alder's rule. An electronic structure analysis was performed through NBO methodology, indicating that the attractive delocalization interaction predominates over the steric repulsive interaction in the endo adducts. In summary, for the studied cycloaddition reaction the endo adduct is the thermodynamic and kinetic product, which can be also confirmed by experimental data mentioned in this work. (author)

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

Science.gov (United States)

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

2014-08-06

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

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

Science.gov (United States)

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…

High-level Computational Study of the Site-, Facial- and Stereoselectivities for the Diels-Alder Reaction Between o-Benzoquinone and Norbornadiene

Directory of Open Access Journals (Sweden)

Ronald N. Warrener

2000-12-01

Full Text Available Ab initio and DFT quantum chemical calculations have been applied to a study of the Diels-Alder reaction of o-benzoquinone as diene and norbornadiene as dienophile. Transition states for the different reactions are located and activation energies estimated. The prefered exo-π-facial selectivity and exo,endo-stereoselectivity exhibited in this cycloaddition are readily predicted using RHF/3-21G or higher levels of calculations. Differences between experimentally observed results and calculations may be explained by the postulation of a second, nonconcerted biradical mechanism leading to formation of hetero Diels-Alder products.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

Diels-Alder cyclo-addition as an efficient tool for linking π-donors onto fullerene C60

International Nuclear Information System (INIS)

Hudhomme, P.

2006-01-01

Diels-Alder reaction of endo-cyclic, acyclic 1,3-dienes or (hetero) o-quinodimethanes with the dienophilic fullerene C 60 is presented as an efficient tool for linking electro-active units giving rise to systems where both the donor and C 60 partners take up well defined volumes and orientations with respect to one another. While porphyrin is the most frequently used electron donor in artificial photosynthetic models, C 60 -based tetrathiafulvalene (TTF) or p-conjugated oligomer adducts remain interesting candidates for the preparation of photovoltaic devices. In this account, we focus on the use of the Diels-Alder cyclo-addition and its use in the synthesis of TTF-C 60 dyads, (TTF) n -C 60 polyads and C 60 -TTF-C 60 dumbbells as part of ongoing research into materials which display efficient photo-induced electron transfer. (author)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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)

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

Directory of Open Access Journals (Sweden)

Anne-Katrin Späte

2014-09-01

Full Text Available 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.

Revisiting the stability of endo/exo Diels-Alder adducts between cyclopentadiene and 1,4-benzoquinone

Energy Technology Data Exchange (ETDEWEB)

Tormena, Claudio F. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Lacerda Junior, Valdemar [Universidade Federal do Espirito Santo (UFES), Vitoria, ES (Brazil). Centro de Ciencias Exatas. Dept. de Quimica; Oliveira, Kleber T. de [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas

2010-07-01

In this work it is presented a detailed theoretical analysis of the relative stability of endo/exo Diels-Alder adducts formed by the reaction between cyclopentadiene (1) and 1,4-benzoquinone (2). The intrinsic reaction coordinate (IRC) showed the existence of only one transition state for the reaction studied, for both endo 3 and exo 4 adducts. The energies of both adducts were obtained at high level of theory (CBS-Q) confirming that the endo adduct is more stable than exo, which is in the opposite way to the observed in reactions that usually follow Alder's rule. An electronic structure analysis was performed through NBO methodology, indicating that the attractive delocalization interaction predominates over the steric repulsive interaction in the endo adducts. In summary, for the studied cycloaddition reaction the endo adduct is the thermodynamic and kinetic product, which can be also confirmed by experimental data mentioned in this work. (author)

Naphthalene Diels-Alder in a self-assembled molecular flask.

Science.gov (United States)

Murase, Takashi; Horiuchi, Shinnosuke; Fujita, Makoto

2010-03-10

Despite its inertness toward pericyclic reactions under common conditions, naphthalenes readily undergo Diels-Alder reactions when coencapsulated with a suitable dienophile within the cavity of a self-assembled host. Localization of the reactant pair significantly reduces the entropic cost of the reaction, and preorganization within the host cavity controls both the regio- and stereoselectivity of the reaction: electronically disfavored exo adducts were obtained, and with substituted naphthalenes, the reaction takes place on the less electron-rich, unsubstituted ring. Our findings highlight the fact that judicious tuning of substrate size and shape within molecular flasks can unveil new and unusual reactivities for otherwise unreactive molecules.

Theory of Brownian motion with the Alder-Wainwright effect

International Nuclear Information System (INIS)

Okabe, Y.

1986-01-01

The Stokes-Boussinesq-Langevin equation, which describes the time evolution of Brownian motion with the Alder-Wainwright effect, can be treated in the framework of the theory of KMO-Langevin equations which describe the time evolution of a real, stationary Gaussian process with T-positivity (reflection positivity) originating in axiomatic quantum field theory. After proving the fluctuation-dissipation theorems for KMO-Langevin equations, the authors obtain an explicit formula for the deviation from the classical Einstein relation that occurs in the Stokes-Boussinesq-Langevin equation with a white noise as its random force. The authors interested in whether or not it can be measured experimentally

Diels-Alder Reaction of Isobenzofurans/Cyclopentadienones with Tetrathiafulvalene: Preparation of Naphthalene, Fluoranthene, and Fluorenone Derivatives.

Science.gov (United States)

Karunakaran, Jayachandran; Mohanakrishnan, Arasambattu K

2018-02-16

Diels-Alder reaction of 1,3-diarylbenzo[c]furan/cyclopentadienone with TTF followed by triflic acid mediated cleavage of the resulting adducts led to the formation of the respective 1,4-diaryl substituted naphthalenes, fluoranthenes, and fluorenones. The photophysical properties of representative diaryl-substituted hydrocarbons are also reported.

Retro-Diels-Alder reaction in aqueous solution : Toward a better understanding of organic reactivity in water

NARCIS (Netherlands)

Wijnen, J.W.; Engberts, Jan B.F.N.

1997-01-01

The retro-Diels-Alder (RDA) reaction of anthracenedione 1a proceeds considerably faster in aqueous solutions than in organic solvents. Addition of organic solvents to water retards the reaction, whereas glucose induces a modest acceleration. SDS micelles induce a considerable retardation, but even

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

Directory of Open Access Journals (Sweden)

Magnus Rueping

2012-10-01

Full Text Available 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.

Stepwise or concerted? DFT study on the mechanism of ionic Diels-Alder reaction of chromanes

Directory of Open Access Journals (Sweden)

Haghdadi Mina

2016-01-01

Full Text Available The stepwise and concerted Ionic Diels-Alder reaction between phenyl (pyridin-2-ylmethylene oxonium and styrene derivatives are explored using theoretical method. The results support using computational method via persistent intermediates. The DFT method was essential to reproduce a reasonable potential energy surface for these challenging systems.

Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

KAUST Repository

Yang, Limin; Wang, Fei; Lee, Richmond; Lv, Yunbo; Huang, Kuo-Wei; Zhong, Guofu

2014-01-01

A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study

Cascade olefin isomerization/intramolecular Diels-Alder reaction catalyzed by N-heterocyclic carbenes.

Science.gov (United States)

Kowalczyk, Marcin; Lupton, David W

2014-05-19

The addition of an N-heterocyclic carbene to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels-Alder reaction, for which mechanistic studies implicate Lewis base catalysis. Preliminary studies into the utility of the products have been undertaken with reductive and oxidative cleavage, giving materials for potential use in complex-target synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intramolecular anionic diels-alder reactions of 1-aryl-4-oxahepta-1,6-diyne systems in DMSO.

Science.gov (United States)

Kudoh, Takayuki; Mori, Tomoko; Shirahama, Mitsuhito; Yamada, Masashi; Ishikawa, Teruhiko; Saito, Seiki; Kobayashi, Hisayoshi

2007-04-25

Base-promoted cycloaddition reactions of 1-aryl- or 1-aryl-7-substituted-4-oxahepta-1,6-diyne systems in DMSO have proven to involve an anionic intramolecular Diels-Alder process taking place even at room temperature in spite of the reaction suffering from temporary disruption of aromaticity. Although initially formed alpha-arylallenide anion can be protonated by DMSO, it can be back to the allenide anion probably because of a small acidity difference between alpha-arylallene and DMSO. The alpha-arylallenide anion in combination with the alpha-aryl substituent can constitute an anionic diene structure that undergoes the intramolecular Diels-Alder reaction involving the C(6)-yne part, a very fast process probably because of the increased HOMO-1 level of the anionic diene, as shown by DFT calculations. Diversified substituted naphthalenes, benzofurans, phenanthrenes, and quinolines, including biaryl architectures, are available from 4-oxahepta-1,6-diynes in a highly expeditious way.

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

Science.gov (United States)

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

2013-08-14

In order to mimic the natural cartilage extracellular matrix, a novel biological degradable interpenetrating network hydrogel was synthesized from the gelatin (G), hyaluronic acid (HA) and chondroitin sulfate (CS) by Diels-Alder "click" chemistry. HA was modified with furylamine and G was modified with furancarboxylic acid respectively. (1)H NMR spectra and elemental analysis showed that the substitution degrees of HA-furan and G-furan were 71.5% and 44.5%. Then the hydrogels were finally synthesized by cross-linking furan-modified HA and G derivatives with dimaleimide poly(ethylene glycol) (MAL-PEG-MAL). The mechanical and degradation properties of the hydrogels could be tuned simply through varying the molar ratio between furan and maleimide. Rheological, mechanical and degradation studies demonstrated that the Diels-Alder "click" chemistry is an efficient method for preparing high performance biological interpenetrating hydrogels. This biomimic hydrogel with improved mechanical properties could have great potential applications in cartilage tissue engineering. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Czech Academy of Sciences Publication Activity Database

Yameen, B.; Rodriguez-Emmenegger, C.; Preuss, C. M.; Pop-Georgievski, Ognen; Verveniotis, Elisseos; Trouillet, V.; Rezek, Bohuslav; Barner-Kowollik, C.

2013-01-01

Roč. 49, č. 77 (2013), s. 8623-8625 ISSN 1359-7345 R&D Projects: GA ČR GBP205/12/G118; GA ČR GAP108/11/1857; GA ČR(CZ) GBP108/12/G108 Institutional support: RVO:61389013 ; RVO:68378271 Keywords : conductive poly(3-hexylthiophen) brushes * Diels-Alder ligation * Kelvin Probe Force Microscopy (KFM) Subject RIV: CD - Macromolecular Chemistry Impact factor: 6.718, year: 2013

One-step versus two-step mechanism of Diels-Alder reaction of 1-chloro-1-nitroethene with cyclopentadiene and furan.

Science.gov (United States)

Jasiński, Radomir

2017-08-01

DFT computational study shows that Diels-Alder (DA) reactions of 1-chloro-1-nitroethene with cyclopentadiene and furan have polar nature. However, their mechanism is substantially different. In particular, 1-chloro-1-nitroethene react with cyclopentadiene according to one-step mechanism. In the same time, more favourable channel associated with the P-DA reaction between furan and 1-chloro-1-nitroethene is a domino process, that comprises an initial hetero-Diels-Alder reaction yielding a [2+4] cycloadduct, which experiences a subsequent [3,3] sigmatropic shift to yield the expected formal [4+2] cycloadduct. This is a consequence of more polar nature of reaction, due to higher nucleophilicity of furan in comparison to cyclopentadiene. Copyright © 2017 Elsevier Inc. All rights reserved.

Dendrogeochronologic and Anatomic Analysis of Excavated Plains Cottonwoods Determine Overbank Sedimentation Rates and Historical Channel Positions Along the Interior of a Migrating Meander Bend, Powder River, Montana

Science.gov (United States)

Metzger, T. L.; Pizzuto, J. E.; Schook, D. M.; Hasse, T. R.; Affinito, R. A.

2017-12-01

Dendrochronological dating of buried trees precisely determines the germination year and identifies the stratigraphic context of germination for the trees. This recently developed application of dendrochronology provides accurate time-averaged sedimentation rates of overbank deposition along floodplains and can be used to identify burial events. Previous studies have demonstrated that tamarisk (Tamarix ramosissima) and sandbar willow (Salix exigua) develop anatomical changes within the tree rings (increased vessel size and decreased ring widths) on burial, but observations of plains cottonwood (Populus deltoides ssp. monilifera) are lacking. In September 2016 and June 2017, five buried plains cottonwoods were excavated along a single transect of the interior of a meander bend of the Powder River, Montana. Sediment samples were obtained near each tree for 210Pb and 137Cs dating, which will allow for comparison between dendrochronological and isotopic dating methods. The plains cottonwood samples collected exhibit anatomical changes associated with burial events that are observed in other species. All trees germinated at the boundary between thinly bedded fine sand and mud and coarse sand underlain by sand and gravel, indicating plains cottonwoods germinate on top of point bars prior to overbank deposition. The precise germination age and depth provide elevations and minimum age constraints for the point bar deposits and maximum ages for the overlying sediment, helping constrain past channel positions and overbank deposition rates. Germination years of the excavated trees, estimated from cores taken 1.5 m above ground level, range from 2014 to 1862. Accurate establishment years determined by cross-dating the buried section of the tree can add an additional 10 years to the cored age. The sedimentation rate and accumulation thickness varied with tree age. The germination year, total sediment accumulation, and average sedimentation rate at the five sampled trees is

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

Directory of Open Access Journals (Sweden)

Grzegorz Mlostoń

2015-04-01

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

Managing young upland forests in southeast Alaska for wood products, wildlife, aquatic resources, and fishes: problem analysis and study plan.

Science.gov (United States)

Mark S. Wipfli; Robert L. Deal; Paul E. Hennon; Adelaide C. Johnson; Toni L. de Santo; Thomas A. Hanley; Mark E. Schultz; Mason D. Bryant; Richard T. Edwards; Ewa H. Orlikowska; Takashi Gomi

2002-01-01

Red alder (Alnus rubra Bong.) appears to influence the productivity of young-growth conifer forests and affect the major resources (timber, wildlife, and fisheries) of forested ecosystems in southeast Alaska. We propose an integrated approach to understanding how alder influences trophic links and processes in young-growth ecosystems. The presence...

Activation-Strain Analysis Reveals Unexpected Origin of Fast Reactivity in Heteroaromatic Azadiene Inverse-Electron-Demand Diels-Alder Cycloadditions

NARCIS (Netherlands)

Talbot, Austin; Devarajan, Deepa; Gustafson, Samantha J.; Fernandez, Israel; Bickelhaupt, F. Matthias; Ess, Daniel H.

2014-01-01

Heteroaromatic azadienes, especially 1,2,4,5-tetrazines, are extremely reactive partners with alkenes in inverse-electron-demand Diels–Alder reactions. Azadiene cycloaddition reactions are used to construct heterocycles in synthesis and are popular as bioorthogonal reactions. The origin of fast

Assessment of a novel alder biorefinery concept to meet demands of economic feasibility, energy production and long term environmental sustainability

DEFF Research Database (Denmark)

Thomsen, Tobias; Ahrenfeldt, Jesper; Thomsen, Sune Tjalfe

2013-01-01

A biorefinery concept based on alder tree plantations on degenerated soil is developed to comply with indicators of economic feasibility, fossil fuel depletion concerns, and long term sustainability issues. The potential performance of feedstock and biorefinery has been assessed through a literat......A biorefinery concept based on alder tree plantations on degenerated soil is developed to comply with indicators of economic feasibility, fossil fuel depletion concerns, and long term sustainability issues. The potential performance of feedstock and biorefinery has been assessed through...... degenerated soils. Integrating a biomass handling system, an LTCFB gasifier, a diarylheptanoids production chain, an anaerobic digestion facility, a slow pyrolysis unit, gas upgrading and various system integration units, the biorefinery could obtain the following production characteristics accounted...

Silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes.

Science.gov (United States)

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

2012-06-06

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.

Asymmetric Diels-Alder Reaction of α,β-Unsaturated Oxazolidin-2-one Derivatives Catalyzed by a Chiral Fe(III)-Bipyridine Diol Complex.

Science.gov (United States)

Li, Mao; Carreras, Virginie; Jalba, Angela; Ollevier, Thierry

2018-02-16

An asymmetric Fe III -bipyridine diol catalyzed Diels-Alder reaction of α,β-unsaturated oxazolidin-2-ones has been developed. Among various Fe II /Fe III salts, Fe(ClO 4 ) 3 ·6H 2 O was selected as the Lewis acid of choice. The use of a low catalyst loading (2 mol % of Fe(ClO 4 ) 3 ·6H 2 O and 2.4 mol % of Bolm's ligand) afforded high yields (up to 99%) and high enantiomeric excesses (up to 98%) of endo-cycloadducts for the Diels-Alder reaction between cyclopentadiene and substituted acryloyloxazolidin-2-ones. Other noncyclic dienes led to decreased enantioselectivities. A proposed model supports the observed stereoinduction.

Origins of the Unfavorable Activation and Reaction Energies of 1-Azadiene Heterocycles Compared to 2-Azadiene Heterocycles in Diels-Alder Reactions.

Science.gov (United States)

Fell, Jason S; Martin, Blanton N; Houk, K N

2017-02-17

The reactivities of butadiene, cyclopentadiene, furan, thiophene, pyrrole, and their 1-aza- and 2-aza-derivatives in Diels-Alder reactions with ethylene and fumaronitrile were investigated with density functional theory (M06-2X/6-311G(d,p)). The activation free energies for the Diels-Alder reactions of cyclic 1-azadienes are 10-14 kcal mol -1 higher than those of cyclic 2-azadienes, and the reaction free energies are 17-20 kcal mol -1 more endergonic. The distortion/interaction model shows that the increased activation energies of cyclic 1-azadienes originate from increased transition state distortion energies and unfavorable interaction energies, arising from addition to the nitrogen terminus of the C═N bond.

Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium

Directory of Open Access Journals (Sweden)

Pégot Bruce

2006-09-01

Full Text Available Abstract The asymmetric aza-Diels-Alder reaction of chiral imines with Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their efficiency is preserved.

The Intramolecular Diels–Alder Reaction of Tryptamine-Derived Zincke Aldehydes Is a Stepwise Process

OpenAIRE

Pham, Hung V.; Martin, David B. C.; Vanderwal, Christopher D.; Houk, K. N.

2012-01-01

Computational studies show that the base-mediated intramolecular Diels–Alder of tryptamine-derived Zincke aldehydes, used as a key step in the synthesis of the Strychnos alkaloids norfluorocurarine and strychnine, proceeds via a stepwise pathway. The experimentally determined importance of a potassium counterion in the base is explained by its ability to preorganize the Zincke aldehyde diene in an s-cis conformation suitable to bicyclization. Computation also supports the thermodynamic import...

Cross-linking of rubber in the presence of multi-functional cross-linking aids via thermoreversible Diels-Alder chemistry

NARCIS (Netherlands)

Polgar, L. M.; Fortunato, G.; Araya-Hermosilla, R.; van Duin, M.; Pucci, A.; Picchioni, F.

Furan-functionalized polyketone (PK-FU) was added to a furan-functionalized ethylene-propylene rubber (EPM-FU). The mixture was subsequently cross-linked with a bismaleimide through Diels-Alder chemistry in order to improve the mechanical properties of the rubber. Infrared spectroscopy showed the

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

Science.gov (United States)

Pacheco, Joshua J.; Davis, Mark E.

2014-01-01

Terephthalic acid (PTA), a monomer in the synthesis of polyethylene terephthalate (PET), is obtained by the oxidation of petroleum-derived p-xylene. There is significant interest in the synthesis of renewable, biomass-derived PTA. Here, routes to PTA starting from oxidized products of 5-hydroxymethylfurfural (HMF) that can be produced from biomass are reported. These routes involve Diels-Alder reactions with ethylene and avoid the hydrogenation of HMF to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with high pressure ethylene over a pure-silica molecular sieve containing framework tin (Sn-Beta) to produce the Diels-Alder dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with 31% selectivity at 61% HMFA conversion after 6 h at 190 °C. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of Sn-Beta for 2 h to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with 46% selectivity at 28% MMFC conversion or in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) for 6 h to produce MMBC with 81% selectivity at 26% MMFC conversion. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder dehydration product is observed. PMID:24912153

Avian response to bottomland hardwood reforestation: the first 10 years

Science.gov (United States)

Twedt, D.J.; Wilson, R.R.; Henne-Kerr, J.L.; Grosshuesch, D.A.

2002-01-01

Bttomland hardwood forests were planted on agricultural fields in Mississippi and Louisiana using either predominantly Quercus species (oaks) or Populus deltoides (eastern cottonwood). We assessed avian colonization of these reforested sites between 2 and 10 years after planting. Rapid vertical growth of cottonwoods (circa 2 - 3 m / yr) resulted in sites with forest structure that supported greater species richness of breeding birds, increased Shannon diversity indices, and supported greater territory densities than on sites planted with slower-growing oak species. Grassland birds (Spiza americana [Dickcissel], and Sturnella magna [Eastern Meadowlark]) were indicative of species breeding on oak-dominated reforestation # 10 years old. Agelaius phoeniceus (Red-winged Blackbird) and Colinus virginianus (Northern Bobwhite) characterized cottonwood reforestation # 4 years old, whereas 14 species of shrub-scrub birds (e.g., Passerina cyanea [Indigo Bunting]) and early-successional forest birds (e.g., Vireo gilvus [Warbling Vireo]) typified cottonwood reforestation 5 to 9 years after planting. Rates of daily nest survival did not differ between reforestation strategies. Nest parasitism increased markedly in older cottonwood stands, but was overwhelmed by predation as a cause of nest failure. Based on Partners in Flight prioritization scores and territory densities, the value of cottonwood reforestation for avian conservation was significantly greater than that of oak reforestation during their first 10 years. Because of benefits conferred on breeding birds, we recommend reforestation of bottomland hardwoods include a high proportion of fast-growing, early successional species such as cottonwood.

Solar ultraviolet radiation alters alder and birch litter chemistry that in turn affects decomposers and soil respiration.

Science.gov (United States)

Kotilainen, Titta; Haimi, Jari; Tegelberg, Riitta; Julkunen-Tiitto, Riitta; Vapaavuori, Elina; Aphalo, Pedro Jose

2009-10-01

Solar ultraviolet (UV)-A and UV-B radiation were excluded from branches of grey alder (Alnus incana) and white birch (Betula pubescens) trees in a field experiment. Leaf litter collected from these trees was used in microcosm experiments under laboratory conditions. The aim was to evaluate the effects of the different UV treatments on litter chemical quality (phenolic compounds, C, N and lignin) and the subsequent effects of these changes on soil fauna and decomposition processes. We measured the decomposition rate of litter, growth of woodlice (Porcellio scaber), soil microbial respiration and abundance of nematodes and enchytraeid worms. In addition, the chemical quality of woodlice feces was analyzed. The exclusion of both UV-A and UV-B had several effects on litter chemistry. Exclusion of UV-B radiation decreased the C content in litter in both tree species. In alder litter, UV exclusion affected concentration of phenolic groups variably, whereas in birch litter there were no significant differences in phenolic compounds. Moreover, further effects on microbial respiration and chemical quality of woodlice feces were apparent. In both tree species, microbial CO(2) evolution was lower in soil with litter produced under exclusion of both UV-A and UV-B radiation when compared to soil with control litter. The N content was higher in the feces of woodlice eating alder litter produced under exclusion of both UV-A and UV-B compared to the control. In addition, there were small changes in the concentration of individual phenolic compounds analyzed from woodlice feces. Our results demonstrate that both UV-A and UV-B alter litter chemistry which in turn affects decomposition processes.

Hydrogen Abstraction Acetylene Addition and Diels-Alder Mechanisms of PAH Formation:  A Detailed Study Using First Principles Calculations.

Science.gov (United States)

Kislov, V V; Islamova, N I; Kolker, A M; Lin, S H; Mebel, A M

2005-09-01

Extensive ab initio Gaussian-3-type calculations of potential energy surfaces (PES), which are expected to be accurate within 1-2 kcal/mol, combined with statistical theory calculations of reaction rate constants have been applied to study various possible pathways in the hydrogen abstraction acetylene addition (HACA) mechanism of naphthalene and acenaphthalene formation as well as Diels-Alder pathways to acenaphthalene, phenanthrene, and pyrene. The barrier heights; reaction energies; and molecular parameters of the reactants, products, intermediates, and transition states have been generated for all types of reactions involved in the HACA and Diels-Alder mechanisms, including H abstraction from various aromatic intermediates, acetylene addition to radical sites, ring closures leading to the formation of additional aromatic rings, elimination of hydrogen atoms, H disproportionation, C2H2 cycloaddition, and H2 loss. The reactions participating in various HACA sequences (e.g., Frenklach's, alternative Frenklach's, and Bittner and Howard's routes) are demonstrated to have relatively low barriers and high rate constants under combustion conditions. A comparison of the significance of different HACA mechanisms in PAH growth can be made in the future using PES and molecular parameters obtained in the present work. The results show that the Diels-Alder mechanism cannot compete with the HACA pathways even at high combustion temperatures, because of high barriers and consequently low reaction rate constants. The calculated energetic parameters and rate constants have been compared with experimental and theoretical data available in the literature.

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

Science.gov (United States)

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.

First catalytic hetero-Diels-Alder reaction of imidazole-2-thiones and in silico biological evaluation of the cycloadducts

NARCIS (Netherlands)

Eleftheriadis, Nikolaos; Samatidou, Evanthia; Neochoritis, Constantinos G.

The Lewis acid-catalyzed Diels-Alder reactions of suitably substituted imidazole-2-thiones with dienes were studied. It was found that the electron density of the imidazole core influenced the reaction, since electron withdrawing groups led to the novel spiro-derivatives 2 whereas electron donating

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

Science.gov (United States)

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…

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

Science.gov (United States)

Kocsis, Laura S.; Benedetti, Erica

2012-01-01

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

A thermal dehydrogenative Diels-Alder reaction of styrenes for the concise synthesis of functionalized naphthalenes.

Science.gov (United States)

Kocsis, Laura S; Benedetti, Erica; Brummond, Kay M

2012-09-07

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

Methane Fluxes at the Tree Stem, Soil, and Ecosystem-scales in a Cottonwood Riparian Forest

Science.gov (United States)

Flanagan, L. B.; Nikkel, D. J.; Scherloski, L. M.; Tkach, R. E.; Rood, S. B.

2017-12-01

Trees can emit methane to the atmosphere that is produced by microbes inside their decaying stems or by taking up and releasing methane that is produced by microbes in adjacent, anoxic soil layers. The significance of these two methane production pathways for possible net release to the atmosphere depends on the magnitude of simultaneous oxidation of atmospheric methane that occurs in well-aerated, shallow soil zones. In order to quantify the significance of these processes, we made methane flux measurements using the eddy covariance technique at the ecosystem-scale and via chamber-based methods applied on the soil surface and on tree stems in a riparian cottonwood ecosystem in southern Alberta that was dominated by Populus tree species and their natural hybrids. Tree stem methane fluxes varied greatly among individual Populus trees and changed seasonally, with peak growing season average values of 4 nmol m-2 s-1 (tree surface area basis). When scaled to the ecosystem, the tree stem methane emissions (0.9 nmol m-2 s-1, ground area basis) were slightly higher than average soil surface methane uptake rates (-0.8 nmol m-2 s-1). In addition, we observed regular nighttime increases in methane concentration within the forest boundary layer (by 300 nmol mol-1 on average at 22 m height during July). The majority of the methane concentration build-up was flushed from the ecosystem to the well-mixed atmosphere, with combined eddy covariance and air column storage fluxes reaching values of 70-80 nmol m-2 s-1 for approximately one hour after sunrise. Daily average net methane emission rates at the ecosystem-scale were 4.4 nmol m-2 s-1 during July. Additional lab studies demonstrated that tree stem methane was produced via the CO2-reduction pathway, as tissue in the central stem of living Populus trees was being decomposed. This study demonstrated net methane emission from an upland, cottonwood forest ecosystem, resulting from microbe methane production in tree stems that

Determining bioclimatic space of Himalayan alder for agroforestry systems in Nepal

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Santosh Kumar Rana

2018-02-01

Full Text Available Himalayan alder species are proven to be very useful in traditional as well as contemporary agroforestry practice. These nitrogen-fixing trees are also useful in the land restoration. Therefore, understanding the distribution of Himalayan alder and the potential zone for plantation is meaningful in the agroforestry sector. Suitable climatic zones of Alnus spp. were modelled in MaxEnt software using a subset of least correlated bioclimatic variables for current conditions (1950–2000, topographic variables (DEM derived and Landuse Landcover (LULC data. We generated several models and selected the best model against random models using ANOVA and t-test. The environmental variables that best explained the current distribution of the species were identified and used to project into the future. For future projections, ensemble scenarios of climate change projection derived from the results of 19 Earth System Models (ESM were used. Our model revealed that the most favorable conditions for Alnus nepalensis are in central Nepal in the moist north-west facing slope, whereas for Alnus nitida they are in western Nepal. The major climatic factor that contributes to Alnus species distribution in Nepal appears to be precipitation during the warmest quarter for A. nepalensis and precipitation during the driest quarter for A. nitida. Future projections revealed changes in the probability distribution of these species, as well as where they need conservation and where they can be planted. Also, our model predicts that the distribution of Alnus spp. in hilly regions will remain unchanged, and therefore may represent sites that can be used to revitalize traditional agroforestry systems and extract source material for land restoration.

Substituent Effects on Regioselectivity of the Diels-Alder Reactions: Reactions of 10-Allyl-1,8-dichloroanthracene with 2-Chloroacrylonitrile, 1-Cyanovinyl Acetate and Phenyl Vinyl Sulfone

Directory of Open Access Journals (Sweden)

Mujeeb A. Sultan

2016-01-01

Full Text Available Diels-Alder reaction of 10-allyl-1,8-dichloroanthracene (3 with 2-chloroacrylonitrile (4 and 1-cyanovinyl acetate (5 gives exclusively the ortho isomer while its reaction with phenyl vinyl sulfone (10 yields a mixture of two isomeric adducts with priority to ortho isomer. The reactions proceeded under microwave condition in xylene. Configurations of these isomers have been assigned with the help of NMR spectra. The results indicated that the steric effect is dominating toward the isomer regioselectivity in the Diels-Alder reaction of the present compounds.

Investigating radical cation chain processes in the electrocatalytic Diels-Alder reaction.

Science.gov (United States)

Imada, Yasushi; Okada, Yohei; Chiba, Kazuhiro

2018-01-01

Single electron transfer (SET)-triggered radical ion-based reactions have proven to be powerful options in synthetic organic chemistry. Although unique chain processes have been proposed in various photo- and electrochemical radical ion-based transformations, the turnover number, also referred to as catalytic efficiency, remains unclear in most cases. Herein, we disclose our investigations of radical cation chain processes in the electrocatalytic Diels-Alder reaction, leading to a scalable synthesis. A gram-scale synthesis was achieved with high current efficiency of up to 8000%. The reaction monitoring profiles showed sigmoidal curves with induction periods, suggesting the involvement of intermediate(s) in the rate determining step.

A Tri-O-Bridged Diels-Alder Adduct from Cortex Mori Radicis

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An-Qi Lu

2018-01-01

Full Text Available Sanggenon X, an unusual tri-O-bridged Diels-Alder adduct, was isolated from Cortex Mori Radicis. Its structure was established by spectroscopic analysis, including NMR and HR-MS (High Resolution Mass Spectrometry. Sanggenon X contained three O-bridged rings, where the oxygenated bridgeheads were all quaternary carbons. Chemical methylation was carried out to deduce the linkages of the three O-bridges. The absolute configuration was determined by calculating the ECD (Electronic Circular Dichroism using the TDDFT (Time-Dependent Density Functional Theory method. Sanggenon X showed significant antioxidant activity against Fe2+-Cys-induced lipid peroxidation in rat liver microsomes, and was as effective as the positive control, curcumin.

Organoplatinum complex promoted the asymmetric endo stereochemically controlled Diels-Alder reaction between 3-diphenylphosphinofuran and diphenylvinylphosphine.

Science.gov (United States)

Liu, Fengli; Pullarkat, Sumod A; Tan, Kien-Wee; Li, Yongxin; Leung, Pak-Hing

2009-12-07

The organoplatinum complex containing ortho-metalated (R)-(1-(dimethylamino)ethyl)-naphthalene as the chiral auxiliary has been used efficiently to promote the asymmetric [4 + 2] Diels-Alder reaction between diphenylvinylphosphine and 3-diphenylphosphinofuran to generate two chelating diphosphine endocycloadducts in the ratio 17:1. The absolute configurations of the three newly generated stereocenters have been assigned by single-crystal X-ray analysis.

N,N-Diethyl-1-Tosyl-3-Indoleglyoxylamide as a Dienophile in Diels-Alder Reactions. Hyperbaric vs. Thermal Conditions

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B. Biolatto

2000-03-01

Full Text Available Under high pressure conditions, the Diels-Alder reaction involving N,N-diethyl-1-tosyl-3-indoleglyoxylamide and 1-(N-acetyl-N-propylamino-1,3-butadiene produces a highly functionalized intermediate for the synthesis of Indole Alkaloids, in shorter times and higher yields than under thermal conditions.

A review of the characteristics of black alder (Alnus glutinosa (L.) Gaertn.) and their implications for silvicultural practices

NARCIS (Netherlands)

Claessens, H.; Oosterbaan, A.; Savill, P.; Rondeux, J.

2010-01-01

Black alder is a scattered, widespread and short-lived species that thrives in low-lying damp and riparian places. It has a use in flood control, stabilization of riverbanks and in functioning of the river ecosystems. To thrive, precipitation must exceed 1500 mm if access to groundwater is not

Diels-Alder Synthesis of endo-cis-N-phenylbicyclo[2.2.2]oct-5-en-2,3-dicarboximide

Science.gov (United States)

Baar, Marsha R.; Wustholz, Kristin

2005-01-01

A study investigated the Diels-Alder synthesis of endo-cis-N-phenylbicyclo [2.2.2]oct-5-en-2,3-dicarboximide. The amount of time taken by a reaction between the 1,3-cyclohexadiene and N-phenylmaleimide at room temperature and also whether the desired cycloadduct would precipitate directly from the reaction mixture was examined.

Ti(Oi-Pr)4-promoted photoenolization Diels-Alder reaction to construct polycyclic rings and its synthetic applications.

Science.gov (United States)

Yang, Baochao; Lin, Kuaikuai; Shi, Yingbo; Gao, Shuanhu

2017-09-20

Stereoselective construction of polycyclic rings with all-carbon quaternary centers, and vicinal all-carbon quaternary stereocenters, remains a significant challenge in organic synthesis. These structures can be found in a wide range of polycyclic natural products and drug molecules. Here we report a Ti(Oi-Pr) 4 -promoted photoenolization/Diels-Alder (PEDA) reaction to construct hydroanthracenol and related polycyclic rings bearing all-carbon quaternary centers. This photolysis proceeds under mild conditions and generates a variety of photo-cycloaddition products in good reaction efficiency and stereoselectivity (48 examples), and has been successfully used in the construction of core skeleton of oncocalyxones, tetracycline and pleurotin. It also provides a reliable method for the late-stage modification of natural products bearing enone groups, such as steroids. The total synthesis of oncocalyxone B was successfully achieved using this PEDA approach.Anthracenols with multiple chiral centres are common motifs in natural products. Here, the authors show a highly stereoselective photoenolization/Diels-Alder methodology involving a key Lewis acid reagent enabling the efficient construction of a family of anthracenol derivatives with quaternary centers.

Lateral extension of π conjugation along the bay regions of bisanthene through a diels-alder cycloaddition reaction

KAUST Repository

Li, Jinling; Jiao, Chongjun; Huang, Kuo-Wei; Wu, Jishan

2011-01-01

Diels-Alder cycloaddition reactions at the bay regions of bisanthene (1) with dienophiles such as 1,4-naphthoquinone have been investigated. The products were submitted to nucleophilic addition followed by reductive aromatization reactions to afford the laterally extended bisanthene derivatives 2 and 3. Attempted synthesis of a larger expanded bisanthene 4 revealed an unexpected hydrogenation reaction at the last reductive aromatization step. Unusual Michael addition was observed on quinone 14, which was obtained by Diels-Alder reaction between 1 and 1,4-anthraquinone. Compounds 1-3 exhibited near-infrared (NIR) absorption and emission with high-to-moderate fluorescent quantum yields. Their structures and absorption spectra were studied by density function theory and non-planar twisted structures were calculated for 2 and 3. All compounds showed amphoteric redox behavior with multiple oxidation/reduction waves. Oxidative titration with SbCl 5 gave stable radical cations, and the process was followed by UV/Vis/NIR spectroscopic measurements. Their photostability was measured and correlated to their different geometries and electronic structures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lateral extension of π conjugation along the bay regions of bisanthene through a diels-alder cycloaddition reaction

KAUST Repository

Li, Jinling

2011-11-14

Diels-Alder cycloaddition reactions at the bay regions of bisanthene (1) with dienophiles such as 1,4-naphthoquinone have been investigated. The products were submitted to nucleophilic addition followed by reductive aromatization reactions to afford the laterally extended bisanthene derivatives 2 and 3. Attempted synthesis of a larger expanded bisanthene 4 revealed an unexpected hydrogenation reaction at the last reductive aromatization step. Unusual Michael addition was observed on quinone 14, which was obtained by Diels-Alder reaction between 1 and 1,4-anthraquinone. Compounds 1-3 exhibited near-infrared (NIR) absorption and emission with high-to-moderate fluorescent quantum yields. Their structures and absorption spectra were studied by density function theory and non-planar twisted structures were calculated for 2 and 3. All compounds showed amphoteric redox behavior with multiple oxidation/reduction waves. Oxidative titration with SbCl 5 gave stable radical cations, and the process was followed by UV/Vis/NIR spectroscopic measurements. Their photostability was measured and correlated to their different geometries and electronic structures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of 2,5-Disubstituted Octahydroquinolin-4-ones via anIntramolecular Hetero Diels-Alder Reaction

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J. Antonio Palenzuela

2007-02-01

Full Text Available A route for the preparation of 2,5-disubstituted octahydroquinolin-4-ones, synthetic precursors of the decahydroquinoline-type toxins, is presented. The key steps are an asymmetric epoxidation and an intramolecular hetero Diels-Alder reaction between an activated diene and an imine. The presence of an allylic stereogenic center induces some selectivity and thus only two cycloadducts are obtained in 70:30 ratio and good yield.

Continuous-flow retro-Diels-Alder reaction: an efficient method for the preparation of pyrimidinone derivatives.

Science.gov (United States)

Nekkaa, Imane; Palkó, Márta; Mándity, István M; Fülöp, Ferenc

2018-01-01

The syntheses of various pyrimidinones as potentially bioactive products by means of the highly controlled continuous-flow retro-Diels-Alder reaction of condensed pyrimidinone derivatives are presented. Noteworthy, the use of this approach allowed us to rapidly screen a selection of conditions and quickly confirm the viability of preparing the desired pyrimidinones in short reaction times. Yields typically higher than those published earlier using conventional batch or microwave processes were achieved.

Use of Diels-Alder Chemistry for Thermoreversible Cross-Linking of Rubbers : The Next Step toward Recycling of Rubber Products?

NARCIS (Netherlands)

Polgar, L. M.; van Duin, M.; Broekhuis, A. A.; Picchioni, F.

2015-01-01

A proof of principle for the use of Diels-Alder chemistry as a thermoreversible cross-linking tool for rubber products is demonstrated. A commercial ethylene-propylene rubber grafted with maleic anhydride has been thermoreversibly cross-linked in two steps. The pending anhydride rings were first

Magnetic hyaluronic acid nanospheres via aqueous Diels-Alder chemistry to deliver dexamethasone for adipose tissue engineering.

Science.gov (United States)

Jia, Yang; Fan, Ming; Chen, Huinan; Miao, Yuting; Xing, Lian; Jiang, Bohong; Cheng, Qifan; Liu, Dongwei; Bao, Weikang; Qian, Bin; Wang, Jionglu; Xing, Xiaodong; Tan, Huaping; Ling, Zhonghua; Chen, Yong

2015-11-15

Biopolymer-based nanospheres have great potential in the field of drug delivery and tissue regenerative medicine. In this work, we present a flexible way to conjugate a magnetic hyaluronic acid (HA) nanosphere system that are capable of vectoring delivery of adipogenic factor, e.g. dexamethasone, for adipose tissue engineering. Conjugation of nanospheres was established by aqueous Diels-Alder chemistry between furan and maleimide of HA derivatives. Simultaneously, a furan functionalized dexamethasone peptide, GQPGK, was synthesized and covalently immobilized into the nanospheres. The magnetic HA nanospheres were fabricated by encapsulating super-paramagnetic iron oxide nanoparticles, which exhibited quick magnetic sensitivity. The aqueous Diels-Alder chemistry made nanospheres high binding efficiency of dexamethasone, and the vectoring delivery of dexamethasone could be easily controlled by a external magnetic field. The potential application of the magnetic HA nanospheres on vectoring delivery of adipogenic factor was confirmed by co-culture of human adipose-derived stem cells (ASCs). In vitro cytotoxicity tests demonstrated that incorporation of dexamethasone into magnetic HA nanospheres showed high efficiency to promote ASCs viabilities, in particular under a magnetic field, which suggested a promising future for adipose regeneration applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Synthesis of Precursors of the Agalacto (Exo) Fragment of the Quartromicins via an Auxiliary-Controlled Exo-Selective Diels-Alder Reaction

Science.gov (United States)

Qi, Jun; Roush, William R.

2008-01-01

A direct synthesis of the α-hydroxyaldehyde exo-5, a precursor of the exo-spirotetronate subunit o f the quartromicins, was achieved through an exo-selective Lewis acid-catalyzed Diels-Alder reaction of dienophile 12a and diene 1. PMID:16774259

Facile approach to prepare pH and redox-responsive nanogels via Diels-Alder click reaction

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C. M. Q. Le

2018-08-01

Full Text Available A novel pH and redox responsive system of sub-100 nm nanogels was prepared by arm-first approach via Diels-Alder click reaction. First, well-defined poly(ethylene glycol-block-poly(styrene-alt-maleic anhydride (PEG-b-PSM was synthesized and subsequently functionalized with furfuryl amine, leading to the formation of the dual-functional block copolymer of PEG-b-PSMf. The furfuryl groups in the PSMf block were employed to incorporate a redox-responsive linkage and the carboxylic acid moieties generated through functionalization acted as a pH-responsive part. The Diels-Alder click reaction between a bismaleimide crosslinker and PEG-b-PSMf was conducted at 60 °C, affording star-like nanogel structures. Doxorubicin, a model anticancer drug, was loaded into to the core of the nanogels primarily by the ionic interaction with carboxylates of core blocks and a highest drug loading capacity of 38.1% was obtained. Furthermore, the in vitro profile showed a low release percentage (11.2% of DOX at PBS pH 7.4, whereas a burst release (62% at pH 5.0 in the presence of 10 mM glutathione, indicating the effective pH and redox responsive characteristic of the PEG-b-PSMf nanogels.

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

Science.gov (United States)

Bodnar, Brian S.

2014-01-01

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

Synthesis of α- and β-lapachone derivatives from hetero diels-alder trapping of alkyl and aryl o-quinone methides

International Nuclear Information System (INIS)

Silva, Fernando de C. da; Ferreira, Sabrina B.; Ferreira, Vitor F.; Kaiser, Carlos R.; Pinto, Angelo C.

2009-01-01

Methylene and aryl o-quinone methides (o-QMs) generated by Knoevenagel condensation of 2-hydroxy-1,4-naphthoquinone with formaldehyde and arylaldehydes, undergo facile hetero Diels-Alder reaction with some substituted styrenes (as dienophiles) in aqueous ethanol media providing derivatives of α- and β-lapachone (author)

Environmental Assessment for the Aeromedical Evacuation Formal Training Unit, Wright-Patterson Air Force Base

Science.gov (United States)

2012-05-01

pennsylvanica), White Ash (Fraxinus americana), Shingle Oak (Quercus imbricaria), Northern Red Oak (Quercus rubra), Slippery Elm (Ulmus rubra...American Elm (Ulmus americana), Eastern Cottonwood (Populus deltoides), Silver Maple (Acer saccharinum), Sassafras (Sassafras albidum), Post Oak (Quercus

N2 fixing alder (Alnus viridis spp.fruticosa) effects on soil properties across a secondary successional chronosequence in interior Alaska

Science.gov (United States)

Jennifer S. Mitchell; Roger W. Ruess

2009-01-01

Green alder (Alnus viridis ssp. fruticosa) is a dominant understory shrub during secondary successional development of upland forests throughout interior Alaska, where it contributes substantially to the nitrogen (N) economy through atmospheric N2 fixation. Across a replicated 200+ year old vegetation...

Simultaneous analysis of 70 pesticides using HPlc/MS/MS: a comparison of the multiresidue method of Klein and Alder and the QuEChERS method.

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Riedel, Melanie; Speer, Karl; Stuke, Sven; Schmeer, Karl

2010-01-01

Since 2003, two new multipesticide residue methods for screening crops for a large number of pesticides, developed by Klein and Alder and Anastassiades et al. (Quick, Easy, Cheap, Effective, Rugged, and Safe; QuEChERS), have been published. Our intention was to compare these two important methods on the basis of their extraction efficiency, reproducibility, ruggedness, ease of use, and speed. In total, 70 pesticides belonging to numerous different substance classes were analyzed at two concentration levels by applying both methods, using five different representative matrixes. In the case of the QuEChERS method, the results of the three sample preparation steps (crude extract, extract after SPE, and extract after SPE and acidification) were compared with each other and with the results obtained with the Klein and Alder method. The extraction efficiencies of the QuEChERS method were far higher, and the sample preparation was much quicker when the last two steps were omitted. In most cases, the extraction efficiencies after the first step were approximately 100%. With extraction efficiencies of mostly less than 70%, the Klein and Alder method did not compare favorably. Some analytes caused problems during evaluation, mostly due to matrix influences.

Diels-Alder functionalized carbon nanotubes for bone tissue engineering: in vitro/in vivo biocompatibility and biodegradability

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Mata, D.; Amaral, M.; Fernandes, A. J. S.; Colaço, B.; Gama, A.; Paiva, M. C.; Gomes, P. S.; Silva, R. F.; Fernandes, M. H.

2015-05-01

The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT membranes (p,f-CNTs). The in vivo subcutaneously implanted materials showed a higher biological reactivity, thus inducing a slighter intense inflammatory response compared to non-functionalized CNT membranes (p-CNTs), but still showing a reduced cytotoxicity profile. Moreover, the in vivo biodegradation of CNTs was superior for p,f-CNT membranes, likely mediated by the oxidation-induced myeloperoxidase (MPO) in neutrophil and macrophage inflammatory milieus. This proves the biodegradability faculty of functionalized CNTs, which potentially avoids long-term tissue accumulation and triggering of acute toxicity. On the whole, the proposed Diels-Alder functionalization accounts for the improved CNT biological response in terms of the biocompatibility and biodegradability profiles. Therefore, CNTs can be considered for use in bone tissue engineering without notable toxicological threats.The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT

Illustrating the Utility of X-Ray Crystallography for Structure Elucidation through a Tandem Aldol Condensation/Diels-Alder Reaction Sequence

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Hoang, Giang T.; Kubo, Tomohiro; Young, Victor G., Jr.; Kautzky, Jacob A.; Wissinger, Jane E.

2015-01-01

Two introductory organic chemistry laboratory experiments are described based on the Diels-Alder reaction of 2,3,4,5-tetraphenylcyclopentadienone, which is synthesized prior to or in a one-pot reaction, with styrene. Students are presented with three possible products, the "endo" and "exo" diastereomers and the decarbonylated…

Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

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Flores-Conde, Maria Ines; Reyes, Leonor; Herrera, Rafael; Rios, Hulme; Vazquez, Miguel A.; Miranda, Rene; Tamariz, Joaquin; Delgado, Francisco

2012-01-01

Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17), under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO) calculations. PMID:22489113

Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

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Francisco Delgado

2012-02-01

Full Text Available Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17, under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO calculations.

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

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Katrina L Callender

Full Text Available Phytotechnologies are rapidly replacing conventional ex-situ remediation techniques as they have the added benefit of restoring aesthetic value, important in the reclamation of mine sites. Alders are pioneer species that can tolerate and proliferate in nutrient-poor, contaminated environments, largely due to symbiotic root associations with the N2-fixing bacteria, Frankia and ectomycorrhizal (ECM fungi. In this study, we investigated the growth of two Frankia-inoculated (actinorhizal alder species, A. crispa and A. glutinosa, in gold mine waste rock from northern Quebec. Alder species had similar survival rates and positively impacted soil quality and physico-chemical properties in similar ways, restoring soil pH to neutrality and reducing extractable metals up to two-fold, while not hyperaccumulating them into above-ground plant biomass. A. glutinosa outperformed A. crispa in terms of growth, as estimated by the seedling volume index (SVI, and root length. Pyrosequencing of the bacterial 16S rRNA gene for bacteria and the ribosomal internal transcribed spacer (ITS region for fungi provided a comprehensive, direct characterization of microbial communities in gold mine waste rock and fine tailings. Plant- and treatment-specific shifts in soil microbial community compositions were observed in planted mine residues. Shannon diversity and the abundance of microbes involved in key ecosystem processes such as contaminant degradation (Sphingomonas, Sphingobium and Pseudomonas, metal sequestration (Brevundimonas and Caulobacter and N2-fixation (Azotobacter, Mesorhizobium, Rhizobium and Pseudomonas increased over time, i.e., as plants established in mine waste rock. Acetate mineralization and most probable number (MPN assays showed that revegetation positively stimulated both bulk and rhizosphere communities, increasing microbial density (biomass increase of 2 orders of magnitude and mineralization (five-fold. Genomic techniques proved useful in

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

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Sambasivarao Kotha

2015-07-01

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

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

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Kotha, Sambasivarao; Ravikumar, Ongolu

2015-01-01

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

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

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

2015-11-01

A robust synthetic strategy of biopolymer-based hydrogels has been developed where hyaluronic acid derivatives reacted through aqueous Diels-Alder chemistry without the involvement of chemical catalysts, allowing for control and sustain release of dexamethasone. To conjugate the hydrogel, furan and maleimide functionalized hyaluronic acid were synthesized, respectively, as well as furan functionalized dexamethasone, for the covalent immobilization. Chemical structure, gelation time, morphologies, swelling kinetics, weight loss, compressive modulus and dexamethasone release of the hydrogel system in PBS at 37°C were studied. The results demonstrated that the aqueous Diels-Alder chemistry provides an extremely selective reaction and proceeds with high efficiency for hydrogel conjugation and covalent immobilization of dexamethasone. Cell culture results showed that the dexamethasone immobilized hydrogel was noncytotoxic and preserved proliferation of entrapped human adipose-derived stem cells. This synthetic approach uniquely allows for the direct fabrication of biologically functionalized gel scaffolds with ideal structures for adipose tissue engineering, which provides a competitive alternative to conventional conjugation techniques such as copper mediated click chemistry. Copyright © 2015. Published by Elsevier B.V.

Vegetation in the Flood Plain Adjacent to the Mississippi River between Cairo, Illinois, and St. Paul, Minnesota, and in the Flood Plain of the Illinois River between Grafton, Illinois, and Chicago, and the Possible Impacts That Will Result from the Construction of L & D 26 and the Associated Increase in Barge Traffic,

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1975-01-20

and pecan ( Carya illinoensis ). In the southernmost region of the study area (i.e., Alexander and Union counties, Illinois), swamp cottonwood is a...ash (Fraxinus lanceolata), pecan ( Carya illinoensis ), box elder (Acer negundo), and red mulberry (Morus rubra). Shrubs occurring in the Silver Maple...americana), green ash (Fraxinus lanceolata), pecan ( Carya illinoensis ), sugarberry (Celtis laevigata), and red mulberry (Morus rubra). Also

C2-symmetric bisamidines: Chiral Brønsted bases catalysing the Diels-Alder reaction of anthrones

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2008-08-01

Full Text Available C2-symmetric bisamidines 8 have been tested as chiral Brønsted bases in the Diels-Alder reaction of anthrones and N-substituted maleimides. High yields of cycloadducts and significant asymmetric inductions up to 76% ee are accessible. The proposed mechanism involves proton transfer between anthrone and bisamidine, association of the resulting ions and finally a cycloaddition step stereoselectively controlled by the chiral ion pair.

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

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

2017-05-22

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. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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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.

Synthesis and Computational Studies Demonstrate the Utility of an Intramolecular Styryl Diels-Alder Reaction and Di-t-butylhydroxytoluene Assisted [1,3]-Shift to Construct Anticancer dl-Deoxypodophyllotoxin.

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Saavedra, Diana I; Rencher, Benjamin D; Kwon, Doo-Hyun; Smith, Stacey J; Ess, Daniel H; Andrus, Merritt B

2018-02-16

Deoxypodophyllotoxin is a secondary metabolite lignan possessing potent anticancer activity with potential as a precursor for known anticancer drugs, but its use is limited by scarcity from natural sources. We here report the total synthesis of racemic deoxypodophyllotoxin in seven steps using an intramolecular styryl Diels-Alder reaction strategy uniquely suited to assemble the deoxypodophyllotoxin core. Density functional theory was used to analyze concerted, polar, and singlet-open-shell diradical reaction pathways, which identified a low-energy concerted [4 + 2] Diels-Alder pathway followed by a faster di-t-butylhydroxytoluene assisted [1,3]-formal hydrogen shift.

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

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Sexton, Thomas; Kraka, Elfi; Cremer, Dieter

2016-02-25

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

Mono- and polyadducts of C60 with anthracenes by Diels-Alder-reactions

International Nuclear Information System (INIS)

Duarte-Ruiz, A.

2000-09-01

This work describes the synthesis and characterization of seven new mono-adducts of 9-methylanthracene, 9,10-dimethylanthracene, 9-bromoanthracene. 2,3,6,7-tetramethylanthracene, 1-methylanthracene, 2,6-di-tert-butylanthracen, as well as 2-methylanthracene to fullerene C60 in solution at r.t. by means of [4+2] Diels-Alder reactions. It could be shown that the mono-adducts with 9-methylanthracene, 9,10-dimethylanthracene, and 1-methylanthracene form the corresponding antipodal bis-adduct 'trans-1' on heating the solid to 180 o C. Furthermore the functionalization of fullerene C60 anthracene mono-adduct (C60C14H10) with anthracene through [4+2] Diels-Alder reactions was investigated which made it possible to separate and to characterize the five possible bis-adducts ('trans-1', 'trans-2', 'trans-3', 'trans-4', and 'e') that can form when the second anthracene adds either 'trans' to the opposite hemisphere (compared to the first addition of anthracene) or to an equatorial position. An exact identification of the bis-adducts 'trans-2' and 'trans-4' could only be acquired with spectroscopic methods, fortunately the bis-adducts 'trans-4', 'trans-3', and 'e' could also be examined by x-ray, thus all five could be fully characterized. No bis-adducts on the same hemisphere ('cis') were found. UV/VIS-spectra of the bis-adducts opened up the possibility to identify other [4+2] Diels-Alder products in the future. It has been noticed that the eluation sequence of the bis-adducts ('trans-1' before 'trans-2' before 'trans-4' before 'trans-3' before 'e') doesn't strictly correlate with the dipole moments. Furthermore six new tris-adducts ('t4t4t2', 't3t3t3', 't3t3t4', 'et3t2', 'et3t4', and 'eee') and one tetra-adduct ('eeet3') were separated and characterized. The tris-adduct 't3t3t3' was additionally characterized by x-ray which showed that the crystal contains only one enatiomer. All bis- and tris-adducts form the antipodal bis-adduct 'trans-1' on heating to 180 o C for 10 min

Ambrosia Beetle (Coleoptera: Scolytidae) Species, Flight, and Attack on Living Eastern Cottonwood Trees.

Energy Technology Data Exchange (ETDEWEB)

Coyle, D R; D.C. Booth: M.S. Wallace

2005-12-01

ABSTRACT In spring 2002, ambrosia beetles (Coleoptera: Scolytidae) infested an intensively managed 22-ha tree plantation on the upper coastal plain of South Carolina. Nearly 3,500 scolytids representing 28 species were captured in ethanol-baited traps from 18 June 2002 to 18 April 2004. More than 88% of total captures were exotic species. Five species [Dryoxylon onoharaensum (Murayama), Euwallacea validus (Eichhoff), Pseudopityophthorus minutissimus (Zimmermann), Xyleborus atratus Eichhoff, and Xyleborus impressus Eichhoff]) were collected in South Carolina for the first time. Of four tree species in the plantation, eastern cottonwood, Populus deltoides Bartram, was the only one attacked, with nearly 40% of the trees sustaining ambrosia beetle damage. Clone ST66 sustained more damage than clone S7C15. ST66 trees receiving fertilization were attacked more frequently than trees receiving irrigation, irrigation_fertilization, or controls, although the number of S7C15 trees attacked did not differ among treatments. The study location is near major shipping ports; our results demonstrate the necessity for intensive monitoring programs to determine the arrival, spread, ecology, and impact of exotic scolytids.

Accumulation of 137Cs and 90Sr in wood and bark of various types of oak and black alder plantings

International Nuclear Information System (INIS)

Perevolotskij, A.N.; Bulavik, I.M.; Perevolotskaya, T.V.; Paskrobko, L.A.; Andrush, S.N.

2008-01-01

Results of the evaluation of the influence of types of habitat edaphic conditions on 137Cs and 90Sr transition coefficients and their accumulation by wood and bark of English oak (Quercus robur L.) and black alder (Alnus glutinosa (L.) Gaertn) were presented. There was observed the particular influence of edaphic conditions on 137Cs and 90Sr accumulation by wood and bark of English oak. Lowering of 137Cs transition coefficients for the studied elements of phytomass was noted in the conditions of soil fertility increasing. Influence of soil moistening on 137Cs transition into wood and bark of oak trees was stated only in wood-sorrel and glague types of forests. Differences in accumulation of 90Sr by wood and bark of English oak in the studied range of edaphotopes were not proved. There was not found any differences in accumulation of both radionuclides by black alder trees in the typical for them edaphic conditions

Asymmetric Diels-Alder Reaction of α-Substituted and β,β-Disubstituted α,β-Enals via Diarylprolinol Silyl Ether for the Construction of All-Carbon Quaternary Stereocenters.

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Hayashi, Yujiro; Bondzic, Bojan P; Yamazaki, Tatsuya; Gupta, Yogesh; Ogasawara, Shin; Taniguchi, Tohru; Monde, Kenji

2016-10-24

The asymmetric Diels-Alder reaction of α-substituted acrolein proceeds in the presence of the trifluoroacetic acid salt of trifluoromethyl-substituted diarylprolinol silyl ether to afford the exo-isomer with both excellent diastereoselectivity and high enantioselectivity. In the Diels-Alder reaction of a β,β-disubstituted α,β-unsaturated aldehyde, good exo-selectivity and excellent enantioselectivity was obtained when the perchloric acid salt of the bulky triisopropyl silyl ether of trifluoromethyl substituted diarylprolinol was employed as an organocatalyst in the presence of water. In both cases, all-carbon quaternary stereocenters are constructed enantioselectively. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An intermolecular Diels-Alder cycloaddition under various condition between 1,3-cyclohexadiene and 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate

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Özgür Yılmaz

2017-10-01

Full Text Available The reaction between 1,3-cyclohexadiene and dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate both without a catalyst and with different catalysts, in both atmospheric and at high pressure, over 20 days were studied. At the end of the reactions, different products (retro Diels-Alder addition product 5 and Diels-Alder addition product 6 were obtained in different yields. When we look at the percentage of the addition product, it is observed that the yield of reaction at high pressure in water is the highest. All structures of these products were characterized by 1H-NMR, 13C-NMR, MS, and IR spectroscopy.

Stable elements and radionuclides in shoreline alder stands at Olkiluoto in 2005

International Nuclear Information System (INIS)

Roivainen, P.

2006-08-01

In Finland, the final disposal of spent nuclear fuel from Finnish nuclear power plants is to take place in a repository, which will be built in Olkiluoto bedrock. According to the current plans, operation of the facility will start in 2020. Before this, a safety case has to be drawn up to substantiate the safety of the final disposal solution. The drawing up of the safety case also involves an assessment of impact on organisms other than human. Several radionuclides have a stable chemical analogue. Chemical analogues often display similar behaviour in the forest ecosystem. For this reason, information about radionuclides can also be obtained by studying stable elements. The purpose of this thesis was to study the migration of elements, radionuclides in particular, in the food webs of the Olkiluoto forest ecosystem. The objective was to produce concentration ratios between the various sub-components of the forest ecosystem. These ratios can be utilised in modelling. Three alder stands on the shores of Olkiluoto were used as monitoring plots. Littoral alder stands are an important biotope in terms of a recipient of the potential radionuclide contamination from the repository. Yet, research on littoral alder stands has so far been quite limited. From all the monitoring plots, a sample was taken of humus, mineral soil, understorey, plant roots and forest litter. Small mammals and earthworms were also to be caught from the monitoring plots, but no earthworms could be caught in any of the areas. All the collected samples were analysed for element concentrations using the ICP-AES method. Soil and plant samples were also analysed with a gamma spectrometer for activity concentrations of gamma active radionuclides. Activity concentrations of Cs-137 and K-40 could be determined in all soil and plant samples. The highest activity concentration of Cs-137 was found in humus, and the lowest in mineral soil. The activity concentration of K-40 was at its highest in mineral soil and

A Tunable and Enantioselective Hetero-Diels-Alder Reaction Provides Access to Distinct Piperidinoyl Spirooxindoles.

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Jayakumar, Samydurai; Louven, Kathrin; Strohmann, Carsten; Kumar, Kamal

2017-12-11

The active complexes of chiral N,N'-dioxide ligands with dysprosium and magnesium salts catalyze the hetero-Diels-Alder reaction between 2-aza-3-silyloxy-butadienes and alkylidene oxindoles to selectively form 3,3'- and 3,4'-piperidinoyl spirooxindoles, respectively, in very high yields and with excellent enantioselectivities. The exo-selective asymmetric cycloaddition successfully regaled the construction of sp 3 -rich and highly substituted natural-product-based spirooxindoles supporting many chiral centers, including contiguous all-carbon quaternary centers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies toward the synthesis of palhinine lycopodium alkaloids: a Morita-Baylis-Hillman/intramolecular Diels-Alder approach.

Science.gov (United States)

Sizemore, Nicholas; Rychnovsky, Scott D

2014-02-07

A synthetic route to the isotwistane core of palhinine lycopodium alkaloids is described. A Morita-Baylis-Hillman/intramolecular Diels-Alder (IMDA) strategy sets the vicinal all-carbon quaternary centers present in this family of natural products. The regioselectivity of the IMDA reaction is dictated by the conditions employed for silyl enol ether formation, with one set of conditions providing the core of cardionine and alternate conditions generating the desired isotwistane core of isopalhinine.

Peak discharge, flood frequency, and peak stage of floods on Big Cottonwood Creek at U.S. Highway 50 near Coaldale, Colorado, and Fountain Creek below U.S. Highway 24 in Colorado Springs, Colorado, 2016

Science.gov (United States)

Kohn, Michael S.; Stevens, Michael R.; Mommandi, Amanullah; Khan, Aziz R.

2017-12-14

The U.S. Geological Survey (USGS), in cooperation with the Colorado Department of Transportation, determined the peak discharge, annual exceedance probability (flood frequency), and peak stage of two floods that took place on Big Cottonwood Creek at U.S. Highway 50 near Coaldale, Colorado (hereafter referred to as “Big Cottonwood Creek site”), on August 23, 2016, and on Fountain Creek below U.S. Highway 24 in Colorado Springs, Colorado (hereafter referred to as “Fountain Creek site”), on August 29, 2016. A one-dimensional hydraulic model was used to estimate the peak discharge. To define the flood frequency of each flood, peak-streamflow regional-regression equations or statistical analyses of USGS streamgage records were used to estimate annual exceedance probability of the peak discharge. A survey of the high-water mark profile was used to determine the peak stage, and the limitations and accuracy of each component also are presented in this report. Collection and computation of flood data, such as peak discharge, annual exceedance probability, and peak stage at structures critical to Colorado’s infrastructure are an important addition to the flood data collected annually by the USGS.The peak discharge of the August 23, 2016, flood at the Big Cottonwood Creek site was 917 cubic feet per second (ft3/s) with a measurement quality of poor (uncertainty plus or minus 25 percent or greater). The peak discharge of the August 29, 2016, flood at the Fountain Creek site was 5,970 ft3/s with a measurement quality of poor (uncertainty plus or minus 25 percent or greater).The August 23, 2016, flood at the Big Cottonwood Creek site had an annual exceedance probability of less than 0.01 (return period greater than the 100-year flood) and had an annual exceedance probability of greater than 0.005 (return period less than the 200-year flood). The August 23, 2016, flood event was caused by a precipitation event having an annual exceedance probability of 1.0 (return

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

Science.gov (United States)

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

2016-09-23

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

Bicyclic Guanidine Catalyzed Asymmetric Tandem Isomerization Intramolecular-Diels-Alder Reaction: The First Catalytic Enantioselective Total Synthesis of (+)-alpha-Yohimbine.

Science.gov (United States)

Feng, Wei; Jiang, Danfeng; Kee, Choon-Wee; Liu, Hongjun; Tan, Choon-Hong

2016-02-04

Hydroisoquinoline derivatives were prepared in moderate to good enantioselectivities via a bicyclic guanidine-catalyzed tandem isomerization intramolecular-Diels-Alder (IMDA) reaction of alkynes. With this synthetic method, the first enantioselective synthesis of (+)-alpha-yohimbine was completed in 9 steps from the IMDA products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

Reactivity of Single-Walled Carbon Nanotubes in the Diels-Alder Cycloaddition Reaction: Distortion-Interaction Analysis along the Reaction Pathway.

Science.gov (United States)

Li, Yingzi; Osuna, Sílvia; Garcia-Borràs, Marc; Qi, Xiaotian; Liu, Song; Houk, Kendall N; Lan, Yu

2016-08-26

Diels-Alder cycloaddition is one of the most powerful tools for the functionalization of single-walled carbon nanotubes (SWCNTs). Density functional theory at the B3-LYP level of theory has been used to investigate the reactivity of different-diameter SWCNTs (4-9,5) in Diels-Alder reactions with 1,3-butadiene; the reactivity was found to decrease with increasing SWCNT diameter. Distortion/interaction analysis along the whole reaction pathway was found to be a better way to explore the reactivity of this type of reaction. The difference in interaction energy along the reaction pathway is larger than that of the corresponding distortion energy. However, the distortion energy plots for these reactions show the same trend. Therefore, the formation of the transition state can be determined from the interaction energy. A lower interaction energy leads to an earlier transition state, which indicates a lower activation energy. The computational results also indicate that the original distortion of the SWCNTs leads to an increase in the reactivity of the SWCNTs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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Stefan Bräse

2012-08-01

Full Text Available 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.

Fast Hetero-Diels-Alder Reactions Using 4-Phenyl-1,2,4-Triazoline-3,5-Dione (PTAD) as the Dienophile

Science.gov (United States)

Celius, Tevye C.

2010-01-01

A hetero-Diels-Alder reaction that proceeds rapidly and only requires a simple filtration to purify the product is presented. The dienophile, 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), is prepared by the heterogeneous oxidation of 4-phenylurazole by the bromenium ion, Br[superscript +], generated in situ by the oxidation of potassium bromide by…

Petasis/Diels-Alder/Cyclization Cascade Reactions for the Generation of Scaffolds with Multiple Stereogenic Centers and Orthogonal Handles for Library Production

DEFF Research Database (Denmark)

Flagstad, Thomas; Azevedo, Carlos M. G.; Min, Geanna

2018-01-01

A new effective strategy for the synthesis of sp3‐rich small molecules for library production is presented. The key steps to generate complexity highlight Petasis 3‐component reaction followed by an intramolecular Diels‐Alder and cyclization to generate a densely enriched tricyclic or tetracyclic...

A Catalyst-Enabled Diastereodivergent Aza-Diels-Alder Reaction: Complementarity of N-Heterocyclic Carbenes and Chiral Amines.

Science.gov (United States)

Rong, Zi-Qiang; Wang, Min; Chow, Chi Hao Eugene; Zhao, Yu

2016-07-04

Highly efficient and diastereodivergent aza-Diels-Alder reactions have been developed to access either diastereomeric series of benzofuran-fused δ-lactams and dihydropyridines in nearly perfect stereoselectivity (d.r. >20:1, >99 % ee for all examples). The complementarity of N-heterocyclic carbene and chiral amine as the catalyst was demonstrated for the first time, together with an excellent level of catalytic efficiency (1 mol % loading). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of stimuli-responsive chitosan-based hydrogels by Diels-Alder cross-linking `click´ reaction as potential carriers for drug administration.

Science.gov (United States)

Guaresti, O; García-Astrain, C; Aguirresarobe, R H; Eceiza, A; Gabilondo, N

2018-03-01

Stimuli-responsive chitosan-based hydrogels for biomedical applications using the Diels-Alder reaction were prepared. Furan modified chitosan (Cs-Fu) was cross-linked with polyetheramine derived bismaleimide at different equivalent ratios in order to determine the effect in the swelling and release properties on the final CsFu:BMI hydrogels. The Diels Alder cross-linking reaction was monitored by UV-vis spectroscopy and rheological measurements. Both the sol-gel transition value and the final storage modulus for the different formulations were similar and close to 40 min and 400 Pa, respectively. On the contrary, the swelling degree was found to be strongly dependent on the amount of bismaleimide, mainly in acidic medium, where the increased cross-linking reduced the swelling value in 25%, but maintaining the sustained drug release in the simulated gastrointestinal environment. Our study suggested that these DA-cross-linked chitosan hydrogels could be potential carriers for targeted drug administration. Copyright © 2017 Elsevier Ltd. All rights reserved.

A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives

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Hamzehloueian Mahshid

2014-01-01

Full Text Available The present study reports a systematic computational analysis of the two possible pathways, fused and bridged, for an intramolecular hetero Diels-Alder (IMHDA and an intramolecular 1,3-dipolar cycloaddition (IMDCA of 2-vinyloxybenzaldehyde derivatives. The potential energy surface analysis for both reactions is in agreement with experimental observations. The activation energies associated with the two regioisomeric channels in IMHDA reaction show that the bridged product is favored, although in IMDCA, the most stable TS results the fused product. The global electronic properties of fragments within each molecule were studied to discuss the reactivity patterns and charge transfer direction in the intramolecular processes. The asynchronicity of the bond formation and aromaticity of the optimized TSs in the Diels-Alder reaction as well as cycloaddition reaction were evaluated. Finally, 1H NMR chemical shifts of the possible regioisomers have been calculated using the GIAO method which of the most stable products are in agreement with the experimental data in the both reaction.

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

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Mujeeb A. Sultan

2016-09-01

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

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

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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-2 H -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.

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

Science.gov (United States)

Beniwal, Vijay; Manna, Arpan; Kumar, Anil

2016-07-04

The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A computational study of the Diels Alder reactions involving acenes: reactivity and aromaticity

Science.gov (United States)

Cheng, Mei-Fun; Li, Wai-Kee

2003-01-01

Ab initio and DFT methods have been used to study the Diels-Alder reactivity and the aromaticity of four linear acenes, namely, naphthalene, anthracene, tetracene and pentacene. In total, eight additional pathways between ethylene and four acenes have been studied and all of them are concerted and exothermic reactions. It is found that the most reactive sites on the acenes are the center ring's meso-carbons. Also, reactivity decreases along the series pentacene > tetracene > anthracene > naphthalene. In addition, the NICS results indicate that the most reactive rings in the acenes are those with the highest aromaticity. These results are consistent with those of other theoretical studies and experiments.

Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

KAUST Repository

Yang, Limin

2014-08-01

A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations. © 2014 American Chemical Society.

A hetero retro Diels-Alder reaction in aqueous solution : A dramatic water-induced increase of the equilibrium constant and inhibition of cycloreversion

NARCIS (Netherlands)

Wijnen, J.W; Engberts, J.B.F.N.

The adduct of the Diels-Alder reaction of nitrosobenzene with cyclopentadiene is not stable in solution. The equilibrium constant for the reaction depends strongly on the medium and water induces a spectacular shift to the adduct. Comparison with the bimolecular addition of nitrosobenzene to

Microwave- assisted solvent-free Diels-Alder reaction – a fast and simple route to various 5,6-substituted norbornenes and polychlorinated norbornenes

Czech Academy of Sciences Publication Activity Database

Dejmek, Milan; Hřebabecký, Hubert; Šála, Michal; Dračínský, Martin; Nencka, Radim

-, č. 24 (2011), s. 4077-4083 ISSN 0039-7881 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : Diels - Alder reaction * polychlorinated norbornanes * norbornene Subject RIV: CC - Organic Chemistry Impact factor: 2.466, year: 2011

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

Science.gov (United States)

Kotha, Sambasivarao; Gunta, Rama

2015-01-01

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

Pyrolysis and Combustion Kinetics of Raw and Carbonized Cottonwood and Switchgrass Agroforests

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Sammy Sadaka

2015-06-01

Full Text Available Raw biomass is not commonly suitable as feedstock for existing power plants, mainly because of the substantial required infrastructural changes. As a result, most raw feedstock requires pre-treatment to improve its physical and thermal characteristics. Biomass carbonization is one of the pre-treatments that produces charcoal-like feedstock. This paper explores the effects of the carbonization process on the physiochemical characteristics of biomass produced from two cottonwood clones, S7C20 and ST66, and switchgrass (var. Alamo. Additionally, it studies the thermal degradation kinetics of raw and carbonized agroforestry products in nitrogen and air environments. Feedstock samples were carbonized in a batch reactor at 400 °C in an oxygen-free environment for 2 hours. Carbonization decreased biomass bulk density, moisture content, and volatile solids while increasing fixed carbon, ash content, pH, and heating values. The heating value of S7C20, ST66, and switchgrass increased by 58.6%, 60.3%, and 69.7%, respectively. Carbonization increased the activation energy values under the condition of pyrolysis and decreased these values under the condition of combustion. The carbonization process produced a charcoal-like feedstock that may be processed with coal or even replace it.

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

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Lucie Brulíková

2016-09-01

Full Text Available 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.

Recreational Appendix Report, Elm Fork Flood Control Project, Dallas and Denton Counties, Texas.

Science.gov (United States)

1973-05-01

Juniperus virginiana 2. Willow Salix nigra 3. Cottonwood Populus deltoides 4. Black Walnut Juglans migra 5. Pecan Carya illinoensis 6. Bur Oak...Maclura pomifera 12. Red Mulberry Morus rubra 13. Sycamore Platanus occidentailis 14. Red Haw Crataegus, sps. 15. Wild Plum Prunus mexicana 16. Mesquite...also provides a habitat for a number of mammals including: 1. Opossum Didelphis virginiana 2. Shrews Blarina brevicuada and Cryptotis parva 3. Raccoon

Studies on the interactions of 5-R-3-(2-pyridyl)-1,2,4-triazines with arynes: inverse demand aza-Diels-Alder reaction versus aryne-mediated domino process.

Science.gov (United States)

Kopchuk, Dmitry S; Nikonov, Igor L; Khasanov, Albert F; Giri, Kousik; Santra, Sougata; Kovalev, Igor S; Nosova, Emiliya V; Gundala, Sravya; Venkatapuram, Padmavathi; Zyryanov, Grigory V; Majee, Adinath; Chupakhin, Oleg N

2018-05-02

The interactions between substituted 5-R-3-(pyridyl-2)-1,2,4-triazines with in situ generated substituted aryne intermediates have been studied. The reaction afforded either inverse demand (ID) aza-Diels-Alder products or 1,2,4-triazine ring rearrangement (domino) products as major ones depending on the nature of both the substituents at the C5 position of the 1,2,4-triazine core or in the aryne moiety. The structures of the key products were confirmed based on X-ray data. Based on the density functional theoretical (DFT) studies of the Diels-Alder transition state geometries, the influence of the nature of arynes on the direction of the 1,2,4-triazine transformation has been proposed.

Integration of Computational and Preparative Techniques to Demonstrate Physical Organic Concepts in Synthetic Organic Chemistry: An Example Using Diels-Alder Reaction

Science.gov (United States)

Palmer, David R. J.

2004-01-01

The Diels-Alder reaction is used as an example for showing the integration of computational and preparative techniques, which help in demonstrating the physical organic concepts in synthetic organic chemistry. These experiments show that the students should not accept the computational results without questioning them and in many Diels-Alder…

The Synthesis of "N"-Benzyl-2-Azanorbornene via Aqueous Hetero Diels-Alder Reaction: An Undergraduate Project in Organic Synthesis and Structural Analysis

Science.gov (United States)

Sauvage, Xavier; Delaude, Lionel

2008-01-01

The synthesis of "N"-benzyl-2-azanorbornene via aqueous hetero Diels-Alder reaction of cyclopentadiene and benzyliminium chloride formed in situ from benzylamine hydrochloride and formaldehyde is described. Characterization of the product was achieved by IR and NMR spectroscopies. The spectral data acquired are thoroughly discussed. Numerous…

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

Science.gov (United States)

Zhao, Pei; Zhao, Xiang; Ehara, Masahiro

2016-09-16

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

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

Science.gov (United States)

Shiramizu, Mika; Toste, F Dean

2011-10-24

Polyethylene terephthalate (PET) is a polymeric material with high global demand. Conventionally, PET is produced from fossil-fuel-based materials. Herein, we explored the feasibility of a sustainable method for PET production by using solely bio-renewable resources. Specifically, 2,5-dimethylfuran (derived from lignocellulosic biomass through 5-(hydroxymethyl)furfural) and acrolein (produced from glycerol, a side product of biodiesel production) were converted into the key intermediate p-xylene (a precursor of terephthalic acid). This synthesis consists of a sequential Diels-Alder reaction, oxidation, dehydration, and decarboxylation. In particular, the pivotal first step, the Diels-Alder reaction, was studied in detail to provide useful kinetic and thermodynamic data. Although it was found that this reaction requires low temperature to proceed efficiently, which presents a limitation on economic feasibility on an industrial scale, the concept was realized and bio-derived p-xylene was obtained in 34% overall yield over four steps. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Asymmetric Diels–Alder reaction with >C=P– functionality of the 2-phosphaindolizine-η1-P-aluminium(O-menthoxy dichloride complex: experimental and theoretical results

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Rajendra K. Jangid

2013-02-01

Full Text Available The Diels–Alder reaction of the 2-phosphaindolizine-η1-P-aluminium(O-menthoxy dichloride complex with dimethylbutadiene was investigated experimentally and computationally. The >C=P– functionality of the complex reacts with 2,3-dimethylbutadiene with complete diastereoselectivity to afford [2 + 4] cycloadducts. Calculation of the model substrate, 3-methoxycarbonyl-1-methyl-2-phosphaindolizine-P-aluminium(O-menthoxy dichloride (7a, at the DFT (B3LYP/6-31+G* level reveals that the O-menthoxy moiety blocks the Re face of the >C=P– functionality, due to which the activation barrier of the Diels–Alder reaction of 7a with 1,3-butadiene, involving its attack from the Si face, is lower. It is found that in this case, the exo approach of the diene is slightly preferred over the endo approach.

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

Science.gov (United States)

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.

Performance of Asian longhorned beetle among tree species

Science.gov (United States)

Kelli Hoover; Scott Ludwig; James Sellmer; Deborah McCullough; Laura Lazarus

2003-01-01

Two procedures were evaluated for assessing susceptibility of a variety of tree species to Anoplophora glabripennis. In the first procedure, adult beetles were caged with a section of sugar maple, northern red oak, white oak, honeylocust, eastern cottonwood, sycamore or tulip poplar wood and allowed to oviposit.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

Alder and the Golden Fleece: high diversity of Frankia and ectomycorrhizal fungi revealed from Alnus glutinosa subsp. barbata roots close to a Tertiary and glacial refugium

Directory of Open Access Journals (Sweden)

Melanie Roy

2017-07-01

Full Text Available Background Recent climatic history has strongly impacted plant populations, but little is known about its effect on microbes. Alders, which host few and specific symbionts, have high genetic diversity in glacial refugia. Here, we tested the prediction that communities of root symbionts survived in refugia with their host populations. We expected to detect endemic symbionts and a higher species richness in refugia as compared to recolonized areas. Methods We sampled ectomycorrhizal (EM root tips and the nitrogen-fixing actinomycete Frankia communities in eight sites colonized by Alnus glutinosa subsp. barbata close to the Caucasus in Georgia. Three sites were located in the Colchis, one major Eurasian climatic refugia for Arcto-Tertiary flora and alders, and five sites were located in the recolonized zone. Endemic symbionts and plant ITS variants were detected by comparing sequences to published data from Europe and another Tertiary refugium, the Hyrcanian forest. Species richness and community structure were compared between sites from refugia and recolonized areas for each symbionts. Results For both symbionts, most MOTUs present in Georgia had been found previously elsewhere in Europe. Three endemic Frankia strains were detected in the Colchis vs two in the recolonized zone, and the five endemic EM fungi were detected only in the recolonized zone. Frankia species richness was higher in the Colchis while the contrary was observed for EM fungi. Moreover, the genetic diversity of one alder specialist Alnicola xanthophylla was particularly high in the recolonized zone. The EM communities occurring in the Colchis and the Hyrcanian forests shared closely related endemic species. Discussion The Colchis did not have the highest alpha diversity and more endemic species, suggesting that our hypothesis based on alder biogeography may not apply to alder’s symbionts. Our study in the Caucasus brings new clues to understand symbioses biogeography and

Insight into the informational-structure behavior of the Diels-Alder reaction of cyclopentadiene and maleic anhydride.

Science.gov (United States)

Molina-Espíritu, Moyocoyani; Esquivel, Rodolfo O; Kohout, Miroslav; Angulo, Juan Carlos; Dobado, José A; Dehesa, Jesús S; LópezRosa, Sheila; Soriano-Correa, Catalina

2014-08-01

The course of the Diels-Alder reactions of cyclopentadiene and maleic anhydride were studied. Two reaction paths were modelled: endo- and exo-selective paths. All structures within the transient region were characterized and analyzed by means of geometrical descriptors, physicochemical parameters and information-theoretical measures in order to observe the linkage between chemical behavior and the carriage of information. We have shown that the information-theoretical characterization of the chemical course of the reaction is in complete agreement with its phenomenological behavior in passing from reactants to products. In addition, we were able to detect the main differences between the two reaction mechanisms. This type of informational analysis serves to provide tools to help understand the chemical reactivity of the two simplest Diels-Alder reactions, which permits the establishment of a connection between the quantum changes that molecular systems exert along reaction coordinates and standard physicochemical phenomenology. In the present study, we have shown that every reaction stage has a family of subsequent structures that are characterized not solely by their phenomenological behavior but also by informational properties of their electronic density distribution (localizability, order, uniformity). Moreover, we were able to describe the main differences between endo-adduct and exo-adduct pathways. With the advent of new experimental techniques, it is in principle possible to observe the structural changes in the transient regions of chemical reactions. Indeed, through this work we have provided the theoretical concepts needed to unveil the concurrent processes associated with chemical reactions.

Cultural Resources Survey and Testing Along Ditch 19 and Extensive Testing of 23DU289, Dunklin and Stoddard Counties, Missouri.

Science.gov (United States)

1988-06-30

Carya illinoensis ) 1 1 Persimmon (Diospyros virginiana) T 2 2 Pl.um (Prunus sp.) T Red Haw (Crataegus sp.) T 1 11 Red Mulberry (Morus rubra) T...2 Cherry (Prunus sp.) T Cottonwood (Populus sp.) 1 3 Dogwood (Cornus sp.) 1 Hackberry (Celtus occidentalis) 12 9 Hickory, ( Carya sp.) 5 4 Shellhark... Carya laciniosa) T Hornbeam (Ostrya virginiana) 2 Kentucky Coffee Tree( Gymnoeladus dioica)T Locust, T Black (Robinia pseudo-acacia) T Honey

Molecular Design of a Chiral Brønsted Acid with Two Different Acidic Sites: Regio-, Diastereo-, and Enantioselective Hetero-Diels-Alder Reaction of Azopyridinecarboxylate with Amidodienes Catalyzed by Chiral Carboxylic Acid-Monophosphoric Acid.

Science.gov (United States)

Momiyama, Norie; Tabuse, Hideaki; Noda, Hirofumi; Yamanaka, Masahiro; Fujinami, Takeshi; Yamanishi, Katsunori; Izumiseki, Atsuto; Funayama, Kosuke; Egawa, Fuyuki; Okada, Shino; Adachi, Hiroaki; Terada, Masahiro

2016-09-07

A chiral Brønsted acid containing two different acidic sites, chiral carboxylic acid-monophosphoric acid 1a, was designed to be a new and effective concept in catalytic asymmetric hetero-Diels-Alder reactions of azopyridinecarboxylate with amidodienes. The multipoint hydrogen-bonding interactions among the carboxylic acid, monophosphoric acid, azopyridinecarboxylate, and amidodiene achieved high catalytic and chiral efficiency, producing substituted 1,2,3,6-tetrahydropyridazines with excellent stereocontrol in a single step. This constitutes the first example of regio-, diastereo-, and enantioselective azo-hetero-Diels-Alder reactions by chiral Brønsted acid catalysis.

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

Directory of Open Access Journals (Sweden)

Javier Miró

2015-08-01

Full Text Available 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.

An Inverse Electron Demand Azo-Diels-Alder Reaction of o-Quinone Methides and Imino Ethers: Synthesis of Benzocondensed 1,3-Oxazines.

Science.gov (United States)

Osipov, Dmitry V; Osyanin, Vitaly A; Khaysanova, Guzel' D; Masterova, Elvira R; Krasnikov, Pavel E; Klimochkin, Yuri N

2018-04-20

We have studied the reactions of o-quinone methide precursors with imino ethers. The reaction provides a versatile route to substituted 1,3-benzoxazines. The proposed reaction mechanism involves the generation of the o-quinone methide intermediates, imino-Diels-Alder reaction, and elimination. This cascade process is a rare example of the participation of imino ethers as dienophiles.

Imino Diels-Alder-Based Construction of a Piperidine A-Ring Unit for Total Synthesis of the Marine Hepatotoxin Cylindrospermopsin.

Science.gov (United States)

Heintzelman, Geoffrey R.; Weinreb, Steven M.; Parvez, Masood

1996-07-12

The synthesis of a piperidine A-ring precursor to the alkaloid cylindrospermopsin (1) is described. The initial approach to the A-ring precursor focused on the imino Diels-Alder reaction of diene 8 with ethyl (N-tosylimino)acetate (9) to form the cycloadduct 10 as a single stereoisomer. However, all attempts to convert ester 10 to a requisite diene such as 5 were unsuccessful. An alternative strategy involved the Diels-Alder cycloaddition of N-tosylimine 9 with oxygenated diene 19 under either thermal or Lewis acid-catalyzed conditions to produce a mixture of cis and trans enones 20 and 21. Although the undesired cis-enone 20 was the major product under all reaction conditions, it could be converted to the desired trans enone 21 by acid-catalyzed isomerization. Copper-mediated conjugate addition of vinylmagnesium bromide to cis-enone 20 followed by stereoselective ketone reduction with L-Selectride produced alcohol 23, whose structure was confirmed by X-ray crystallography. Similarly, trans-enone 21 was converted to alcohol 25 whose structure and stereochemistry were also established by X-ray analysis. Alcohol 25 was then protected as the silyl ether 26, which was hydroborated at the terminal olefin to produce primary alcohol ester 28having the stereochemistry and functionality needed for cylindrospermopsin.

Grafting methyl acrylic onto carbon fiber via Diels-Alder reaction for excellent mechanical and tribological properties of phenolic composites

Science.gov (United States)

Fei, Jie; Duan, Xiao; Luo, Lan; Zhang, Chao; Qi, Ying; Li, Hejun; Feng, Yongqiang; Huang, Jianfeng

2018-03-01

Carbon fibers (CFs) were grafted with methyl acrylic via Diels-Alder reaction at the different oil bath temperature effectively creating a carboxyl functionalized surface. The effect of grafting temperature on the surface morphology and functional groups of carbon fibers were investigated by FTIR, Raman spectroscopy, XPS and SEM respectively. The results showed that the optimal grafting temperature was 80 °C, and the relative surface coverage by carboxylic acid groups increased from an initial 5.16% up to 19.30% significantly improved the chemical activity without damaging the skin and core region of the carbon fibers. Mechanical property tests indicated that the shear and tensile strength of the sample with the grafting temperature of 80 °C (CFRP-3) increased obviously by 90.3% and 78.7%, respectively, compared with the pristine carbon fibers reinforced composite. Further, the sample CFRP-3 exhibited higher and more stable friction coefficient and improved wear resistance, while the wear rate decreased 52.7%, from 10.8 × 10-6 to 5.1 × 10-6 mm3/N m. The present work shows that grafting methyl acrylic via Diels-Alder reaction could be a highly efficient and facile method to functionalize carbon fibers for advanced composites.

Syntheses of the hexahydroindene cores of indanomycin and stawamycin by combinations of iridium-catalyzed asymmetric allylic alkylations and intramolecular Diels-Alder reactions.

Science.gov (United States)

Gärtner, Martin; Satyanarayana, Gedu; Förster, Sebastian; Helmchen, Günter

2013-01-02

Short and concise syntheses of the hexahydroindene cores of the antibiotics indanomycin (X-14547 A) and stawamycin are presented. Key methods used are an asymmetric iridium-catalyzed allylic alkylation, a modified Julia olefination, a Suzuki-Miyaura coupling, and an intramolecular Diels-Alder reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of cyclopentadienyl capped polyethylene and subsequent block copolymer formation via hetero Diels-Alder (HDA) chemistry.

Science.gov (United States)

Espinosa, Edgar; Glassner, Mathias; Boisson, Christophe; Barner-Kowollik, Christopher; D'Agosto, Franck

2011-09-15

In the current contribution it is demonstrated - for the first time - that poly(ethylene) (M(n) = 1,400 as well as 2,800 g  ·  mol(-1) , PDI = 1.2) can be readily equipped with highly reactive cyclopentadienyl (Cp) end groups. The Cp terminal poly(ethylene) can subsequently be reacted in an efficient hetero Diels-Alder (HDA) reaction with macromolecules (poly(isobornyl acrylate) (M(n) = 4,600 g  ·  mol(-1) , PDI = 1.10) and poly(styrene) (M(n) = 6,300 g  ·  mol(-1) , PDI = 1.13) featuring strongly electron withdrawing thiocarbonyl thio end groups, prepared via reversible addition fragmentation chain transfer (RAFT) polymerization employing benzylpyridin-2-yldithioformate (BPDF) as transfer agent. The resulting block copolymers have been analyzed via high-temperature size exclusion chromatography (SEC) as well as nuclear magnetic resonance (NMR) spectroscopy. The current system allows for the removal of the excess of the non-poly(ethylene) containing segment via filtration of the poly(ethylene)-containing block copolymer. However, the reaction temperatures need to be judiciously selected. Characterization of the generated block copolymers at elevated temperatures can lead - depending on the block copolymer type - to the occurrence of retro Diels-Alder processes. The present study thus demonstrates that RAFT-HDA ligation can be effectively employed for the generation of block copolymers containing poly(ethylene) segments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Pyrrolo[1,2-a]pyrimidine Enantiomers via Domino Ring-Closure followed by Retro Diels-Alder Protocol

Directory of Open Access Journals (Sweden)

Beáta Fekete

2017-04-01

Full Text Available From 2-aminonorbornene hydroxamic acids, a simple and efficient method for the preparation of pyrrolo[1,2-a]pyrimidine enantiomers is reported. The synthesis is based on domino ring-closure followed by microwave-induced retro Diels-Alder (RDA protocols, where the chirality of the desired products is transferred from norbornene derivatives. The stereochemistry of the synthesized compounds was proven by X-ray crystallography. The absolute configuration of the product is determined by the configuration of the starting amino hydroxamic acid.

Cross-conjugated Trienamine Catalysis with α'-Alkylidene 2-Cyclohexenones: Application in β,γ-Regioselective Aza-Diels-Alder Reaction.

Science.gov (United States)

Zhou, Zhi; Wang, Zhou-Xiang; Ouyang, Qin; Xiao, Wei; Du, Wei; Chen, Ying-Chun

2017-02-24

Endo-type cross-conjugated trienamines between highly congested α'-alkylidene 2-cyclohexenones and a chiral primary amine catalyst serve as HOMO-raised dienophiles in inverse-electron-demand aza-Diels-Alder cycloadditions with a number of 1-azadiene substrates. The reactions exhibit exclusive β,γ-regioselectivity, and multifunctional products with high molecular complexity are efficiently constructed in excellent diastereo- and enantioselectivity (>19:1 d.r., up to 99 % ee). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Pyrrolo[1,2-a]pyrimidine Enantiomers via Domino Ring-Closure followed by Retro Diels-Alder Protocol.

Science.gov (United States)

Fekete, Beáta; Palkó, Márta; Haukka, Matti; Fülöp, Ferenc

2017-04-13

From 2-aminonorbornene hydroxamic acids, a simple and efficient method for the preparation of pyrrolo[1,2- a ]pyrimidine enantiomers is reported. The synthesis is based on domino ring-closure followed by microwave-induced retro Diels-Alder (RDA) protocols, where the chirality of the desired products is transferred from norbornene derivatives. The stereochemistry of the synthesized compounds was proven by X-ray crystallography. The absolute configuration of the product is determined by the configuration of the starting amino hydroxamic acid.

Nitroso Diels-Alder (NDA) Reaction as an Efficient Tool for the Functionalization of Diene-Containing Natural Products

Science.gov (United States)

Carosso, Serena; Miller, Marvin J.

2014-01-01

This review describes the use of nitroso Diels-Alder reactions for the functionalization of complex diene-containing natural products in order to generate libraries of compounds with potential biological activity. The application of this methodology to the structural modification of a series of natural products (thebaine, steroidal dienes, rapamycin, leucomycin, colchicine, isocolchicine and piperine) is discussed using relevant examples from the literature from 1973 onwards. The biological activity of the resulting compounds is also discussed. Additional comments are provided that evaluate the methodology as a useful tool in organic, bioorganic and medicinal chemistry. PMID:25119424

Ground states of molecules. XLIX. MINDO/3 study of the retro-diels-alder reaction of cyclohexene

International Nuclear Information System (INIS)

Dewar, M.J.S.; Olivella, S.; Rzepa, H.S.

1978-01-01

The retro-Diels-Alder reaction of cyclohexene to form ethylene and butadiene has been studied, using MINDO/3. The transition state is predicted to be very unsymmetric, corresponding to weakening of one of the two breaking CC bonds. The calculated entropy of activation agrees well with experiment and the calculated secondary isotope effects for 4,4-dideuteriocyclohexene and 4,4,5,5-tetradeuteriocyclohexene are similar to those measured for an analogous reaction by Taagepera and Thornton. Discrepancies between the conclusions reached here and those from recent ab-initio calculations are discussed. 4 tables, 3 figures, 53 references

Black Willow

Science.gov (United States)

R. M. Krinard

1980-01-01

Black willow and other species of Salix together comprise a majority of the stocking. Cottonwood is the chief associate, particularly in the early stages, but green ash, sycamore, pecan, persimmon, waterlocust, American elm, baldcypress, red maple, sugarberry, box-elder, and in some areas, silver maple are invaders preceding the next successional stage.

High Pressure Diels Alder Reactions of 1-Vinyl-2,2,6-trimethylcyclohexene Catalyzed by Chiral Lewis Acids; An Enantioselective Route to a Drimane Sesquiterpene Precursor.

NARCIS (Netherlands)

Knol, Joop; Meetsma, Auke; Feringa, Bernard

1995-01-01

The Diels Alder reaction of 1-vinyl-2,2,6-trimethylcyclohexene and 3-((E)-3-(methoxycarbonyl)propenoyl)-1,3-oxazolidin-2-one under high pressure, catalyzed by a chiral bis-imine copper(II) complex, yields a drimane sesquiterpene precursor in a highly regio- and diastereoselective manner with

Blue-Emitting Arylalkynyl Naphthalene Derivatives via a Hexadehydro-Diels-Alder Cascade Reaction.

Science.gov (United States)

Xu, Feng; Hershey, Kyle W; Holmes, Russell J; Hoye, Thomas R

2016-10-05

We describe here three alkynyl substituted naphthalenes that display promising luminescence characteristics. Each compound is easily and efficiently synthesized in three steps by capitalizing on the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction in which an intermediate benzyne is captured by tetraphenylcyclopentadienone, a classical trap for benzyne itself. These compounds luminesce in the deep blue when stimulated either optically (i.e., photoluminescence in both solution and solid films) or electrically [in a light-emitting diode (LED)]. The photophysical properties are relatively insensitive to the electronic nature of the substituents (H, OMe, CO 2 Me) that define these otherwise identical compounds. Overall, our observations suggest that the twisted nature of the five adjacent aryl groups serves to minimize the intermolecular interaction between core naphthalene units in different sample morphologies. These compounds represent promising leads for the identification of others of value as the emissive component of organic LEDs (OLEDs).

Magnetically Separable Iron Oxide Nanoparticles: An Efficient and Reusable Catalyst for Imino Diels-Alder Reaction

Energy Technology Data Exchange (ETDEWEB)

Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull [Yeungnam University, Gyeongsan (Korea, Republic of)

2016-02-15

Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.

Magnetically Separable Iron Oxide Nanoparticles: An Efficient and Reusable Catalyst for Imino Diels-Alder Reaction

International Nuclear Information System (INIS)

Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull

2016-01-01

Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.

Irreversible endo-Selective Diels–Alder Reactions of Substituted Alkoxyfurans: A General Synthesis of endo-Cantharimides

Science.gov (United States)

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

2015-01-01

The [4+2] cycloaddition of 3-alkoxyfurans with N-substituted maleimides provides the first general route for preparing endo-cantharimides. Unlike the corresponding reaction with 3H furans, the reaction can tolerate a broad range of 2-substitued furans including alkyl, aromatic, and heteroaromatic groups. The cycloaddition products were converted into a range of cantharimide products with promising lead-like properties for medicinal chemistry programs. Furthermore, the electron-rich furans are shown to react with a variety of alternative dienophiles to generate 7-oxabicyclo[2.2.1]heptane derivatives under mild conditions. DFT calculations have been performed to rationalize the activation effect of the 3-alkoxy group on a furan Diels–Alder reaction. PMID:25756502

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

Energy Technology Data Exchange (ETDEWEB)

Do, Phuong T. M. [Univ. of Delaware, Newark, DE (United States); McAtee, Jesse R. [Univ. of Delaware, Newark, DE (United States); Watson, Donald A. [Univ. of Delaware, Newark, DE (United States); Lobo, Raul F. [Univ. of Delaware, Newark, DE (United States)

2012-12-12

The reaction of 2,5-dimethylfuran and ethylene to produce p-xylene represents a potentially important route for the conversion of biomass to high-value organic chemicals. Current preparation methods suffer from low selectivity and produce a number of byproducts. Using modern separation and analytical techniques, the structures of many of the byproducts produced in this reaction when HY zeolite is employed as a catalyst have been identified. From these data, a detailed reaction network is proposed, demonstrating that hydrolysis and electrophilic alkylation reactions compete with the desired Diels–Alder/dehydration sequence. This information will allow the rational identification of more selective catalysts and more selective reaction conditions.

Inverse-Electron-Demand Diels-Alder Reactions: Principles and Applications.

Science.gov (United States)

Png, Zhuang Mao; Zeng, Huining; Ye, Qun; Xu, Jianwei

2017-09-05

Inverse-electron-demand Diels-Alder (iEDDA) reactions are an intriguing class of cycloaddition reactions that have attracted increasing attention for their application in bioorthogonal chemistry, the total synthesis of natural products, and materials science. In many cases, the application of the iEDDA reaction has been demonstrated as an innovative approach to achieve target structures. The theoretical aspects of this class of reactions are of particular interest for scientists as a means to understand the various factors, such as steric strain and electron density of the attached groups, that govern the reaction and thus to elucidate the reaction mechanism. This review aims to summarize both theoretical investigations and application-driven research work on the iEDDA reaction. First, the historical aspects and the theoretical basis of the reaction, especially recent advances in time-dependent density functional theory (TD-DFT) calculations, as well as catalysis strategies will be highlighted and discussed. Second, the applications of this novel reaction in the context of materials science, bioorthogonal chemistry, and total synthesis of natural products will be elaborated with selected recent examples. The challenges and opportunities of the iEDDA reaction will be highlighted to give more insight into its potential applications in many other research areas. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bio-orthogonal Fluorescent Labelling of Biopolymers through Inverse-Electron-Demand Diels-Alder Reactions.

Science.gov (United States)

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.

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

Science.gov (United States)

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.

T3P- A Novel Catalyst for Aza-Diels-Alder Reaction: One-Pot Synthesis of Pyrano[3,2-c]quinolines and furano[3,2-c]quinolines

Directory of Open Access Journals (Sweden)

T. S. R. Prasanna

2011-01-01

Full Text Available T3P was found to be an efficient catalyst for the Aza-Diels–Alder reactions of aldimines with dihydropyran or dihydrofuran to afford the corresponding pyrano-and furo [3,2-c]quinolines in high yields with high diastereoselectivity in a short period of time.

Synthesis of a Self-Healing Polymer Based on Reversible Diels-Alder Reaction: An Advanced Undergraduate Laboratory at the Interface of Organic Chemistry and Materials Science

Science.gov (United States)

Weizman, Haim; Nielsen, Christian; Weizman, Or S.; Nemat-Nasser, Sia

2011-01-01

This laboratory experiment exposes students to the chemistry of self-healing polymers based on a Diels-Alder reaction. Students accomplish a multistep synthesis of a monomer building block and then polymerize it to form a cross-linked polymer. The healing capability of the polymer is verified by differential scanning calorimetry (DSC) experiments.…

Novel UTP derivative with diene-containing spacer arm for Diels-Alder reaction: potential tool for radioactive or fluorescent detection upon its incorporation into ribonucleic acid

Czech Academy of Sciences Publication Activity Database

Točík, Zdeněk; Krásný, Libor; Kovačková, Soňa; Rejman, Dominik; Rosenberg, Ivan

2007-01-01

Roč. 6, č. 5 (2007), s. 357 ISSN 1535-3508. [International Conference of the European Society for Molecular Imaging /2./. 14.06.2007-15.06.2007, Naples] Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50520701 Keywords : UTP derivative * Diels - Alder reaction * diene * spacer arm Subject RIV: CC - Organic Chemistry

Epoxy-Functionalized Porous Organic Polymers via the Diels-Alder Cycloaddition Reaction for Atmospheric Water Capture.

Science.gov (United States)

Byun, Yearin; Coskun, Ali

2018-03-12

The synthesis of highly microporous, epoxy-functionalized porous organic polymers (ep-POPs) by a one-pot, catalyst-free Diels-Alder cycloaddition polymerization is reported. The high oxygen content of ep-POPs offer efficient hydrogen-bonding sites for water molecules, thus leading to high water-uptake capacities up to 39.2-42.4 wt % under a wide temperature range of 5-45 °C, which covers the span of climatic conditions and manufacturing applications in which such materials might be used. Importantly, ep-POPs demonstrated regeneration temperatures as low as 55 °C, as well as excellent water stability, recyclability, and high specific surface areas up to 852 m 2  g -1 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatic catalysis of a Diels-Alder reaction

Science.gov (United States)

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.

Tandem Reaction of Cationic Copolymerization and Concertedly Induced Hetero-Diels-Alder Reaction Preparing Sequence-Regulated Polymers.

Science.gov (United States)

Matsumoto, Suzuka; Kanazawa, Arihiro; Kanaoka, Shokyoku; Aoshima, Sadahito

2017-06-14

A unique tandem reaction of sequence-controlled cationic copolymerization and site-specific hetero-Diels-Alder (DA) reaction is demonstrated. In the controlled cationic copolymerization of furfural and 2-acetoxyethyl vinyl ether (AcOVE), only the furan ring adjacent to the propagating carbocation underwent the hetero-DA reaction with the aldehyde moiety of another furfural molecule. A further and equally important feature of the copolymerization is that the obtained copolymers had unprecedented 2:(1 + 1)-type alternating structures of repeating sequences of two VE and one furfural units in the main chain and one furfural unit in the side chain. The specific DA reaction is attributed to the delocalization of the positive charge to the side furan ring.

Diels-Alder reactions for the rational design of benzo[b]thiophenes: DFT-based guidelines for synthetic chemists

Science.gov (United States)

Brasca, Romina; Kneeteman, María N.; Mancini, Pedro M. E.; Fabian, Walter M. F.

2012-02-01

In this work we studied the capability of several diene/dienophile pairs to undergo Diels-Alder (DA) reactions leading to benzo[b]thiophenes. A variety of synthetically and commercially available nitrothiophenes were chosen as dienophiles. Methyl 5-nitro-3-thiophenecarboxylate was selected as a potential strong electrophilic candidate based on some DFT-based properties and the substitution pattern of the expected product. The mechanistic details concerning the participation of this dienophile in polar DA reactions were investigated through a theoretical point of view. The results were compared with the experimental outcomes. This methodology should allow synthetic chemists to analyze DA reactions in detail in a stage prior to the synthetic job.

Development of a channel classification to evaluate potential for cottonwood restoration, lower segments of the Middle Missouri River, South Dakota and Nebraska

Science.gov (United States)

Jacobson, Robert B.; Elliott, Caroline M.; Huhmann, Brittany L.

2010-01-01

This report documents development of a spatially explicit river and flood-plain classification to evaluate potential for cottonwood restoration along the Sharpe and Fort Randall segments of the Middle Missouri River. This project involved evaluating existing topographic, water-surface elevation, and soils data to determine if they were sufficient to create a classification similar to the Land Capability Potential Index (LCPI) developed by Jacobson and others (U.S. Geological Survey Scientific Investigations Report 2007–5256) and developing a geomorphically based classification to apply to evaluating restoration potential.Existing topographic, water-surface elevation, and soils data for the Middle Missouri River were not sufficient to replicate the LCPI. The 1/3-arc-second National Elevation Dataset delineated most of the topographic complexity and produced cumulative frequency distributions similar to a high-resolution 5-meter topographic dataset developed for the Lower Missouri River. However, lack of bathymetry in the National Elevation Dataset produces a potentially critical bias in evaluation of frequently flooded surfaces close to the river. High-resolution soils data alone were insufficient to replace the information content of the LCPI. In test reaches in the Lower Missouri River, soil drainage classes from the Soil Survey Geographic Database database correctly classified 0.8–98.9 percent of the flood-plain area at or below the 5-year return interval flood stage depending on state of channel incision; on average for river miles 423–811, soil drainage class correctly classified only 30.2 percent of the flood-plain area at or below the 5-year return interval flood stage. Lack of congruence between soil characteristics and present-day hydrology results from relatively rapid incision and aggradation of segments of the Missouri River resulting from impoundments and engineering. The most sparsely available data in the Middle Missouri River were water

Survival and growth for pubescent birch, pendula birch and common alder growing on farmland areas; Oeverlevnad och tillvaext hos glasbjoerk, vaartbjoerk och klibbal planterade paa aakermark

Energy Technology Data Exchange (ETDEWEB)

Johansson, Tord

2000-07-01

Pendula birches (Betula pendula Roth) and pubescent birches (Betula pubescens Ehrh.) were planted on former farmland. Before planting, the ground was harrowed or the ground was sprayed with terbuthylazine. Tree shelters were used as protection against weeds, voles and wild habitat. Birches treated with terbuthylazine showed the lowest survival. Birches growing in tree shelters were tallest and those growing on spots treated with terbuthylazine were smallest. The diameter at 0.1 m did not differ in a statistically significant way between the treatments. In another experiment with different herbicides, common alder (Alnus glutinosa (L.) Gaertn.) and pendula birch (Betula pendula Roth) were planted on former farmland that had been treated with glyphosate, terbuthylazine and propyzamide or after ground had been harrowed or not treated. In the study on herbicide-treated plants, birch had the highest plant survival. Mostly, species treated with glyphosate were thicker than species treated in other ways. Both species appeared sensitive to terbuthylazine, but not to glyphosate. Birch was not sensitive for propyzamide in opposite to alder. Some practical recommendations concerning afforestation of former farmland, especially weeding, are given.

The Role of Phytodiversity in Riparian Alder Forests in Supporting the Provision of Ecosystem Services

Directory of Open Access Journals (Sweden)

Mariničová Patrícia

2016-11-01

Full Text Available Nature, ecosystems and biodiversity provide human society with many benefits known as ecosystem services. Functional diversity is an important aspect of biodiversity. In this paper, we applied inductive approach to the identification, mapping and evaluation of ecosystem services of the Aegopodio-Alnetum glutinosae community in Tribeč Mts. The results from 2015 show that the alder floodplain forest represents one of the most productive forest ecosystems with seasonal maximum production of 59.03 g m−2, species diversity of N0 = 40 and functional diversity of FD = 10. The forage potential of this community is medium, the melliferous potential is high and the therapeutic potential was estimated as extremely rich in medicinal plants. From the functional groups for providing ecosystem services, woody plants and hemicryptophytes play the most significant role.

P-chiral 1-phosphanorbornenes: from asymmetric phospha-Diels-Alder reactions towards ligand design and functionalisation.

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Möller, Tobias; Wonneberger, Peter; Sárosi, Menyhárt B; Coburger, Peter; Hey-Hawkins, Evamarie

2016-02-07

The principle of stereotopic face differentiation was successfully applied to 2H-phospholes which undergo a very efficient and highly stereoselective Diels-Alder reaction giving phosphorus-chiral 1-phosphanorbornenes with up to 87% yield. The observed reaction pathway has been supported by theoretical calculations showing that the cycloaddition reaction between 2H-phosphole 3a and the dienophile (5R)-(-)-menthyloxy-2(5H)-furanone (8) is of normal electron demand. Optically pure phosphanes were obtained by separation of the single diastereomers and subsequent desulfurisation of the sulfur-protected phosphorus atom. Finally, divergent ligand synthesis is feasible by reduction of the chiral auxiliary, subsequent stereospecific intramolecular Michael addition, and various functionalisations of the obtained key compound 13a. Furthermore, the unique structural properties of phospanorbornenes are presented and compared to those of phosphanorbornanes.

Computational Investigation of the Competition between the Concerted Diels-Alder Reaction and Formation of Diradicals in Reactions of Acrylonitrile with Non-Polar Dienes

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James, Natalie C.; Um, Joann M.; Padias, Anne B.; Hall, H. K.; Houk, K. N.

2013-01-01

The energetics of the Diels-Alder cycloaddition reactions of several 1,3-dienes with acrylonitrile, and the energetics of formation of diradicals, were investigated with density functional theory (B3LYP and M06-2X) and compared to experimental data. For the reaction of 2,3-dimethyl-1,3-butadiene with acrylonitrile, the concerted reaction is favored over the diradical pathway by 2.5 kcal/mol using B3LYP/6-31G(d); experimentally this reaction gives both cycloadduct and copolymer. The concerted cycloaddition of cyclopentadiene with acrylonitrile is preferred computationally over the stepwise pathway by 5.9 kcal/mol; experimentally, only the Diels-Alder adduct is formed. For the reactions of (E)-1,3-pentadiene and acrylonitrile, both cycloaddition and copolymerization were observed experimentally; these trends were mimicked by the computational results, which showed only a 1.2 kcal/mol preference for the concerted pathway. For the reactions of (Z)-1,3-pentadiene and acrylonitrile, the stepwise pathway is preferred by 3.9 kcal/mol, in agreement with previous experimental findings that only polymerization occurs. M06-2X is known to give more accurate activation and reaction energetics but the energies of diradicals are too high. PMID:23758325

Spatial variation in population dynamics of Sitka mice in floodplain forests.

Science.gov (United States)

T.A. Hanley; J.C. Barnard

1999-01-01

Population dynamics and demography of the Sitka mouse, Peromyscus keeni sitkensis, were studied by mark-recapture live-trapping over a 4-year period in four floodplain and upland forest habitats: old-growth Sitka spruce (Picea sitchensis) floodplain; red alder (Alnus rubra) floodplain; beaver-pond...

25 CFR 309.12 - What are examples of basketry that are Indian products?

Science.gov (United States)

2010-04-01

... to, birchbark, black ash, brown ash, red cedar, yellow cedar, alder, vine maple, willow, palmetto..., willow burden baskets, honeysuckle sewing baskets, black ash picnic baskets, cedar capes and dresses... containers, baleen baskets, rye grass dance fans, brown ash strawberry baskets, sumac wedding baskets, cedar...

Enantioselective Diels-Alder Reaction Using Chiral Mg Complexes Derived from Chiral 2-[2-[(Alkyl- or 2-[2-[(Arylsulfonyl)amino]phenyl]-4-phenyl-1,3-oxazoline.

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Ichiyanagi, Tsuyoshi; Shimizu, Makoto; Fujisawa, Tamotsu

1997-11-14

Magnesium complexes derived from (R)-2-[2-[(alkyl- or (R)-2-[2-[(arylsulfonyl)amino]phenyl]-4-phenyl-1,3-oxazolines and methylmagnesium iodide were found to be efficient Lewis acid catalysts for the Diels-Alder reaction of 3-alkenoyl-1,3-oxazolidin-2-one with cyclopentadiene. Chiral ligands were easily prepared from readily available D-phenylglycinol in good yields. The reaction of 3-acryloyl-1,3-oxazolidin-2-one with cyclopentadiene catalyzed by a stoichiometric amount of the Lewis acid gave exclusively the endo-cycloaddition product in up to 92% ee. The sulfonamide group on the chiral ligand strongly influenced the enantiofacial selectivity: the use of a toluene-, benzene-, 1- or 2-naphthalene-, or methanesulfonamide group in the chiral ligand gave the endo-(2R)-cycloaddition product, while a trifluoromethanesulfonamide group predominantly gave its enantiomer, the endo-(2S)-cycloaddition product, in 65% ee. The scope and limitations of the catalytic effect of chiral Mg(II) complexes on the enantioselectivity of the Diels-Alder reaction were investigated. The reaction mechanism of the Mg(II)-catalyzed reaction is also discussed on the basis of the experimental results.

The Brønsted Acid-Catalyzed, Enantioselective Aza-Diels-Alder Reaction for the Direct Synthesis of Chiral Piperidones.

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Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph

2017-01-12

We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Classical Example of Total Kinetic and Thermodynamic Control: The Diels-Alder Reaction between DMAD and Bis-furyl Dienes.

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Borisova, Kseniya K; Kvyatkovskaya, Elizaveta A; Nikitina, Eugeniya V; Aysin, Rinat R; Novikov, Roman A; Zubkov, Fedor I

2018-04-20

A rare example of chemospecificity in the tandem Diels-Alder reaction of activated alkynes and bis-dienes has been revealed. The reaction between bis-furyl dienes and DMAD occurs at 25-80 °C and leads to kinetically controlled "pincer" adducts, 4a,8a-disubstituted 1,4:5,8-diepoxynaphthalenes. On the contrary, only thermodynamically controlled "domino" adducts (2,3-disubstituted 1,4:5,8-diepoxynaphthalenes) are formed in the same reaction at 140 °C. The "pincer" adducts can be transformed to the "domino" adducts at heating. The rate constants for reactions of both types were calculated using dynamic 1 H NMR spectroscopy.

Tree mortality in mature riparian forest: Implications for Fremont cottonwood conservation in the American southwest

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Andersen, Douglas

2015-01-01

Mature tree mortality rates are poorly documented in desert riparian woodlands. I monitored deaths and calculated annual survivorship probability (Ps) in 2 groups of large (27–114 cm DBH), old (≥40 years old) Fremont cottonwood (Populus fremontii Wats.) in a stand along the free-flowing Yampa River in semiarid northwestern Colorado. Ps = 0.993 year-1 in a group (n = 126) monitored over 2003–2013, whereas Ps = 0.985 year-1 in a group (n = 179) monitored over the same period plus 3 earlier years (2000–2003) that included drought and a defoliating insect outbreak. Assuming Ps was the same for both groups during the 10-year postdrought period, the data indicate that Ps = 0.958 year-1 during the drought. I found no difference in canopy dieback level between male and female survivors. Mortality was equal among size classes, suggesting Ps is independent of age, but published longevity data imply that either Ps eventually declines with age or, as suggested in this study, periods with high Ps are interrupted by episodes of increased mortality. Stochastic population models featuring episodes of low Ps suggest a potential for an abrupt decline in mature tree numbers where recruitment is low. The modeling results have implications for woodland conservation, especially for relictual stands along regulated desert rivers.

1-acetylvinyl acrylates: new captodative olefins bearing an internal probe for the evaluation of the relative reactivity of captodative against electron-deficient double bonds in Diels-Alder and Friedel-Crafts reactions

International Nuclear Information System (INIS)

Herrera, Rafael; Universidad Michoacana de San Nicolas de Hidalgo, Morelia, Mich.; Jimenez-Vazquez, Hugo A.; Delgado, Francisco; Tamariz, Joaquin; Soederberg, Bjoern C.G.

2005-01-01

The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemo selectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/6-311G(d,p) calculations. (author)

Environmental and Water Quality Operational Studies. Reservoir Shoreline Revegetation Guidelines.

Science.gov (United States)

1986-11-01

24. Taller trees such as green ash, cottonwood (Populus spp.), red maple (Acer rubrum), and persimmon (Diospyros virginiana ) should be planted in...be left aboveground to prevent moisture loss due to wicking. Any excess should be pruned off. Gray and Leiser (1982) provide the following... pruning , staking woody stems, and installing fencing around individual plants or the entire site to provide protection from animals or humans. Additional

Phylloplane bacteria increase the negative impact of food limitation on insect fitness

NARCIS (Netherlands)

Olson, Grant L.; Myers, Judith H.; Hemerik, Lia; Cory, Jenny S.

2017-01-01

1. When populations of herbivorous insects increase in density, they can alter the quantity or quality of their food. The impacts of diet-related stressors on insect fitness have been investigated singly, but not simultaneously. 2. Foliage quantity and quality of red alder, Alnus rubra, were

A Pyrene-Linked Cavity within a β-Barrel Protein Promotes an Asymmetric Diels-Alder Reaction.

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Himiyama, Tomoki; Taniguchi, Naomasa; Kato, Shunsuke; Onoda, Akira; Hayashi, Takashi

2017-10-23

A unique π-expanded reaction cavity tethering a polycyclic moiety which provides a platform for substrate binding was constructed within the robust β-barrel structure of nitrobindin (NB). NB variants with cavities of different sizes and shapes are coupled with N-(1-pyrenyl)maleimide (Pyr) to prepare a series of NB-Pyr conjugates. The orientation of the pyrene moiety is fixed within the cavity by the coupling reaction. The fluorescent quenching analysis of NB-Pyr indicates that azachalcone (aza), which is a dienophile for a Diels-Alder (DA) reaction, is efficiently incorporated within the pyrene-linked reaction cavity by the aromatic interaction. The DA reaction between aza and cyclopentadiene proceeds within the reaction cavity of NB-Pyr in the presence of Cu II ion in high yield and high enantio- and regioselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Syntheses of the Stemona Alkaloids (±)-Stenine, (±)-Neostenine, and (±)-13-Epineostenine Using a Stereodivergent Diels-Alder/Azido-Schmidt Reaction

Science.gov (United States)

Frankowski, Kevin J.; Golden, Jennifer E.; Zeng, Yibin; Lei, Yao; Aubé, Jeffrey

2009-01-01

A tandem Diels-Alder/azido Schmidt reaction sequence provides rapid access to the core skeleton shared by several Stemona alkaloids including stenine, neostenine, tuberstemonine, and neotubererostemonine. The discovery and evolution of inter- and intramolecular variations of this process and their applications to total syntheses of (±)–stenine and (±)–neostenine is described. The stereochemical outcome of the reaction depends on both substrate type and reaction condition, enabling the preparation of both (±)–stenine and (±)–neostenine from the same diene/dienophile combination. PMID:18396881

Diels-Alder Reactions of 12-Hydroxy-9(10®20-5aH-abeo-abieta-1(10,8(9,12(13-triene-11,14-dione

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Shougang Hu

2013-06-01

Full Text Available 12-Hydroxy-9(10®20-5aH-abeo-abieta-1(10,8(9,12(13-triene-11,14-dione (quinone 2 served as the dienophile in numerous intermolecular Diels-Alder reactions. These cycloadditions were conducted either thermally (including microwave heating or with Lewis acid activation. While most dienes reacted with quinone 2 in good chemical yield, others were incompatible under the experimental conditions used.

Determination of the suitability of chips from selected hardwoods for the production of furfural and charcoal. [Birches, beeches, oaks, alders

Energy Technology Data Exchange (ETDEWEB)

Piotrowski, Z

1979-01-01

Debarked, cut beech, birch, alder, and oak residues from forestry and woodworking operations contain 16.56-19.73% pentosans and as such can be used for hydrolysis to furfural (I). The hydrolytic residue (mostly lignocellulose) can be carbonized at 400 degrees to charcoal. The hydrolysis is carried out continuously with steam at 250-300 degrees and 1.18 MPa. The residue chips are first soaked in water at 90 degrees for 4 hours and then fed into the hydrolyzer countercurrently to the steam. The yields of I are 5-6% and the yields of charcoal are approximately 20% on the chip weight.

Artificial Metalloenzymes with the Neocarzinostatin Scaffold: Toward a Biocatalyst for the Diels-Alder Reaction.

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Ghattas, Wadih; Cotchico-Alonso, Lur; Maréchal, Jean-Didier; Urvoas, Agathe; Rousseau, Maëva; Mahy, Jean-Pierre; Ricoux, Rémy

2016-03-02

A copper(II) cofactor coupled to a testosterone anchor, copper(II)-(5-(Piperazin-1-yl)-1,10-phenanthroline)testosterone-17-hemisuccinamide (10) was synthesized and associated with a neocarzinostatin variant, NCS-3.24 (KD =3 μm), thus generating a new artificial metalloenzyme by following a "Trojan horse" strategy. Interestingly, the artificial enzyme was able to efficiently catalyze the Diels-Alder cyclization reaction of cyclopentadiene (1) with 2-azachalcone (2). In comparison with what was observed with cofactor 10 alone, the artificial enzymes favored formation of the exo products (endo/exo ratios of 84:16 and 62:38, respectively, after 12 h). Molecular modeling studies assigned the synergy between the copper complex and the testosterone (KD =13 μm) moieties in the binding of 10 to good van der Waals complementarity. Moreover, by pushing the modeling exercise to its limits, we hypothesize on the molecular grounds that are responsible for the observed selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substituent effects on an inverse electron demand hetero Diels-Alder reaction in aqueous solution and organic solvents : Cycloaddition of substituted styrenes to di(2-pyridyl)-1,2,4,5-tetrazine

NARCIS (Netherlands)

Wijnen, Jan W.; Zavarise, Silvia; Engberts, Jan B.F.N.; Charton, Marvin

1996-01-01

The kinetics of the Diels-Alder reactions of di(2-pyridyl)-1,2,4,5-tetrazine (1) with substituted styrenes 2 was investigated in aqueous media and in organic solvents. The second-order rate constants ofthis reaction increase dramatically in water-rich media. A decrease in pH accelerates the aqueous

C—C bond formation in the intramolecular Diels-Alder reaction of triene amides

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Abdelilah Benallou

2018-02-01

Full Text Available The mechanism nature of the intramolecular Diels–Alder reaction has been performed; and thus, the changes of C—C bond forming/breaking along IRC are characterized in this study. Conceptual DFT analyses of the most favorable adduct fused/exo shows that the flux electronic will take place from diene to dienophile moiety. Moreover, ELF topological analysis based on the electron density predicts that C—C bond is formed by the coupling of two pseudoradical centers generated at the most significant atoms of the molecules. However, C2 vs C3, also C1 and C4 interaction comes mainly from the global electron density transfer which takes place along the reaction. Two- stage one-step is the proposed mechanism of this reaction, the first stage aims for the formation of C2—C3 σ bond while the second stage aims for C1—C4 σ bond formation. Interestingly, the observed asynchronicity of this IMDA reaction due principally to the asymmetric reorganization of electron density at the most attractive centers.

C-C bond formation in the intramolecular Diels-Alder reaction of triene amides.

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Benallou, Abdelilah; El Alaoui El Abdallaoui, Habib; Garmes, Hocine

2018-02-01

The mechanism nature of the intramolecular Diels-Alder reaction has been performed; and thus, the changes of C-C bond forming/breaking along IRC are characterized in this study. Conceptual DFT analyses of the most favorable adduct fused/exo shows that the flux electronic will take place from diene to dienophile moiety. Moreover, ELF topological analysis based on the electron density predicts that C-C bond is formed by the coupling of two pseudoradical centers generated at the most significant atoms of the molecules. However, C2 vs C3, also C1 and C4 interaction comes mainly from the global electron density transfer which takes place along the reaction. Two- stage one-step is the proposed mechanism of this reaction, the first stage aims for the formation of C2-C3 σ bond while the second stage aims for C1-C4 σ bond formation. Interestingly, the observed asynchronicity of this IMDA reaction due principally to the asymmetric reorganization of electron density at the most attractive centers.

Organic chemistry of graphene: the Diels-Alder reaction.

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Denis, Pablo A

2013-11-11

Herein, by using dispersion-corrected density functional theory, we investigated the Diels-Alder chemistry of pristine and defective graphene. Three dienes were considered, namely 2,3-dimethoxy-1,3-butadiene (DMBD), 9-methylanthracene (9MA), and 9,10-dimethylanthracene (910DMA). The dienophiles that were assayed were tetracyanoethylene (TCNE) and maleic anhydride (MA). When pristine graphene acted as the dienophile, we found that the cycloaddition products were 47-63 kcal mol(-1) less stable than the reactants, thus making the reaction very difficult. The presence of Stone-Wales translocations, 585 double vacancies, or 555-777 reconstructed double vacancies did not significantly improve the reactivity because the cycloaddition products were still located at higher energy than the reactants. However, for the addition of 910DMA to single vacancies, the product showed comparable stability to the separated reactants, whereas for unsaturated armchair edges the reaction was extremely favorable. With regards the reactions with dienophiles, for TCNE, the cycloaddition product was metastable. In the case of MA, we observed a reaction product that was less stable than the reactants by 50 kcal mol(-1) . For the reactions between graphene as a diene and the dienophiles, we found that the most-promising defects were single vacancies and unsaturated armchair edges, because the other three defects were much-less reactive. Thus, we conclude that the reactions with these above-mentioned dienes may proceed on pristine or defective sheets with heating, despite being endergonic. The same statement also applies to the dienophile maleic anhydride. However, for TCNE, the reaction is only likely to occur onto single vacancies or unsaturated armchair edges. We conclude that the dienophile character of graphene is slightly stronger than its behavior as a diene. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Features of the Diels-Alder reaction between 9,10-diphenylanthracene and 4-phenyl-1,2,4-triazoline-3,5-dione

Science.gov (United States)

Kiselev, V. D.; Kornilov, D. A.; Kashaeva, E. A.; Potapova, L. N.; Krivolapov, D. B.; Litvinov, I. A.; Konovalov, A. I.

2014-12-01

The Diels-Alder reaction between substituted anthracenes 1a-1j and 4-phenyl-1,2,4-triazoline-3,5 ( 2) is studied. In all cases except one, the reaction proceeds on the most active 9,10-atoms of substituted anthracenes. The orthogonality of the two phenyl groups at the 9,10-position of diene 1a is found to shield 9,10-reactive centers. No dienophiles with C=C bonds are shown to participate in the Diels-Alder reaction with 1a; however, the reaction 1a + 2 proceeds with the very active dienophile 2,4-phenyl-1,2,4-triazoline-3,5-dione. It is shown that attachment occurs on the less active but sterically accessible 1,4-reactive center of diene 1a. The structure of adduct 3a is proved by 1H and 13C NMR spectroscopy and X-ray diffraction analysis. The following parameters are obtained for reaction 1a + 2 ⇆ 3a in toluene at 25°C: K eq = 2120 M-1, Δ Hf ≠ = 58.6 kJ/mol, Δ Sf ≠ = -97 J/(mol K), Δ Vf ≠ = -17.2 cm3/mol, Δ Hb ≠ = 108.8 kJ/mol, Δ Sb ≠ = 7.3 J/(mol K), Δ Vb ≠ = -0.8 cm3/mol, Δ H r-n = -50.2 kJ/mol, Δ S r-n = -104.3 J/(mol K), Δ V r-n = -15.6 cm3/mol. It is concluded that the values of equilibrium constants of the reactions 1a-1j + 2 ⇆ 3a-3j vary within 4 × 101-1011 M-1.

Higher-order human telomeric G-quadruplex DNA metalloenzymes enhance enantioselectivity in the Diels-Alder reaction.

Science.gov (United States)

Li, Yinghao; Jia, Guoqing; Wang, Changhao; Cheng, Mingpan; Li, Can

2015-03-02

Short human telomeric (HT) DNA sequences form single G-quadruplex (G4 ) units and exhibit structure-based stereocontrol for a series of reactions. However, for more biologically relevant higher-order HT G4 -DNAs (beyond a single G4 unit), the catalytic performances are unknown. Here, we found that higher-order HT G4 -DNA copper metalloenzymes (two or three G4 units) afford remarkably higher enantioselectivity (>90 % ee) and a five- to sixfold rate increase, compared to a single G4 unit, for the Diels-Alder reaction. Electron paramagnetic resonance (EPR) and enzymatic kinetic studies revealed that the distinct catalytic function between single and higher-order G4 -DNA copper metalloenzymes can be attributed to different Cu(II) coordination environments and substrate specificity. Our finding suggests that, like protein enzymes and ribozymes, higher-order structural organization is crucial for G4 -DNA-based catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[3+2] Cycloaddition of propargylic alcohols and α-oxo ketene dithioacetals: synthesis of functionalized cyclopentadienes and further application in a Diels-Alder reaction.

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Fang, Zhongxue; Liu, Jianquan; Liu, Qun; Bi, Xihe

2014-07-07

Cyclopentadienes are valuable intermediates in organic synthesis and also ubiquitous as the Cp ligands in organometallic chemistry. As part of ongoing efforts to develop novel organic reactions that employ functionalized alkynes, a [3+2] cycloaddition of propargylic alcohols and ketene dithioacetals has been developed, which leads to fully substituted 2,5-dialkylthio cyclopentadienes in good to excellent yields. In an unusual dethiolating Diels-Alder reaction, the cyclopentadienes were further reacted with maleimides to afford a family of novel fluorescent polycyclic compounds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An MM and QM Study of Biomimetic Catalysis of Diels-Alder Reactions Using Cyclodextrins

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Wei Chen

2018-01-01

Full Text Available We performed a computational investigation of the mechanism by which cyclodextrins (CDs catalyze Diels-Alder reactions between 9-anthracenemethanol and N-cyclohexylmaleimide. Hydrogen bonds (Hbonds between N-cyclohexylmaleimide and the hydroxyl groups of cyclodextrins were suggested to play an important role in this catalytic process. However, our free energy calculations and molecular dynamics simulations showed that these Hbonds are not stable, and quantum mechanical calculations suggested that the reaction is not promoted by these Hbonds. The binding of 9-anthracenemethanol and N-cyclohexylmaleimide to cyclodextrins was the key to the catalytic process. Cyclodextrins act as a container to hold the two reactants in the cavity, pre-organize them for the reactions, and thus reduce the entropy penalty to the activation free energy. Dimethyl-β-CD was a better catalyst for this specific reaction than β-CD because of its stronger van der Waals interaction with the pre-organized reactants and its better performance in reducing the activation energy. This computational work sheds light on the mechanism of the catalytic reaction by cyclodextrins and introduces new perspectives of supramolecular catalysis.

Random quaternary ammonium Diels-Alder poly(phenylene) copolymers for improved vanadium redox flow batteries

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Largier, Timothy D.; Cornelius, Chris J.

2017-06-01

This study analyzes the effect of quaternary ammonium homopolymer (AmPP) and ionic and non-ionic random unit copolymerization (AmPP-PP) of Diels-Alder poly(phenylene)s on electrochemical and transport properties, vanadium redox flow battery performance, and material stability. AmPP-PP materials were synthesized with IEC's up to 2.2 meq/g, displaying a carbonate form ion conductivity of 17.3 mS/cm and water uptake of 57.3%. Vanadium ion permeability studies revealed that the random copolymers possess superior charge carrier selectivity. For materials of comparable ion content, at 10 mA/cm2 the random copolymer displayed a 14% increase in coulombic efficiency (CE) corresponding to a 7% increase in energy efficiency. All quaternary ammonium materials displayed ex situ degradation in a 0.5 M V5+ + 5 M H2SO4 solution, with the rate of degradation appearing to increase with IEC. Preliminary studies reveal that the neutralizing counter-ion has a significant effect on VRB performance, proportional to changes in vanadium ion molecular diffusion.

Surface confined retro Diels-Alder reaction driven by the swelling of weak polyelectrolytes.

Science.gov (United States)

Lyu, Beier; Cha, Wenli; Mao, Tingting; Wu, Yuanzi; Qian, Hujun; Zhou, Yitian; Chen, Xiuli; Zhang, Shen; Liu, Lanying; Yang, Guang; Lu, Zhongyuan; Zhu, Qiang; Ma, Hongwei

2015-03-25

Recently, the type of reactions driven by mechanical force has increased significantly; however, the number of methods for activating those mechanochemical reactions stays relatively limited. Furthermore, in situ characterization of a reaction is usually hampered by the inherent properties of conventional methods. In this study, we report a new platform that utilizes mechanical force generated by the swelling of surface tethered weak polyelectrolytes. An initiator with Diels-Alder (DA) adduct structure was applied to prepare the polyelectrolyte-carboxylated poly(OEGMA-r-HEMA), so that the force could trigger the retro DA reaction. The reaction was monitored in real time by quartz crystal microbalance and confirmed with atomic force microscopy and X-ray photoelectron spectroscopy. Compared with the conventional heating method, the swelling-induced retro DA reaction proceeded rapidly with high conversion ratio and selectivity. A 23.61 kcal/mol theoretical energy barrier supported the practicability of this retro DA reaction being triggered mechanically at ambient temperature. During swelling, the tensile force was controllable and persistent. This unique feature imparts this mechanochemical platform the potential to "freeze" an intermediate state of a reaction for in situ spectroscopic observations, such as surface-enhanced Raman spectroscopy and frequency generation spectroscopy.

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

Science.gov (United States)

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

2016-11-02

Liquid-crystalline ionic liquids (LCILs) are ordered materials that have untapped potential to be used as reaction media for synthetic chemistry. This paper investigates the potential for the ordered structures of LCILs to influence the stereochemical outcome of the Diels-Alder reaction between cyclopentadiene and methyl acrylate. The ratio of endo- to exo-product from this reaction was monitored for a range of ionic liquids (ILs) and LCILs. Comparison of the endo:exo ratios in these reactions as a function of cation, anion and liquid crystallinity of the reaction media, allowed for the effects of liquid crystallinity to be distinguished from anion effects or cation alkyl chain length effects. These data strongly suggest that the proportion of exo-product increases as the reaction media is changed from an isotropic IL to a LCIL. A detailed molecular dynamics (MD) study suggests that this effect is related to different hydrogen bonding interactions between the reaction media and the exo- and endo-transition states in solvents with layered, smectic ordering compared to those that are isotropic. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Unsymmetrical Annulated 2,2’-Bipyridine Analogues with Attached Cycloalkene and Piperidine Rings via Sequential Diels-Alder Reaction of 5,5’-bi-1,2,4-triazinesâ€

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D. Branowska

2005-12-01

Full Text Available Synthesis of bisfunctionalized unsymmetrical 2,2’-bipyridines 8 or their sulfonyl derivatives 12a,b are described. They were prepared via the Diels-Alder reaction of 1-methyl-4-pyrrolidin-1-yl-1,2,3,6-tetrahydropyridine (6 with 3,3’-bis(methyl- sulfanyl-5,5’-bi-1,2,4-triazine (1. The reaction leads to the single cycloaddition product 7 which undergoes Diels-Alder reaction with cyclic enamines 2a,b to give unsymmetrical 2,2’-bipyridine derivatives 8, consisting of the two different heterocyclic units: cycloalkeno[c]pyridine and 2,6-naphthyridine.

Consumer and manufacturer perceptions of hardwood panels made from character-marked lumber

Science.gov (United States)

D. Nicholls; M. Bumgardner; V. Barber

2010-01-01

Hardwood panels made from edge-glued material are a versatile product that could be within the reach of many smaller wood products firms. However, products would need to be accepted throughout the supply chain for this opportunity to be achieved. This study evaluated preferences of consumers and manufacturers towards edge-glued panels from Alaskan red alder and paper...

Effects of riparian canopy opening and salmon carcass addition on the abundance and growth of resident salmonids

Science.gov (United States)

Margaret A. Wilzbach; Bret C. Harvey; Jason L. White; Rodney J. Nakamoto

2005-01-01

We studied the concurrent effects of riparian canopy opening and salmon carcass addition on salmonid biomass, density and growth rates in small streams over 2 years. In each of six streams in the Smith and Klamath River basins in northern California, red alder (Alnus rubra) and other hardwoods were removed along both banks of a 100-m reach to...

Novel Diels-Alder based self-healing epoxies for aerospace composites

Science.gov (United States)

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.

Seeing red to being red: conserved genetic mechanism for red cone oil droplets and co-option for red coloration in birds and turtles.

Science.gov (United States)

Twyman, Hanlu; Valenzuela, Nicole; Literman, Robert; Andersson, Staffan; Mundy, Nicholas I

2016-08-17

Avian ketocarotenoid pigments occur in both the red retinal oil droplets that contribute to colour vision and bright red coloration used in signalling. Turtles are the only other tetrapods with red retinal oil droplets, and some also display red carotenoid-based coloration. Recently, the CYP2J19 gene was strongly implicated in ketocarotenoid synthesis in birds. Here, we investigate CYP2J19 evolution in relation to colour vision and red coloration in reptiles using genomic and expression data. We show that turtles, but not crocodiles or lepidosaurs, possess a CYP2J19 orthologue, which arose via gene duplication before turtles and archosaurs split, and which is strongly and specifically expressed in the ketocarotenoid-containing retina and red integument. We infer that CYP2J19 initially functioned in colour vision in archelosaurs and conclude that red ketocarotenoid-based coloration evolved independently in birds and turtles via gene regulatory changes of CYP2J19 Our results suggest that red oil droplets contributed to colour vision in dinosaurs and pterosaurs. © 2016 The Author(s).

Thermodynamic and molecular origin of interfacial rate enhancements and endo-selectivities of a Diels-Alder reaction.

Science.gov (United States)

Beniwal, Vijay; Kumar, Anil

2017-02-08

Organic reactions in general display large rate accelerations when performed under interfacial conditions, such as on water or at ionic liquid interfaces. However, a clear picture of the physicochemical factors responsible for this large rate enhancements is not available. To gain an understanding of the thermodynamic and molecular origin of these large rate enhancements, we performed a Diels-Alder reaction between cyclopentadiene and methyl acrylate at ionic liquid/n-hexane interfaces. This study describes, for the first time, a methodology for the calculation of the activation parameters of an interfacial reaction. It has been seen that the energy of activation for an interfacial reaction is much smaller than that of the corresponding homogeneous reaction, resulting into the large rate acceleration for the interfacial reaction. Furthermore, the study describes the effects of the alkyl chain length of ionic liquid cations, the extent of heterogeneity, and the polarity of ionic liquids on the rate constants and stereoselectivity of the reaction.

Temperature-controlled cross-linking of silver nanoparticles with diels-alder reaction and its application on antibacterial property

Science.gov (United States)

Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling

2017-05-01

Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV-vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.

Insights into the Diels-Alder Reaction between 3-Vinylindoles and Methyleneindolinone without and with the Assistance of Hydrogen-Bonding Catalyst Bisthiourea: Mechanism, Origin of Stereoselectivity, and Role of Catalyst.

Science.gov (United States)

Yan, Chao-Xian; Yang, Fan; Yang, Xing; Zhou, Da-Gang; Zhou, Pan-Pan

2017-03-17

The Diels-Alder reaction between 3-vinylindoles and methyleneindolinone can proceed both under catalyst-free conditions and with bisthiourea as the catalyst. The reaction with bisthiourea is much faster and results in higher stereoselectivity of the product. The reaction mechanism, origin of stereoselectivity, and role of the catalyst were elaborated based on quantum mechanical calculations and theoretical methods of reactivity indices, NCI, QTAIM, and distortion/interaction models. In the uncatalyzed reaction, the two C-C bonds that are formed undergo conversion from noncovalent to covalent bonding via a concerted asynchronous mechanism. The weak intermolecular interactions formed in the transition state play important roles. The difference between the interaction and distortion energies is responsible for the stereoselectivity. In the catalyzed reaction, bisthiourea induces both the diene and dienophile to approach it via weak intermolecular interactions, which greatly lowers the energy barrier of the reaction and leads to the product with excellent stereoselectivity. The possible pathways of this reaction were explored, which suggested that the formation of the two C-C bonds goes through either a stepwise or concerted asynchronous mechanism. These results detail the reaction mechanism and shed light on both the significant role of the bisthiourea catalyst and the origin of stereoselectivity for this type of Diels-Alder reaction and related ones.

Gold-catalyzed tandem hydroamination/formal aza-Diels-Alder reaction of homopropargyl amino esters: a combined computational and experimental mechanistic study.

Science.gov (United States)

Miró, Javier; Sánchez-Roselló, María; González, Javier; del Pozo, Carlos; Fustero, Santos

2015-03-27

A tandem gold-catalyzed hydroamination/formal aza-Diels-Alder reaction is described. This process, which employs quaternary homopropargyl amino ester substrates, leads to the formation of an intrincate tetracyclic framework and involves the generation of four bonds and five stereocenters in a highly diastereoselective manner. Theoretical calculations have allowed us to propose a suitable mechanistic rationalization for the tandem protocol. Additionally, by studying the influence of the ligands on the rate of the gold-catalyzed reactions, it was possible to establish optimum conditions in which to perform the process with a variety of substituents on the amino ester substrates. Notably, the asymmetric version of the tandem reaction was also evaluated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inquiring into Red/Red Inquiring

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Ken Gale

2013-05-01

Full Text Available This layered account of an inquiry into ‘red’ emerged out of a collective biography workshop. In the middle of the Wiltshire countryside, an international and interdisciplinary group of scholars gathered together to write and make other things and marks on paper that asked questions of, and into, the spaces between words, people, things and their environments. We did not set out to workshop or write into or paint ‘red’ but, rather, it was red that slipped in, uninvited, and painted and wrote us. Red arose as a blush or a stain seeping amongst us that became referenced obliquely by material objects, metaphors and fairytales. The stain spread, became noticeable through our weekend together and beyond it, creating another (bright red artery vein of connection to write with.

7X performance results - final report : ASCI Red vs Red Storm.

Energy Technology Data Exchange (ETDEWEB)

Dinge, Dennis C. (Cray Inc., Albuquerque, NM); Davis, Michael E. (Cray Inc., Albuquerque, NM); Haskell, Karen H.; Ballance, Robert A.; Gardiner, Thomas Anthony; Stevenson, Joel O.; Noe, John P.

2011-04-01

The goal of the 7X performance testing was to assure Sandia National Laboratories, Cray Inc., and the Department of Energy that Red Storm would achieve its performance requirements which were defined as a comparison between ASCI Red and Red Storm. Our approach was to identify one or more problems for each application in the 7X suite, run those problems at multiple processor sizes in the capability computing range, and compare the results between ASCI Red and Red Storm. The first part of this report describes the two computer systems, the applications in the 7X suite, the test problems, and the results of the performance tests on ASCI Red and Red Storm. During the course of the testing on Red Storm, we had the opportunity to run the test problems in both single-core mode and dual-core mode and the second part of this report describes those results. Finally, we reflect on lessons learned in undertaking a major head-to-head benchmark comparison.

Prediction of the chemo- and regioselectivity of Diels-Alder reactions of o-benzoquinone derivatives with thiophenes by means of DFT-based reactivity indices

Science.gov (United States)

Ghomri, Amina; Mekelleche, Sidi Mohamed

2014-03-01

Global and local reactivity indices derived from density functional theory were used to elucidate the regio- and chemoselectivity of Diels-Alder reactions of masked o-benzoquinones with thiophenes acting as dienophiles. The polarity of the studied reactions is evaluated in terms of the difference of electrophilicity powers between the diene and dienophile partners. Preferential cyclisation modes of these cycloadditions are predicted using Domingo's polar model based on the local electrophilicity index, ωk, of the electrophile and the local nucleophilicity index, Nuk, of the nucleophile. The theoretical calculations, carried out at the B3LYP/6-311G(d,p) level of theory, are in good agreement with experimental findings.

On the Reaction of 1,3-Diphenylisobenzofuran and (2-Iodoethynyl(phenyliodonium Triflate. A Unique Case of Oxygen Transfer from the Diels-Alder Adduct to the Diene

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Mercè Font-Bardia

2012-07-01

Full Text Available Reaction of 1,3-diphenylisobenzofuran (DPIBF with 2-(iodoethynyl(phenyl-iodonium triflate at room temperature gave the expected Diels-Alder adduct, but using an excess of DFIBF (2 equiv. and performing the reaction at 55 °C or heating at this temperature during the concentration stage, the initial orange solution or product mixture became dark brown and the products 1,2-phenylene-1,2-bis(phenylmethanone and 2-(3-iodo-1,4-diphenylnaphthyl(phenyliodonium triflate were obtained, which suggests an oxygen transfer between DPIBF and the initial adduct.

Direct and Indirect Determinations of Elementary Rate Constants H + O2: Chain Branching; the Dehydration of tertiary-Butanol; the Retro Diels-Alder Reaction of Cyclohexene; the Dehydration of Isopropanol

Science.gov (United States)

Heyne, Joshua S.

Due to growing environmental concern over the continued use of fossil fuels, methods to limit emissions and partially replace fossil fuel use with renewable biofuels are of considerable interest. Developing chemical kinetic models for the chemistry that affects combustion properties is important to understanding how new fuels affect combustion energy conversion processes in transportation devices. This thesis reports the experimental study of several important reactions (the H + O2 branching reaction, the key decomposition reactions of tertiary-butanol, the dehydration reaction of isopropanol, and the retro Diels-Alder reaction of cyclohexene) and develops robust analysis methods to estimate the absolute uncertainties of specific elementary rate constants derived from the experimental data. In the study of the above reactions, both a direct and indirect rate constant determination technique with associated uncertainty estimation methodologies are developed. In the study of the decomposition reactions, a direct determination technique is applied to experimental data gathered in preparation of this thesis. In the case of the dehydration reaction of tertiary-butanol and the retro Diels-Alder reaction of cyclohexene, both of which are used as internal standards for relative rate studies (Herzler et al. 1997) and chemical thermometry (Rosado-Reyes et al. 2013) , analysis showed an ˜20 K difference in the reaction rate between the reported results and the previous recommendations. In light of these discrepancies, an uncertainty estimation of previous recommendations illuminated an uncertainty of at least 20 K for the dehydration reaction of tertiary-butanol and the retro Diels-Alder reaction of cyclohexene, thus resolving the discrepancies. The determination of the H + O2 branching reaction and decomposition reactions of isopropanol used an indirect determination technique. The uncertainty of the H + O2 branching reaction rate is shown to be underestimated by previous

Synthesis and characterization of a novel double cross-linked hydrogel based on Diels-Alder click reaction and coordination bonding.

Science.gov (United States)

Li, Shubin; Wang, Lu; Yu, Xuemei; Wang, Chengli; Wang, Zhenyu

2018-01-01

Hydrogels, promising biological materials, need to have both strong mechanical properties and also inherent self-healing properties. In this work a double cross-linked network (DN) hydrogel was designed and prepared by combining a Diels-Alder click reaction and coordination effects. This DN hydrogel had good thermodynamic properties, anti-EDTA performance and self-healing properties. In addition, the mechanical properties, swelling properties and surface morphology of DN hydrogels can be controlled by adjusting the ratio of Fe 3+ -catechol. The adjustment of pH value can change the color, crosslinking mode and mechanical properties of the DN hydrogel. This smart hydrogel created from DA click chemistry and coordination effects has significance for guiding the design of new hydrogels with good mechanical properties, self-healing properties and controlled cross-link density. Copyright © 2017. Published by Elsevier B.V.

Adsorption of procion red and congo red dyes using microalgae Spirulina sp

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Risfidian Mohadi

2017-10-01

Full Text Available Adsorption of procion red and congo red dyes using microalgae Spirulina sp was conducted. Spirulina sp was obtained by cultivation and production in laboratory scale. Spirulina sp was used as adsorbent for adsorption of dyes. Adsorption process was studied by kinetic and thermodynamic in order to know the adsorption phenomena. The results showed that kinetically congo red is reactive than procion red on Spirulina sp. On the other hand, thermodynamically procion red was stable than congo red on Spirulina sp which was indicated by adsorption capacity, enthalpy, and entropy.

Romantic red: red enhances men's attraction to women.

Science.gov (United States)

Elliot, Andrew J; Niesta, Daniela

2008-11-01

In many nonhuman primates, the color red enhances males' attraction to females. In 5 experiments, the authors demonstrate a parallel effect in humans: Red, relative to other achromatic and chromatic colors, leads men to view women as more attractive and more sexually desirable. Men seem unaware of this red effect, and red does not influence women's perceptions of the attractiveness of other women, nor men's perceptions of women's overall likeability, kindness, or intelligence. The findings have clear practical implications for men and women in the mating game and, perhaps, for fashion consultants, product designers, and marketers. Furthermore, the findings document the value of extending research on signal coloration to humans and of considering color as something of a common language, both within and across species. (c) 2008 APA, all rights reserved.

Mild and modular surface modification of cellulose via hetero Diels-Alder (HDA) cycloaddition.

Science.gov (United States)

Goldmann, Anja S; Tischer, Thomas; Barner, Leonie; Bruns, Michael; Barner-Kowollik, Christopher

2011-04-11

A combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and hetero Diels-Alder (HDA) cycloaddition was used to effect, under mild (T ≈ 20 °C), fast, and modular conditions, the grafting of poly(isobornyl acrylate) (M(n) = 9800 g mol(-1), PDI = 1.19) onto a solid cellulose substrate. The active hydroxyl groups expressed on the cellulose fibers were converted to tosylate leaving groups, which were subsequently substituted by a highly reactive cyclopentadienyl functionality (Cp). By employing the reactive Cp-functionality as a diene, thiocarbonyl thio-capped poly(isobornyl acrylate) synthesized via RAFT polymerization (mediated by benzyl pyridine-2-yldithioformiate (BPDF)) was attached to the surface under ambient conditions by an HDA cycloaddition (reaction time: 15 h). The surface-modified cellulose samples were analyzed in-depth by X-ray photoelectron spectroscopy, scanning electron microscopy, elemental analysis, Fourier transform infrared (FT-IR) spectroscopy as well as Fourier transform infrared microscopy employing a focal plane array detector for imaging purposes. The analytical results provide strong evidence that the reaction of suitable dienophiles with Cp-functional cellulose proceeds under mild reaction conditions (T ≈ 20 °C) in an efficient fashion. In particular, the visualization of individual modified cellulose fibers via high-resolution FT-IR microscopy corroborates the homogeneous distribution of the polymer film on the cellulose fibers.

Copper(I)-Catalyzed Asymmetric Desymmetrization through Inverse-Electron-Demand aza-Diels-Alder Reaction: Efficient Access to Tetrahydropyridazines Bearing a Unique α-Chiral Silane Moiety.

Science.gov (United States)

Wei, Liang; Zhou, Yu; Song, Zhi-Min; Tao, Hai-Yan; Lin, Zhenyang; Wang, Chun-Jiang

2017-04-11

An unprecedented copper(I)-catalyzed asymmetric desymmetrization of 5-silylcyclopentadienes with in situ formed azoalkene was realized through an inverse-electron-demand aza-Diels-Alder reaction (IEDDA) pathway, in which 5-silylcyclopentadienes served as efficient enophiles. This new protocol provides a facile access to the biologically important heterocyclic tetrahydropyridazines containing a unique α-chiral silane motif and three adjoining stereogenic centers in generally good yield (up to 92 %) with exclusive regioselectivity, high diastereoselectivity (>20:1 diastereomeric ratio), and excellent enantioselectivity (up to 98 % enantiomeric excess). DFT calculations and control experiments further confirmed the proposed reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influences of Thermo-Vacuum Treatment on Colors and Chemical Compositions of Alder Birch Wood

Directory of Open Access Journals (Sweden)

Yan Yang

2015-10-01

Full Text Available With high temperature-heat treatment, the dimensional stability and durability of wood is improved and wood color is darkened as well. In this paper, alder birch wood (Betula alnoides was treated by the Thermo-Vacuum Treatment (TVT. The changes of wood color parameters and the chemical composition were determined by the CIE1976 L*a*b* method and the chemical analysis method, respectively. The results were revealed as follows: (1 A lower value of lightness, L*, and a higher value of total color difference, △E*, were obtained at the higher heat-treatment temperatures and longer treatment time. (2 The higher the heat-treatment temperatures and the longer the heat-treatment times were, the lower the contents of hemicellulose and cellulose were and the higher the content of lignin was. Moreover, Fourier Transform infrared spectroscopy (FTIR analysis demonstrated that the characteristic absorption peaks of cellulose, hemicellulose, and lignin diminished. The acetylation reaction of hemicellulose and the degradation reaction of groups of lignin side chain occurred during TVT. (3 TVT degraded the chemical composition of cell walls, which resulted in further changes of the wood color. A significant correlation existed between the differences of color indices and the differences of the chemical composition after TVT.

Determination of ergocalciferol in human plasma after Diels-Alder derivatization by LC–MS/MS and its application to a bioequivalence study

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Pritesh Contractor

2017-12-01

Full Text Available An accurate, sensitive and selective method is developed for determination of ergocalciferol (vitamin D2 in human plasma using LC–MS/MS. After liquid-liquid extraction with n-hexane, ergocalciferol was derivatized by reacting with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD, a strong dienophile based on Diels-Alder reaction. Ergocalciferol and its deuterated internal standard, ergocalciferol-d6, were analyzed on X Select CSH C18 (100 mm×4.6 mm, 2.5 µm column using acetonitrile and 0.1% (v/v formic acid in water containing 0.14% methylamine within 6.0 min under gradient elution mode. Tandem mass spectrometry in positive ionization mode was used to quantify ergocalciferol by multiple reaction monitoring (MRM. Entire data processing was done using Watson LIMS™ software which provided excellent data integrity and high throughput with improved operational efficiency. The major advantage of this method includes higher sensitivity (0.10 ng/mL, superior extraction efficiency (≥83% and small sample volume (100 µL for processing. The method was linear in the concentration range of 0.10–100 ng/mL for ergocalciferol. The intra-batch and inter-batch accuracy and precision (% CV values varied from 97.3% to 109.0% and 1.01% to 5.16%, respectively. The method was successfully applied to support a bioequivalence study of 1.25 mg ergocalciferol capsules in 12 healthy subjects. Keywords: Ergocalciferol, Diels-Alder reaction, 4-phenyl-1,2,4-triazoline-3,5-dione, LC–MS/MS, Human plasma

Site-Specific Protein Labeling Utilizing Lipoic Acid Ligase (LplA) and Bioorthogonal Inverse Electron Demand Diels-Alder Reaction.

Science.gov (United States)

Baalmann, Mathis; Best, Marcel; Wombacher, Richard

2018-01-01

Here, we describe a two-step protocol for selective protein labeling based on enzyme-mediated peptide labeling utilizing lipoic acid ligase (LplA) and bioorthogonal chemistry. The method can be applied to purified proteins, protein in cell lysates, as well as living cells. In a first step a W37V mutant of the lipoic acid ligase (LplA W37V ) from Escherichia coli is utilized to ligate a synthetic chemical handle site-specifically to a lysine residue in a 13 amino acid peptide motif-a short sequence that can be genetically expressed as a fusion with any protein of interest. In a second step, a molecular probe can be attached to the chemical handle in a bioorthogonal Diels-Alder reaction with inverse electron demand (DA inv ). This method is a complementary approach to protein labeling using genetic code expansion and circumvents larger protein tags while maintaining label specificity, providing experimental flexibility and straightforwardness.

Diels-Alder reactions using 4,7-dioxygenated indanones as dienophiles for regioselective construction of oxygenated 2,3-dihydrobenz[f]indenone skeleton

Directory of Open Access Journals (Sweden)

2008-05-01

Full Text Available Regioselective construction of 4,8,9-trioxygenated 2,3-dihydrobenz[f]indenones, key intermediates for the synthesis of kinamycin antibiotics, was achieved via Diels-Alder reactions (DAR using 4,7-dioxygenated indanone-type compounds as dienophiles. Reaction of indanetrione with 1-methoxybutadiene gave a 1 : 1 mixture of undesired 4,5,9-trioxygenated 2,3-dihydrobenz[f]indenone and [4.4.3]propellane. The addition of Lewis acid did not affect the product ratio, whereas the use of the 6-bromoindanetrione exclusively afforded the latter propellane. On the other hand, DAR of benzyne derived from bromoindan and furan gave 5,8-epoxy-2,3-dihydrobenz[f]indene, which was subjected to acid-induced ring opening to give 2,3-dihydrobenz[f]indenone with undesired 4,5,9-trioxy functions.

Click and Release: A Chemical Strategy toward Developing Gasotransmitter Prodrugs by Using an Intramolecular Diels-Alder Reaction.

Science.gov (United States)

Ji, Xingyue; Zhou, Cheng; Ji, Kaili; Aghoghovbia, Robert E; Pan, Zhixiang; Chittavong, Vayou; Ke, Bowen; Wang, Binghe

2016-12-19

Prodrug strategies have been proven to be a very effective way of addressing delivery problems. Much of the chemistry in prodrug development relies on the ability to mask an appropriate functional group, which can be removed under appropriate conditions. However, developing organic prodrugs of gasotransmitters represent unique challenges. This is especially true with carbon monoxide, which does not have an easy "handle" for bioreversible derivatization. By taking advantage of an intramolecular Diels-Alder reaction, we have developed a prodrug strategy for preparations of organic CO prodrugs that are stable during synthesis and storage, and yet readily release CO with tunable release rates under near physiological conditions. The effectiveness of the CO prodrug system in delivering a sufficient quantity of CO for possible therapeutic applications has been studied using a cell culture anti-inflammatory assay and a colitis animal model. These studies fully demonstrate the proof of concept, and lay a strong foundation for further medicinal chemistry work in developing organic CO prodrugs. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Product (RED)

DEFF Research Database (Denmark)

Ponte, Stefano

2011-01-01

) and the consumers who buy iconic brand products to help ‘distant others’. While in many other forms of causumerism, labels or certification systems ‘prove’ that a product is just, in RED, aid celebrities provide the proof. From the consumer point of view both labels and celebrities provide a similar simplification...... of complex social, economic, and environmental processes. At the same time, we argue that there are important distinctions as well—labels and certifications are ultimately about improving the conditions of production, whereas RED is about accepting existing production and trade systems and donating......(PRODUCT)RED™ (hereafter RED) is a cobranding initiative launched in 2006 by the aid celebrity Bono to raise money from product sales to support The Global Fund to Fight AIDS, Tuberculosis and Malaria. In this paper we argue that RED is shifting the boundaries of ‘causumerism’ (shopping...

RED-ML

DEFF Research Database (Denmark)

Xiong, Heng; Liu, Dongbing; Li, Qiye

2017-01-01

using diverse RNA-seq datasets, we have developed a software tool, RED-ML: RNA Editing Detection based on Machine learning (pronounced as "red ML"). The input to RED-ML can be as simple as a single BAM file, while it can also take advantage of matched genomic variant information when available...... accurately detect novel RNA editing sites without relying on curated RNA editing databases. We have also made this tool freely available via GitHub . We have developed a highly accurate, speedy and general-purpose tool for RNA editing detection using RNA-seq data....... With the availability of RED-ML, it is now possible to conveniently make RNA editing a routine analysis of RNA-seq. We believe this can greatly benefit the RNA editing research community and has profound impact to accelerate our understanding of this intriguing posttranscriptional modification process....

Red Misfits in the Sloan Digital Sky Survey: properties of star-forming red galaxies

Science.gov (United States)

Evans, Fraser A.; Parker, Laura C.; Roberts, Ian D.

2018-06-01

We study Red Misfits, a population of red, star-forming galaxies in the local Universe. We classify galaxies based on inclination-corrected optical colours and specific star formation rates derived from the Sloan Digital Sky Survey Data Release 7. Although the majority of blue galaxies are star-forming and most red galaxies exhibit little to no ongoing star formation, a small but significant population of galaxies (˜11 per cent at all stellar masses) are classified as red in colour yet actively star-forming. We explore a number of properties of these galaxies and demonstrate that Red Misfits are not simply dusty or highly inclined blue cloud galaxies or quiescent red galaxies with poorly constrained star formation. The proportion of Red Misfits is nearly independent of environment, and this population exhibits both intermediate morphologies and an enhanced likelihood of hosting an active galactic nucleus. We conclude that Red Misfits are a transition population, gradually quenching on their way to the red sequence and this quenching is dominated by internal processes rather than environmentally driven processes. We discuss the connection between Red Misfits and other transition galaxy populations, namely S0s, red spirals, and green valley galaxies.

Highly efficient method for 125I-radiolabeling of biomolecules using inverse-electron-demand Diels-Alder reaction.

Science.gov (United States)

Choi, Mi Hee; Shim, Ha Eun; Yun, Seong-Jae; Kim, Hye Rim; Mushtaq, Sajid; Lee, Chang Heon; Park, Sang Hyun; Choi, Dae Seong; Lee, Dong-Eun; Byun, Eui-Baek; Jang, Beom-Su; Jeon, Jongho

2016-04-19

In this report, we present a rapid and highly efficient method for radioactive iodine labeling of trans-cyclooctene group conjugated biomolecules using inverse-electron-demand Diels-Alder reaction. Radioiodination reaction of the tetrazine structure was carried out using the stannylated precursor 2 to give 125 I-labeled azide ([ 125 I]1) with high radiochemical yield (65±8%) and radiochemical purity (>99%). For radiolabeling application of [ 125 I]1, trans-cyclooctene derived cRGD peptide and human serum albumin were prepared. These substrated were reacted with [ 125 I]1 under mild condition to provide the radiolabeled products [ 125 I]6 and [ 125 I]8, respectively, with excellent radiochemical yields. The biodistribution study of [ 125 I]8 in normal ICR mice showed significantly lower thyroid uptake values than that of 125 I-labeled human serum albumin prepared by a traditional radiolabeling method. Therefore [ 125 I]8 will be a useful radiolabeled tracer in various molecular imaging and biological studies. Those results clearly demonstrate that [ 125 I]1 will be used as a valuable prosthetic group for radiolabeling of biomolecules. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation on the Scratch Strength of Clear Paints Used in Furniture Industries on the Wood Species Beech, Elm, Alder and Spruce

Directory of Open Access Journals (Sweden)

Mohammad Ghofrani

2014-05-01

Full Text Available In This research, the scratch strength (Cross-Cut Test of clear paints (nitrocellulose lacquers and acid catalyst lacquers of wood species Beech, Elm, Alder and spruce were studied as a function of moisture content (MC of the samples. For this purpose, lumbers (550×110×12 mm were cut from sapwood in tangential surfaces and were air dried for one month according to wood drying procedures. Then, for pre-conditioning of moisture content, at the levels of 8%, 12% and 15%, the samples were placed in three clima rooms. Then, finish applied and strength tests were performed. The results revealed that for acid catalyst lacquers the highest scratch strength (10.4% belongs to Elm wood with 8% moisture content, and the lowest scratch strength (53.6% belongs to Spruce wood with nitrocellulose lacquers having 15% moisture content.

Bioavailability and Biokinetics of Anthocyanins From Red Grape Juice and Red Wine

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Roland Bitsch

2004-01-01

Full Text Available In a comparative study, 9 healthy volunteers ingested a single oral dose of 400 mL red grape juice or red wine with dose-adjusted anthocyanin content (283.5 mg or 279.6 mg, resp. in crossover. The content of anthocyanin glucosides was detected in plasma and urinary excretion. Additionally, the plasmatic antioxidant activity was assessed after intake. Based on the plasma content, biokinetic criteria of the single anthocyanins were calculated, such as AUC, cmax, tmax, and the elimination rate t1/2. The urinary excretion of total anthocyanins differed significantly and amounted to 0.18% (red wine and 0.23% (red grape juice of the administered dose. Additionally, the plasmatic antioxidant activity increased to higher levels after juice ingestion compared to wine. The intestinal absorption of the anthocyanins of red grape juice seemed to be improved compared to red wine, suggesting a possible synergistic effect of the glucose content of the juice. The improved absorption resulted in an enhanced plasmatic bioactivity.

What makes red quasars red?. Observational evidence for dust extinction from line ratio analysis

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Kim, Dohyeong; Im, Myungshin

2018-02-01

Red quasars are very red in the optical through near-infrared (NIR) wavelengths, which is possibly due to dust extinction in their host galaxies as expected in a scenario in which red quasars are an intermediate population between merger-driven star-forming galaxies and unobscured type 1 quasars. However, alternative mechanisms also exist to explain their red colors: (i) an intrinsically red continuum; (ii) an unusual high covering factor of the hot dust component, that is, CFHD = LHD/Lbol, where the LHD is the luminosity from the hot dust component and the Lbol is the bolometric luminosity; and (iii) a moderate viewing angle. In order to investigate why red quasars are red, we studied optical and NIR spectra of 20 red quasars at z 0.3 and 0.7, where the usage of the NIR spectra allowed us to look into red quasar properties in ways that are little affected by dust extinction. The Paschen to Balmer line ratios were derived for 13 red quasars and the values were found to be 10 times higher than unobscured type 1 quasars, suggesting a heavy dust extinction with AV > 2.5 mag. Furthermore, the Paschen to Balmer line ratios of red quasars are difficult to explain with plausible physical conditions without adopting the concept of the dust extinction. The CFHD of red quasars are similar to, or marginally higher than, those of unobscured type 1 quasars. The Eddington ratios, computed for 19 out of 20 red quasars, are higher than those of unobscured type 1 quasars (by factors of 3-5), and hence the moderate viewing angle scenario is disfavored. Consequently, these results strongly suggest the dust extinction that is connected to an enhanced nuclear activity as the origin of the red color of red quasars, which is consistent with the merger-driven quasar evolution scenario. Full Table A.1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/610/A31

When red means go : non-normative effects of red under sensation seeking

NARCIS (Netherlands)

Mehta, R.; Demmers, J.; van Dolen, W.M.; Weinberg, C.B.

Although previous research has identified red as the color of compliance, the current work proposes that this effect of red may not hold under high sensation-seeking propensity conditions. It is argued that the color red has the capability to induce arousal, which in turn has been shown to enhance a

Male red ornamentation is associated with female red sensitivity in sticklebacks.

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Ingolf P Rick

Full Text Available Sexual selection theory proposes correlated evolutionary changes in mating preferences and secondary sexual characters based on a positive genetic correlation between preference and the preferred trait. Empirical work has provided support for a genetic covariation between female preference and male attractiveness in several taxa. Here, we study parent and offspring visual traits in threespine sticklebacks, Gasterosteus aculeatus. While focusing on the proximate basis of mating preferences, we compare the red breeding coloration of males, which strongly contributes to female choice, with their daughters' red sensitivity measured by optomotor response thresholds. We show that the red color expression of fathers correlates well with their daughters' red sensitivity. Given that a within-population genetic correlation between signal and preference was experimentally confirmed for the red coloration in sticklebacks, our results indicate a proximate mechanism in terms of perceptual sensitivity being involved in the co-evolution of female preferences and male mating signals.

Aliso en Simbiosis Dual con Frankia y Endomicorrizas y Respuesta a Boro en un Andisol Alder in Dual Symbiosis whith Frankia and Endomycorrhizae and Response at Boron in an Andisol

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Marisol Medina Sierra

2012-06-01

Full Text Available Resumen. Se evaluó la respuesta del aliso (Alnus acuminata Kunth a la inoculación dual con cepas de Frankia spp. y de hongos endomicorrizógenos con dos niveles de boro (B (0,3 y 0,6 mg kg-1 suelo y la aplicación de nitrógeno (N (40 kg ha-1, fósforo (P (30 mg kg-1 suelo y un control sin inoculación ni elementos químicos. Se empleó un diseño completamente aleatorizado, con 41 tratamientos y 20 repeticiones. Para el análisis estadístico de componentes principales se empleó el programa Multibiplot. Las variables respuesta correspondieron a la biomasa seca aérea y sus contenidos de N, P, Calcio (Ca y cenizas (cen. Se encontró que los tratamientos de P y N y las cepas nativas de Frankia spp. (UdeA902, UdeA904 y CUNMS502 combinados con hongos micorrizógenos (UdeA1905 y Glomus fistulosum respectivamente, favorecieron el rendimiento y contenido de N del aliso. La aplicación de B en algunos casos mejoró el rendimiento y en otros lo afectó negativamente; pero potenció la respuesta de algunas inoculaciones especialmente cuando estuvo presente G. fistulosum aún en el caso de estar acompañado de la cepa de Frankia (CUNMS502. Esta cepa, que presentó bajo rendimiento en otros tratamientos, se vio favorecida notablemente con la adición de B. La inoculación dual es efectiva para favorecer el manejo forestal del aliso siempre y cuando se haga la selección adecuada de las cepas, lo cual puede además condicionar la respuesta a algunos nutrientes como en el caso del B.Abstract. It was evaluated the response of alder (Alnus acuminata Kunth to the dual inoculation of strains of Frankia spp. and endomycorrhizal fungi with two levels of boron (B (0.3 and 0.6 mg kg-1 soil and the application of nitrogen (N (40 kg ha-1, phosphorus (P (30 mg kg-1 soil and a control without inoculation or chemical elements. The experimental design was completely randomized; it was composed kg-1of 41 treatments and 20 replications. The statistical analysis consisted

Gold-Catalyzed Cyclization of Furan-Ynes bearing a Propargyl Carbonate Group: Intramolecular Diels-Alder Reaction with In Situ Generated Allenes.

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Sun, Ning; Xie, Xin; Chen, Haoyi; Liu, Yuanhong

2016-09-26

Gold-catalyzed cyclization of various furan-ynes with a propargyl carbonate or ester moiety results in the formation of a series of polycyclic aromatic ring systems. The reactions can be rationalized through a tandem gold-catalyzed 3,3-rearrangement of the propargyl carboxylate moiety in furan-yne substrates to form an allenic intermediate, which is followed by an intramolecular Diels-Alder reaction of furan and subsequent ring-opening of the oxa-bridged cycloadduct. It was found that the steric and electronic properties of phosphine ligands on the gold catalyst had a significant impact on the reaction outcome. In the case of 1,5-furan-yne, the cleavage of the oxa-bridge in the cycloadduct with concomitant 1,2-migration of the R(1) group occurs to furnish anthracen-1(2H)-ones bearing a quaternary carbon center. For 1,4-furan-yne, a facile aromatization of the cycloadduct takes place to give 9-oxygenated anthracene derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents.

Science.gov (United States)

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

2016-02-12

The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH₂, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF₃, CHO, CN, NO₂). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO₂ substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

Two-step protein labeling by using lipoic acid ligase with norbornene substrates and subsequent inverse-electron demand Diels-Alder reaction.

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Best, Marcel; Degen, Anna; Baalmann, Mathis; Schmidt, Tobias T; Wombacher, Richard

2015-05-26

Inverse-electron-demand Diels-Alder cycloaddition (DAinv ) between strained alkenes and tetrazines is a highly bio-orthogonal reaction that has been applied in the specific labeling of biomolecules. In this work we present a two-step labeling protocol for the site-specific labeling of proteins based on attachment of a highly stable norbornene derivative to a specific peptide sequence by using a mutant of the enzyme lipoic acid ligase A (LplA(W37V) ), followed by the covalent attachment of tetrazine-modified fluorophores to the norbornene moiety through the bio-orthogonal DAinv  . We investigated 15 different norbornene derivatives for their selective enzymatic attachment to a 13-residue lipoic acid acceptor peptide (LAP) by using a standardized HPLC protocol. Finally, we used this two-step labeling strategy to label proteins in cell lysates in a site-specific manner and performed cell-surface labeling on living cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature-controlled cross-linking of silver nanoparticles with Diels-Alder reaction and its application on antibacterial property

International Nuclear Information System (INIS)

Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling

2017-01-01

Highlights: • Silver nanoparticles were functionalized by furan groups. • The DA reaction of furan with bismaleimide was used to cross-link the particles. • The reverse cross-linking could be controlled by temperature. • The antibacterial activity of silvers could be adjusted by the cross-linking. - Abstract: Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV–vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.

Temperature-controlled cross-linking of silver nanoparticles with Diels-Alder reaction and its application on antibacterial property

Energy Technology Data Exchange (ETDEWEB)

Liu, Lian; Yang, Pengfei, E-mail: ypf@qlu.edu.cn; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling

2017-05-01

Highlights: • Silver nanoparticles were functionalized by furan groups. • The DA reaction of furan with bismaleimide was used to cross-link the particles. • The reverse cross-linking could be controlled by temperature. • The antibacterial activity of silvers could be adjusted by the cross-linking. - Abstract: Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV–vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.

Supramolecular hydrogel formation between chitosan and hydroxypropyl β-cyclodextrin via Diels-Alder reaction and its drug delivery.

Science.gov (United States)

Zhang, Mengke; Wang, Jinpeng; Jin, Zhengyu

2018-07-15

Chitosan-cyclodextrin hydrogel (CFCD) was prepared via Diels-Alder reaction between furfural functionalized chitosan (CF) and N-maleoyl alanine functionalized hydroxypropyl β-cyclodextrin (HPCD-AMI) in aqueous media without any catalyst or initiator. The CF and HPCD-AMI were confirmed by Fourier transform infrared spectroscopy and 1 H nuclear magnetic resonance spectroscopy. The resultant CFCD hydrogel was characterized in terms of thermal peripteries, microstructure, rheology behavior, and swelling capacity. The rheology analysis found that the storage modulus G' ranged from 1pa to 1200pa as the degree of furfural substitute on chitosan increased from 2.6% to 28.3%, indicating the hydrogel strength can be tuned readily by reaction stoichiometry. The swelling behaviors proved that CFCD hydrogel was pH-responsive with low swelling capacity, which would be preferable for drug delivery. Drug adsorption analysis showed the introduction of cyclodextrin into CFCD hydrogels promoted drug adsorption capacity. In addition, methyl orange cumulative release in PBS buffer was only 48.85% after 24h, suggesting CFCD hydrogel had good sustained release capacity on the loaded drug. Copyright © 2018 Elsevier B.V. All rights reserved.

Noncytotoxic orange and red/green derivatives of DsRed-Express2 for whole-cell labeling

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Glick Benjamin S

2009-04-01

Full Text Available Abstract Background Whole-cell labeling is a common application of fluorescent proteins (FPs, but many red and orange FPs exhibit cytotoxicity that limits their use as whole-cell labels. Recently, a tetrameric red FP called DsRed-Express2 was engineered for enhanced solubility and was shown to be noncytotoxic in bacterial and mammalian cells. Our goal was to create derivatives of this protein with different spectral properties. Results Building on previous studies of DsRed mutants, we created two DsRed-Express2 derivatives: E2-Orange, an orange FP, and E2-Red/Green, a dual-color FP with both red and green emission. We show that these new FPs retain the low cytotoxicity of DsRed-Express2. In addition, we show that these new FPs are useful as second or third colors for flow cytometry and fluorescence microscopy. Conclusion E2-Orange and E2-Red/Green will facilitate the production of healthy, stably fluorescent cell lines and transgenic organisms for multi-color labeling studies.

N,N'-dioxide/nickel(II)-catalyzed asymmetric inverse-electron-demand hetero-diels-alder reaction of β,γ-unsaturated α-ketoesters with enecarbamates.

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Zhou, Yuhang; Zhu, Yin; Lin, Lili; Zhang, Yulong; Zheng, Jianfeng; Liu, Xiaohua; Feng, Xiaoming

2014-12-08

N,N'-Dioxide/nickel(II) complexes have been developed to catalyze the inverse-electron-demand hetero-Diels-Alder reaction of β,γ-unsaturated α-ketoesters with acyclic enecarbamates. After detailed screening of the reaction parameters, mild optimized reaction conditions were established, affording 3,4-dihydro-2H-pyranamines in up to 99 % yield, 99 % ee and more than 95:5 d.r. The catalytic system was also efficient for β-substituted acyclic enecarbamates, affording more challenging 2,3,4-trisubstituted 3,4-dihydro-2H-pyranamine with three contiguous stereogenic centers in excellent yields, diastereoselectivities, and enantioselectivities. The reaction could be scaled up to a gram scale with no deterioration of either enantioselectivity or yield. Based on these experiments and on previous reports, a possible transition state was proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isolation and stereochemical assignment of phthalides resulting from the Diels-Alder reaction between 5-isopropoxyfuran-2(5H)-one and cyclopentadiene

Science.gov (United States)

Resende, G. C.; Alvarenga, E. S.; Willoughby, P. H.

2015-12-01

Naturally occurring phthalides and their synthetic analogs, feature a wide range of bioactivities. In our work, the Diels-Alder reaction between 5-isopropoxyfuran-2(5H)-one and cyclopentadiene was chosen as the key step to obtain tetrahydroisobenzofuran-1(3H)-one derivatives. The anti-endo (major), anti-exo and syn-endo adducts were isolated and structurally elucidated by nmr experiments. In order to rationalize the experimental finding, chemical shifts were predicted by theoretical calculations using density functional theory at B3LYP/6-31G(d,p) and B3LYP/6-311 + G(2d,p) levels. The goodness-of-fit between calculated and experimental data was evaluated by comparing mean absolute errors and applying DP4 probability methodology. Results demonstrated that DP4 probability of combined data (13C and 1H) is the most efficient method for assignment of the correct diastereoisomers.

ESR analysis of irradiated red peppers and commercial red peppers in Japan

International Nuclear Information System (INIS)

Kameya, Hiromi; Ukai, Mitsuko

2011-01-01

ESR analysis of γ-ray irradiated and being treated with different processing red pepper was studied. All the red peppers were commercial expect irradiated one. Processing treatment of red pepper was sun drying, mechanical processing (heating sterilization and powdering treatment). All the samples were weighted and analyzed. The ESR spectrum of the red pepper is composed of a singlet at g=2.00. This signal was originated from organic free radical. It is suggested the effect of heating treatment on the radical formation is not so large and powdering treatment will promote the radical formation of red pepper. ESR singlet signal of the irradiated red pepper showed the large signal intensity and the dose-dependence. The singlet signal intensity of irradiated powder sample showed the almost same value as compared with that of the powder sample with heating treatment. Relaxation times (T 1 and T 2 ) of the singlet signal were calculated. The relaxation behavior and relaxation times of the irradiated sample were different from that of the non-irradiated sample. The value of T 1 , the spin lattice relaxation time, of irradiated sample was increased and T 2 , the spin-spin relaxation time, of irradiated sample was decreased. We concluded that the radical formation of the red pepper is mainly depended on the powdering treatment and irradiation. (author)

Red blood cell production

Science.gov (United States)

... bone marrow of bones. Stem cells in the red bone marrow called hemocytoblasts give rise to all of the formed elements in blood. If a hemocytoblast commits to becoming a cell called a proerythroblast, it will develop into a new red blood cell. The formation of a red blood ...

The [2 + 2] Cycloaddition-Retroelectrocyclization and [4 + 2] Hetero-Diels-Alder Reactions of 2-(Dicyanomethylene)indan-1,3-dione with Electron-Rich Alkynes: Influence of Lewis Acids on Reactivity.

Science.gov (United States)

Donckele, Etienne J; Finke, Aaron D; Ruhlmann, Laurent; Boudon, Corinne; Trapp, Nils; Diederich, François

2015-07-17

The reaction of electrophilic 2-(dicyanomethylene)indan-1,3-dione (DCID) with substituted, electron-rich alkynes provides two classes of push-pull chromophores with interesting optoelectronic properties. The formal [2 + 2] cycloaddition-retroelectrocyclization reaction at the exocyclic double bond of DCID gives cyanobuta-1,3-dienes, and the formal [4 + 2] hetero-Diels-Alder (HDA) reaction at an enone moiety of DCID generates fused 4H-pyran heterocycles. Both products can be obtained in good yield and excellent selectivity by carefully tuning the reaction conditions; in particular, the use of Lewis acids dramatically enhances formation of the HDA adduct.

Exploring conditions for the enhancement of acene semiconductors through the use of the Diels-alder reaction

Science.gov (United States)

Qualizza, Brittni A.

This dissertation demonstrates the application of SAMs to the surface of acene crystals, specifically of tetracene and rubrene, using the Diels-Alder reaction. The second chapter details preliminary reaction results and two analytical methods which were employed to confirm adsorption of the dienophile on the surface of single crystals, tetracene and rubrene. These were mass spectrometry and X-ray photoelectron spectroscopy (XPS). Mass spectrometry experiments distinguish the chemical identity of adduct on the crystals and also it discerned chemi- and physisorbed molecules from one another. XPS was used to prove face selectivity of the reaction by the detection of dichloromaleic anhydride. From a mechanistic standpoint, this system demonstrated unusual steric effects: the reaction of one face of the tetracene crystal was virtually inert, while another face was facile. The dienophiles' steric bulk was also expected to play critical role for these confined systems, however analysis of surface data was hindered by the relative lack of corresponding solution kinetic data. While the rate of anthracene's reaction has been studied extensively with a range of dienophiles and tetracene/pentacene has been studied theoretically (with limited experimental reports), an expansive report was generated to aid in future interpretations of acene systems. These kinetic results constitute chapter three.

Spiroketals of Pestalotiopsis fici provide evidence for a biosynthetic hypothesis involving diversified Diels-Alder reaction cascades.

Science.gov (United States)

Liu, Ling; Li, Yan; Li, Li; Cao, Ya; Guo, Liangdong; Liu, Gang; Che, Yongsheng

2013-04-05

Chloropestolides B-G (1-6), six new metabolites featuring the chlorinated spiro[benzo[d][1,3]dioxine-2,7'-bicyclo[2.2.2]octane]-4,8'-dione (1-3) and spiro[benzo[d][1,3]dioxine-2,1'-naphthalene]-2',4-dione (4-6) skeletons, and their putative biosynthetic precursor dechloromaldoxin (7) were isolated from the scale-up fermentation cultures of the plant endophytic fungus Pestalotiopsis fici . The structures of 1-7 were determined mainly by NMR experiments. The absolute configurations of 1-3 were deduced by analogy to the previously isolated metabolites from the same fungus (9 and 13-18), whereas those of 4, 5, and 7 were assigned by electronic circular dichroism (ECD) calculations. Structurally, the spiroketal skeletons found in 1-3 and 4-6 could be derived from 2,6-dihydroxy-4-methylbenzoic acid with chlorinated bicyclo[2.2.2]oct-2-en-5-one and 4a,5,8,8a-tetrahydronaphthalen-2(1H)-one, respectively. Biogenetically, compounds 1-6 were derived from the same Diels-Alder precursors as the previously isolated 9 and 12-18. In addition, compounds 2 and 3 were proposed as the biosynthetic intermediates of 17 and 16, respectively. Compound 1 was cytotoxic to three human tumor cell lines.

Preparation of strained axially chiral (1,5)naphthalenophanes by photo-dehydro-Diels-Alder reaction.

Science.gov (United States)

Wessig, Pablo; Matthes, Annika

2011-03-02

The preparation of 10 (1,5)naphthalenophanes (10a-j) by photo-dehydro-Diels-Alder (PDDA) reaction is described. Owing to hindered rotation around the biaryl axis, compounds 10 are axially chiral and the separation of enantiomers by chiral HPLC was demonstrated in three cases (10a,b,e). The absolute configuration of the isolated enantiomers could be unambiguously determined by comparison of calculated and measured circular dichroism (CD) spectra. Furthermore, we analyzed ring strain phenomena of (1,5)naphthalenophanes 10. Depending on the length of the linker units, one can distinguish three classes of naphthalenophanes. Compounds 10a-c are highly strained (E(STR) = 7-31 kcal/mol), and the strain is caused by small bond angles in the linker unit and deformation of the naphthalene moiety. Another type of strain is observed if the linker unit becomes relatively long (10g,h) originating from transannular interactions and is comparable with the well-known strain of medium sized rings. The naphthalenophanes 10d-f with a linker length of 10-14 atoms are only marginally strained. To clearly discriminate the different sources of strain, we defined two geometrical parameters (average central dihedral angle δ(C) and naphthalene thickness D(N)) and demonstrated that they are well-suited to indicate naphthalene deformation of our naphthalenophanes 10 as well as of ten model naphthalenophanes (I-X) with different linker lengths and linking positions.

Microwave-assisted intramolecular dehydrogenative Diels-Alder reactions for the synthesis of functionalized naphthalenes/solvatochromic dyes.

Science.gov (United States)

Kocsis, Laura S; Benedetti, Erica; Brummond, Kay M

2013-04-01

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to the preparation of new organic dyes. Although numerous strategies have been reported to access naphthalene scaffolds, many procedures still present limitations in terms of incorporating functionality, which in turn narrows the range of available substrates. The development of versatile methods for direct access to substituted naphthalenes is therefore highly desirable. The Diels-Alder (DA) cycloaddition reaction is a powerful and attractive method for the formation of saturated and unsaturated ring systems from readily available starting materials. A new microwave-assisted intramolecular dehydrogenative DA reaction of styrenyl derivatives described herein generates a variety of functionalized cyclopenta[b]naphthalenes that could not be prepared using existing synthetic methods. When compared to conventional heating, microwave irradiation accelerates reaction rates, enhances yields, and limits the formation of undesired byproducts. The utility of this protocol is further demonstrated by the conversion of a DA cycloadduct into a novel solvatochromic fluorescent dye via a Buchwald-Hartwig palladium-catalyzed cross-coupling reaction. Fluorescence spectroscopy, as an informative and sensitive analytical technique, plays a key role in research fields including environmental science, medicine, pharmacology, and cellular biology. Access to a variety of new organic fluorophores provided by the microwave-assisted dehydrogenative DA reaction allows for further advancement in these fields.

Synthesis and properties of sulfonated poly(phenylene sulfone)s without ether linkage by Diels–Alder reaction for PEMFC application

International Nuclear Information System (INIS)

Lim, Youngdon; Lee, Hyunchul; Lee, Soonho; Jang, Hohyoun; Hossain, Md. Awlad; Cho, Younggil; Kim, Taeho; Hong, Youngtaik; Kim, Whangi

2014-01-01

A new sulfonated poly(phenylene sulfone) polymer (SPPS) was synthesized by Diels-Alder polymerization from 1,4-bis(2,4,5-triphenylcyclopentadienone)benzene (BTPCPB) and 4,4′-diethynylphenylsulfone, and followed by sulfonation reaction with chlorosulfuric acid. A series of sulfonated poly(phenylene sulfone)s (SPPS) with different degrees of sulfonation was prepared in a controllable manner with chlorosulfuric acid. These polymers showed good solubility in aprotic polar solvents, dimethyl acetamide (DMAC) and dimethyl sulfoxide (DMSO). Three different polymer membranes were studied by 1 H NMR spectroscopy, and thermogravimetric analysis (TGA). The ion exchange capacity (IEC) and proton conductivity of SPPS were evaluated according to the degrees of sulfonation. The water uptake (WU) of the synthesized SPPS membranes ranged from 38%∼75%, compared with 32% for Nafion 211 ® at 80 °C. The SPPS membranes exhibited proton conductivities (at 80 °C under 90% RH) of 110.2 mS/cm compared with 102.7 mS/cm for Nafion 211 ® . Power density was performed by single cell and showed similar to Nafion value

A Review of Prevention, Diagnosis and Treatment of Relative Energy Deficiency in Sport (RED-S) in Artistic (Synchronized) Swimming.

Science.gov (United States)

Robertson, Sherry; Mountjoy, Margo

2018-05-03

The syndrome Relative Energy Deficiency in Sport (RED-S) is a clinical entity characterized by low energy availability (LEA), which can negatively affect the health and performance of both male and female athletes. The underlying mechanism of RED-S is an inadequacy of dietary energy to support optimal health and performance. This syndrome refers to impaired physiological function including metabolic rate, menstrual function, bone health, immunity, protein synthesis, and cardiovascular health, with psychological consequences which can either precede (through restrictive dietary habits) or result from RED-S. The term RED-S extends beyond the condition termed the "Female Athlete Triad". Formerly known as synchronized swimming, artistic swimming is an Olympic sport requiring a high level of fitness as well as technical skill and artistry. The risk of RED-S is high in artistic swimming as it is an aesthetic, judged sport with an emphasis on a lean physique. RED-S is of significant concern in the sport of artistic swimming because of the potential negative effects on physical and mental health as well as consequences on athletic performance. This paper reviews health and performance consequences associated with LEA resulting in RED-S in artistic swimming. Medical and nutritional considerations specific to artistic swimming are reviewed and methods to help detect and manage RED-S are discussed. Prevention and management of RED-S in this athlete population should be a priority for coaches and the sport medicine professionals working with artistic swimming athletes should utilize the RED-S CAT, a Clinical Assessment Tool for screening and managing RED-S.

Winter behavior and ecology of the Alder Flycatcher (Empidonax alnorum) in Peru

Science.gov (United States)

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.

Formation and spreading of Red Sea Outflow Water in the Red Sea

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Zhai, Ping; Bower, Amy S.; Smethie, William M.; Pratt, Larry J.

2015-09-01

Hydrographic data, chlorofluorocarbon-12 (CFC-12) and sulfur hexafluoride (SF6) measurements collected in March 2010 and September-October 2011 in the Red Sea, as well as an idealized numerical experiment are used to study the formation and spreading of Red Sea Outflow Water (RSOW) in the Red Sea. Analysis of inert tracers, potential vorticity distributions, and model results confirm that RSOW is formed through mixed-layer deepening caused by sea surface buoyancy loss in winter in the northern Red Sea and reveal more details on RSOW spreading rates, pathways, and vertical structure. The southward spreading of RSOW after its formation is identified as a layer with minimum potential vorticity and maximum CFC-12 and SF6. Ventilation ages of seawater within the RSOW layer, calculated from the partial pressure of SF6 (pSF6), range from 2 years in the northern Red Sea to 15 years at 17°N. The distribution of the tracer ages is in agreement with the model circulation field which shows a rapid transport of RSOW from its formation region to the southern Red Sea where there are longer circulation pathways and hence longer residence time due to basin wide eddies. The mean residence time of RSOW within the Red Sea estimated from the pSF6 age is 4.7 years. This time scale is very close to the mean transit time (4.8 years) for particles from the RSOW formation region to reach the exit at the Strait of Bab el Mandeb in the numerical experiment.

Novel N-allyl/propargyl tetrahydroquinolines: Synthesis via Three-component Cationic Imino Diels-Alder Reaction, Binding Prediction, and Evaluation as Cholinesterase Inhibitors.

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Rodríguez, Yeray A; Gutiérrez, Margarita; Ramírez, David; Alzate-Morales, Jans; Bernal, Cristian C; Güiza, Fausto M; Romero Bohórquez, Arnold R

2016-10-01

New N-allyl/propargyl 4-substituted 1,2,3,4-tetrahydroquinolines derivatives were efficiently synthesized using acid-catalyzed three components cationic imino Diels-Alder reaction (70-95%). All compounds were tested in vitro as dual acetylcholinesterase and butyryl-cholinesterase inhibitors and their potential binding modes, and affinity, were predicted by molecular docking and binding free energy calculations (∆G) respectively. The compound 4af (IC50 = 72 μm) presented the most effective inhibition against acetylcholinesterase despite its poor selectivity (SI = 2), while the best inhibitory activity on butyryl-cholinesterase was exhibited by compound 4ae (IC50 = 25.58 μm) with considerable selectivity (SI = 0.15). Molecular docking studies indicated that the most active compounds fit in the reported acetylcholinesterase and butyryl-cholinesterase active sites. Moreover, our computational data indicated a high correlation between the calculated ∆G and the experimental activity values in both targets. © 2016 The Authors Chemical Biology & Drug Design Published by John Wiley & Sons Ltd.

Density functional theory studies on electronic properties of thiophene s oxides as aromatic dienophiles for reactivity prediction in diels-alder reactions

International Nuclear Information System (INIS)

Banjo, S.

2013-01-01

The reactivity of thiophene S-oxides was discussed with special emphasis on the use of thiophene S-oxides as dienophiles in Diels-Alder type reactions. The omega values obtained for thiophene S-oxide (TO) with electron-donating group (-CH/sub 3/) increased the nucleophilicity power whereas substitution with electron-withdrawing groups (such as -NO/sub 2/ and -CO/sub 2/CH/sub 2/CH/sub 3/) increased the electrophilicity power, indicating an increase of reactivity towards a nucleophiles. The higher the value of delta omega the more favourable the D-A process, therefore apart from (4+2) addition reactions of these TO as diene with the typical dienophiles like 1,2-dicyanoethene and 1,2-dicyanoethene, it could be possible for TO with strong electron withdrawing substituents to serve as dienophile, e.g. heterocycles Ie and If. Also, from the value of delta omega heterocycle 1d could involve in (4+2) addition reactions with heterocyles 1e and If. (author)

Physical and Chemical Properties of Sintering Red Mud and Bayer Red Mud and the Implications for Beneficial Utilization

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Wang, Ping; Liu, Dong-Yan

2012-01-01

Performances of two common types of red mud, Bayer red mud and Sintering red mud, were investigated in this research. Their compositions, mechanical properties and microstructure characterization were measured through XRD, TG and SEM analysis. Their shear strength, particle size, density and hydraulic characteristics also had been performed. Huge differences between the basic mineral types of these two kinds of red mud also can be found. The comparison of compositions shows that CaCO3 content in Sintering red mud is higher, Bayer red mud has more hazardous elements such as As, Pb and Hg and both have a high concentration of radioactivity. The micro particle of Bayer red mud is finer and more disperse, but the Sintering red mud has higher shear strength. Combining the TG and hydraulic characteristics analysis, it can be shown that Bayer red mud has higher value of water content and Sintering red mud has higher hydraulic conductivity. The paper then illustrates that Sintering red mud can become the main filling material of supporting structure of red mud stocking yard. Bayer red mud has a high reuse value and also can be used as a mixing material of masonry mortar.

Multifunctional Hydrogel with Good Structure Integrity, Self-Healing, and Tissue-Adhesive Property Formed by Combining Diels-Alder Click Reaction and Acylhydrazone Bond.

Science.gov (United States)

Yu, Feng; Cao, Xiaodong; Du, Jie; Wang, Gang; Chen, Xiaofeng

2015-11-04

Hydrogel, as a good cartilage tissue-engineered scaffold, not only has to possess robust mechanical property but also has to have an intrinsic self-healing property to integrate itself or the surrounding host cartilage. In this work a double cross-linked network (DN) was designed and prepared by combining Diels-Alder click reaction and acylhydrazone bond. The DA reaction maintained the hydrogel's structural integrity and mechanical strength in physiological environment, while the dynamic covalent acylhydrazone bond resulted in hydrogel's self-healing property and controlled the on-off switch of network cross-link density. At the same time, the aldehyde groups contained in hydrogel further promote good integration of the hydrogel to surrounding tissue based on aldehyde-amine Schiff-base reaction. This kind of hydrogel has good structural integrity, autonomous self-healing, and tissue-adhesive property and simultaneously will have a good application in tissue engineering and tissue repair field.

Soils and late-Quaternary landscape evolution in the Cottonwood River basin, east-central Kansas: Implications for archaeological research

Science.gov (United States)

Beeton, J.M.; Mandel, R.D.

2011-01-01

Temporal and spatial patterns of landscape evolution strongly influence the temporal and spatial patterns of the archaeological record in drainage systems. In this geoarchaeological investigation we took a basin-wide approach in assessing the soil stratigraphy, lithostratigraphy, and geochronology of alluvial deposits and associated buried soils in the Cottonwood River basin of east-central Kansas. Patterns of landscape evolution emerge when stratigraphic sequences and radiocarbon chronologies are compared by stream size and landform type. In the valleys of high-order streams (???4th order) the Younger Dryas Chronozone (ca. 11,000-10,000 14C yr B.P.) was characterized by slow aggradation accompanied by pedogenesis, resulting in the development of organic-rich cumulic soils. Between ca. 10,000 and 4900 14C yr B.P., aggradation punctuated by soil formation was the dominant process in those valleys. Alluvial fans formed on the margins of high-order stream valleys during the early and middle Holocene (ca. 9000-5000 14C yr B.P.) and continued to develop slowly until ca. 3000-2000 14C yr B.P. The late-Holocene record of high-order streams is characterized by episodes of entrenchment, rapid aggradation, and slow aggradation punctuated by soil development. By contrast, the early and middle Holocene (ca. 10,000-5000 14C yr B.P.) was a period of net erosion in the valleys of low-order streams. However, during the late Holocene small valleys became zones of net sediment storage. Consideration of the effects of these patterns of landscape evolution on the archaeological record is crucial for accurately interpreting that record and searching for buried archaeological deposits dating to specific cultural periods. ?? 2011 Wiley Periodicals, Inc. ?? 2011 Wiley Periodicals, Inc..

Multiscale Treatment for the Molecular Mechanism of a Diels-Alder Reaction in Solution: A QM/MM-MD Study.

Science.gov (United States)

Soto-Delgado, Jorge; Tapia, Ricardo A; Torras, Juan

2016-10-11

Thermodynamics and the solvent role in the acceleration of the Diels-Alder reaction between cyclopentadiene (CPD) and methyl vinyl ketone (MVK) have been revisited. In this work we use an ab initio hybrid QM/MM-MD scheme combined with multiple steered molecular dynamics to extract the free energy pofile in water and methanol using the bidirectional Minh-Adib estimator. We obtain 18.7 kcal mol -1 and 20.8 kcal mol -1 free energy barrier for the reaction in water and methanol, respectively. This methodology reproduces experimental values with an absolute error of about 0.8 kcal mol -1 . The experimental difference between the activation free-energy barriers of water and methanol is also reproduced with an absolute error of about 0.1 kcal mol -1 . We explore the charge transfer evolution along reaction coordinates to characterize the electronic behavior for this reaction. It is shown that the solvent molecules around the reaction system produce a global polarization along the reaction coordinate which is consistent with the solvent polarity. The results highlight the role of hydrogen bonding formed in the transition state to stabilize the system charge reorganization in the reaction process.

On the Catalytic Effect of Water in the Intramolecular Diels–Alder Reaction of Quinone Systems: A Theoretical Study

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Renato Contreras

2012-11-01

Full Text Available The mechanism of the intramolecular Diels–Alder (IMDA reaction of benzoquinone 1, in the absence and in the presence of three water molecules, 1w, has been studied by means of density functional theory (DFT methods, using the M05-2X and B3LYP functionals for exploration of the potential energy surface (PES. The energy and geometrical results obtained are complemented with a population analysis using the NBO method, and an analysis based on the global, local and group electrophilicity and nucleophilicity indices. Both implicit and explicit solvation emphasize the increase of the polarity of the reaction and the reduction of activation free energies associated with the transition states (TSs of this IMDA process. These results are reinforced by the analysis of the reactivity indices derived from the conceptual DFT, which show that the increase of the electrophilicity of the quinone framework by the hydrogen-bond formation correctly explains the high polar character of this intramolecular process. Large polarization at the TSs promoted by hydrogen-bonds and implicit solvation by water together with a high electrophilicity-nucleophilicity difference consistently explains the catalytic effects of water molecules.

Red is Romantic, but Only for Feminine Females: Sexual Dimorphism Moderates Red Effect on Sexual Attraction

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Fangfang Wen

2014-10-01

Full Text Available Previous researchers have documented that the color red enhances one's sexual attraction to the opposite sex. The current study further examined the moderating role of sexual dimorphism in red effects. The results indicated that red enhanced men's sexual attraction to women with more feminine facial characteristics but had no effect on ratings of perceived general attractiveness. Red clothing also had a marginally significant effect on men's sexual attractiveness. In addition, regardless of sexual dimorphism cues, male participants rated women with red as warmer and more competent. The underlying mechanisms of the red effect, the limitations of the current study, and suggestions for future directions are discussed.

Seeing Red: Inside the Science and Politics of the IUCN Red List

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Lisa M Campbell

2012-01-01

Full Text Available The Red List of Threatened Species™ (hereafter Red List is the International Union for the Conservation of Nature′s most recognisable product. The Red List categorises the conservation status of species on a global scale using ′the most objective, scientifically-based information′. Completing Red List assessments is the job of the Species Survival Commission (SSC, and assessments are most often conducted by species specialist groups within the SSC. In the SSC′s Marine Turtle Specialist Group (MTSG, assessments have been contested. Debate is often couched in scientific terms, focused on data availability and the relevance of Red List criteria for marine turtles. However, given the potential conservation impacts of such listings, much more is at stake. In this paper, I analyse an exchange among MTSG members that resulted when the draft Red List assessment for the hawksbill sea turtle was circulated to the group in June 2007. The suggested listing of hawksbill turtles as ′critically endangered′ sparked an email exchange that highlighted not only the scientific, but also the political, economic, and value-based dimensions of the debate. I draw on ideas of co-production and boundary work to analyse both the debate and the MTSG′s response to an associated crisis of legitimacy, and to provide insights into the science-policy interface in conservation.

Comparative Study of Betacyanin Profile and Antimicrobial Activity of Red Pitahaya (Hylocereus polyrhizus) and Red Spinach (Amaranthus dubius).

Science.gov (United States)

Yong, Yi Yi; Dykes, Gary; Lee, Sui Mae; Choo, Wee Sim

2017-03-01

Betacyanins are reddish to violet pigments that can be found in red pitahaya (Hylocereus polyrhizus) and red spinach (Amaranthus dubius). This study investigated the impact of sub-fractionation (solvent partitioning) on betacyanin content in both plants. Characterization of betacyanins and evaluation of their antimicrobial activities were also carried out. Betanin was found in both plants. In addition, isobetanin, phyllocactin and hylocerenin were found in red pitahaya whereas amaranthine and decarboxy-amaranthine were found in red spinach. Sub-fractionated red pitahaya and red spinach had 23.5 and 121.5 % more betacyanin content, respectively, than those without sub-fractionation. Sub-fractionation increased the betanin and decarboxy-amaranthine content in red pitahaya and red spinach, respectively. The betacyanin fraction from red spinach (minimum inhibitory concentration [MIC] values: 0.78-3.13 mg/mL) demonstrated a better antimicrobial activity profile than that of red pitahaya (MIC values: 3.13-6.25 mg/mL) against nine Gram-positive bacterial strains. Similarly, the red spinach fraction (MIC values: 1.56-3.13 mg/mL) was more active than the red pitahaya fraction (MIC values: 3.13-6.25 mg/mL) against five Gram-negative bacterial strains. This could be because of a higher amount of betacyanin, particularly amaranthine in the red spinach.

Skin quality in red potatoes

Science.gov (United States)

Attractive appearance is a highly desirable characteristic of fresh market red-skinned potatoes. The ideal red potato has a rich, uniform, deep red color. Color fading, netting, browning, and discoloration caused by skinning and disease decrease marketability and may reduce profits to growers and pa...

The role of achiral pyrazolidinone templates in enantioselective Diels-Alder reactions: scope, limitations, and conformational insights.

Science.gov (United States)

Sibi, Mukund P; Stanley, Levi M; Nie, Xiaoping; Venkatraman, Lakshmanan; Liu, Mei; Jasperse, Craig P

2007-01-17

We have evaluated the role of achiral pyrazolidinone templates in conjunction with chiral Lewis acids in room temperature, enantioselective Diels-Alder cycloadditions. The role of the fluxional N(1) substituent was examined, with the bulky 1-naphthylmethyl group providing enantioselectivities up to 99% ee, while templates with smaller fluxional groups gave lower selectivities. High selectivities were also observed in reactions of 7d with chiral Lewis acids derived from relatively small chiral ligands, suggesting the pyrazolidinone templates are capable of relaying stereochemical information from the ligand to the reaction center. Lewis acids capable of adapting square planar geometries, such as Cu(OTf)2, Cu(ClO4)2, and Pd(ClO4)2, were found to be particularly effective at providing high selectivities. Additionally, substitution at the C-5 position of the pyrazolidinone templates has been shown to be critical for optimal selectivity. Reactions of the optimal pyrazolidinone appended with a number of common dienophiles and various dienes demonstrate the utility of this achiral template. Furthermore, catalytic loadings could be lowered to 2.5 mol % with essentially no loss in selectivity. Pi-Pi interactions were evaluated as a means to explain the unusually high selectivity observed at room temperature. Finally, non-C2-symmetric ligands were employed as a test to determine if chiral relay was operative.

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

Science.gov (United States)

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.

Astrophysics of Red Supergiants

Science.gov (United States)

Levesque, Emily M.

2017-12-01

'Astrophysics of Red Supergiants' is the first book of its kind devoted to our current knowledge of red supergiant stars, a key evolutionary phase that is critical to our larger understanding of massive stars. It provides a comprehensive overview of the fundamental physical properties of red supergiants, their evolution, and their extragalactic and cosmological applications. It serves as a reference for researchers from a broad range of fields (including stellar astrophysics, supernovae, and high-redshift galaxies) who are interested in red supergiants as extreme stages of stellar evolution, dust producers, supernova progenitors, extragalactic metallicity indicators, members of massive binaries and mergers, or simply as compelling objects in their own right. The book is accessible to a range of experience levels, from graduate students up to senior researchers.

Red - take a closer look.

Directory of Open Access Journals (Sweden)

Vanessa L Buechner

Full Text Available Color research has shown that red is associated with avoidance of threat (e.g., failure or approach of reward (e.g., mating depending on the context in which it is perceived. In the present study we explored one central cognitive process that might be involved in the context dependency of red associations. According to our theory, red is supposed to highlight the relevance (importance of a goal-related stimulus and correspondingly intensifies the perceivers' attentional reaction to it. Angry and happy human compared to non-human facial expressions were used as goal-relevant stimuli. The data indicate that the color red leads to enhanced attentional engagement to angry and happy human facial expressions (compared to neutral ones - the use of non-human facial expressions does not bias attention. The results are discussed with regard to the idea that red induced attentional biases might explain the red-context effects on motivation.

Coevolution of floodplain and riparian forest dynamics on large, meandering rivers

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Stella, J. C.; Riddle, J. D.; Battles, J. J.

2012-12-01

On large meandering rivers, riparian forests coevolve with the floodplains that support them. Floodplain characteristics such as local disturbance regime, deposition rates and sediment texture drive plant community dynamics, which in turn feed back to the abiotic processes. We investigated floodplain and riparian forest coevolution along the along the Sacramento River (California, USA), a large, mediterranean-climate river that has been extensively regulated for 70 years, but whose 160-km middle reach (Red Bluff to Colusa) retains some channel mobility and natural forest stands. Guided by maps of floodplain change over time and current vegetation cover, we conducted an extensive forest inventory and chronosequence analysis to quantify how abiotic conditions and forest structural characteristics such as tree density, basal area and biomass vary with floodplain age. We inventoried 285 fixed-area plots distributed across 19 large point bars within vegetation patches ranging in age from 4 to 107 years. Two successional trajectories were evident: (1) shifting species dominance over time within forested areas, from willow to cottonwood to walnut, boxelder and valley oak; and (2) patches of shrub willow (primarily Salix exigua) that maintained dominance throughout time. Sediment accretion was reduced in the persistent willow plots compared to the successional forest stands, suggesting an association between higher flood energy and arrested succession. Forested stands 40-60 years old were the most extensive across the chronosequence in terms of floodplain area, and supported the highest biomass, species diversity, and functional wildlife habitat. These stands were dominated by Fremont cottonwood (Populus fremontii) and reached their maxima in terms of tree size and biomass at age 50 years. The persistent willow stands reached their structural maxima earlier (32 years) and supported lower biomass. Basal area and abundance of large trees decreased in stands >90 years old

Functional species traits of carabid beetles living in two riparian alder forests of the Sila plateau subject to different disturbance factors (Coleoptera: Carabidae

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Antonio Mazzei

2015-06-01

Full Text Available We studied carabid beetle assemblages found in riparian black alder forests in the Sila plateau (Southern Apennines. These carabid assemblages are characterized by a high incidence of endemic small-sized, low dispersal, highly stenotopic (hygrophilic, and trophycally specialized species. To evaluate the influence of anthropogenic disturbance on these insects, we compared carabid assemblage of an old undisturbed forest (65-170y, wilderness landscape with that of a younger, partly grazed stand (40-60y, cropland landscape. The carabid assemblage of the disturbed stand was characterized by a higher number of species, but showed a lower incidence of zoophagous specialists and brachypterous beetles, with many species probably coming from an adjacent cropland. However, the disturbed stand maintains almost 80% of the core species found in the older forest, which suggests that these insects are not particularly sensitive to disturbance factors represented by periodic wood harvesting and extensive cattle grazing.

Growth and replication of red rain cells at 121°C and their red fluorescence

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Gangappa, Rajkumar; Wickramasinghe, Chandra; Wainwright, Milton; Kumar, A. Santhosh; Louis, Godfrey

2010-09-01

We have shown that the red cells found in the Red Rain (which fell on Kerala, India, in 2001) survive and grow after incubation for periods of up to two hours at 121°C . Under these conditions daughter cells appear within the original mother cells and the number of cells in the samples increases with length of exposure to 121°C. No such increase in cells occurs at room temperature, suggesting that the increase in daughter cells is brought about by exposure of the Red Rain cells to high temperatures. This is an independent confirmation of results reported earlier by two of the present authors, claiming that the cells can replicate under high pressure at temperatures upto 300°C. The flourescence behaviour of the red cells is shown to be in remarkable correspondence with the extended red emission observed in the Red Rectagle planetary nebula and other galactic and extragalactic dust clouds, suggesting, though not proving an extraterrestrial origin.

Nonlinear analysis of RED - a comparative study

International Nuclear Information System (INIS)

Jiang Kai; Wang Xiaofan; Xi Yugeng

2004-01-01

Random Early Detection (RED) is an active queue management (AQM) mechanism for routers on the Internet. In this paper, performance of RED and Adaptive RED are compared from the viewpoint of nonlinear dynamics. In particular, we reveal the relationship between the performance of the network and its nonlinear dynamical behavior. We measure the maximal Lyapunov exponent and Hurst parameter of the average queue length of RED and Adaptive RED, as well as the throughput and packet loss rate of the aggregate traffic on the bottleneck link. Our simulation scenarios include FTP flows and Web flows, one-way and two-way traffic. In most situations, Adaptive RED has smaller maximal Lyapunov exponents, lower Hurst parameters, higher throughput and lower packet loss rate than that of RED. This confirms that Adaptive RED has better performance than RED

Nonlinear analysis of RED - a comparative study

Energy Technology Data Exchange (ETDEWEB)

Jiang Kai; Wang Xiaofan E-mail: xfwang@sjtu.edu.cn; Xi Yugeng

2004-09-01

Random Early Detection (RED) is an active queue management (AQM) mechanism for routers on the Internet. In this paper, performance of RED and Adaptive RED are compared from the viewpoint of nonlinear dynamics. In particular, we reveal the relationship between the performance of the network and its nonlinear dynamical behavior. We measure the maximal Lyapunov exponent and Hurst parameter of the average queue length of RED and Adaptive RED, as well as the throughput and packet loss rate of the aggregate traffic on the bottleneck link. Our simulation scenarios include FTP flows and Web flows, one-way and two-way traffic. In most situations, Adaptive RED has smaller maximal Lyapunov exponents, lower Hurst parameters, higher throughput and lower packet loss rate than that of RED. This confirms that Adaptive RED has better performance than RED.

Sn-PILC: A novel Efficient and Recyclable Catalyst for One-pot Three Component Povarov’s Inverse-electron-demand Hetero Diels-Alder Reaction for a Facile Synthesis of Tetrahydropyranoquinoline Derivatives under Neat Conditions

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Megha Rai

2016-07-01

Full Text Available The Povarov’s inverse-electron-demand hetero Diels–Alder one-pot three components reaction of aromatic aldehyde, aromatic amine with DHF has been developed using Sn-PILC as a catalyst under a neat condition which may helpful to society to get pharmacologically more active compounds. In the present study a novel series of tetrahydroquinoline 4(a-f were synthesized and characterized by IR, 1HNMR, 13CNMR, Mass spectral analysis and elemental analysis. The synthetic details and characterization results are discussed. DOI: http://dx.doi.org/10.17807/orbital.v8i3.801

21 CFR 640.10 - Red Blood Cells.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 7 2010-04-01 2010-04-01 false Red Blood Cells. 640.10 Section 640.10 Food and... ADDITIONAL STANDARDS FOR HUMAN BLOOD AND BLOOD PRODUCTS Red Blood Cells § 640.10 Red Blood Cells. The proper name of this product shall be Red Blood Cells. The product is defined as red blood cells remaining...

EFSA NDA Panel (EFSA Panel on Dietetic Products, Nutrition and Allergies), 2013. Scientific Opinion on the substantiation of a health claim related to a combination of red spinach, green spinach, red chicory, green chicory, green leaf chard, red leaf chard, red Swiss chard, golden Swiss chard

DEFF Research Database (Denmark)

Tetens, Inge

related to a combination of red spinach, green spinach, red chicory, green chicory, green leaf chard, red leaf chard, red Swiss chard, golden Swiss chard and white Swiss chard and maintenance of normal blood cholesterol concentration. The food that is the subject of the health claim, a combination of red...... spinach (Spinacia oleracea L.), green spinach (Spinacia oleracea L.), red chicory (Cichorium intybus L.), green chicory (Cichorium intybus L.), green leaf chard (Beta vulgaris L. var. cicla), red leaf chard (Beta vulgaris L. var. cicla), red Swiss chard (Beta vulgaris L. var. cicla), golden Swiss chard...... for the scientific substantiation of the claim were provided by the applicant. The Panel concludes that a cause and effect relationship has not been established between consumption of a combination of red spinach, green spinach, red chicory, green chicory, green leaf chard, red leaf chard, red Swiss chard, golden...

Base-catalyzed tandem Michael/dehydro-Diels-Alder reaction of α,α-dicyanoolefins with electron-deficient 1,3-conjugated enynes: a facile entry to angularly fused polycycles.

Science.gov (United States)

Zhang, Mingrui; Zhang, Junliang

2014-01-07

Angularly fused carbocyclic frameworks and their heteroatom-substituted analogues exist in many natural products that display a broad and interesting range of biological activities. Preparation of polycyclic products by cycloaddition reactions have been the long-standing hot topic in the synthetic community. Dehydro-Diels-Alder (DDA) reactions are one class of dehydropericyclic reactions that are derived conceptually by systematic removal of hydrogen atom pairs. A base-promoted tandem Michael addition and DDA reaction of α,α-dicyanoolefins with electron-deficient 1,3-conjugated enynes was realized in which a DDA reaction takes place between the arylalkynes and electron-deficient tetrasubstituted olefin. The control experiments support the stepwise anionic reaction pathway rather than the concerted reaction pathway. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NMR water-proton spin-lattice relaxation time of human red blood cells and red blood cell suspensions

International Nuclear Information System (INIS)

Sullivan, S.G.; Rosenthal, J.S.; Winston, A.; Stern, A.

1988-01-01

NMR water-proton spin-lattice relaxation times were studied as probes of water structure in human red blood cells and red blood cell suspensions. Normal saline had a relaxation time of about 3000 ms while packed red blood cells had a relaxation time of about 500 ms. The relaxation time of a red blood cell suspension at 50% hematocrit was about 750 ms showing that surface charges and polar groups of the red cell membrane effectively structure extracellular water. Incubation of red cells in hypotonic saline increases relaxation time whereas hypertonic saline decreases relaxation time. Relaxation times varied independently of mean corpuscular volume and mean corpuscular hemoglobin concentration in a sample population. Studies with lysates and resealed membrane ghosts show that hemoglobin is very effective in lowering water-proton relaxation time whereas resealed membrane ghosts in the absence of hemoglobin are less effective than intact red cells. 9 refs.; 3 figs.; 1 table

Ross operation in children and young adults: the Alder Hey case series

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Pozzi Marco

2004-04-01

Full Text Available Abstract Background The ideal prosthesis for aortic valve replacement in children and young adults has not been found yet. In recent years there has been a renewed interest in the replacement of aortic valve with the pulmonary autograft owing to its advantages of lack of anticoagulation, potential for growth and excellent haemodynamic performance. The purpose of this study was to review our institutional experience at Alder Hey hospital with the Ross procedure in children and young adults. Methods From November 1996 to September 2003, 38 patients (mean age, 13.1 ± 5.7 years underwent the Ross procedure for various aortic valve diseases using the root replacement technique. Clinical and echocardiographic follow-up was performed early (within 30 days, 3 to 6 months, and yearly after surgery. Medical records of all patients were reviewed retrospectively. Results There was 1 perioperative death. The patients were followed-up for a median interval of 36 months and up to 7 years. One patient died 3 years after surgery secondary to ventricular arrhythmia with overall mortality of 5.3%. Actuarial survival at 7 years was 94 ± 2.5% and there was 100% freedom from reoperation for autograft valve dysfunction or any other cause. Balloon dilatation was required in 2 patients for pulmonary homograft stenosis. The haemodynamics at the latest follow-up were also similar to those at the time of discharge after surgery. There was no progression in the degree of aortic regurgitation for 11 patients with trivial and 3 with mild regurgitation. Conclusion Our experience demonstrates that Ross operation is an attractive option for aortic valve replacement in children and young adults. Not only can the operation be accomplished with a low operative risk but the valve function stays normal over a long period of time with minimal alteration in lifestyle and no need for repeated operations to replace the valve as a result of somatic growth of the children.

The acute stress response of red porgy, Pagrus pagrus, kept on a red or white background

NARCIS (Netherlands)

Salm, A.L. van der; Pavlidis, M; Flik, G.; Wendelaar Bonga, S.E.

2005-01-01

The skin colour of red porgy, Pagrus pagrus, can be modified by exposure to different background colours. Red and white background colours brighten the dark skin colour that develops under common culture conditions in red porgy. To assess whether skin colour is also modified by aquaculture related

EFSA NDA Panel (EFSA Panel on Dietetic Products, Nutrition and Allergies), 2013. Scientific Opinion on the substantiation of a health claim related to a combination of red spinach, green spinach, red chicory, green chicory, green leaf chard, red leaf chard, red Swiss chard, golden Swiss chard

DEFF Research Database (Denmark)

Tetens, Inge

related to a combination of red spinach, green spinach, red chicory, green chicory, green leaf chard, red leaf chard, red Swiss chard, golden Swiss chard and white Swiss chard and protection of blood lipids from oxidative damage. The food that is the subject of the health claim, a combination...... of the following frozen vegetables: red spinach (Spinacia oleracea L.), green spinach (Spinacia oleracea L.), red chicory (Cichorium intybus L.), green chicory (Cichorium intybus L.), green leaf chard (Beta vulgaris L. var. cicla), red leaf chard (Beta vulgaris L. var. cicla), red Swiss chard (Beta vulgaris L. var...... conclusions could be drawn for the scientific substantiation of the claim were provided by the applicant. The Panel concludes that a cause and effect relationship has not been established between consumption of a combination of red spinach, green spinach, red chicory, green chicory, green leaf chard, red leaf...

Next generation red teaming

CERN Document Server

Dalziel, Henry

2015-01-01

Red Teaming is can be described as a type of wargaming.In private business, penetration testers audit and test organization security, often in a secretive setting. The entire point of the Red Team is to see how weak or otherwise the organization's security posture is. This course is particularly suited to CISO's and CTO's that need to learn how to build a successful Red Team, as well as budding cyber security professionals who would like to learn more about the world of information security. Teaches readers how to dentify systemic security issues based on the analysis of vulnerability and con

Tests of two convection theories for red giant and red supergiant envelopes

Science.gov (United States)

Stothers, Richard B.; Chin, Chao-Wen

1995-01-01

Two theories of stellar envelope convection are considered here in the context of red giants and red supergiants of intermediate to high mass: Boehm-Vitense's standard mixing-length theory (MLT) and Canuto & Mazzitelli's new theory incorporating the full spectrum of turbulence (FST). Both theories assume incompressible convection. Two formulations of the convective mixing length are also evaluated: l proportional to the local pressure scale height (H(sub P)) and l proportional to the distance from the upper boundary of the convection zone (z). Applications to test both theories are made by calculating stellar evolutionary sequences into the red zone (z). Applications to test both theories are made by calculating stellar evolutionary sequences into the red phase of core helium burning. Since the theoretically predicted effective temperatures for cool stars are known to be sensitive to the assigned value of the mixing length, this quantity has been individually calibrated for each evolutionary sequence. The calibration is done in a composite Hertzsprung-Russell diagram for the red giant and red supergiant members of well-observed Galactic open clusters. The MLT model requires the constant of proportionality for the convective mixing length to vary by a small but statistically significant amount with stellar mass, whereas the FST model succeeds in all cases with the mixing lenghth simply set equal to z. The structure of the deep stellar interior, however, remains very nearly unaffected by the choices of convection theory and mixing lenghth. Inside the convective envelope itself, a density inversion always occurs, but is somewhat smaller for the convectively more efficient MLT model. On physical grounds the FST model is preferable, and seems to alleviate the problem of finding the proper mixing length.

The IOC consensus statement: beyond the Female Athlete Triad--Relative Energy Deficiency in Sport (RED-S).

Science.gov (United States)

Mountjoy, Margo; Sundgot-Borgen, Jorunn; Burke, Louise; Carter, Susan; Constantini, Naama; Lebrun, Constance; Meyer, Nanna; Sherman, Roberta; Steffen, Kathrin; Budgett, Richard; Ljungqvist, Arne

2014-04-01

Protecting the health of the athlete is a goal of the International Olympic Committee (IOC). The IOC convened an expert panel to update the 2005 IOC Consensus Statement on the Female Athlete Triad. This Consensus Statement replaces the previous and provides guidelines to guide risk assessment, treatment and return-to-play decisions. The IOC expert working group introduces a broader, more comprehensive term for the condition previously known as 'Female Athlete Triad'. The term 'Relative Energy Deficiency in Sport' (RED-S), points to the complexity involved and the fact that male athletes are also affected. The syndrome of RED-S refers to impaired physiological function including, but not limited to, metabolic rate, menstrual function, bone health, immunity, protein synthesis, cardiovascular health caused by relative energy deficiency. The cause of this syndrome is energy deficiency relative to the balance between dietary energy intake and energy expenditure required for health and activities of daily living, growth and sporting activities. Psychological consequences can either precede RED-S or be the result of RED-S. The clinical phenomenon is not a 'triad' of the three entities of energy availability, menstrual function and bone health, but rather a syndrome that affects many aspects of physiological function, health and athletic performance. This Consensus Statement also recommends practical clinical models for the management of affected athletes. The 'Sport Risk Assessment and Return to Play Model' categorises the syndrome into three groups and translates these classifications into clinical recommendations.

Silvical characteristics of red maple (Acer rubrum)

Science.gov (United States)

Russell J. Hutnik; Harry W. Yawney

1961-01-01

Red maple (Acer rubrum L.) is also known as Carolina red maple, scarlet maple, soft maple, swamp maple, water maple, and white maple. Taxonomists recognize several varieties of red maple. The most common is Drummond red maple (Acer rubrum var. drummondii (Hook, & Arn.) Sarg.).

Lipase-catalyzed asymmetric synthesis of naphtho[2,3-c]furan-1(3H)-one derivatives by a one-pot dynamic kinetic resolution/intramolecular Diels-Alder reaction: Total synthesis of (-)-himbacine.

Science.gov (United States)

Sugiyama, Koji; Kawanishi, Shinji; Oki, Yasuhiro; Kamiya, Marin; Hanada, Ryosuke; Egi, Masahiro; Akai, Shuji

2018-04-01

One-pot sequential reactions using the acyl moieties installed by enzymatic dynamic kinetic resolution of alcohols have been little investigated. In this work, the acryloyl moiety installed via the lipase/oxovanadium combo-catalyzed dynamic kinetic resolution of a racemic dienol [4-(cyclohex-1-en-1-yl)but-3-en-2-ol or 1-(cyclohex-1-en-1-yl)but-2-en-1-ol] with a (Z)-3-(phenylsulfonyl)acrylate underwent an intramolecular Diels-Alder reaction in a one-pot procedure to produce an optically active naphtho[2,3-c]furan-1(3H)-one derivative (98% ee). This method was successfully applied to the asymmetric total synthesis of (-)-himbacine. Copyright © 2017 Elsevier Ltd. All rights reserved.

Red Sirius

Energy Technology Data Exchange (ETDEWEB)

Martynov, D Ya

1976-01-01

A hypothesis is proposed explaining the assumption that Sirius changed its colour from red in the second century to pale blue in the tenth century A.D. The hypothesis is based on the possibility of transformation of a Sirius satellite (Sirius B) from a red giant in the past to a white dwarf in the present. Such a transformation would have been accompanied by an explosion of Sirius B, which is clearly visible from the Earth. The fact that the increase in Sirius brightness by 4-5 units is not reflected in historical chronicles is attributed to the degradation of sciences in Europe in 4-10 centuries.

RED Alert – Early warning or detection of global re-emerging infectious disease (RED)

Energy Technology Data Exchange (ETDEWEB)

Deshpande, Alina [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-07-13

This is the PDF of a presentation for a webinar given by Los Alamos National Laboratory (LANL) on the early warning or detection of global re-emerging infectious disease (RED). First, there is an overview of LANL biosurveillance tools. Then, information is given about RED Alert. Next, a demonstration is given of a component prototype. RED Alert is an analysis tool that can provide early warning or detection of the re-emergence of an infectious disease at the global level, but through a local lens.

Abundance of Alnus incana ssp. rugosa in Adirondack Mountain shrub wetlands and its influence on inorganic nitrogen

International Nuclear Information System (INIS)

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

2003-01-01

The presence of the nitrogen-fixing shrub, Alnus incana ssp. rugosa, influences the concentration of inorganic nitrogen in surface waters in the Adirondack Mountain region of northern New York. - The purpose of this research was to determine the abundance of the nitrogen-fixing shrub, Alnus incana ssp. rugosa (speckled alder), in shrub wetlands of the Adirondack Mountain region of New York State and to determine whether its abundance affects the concentration or accumulation of inorganic nitrogen in wetland substrates. Alder/willow wetlands are the second most common wetland type in the Adirondack region. The Adirondack Park Agency's digital GIS database of wetland types was used to determine the areal extent of alder/willow wetlands in the Adirondacks. Randomly selected wetlands were sampled to determine the size and abundance of alder. Alder densities averaged ∼7000 stems ha -1 and alder was present in 75% of the wetlands. As an indication of short-term accumulation of NO 3 - and NH 4 + in wetland substrates, ion exchange resins were used to sample ground water in high and low alder density wetlands as well as from wetlands lacking alder and dominated by conifers. Additionally, NO 3 - and NH 4 + concentrations in ground water samples were measured. NH 4 + accumulation levels from exchange resins were low for all wetland types while groundwater NH 4 + concentration was highest in the low-density alder sites. Wetlands with high alder density had approximately six times higher NO 3 - accumulation than other wetlands. Substrate groundwater NO 3 - concentrations in wetlands of high-density alder exceeded by three times levels in low or no alder wetlands, showing the importance of alder to local N budgets. To assess the recovery of shrub wetlands from acidification, future studies should determine the fate of fixed N in wetland systems

Metagenomic studies of the Red Sea.

Science.gov (United States)

Behzad, Hayedeh; Ibarra, Martin Augusto; Mineta, Katsuhiko; Gojobori, Takashi

2016-02-01

Metagenomics has significantly advanced the field of marine microbial ecology, revealing the vast diversity of previously unknown microbial life forms in different marine niches. The tremendous amount of data generated has enabled identification of a large number of microbial genes (metagenomes), their community interactions, adaptation mechanisms, and their potential applications in pharmaceutical and biotechnology-based industries. Comparative metagenomics reveals that microbial diversity is a function of the local environment, meaning that unique or unusual environments typically harbor novel microbial species with unique genes and metabolic pathways. The Red Sea has an abundance of unique characteristics; however, its microbiota is one of the least studied among marine environments. The Red Sea harbors approximately 25 hot anoxic brine pools, plus a vibrant coral reef ecosystem. Physiochemical studies describe the Red Sea as an oligotrophic environment that contains one of the warmest and saltiest waters in the world with year-round high UV radiations. These characteristics are believed to have shaped the evolution of microbial communities in the Red Sea. Over-representation of genes involved in DNA repair, high-intensity light responses, and osmoregulation were found in the Red Sea metagenomic databases suggesting acquisition of specific environmental adaptation by the Red Sea microbiota. The Red Sea brine pools harbor a diverse range of halophilic and thermophilic bacterial and archaeal communities, which are potential sources of enzymes for pharmaceutical and biotechnology-based application. Understanding the mechanisms of these adaptations and their function within the larger ecosystem could also prove useful in light of predicted global warming scenarios where global ocean temperatures are expected to rise by 1-3°C in the next few decades. In this review, we provide an overview of the published metagenomic studies that were conducted in the Red Sea, and

Antibacterial Compounds from Red Seaweeds (Rhodophyta

Directory of Open Access Journals (Sweden)

Noer Kasanah

2015-07-01

Full Text Available Seaweeds produce great variety of metabolites benefit for human. Red seaweeds (Rhodophyta are well known as producer of phycocolloids such agar, agarose, carragenan and great variety of secondary metabolites. This review discusses the red algal secondary metabolites with antibacterial activity. The chemical constituents of red algae are steroid, terpenoid, acetogenin and dominated by halogenated compounds mainly brominated compounds. Novel compounds with intriguing skeleton are also reported such as bromophycolides and neurymenolides. In summary, red seaweeds are potential sources for antibacterial agents and can serve as lead in synthesis of new natural medicines.

"Congo" red: out of Africa?

Science.gov (United States)

Steensma, D P

2001-02-01

Congo red is the essential histologic stain for demonstrating the presence of amyloidosis in fixed tissues. To the best of my knowledge, nothing has been written about why the stain is named "Congo." To understand the etymology and history of the Congo red histologic stain. Primary sources were consulted extensively, including 19th-century corporate documents, newspapers, legal briefs, patents, memoirs, and scientific papers. Sources were obtained from multiple university libraries and German corporate archives. To Europeans in 1885, the word Congo evoked exotic images of far-off central Africa known as The Dark Continent. The African Congo was also a political flashpoint during the Age of Colonialism. "Congo" red was introduced in Berlin in 1885 as the first of the economically lucrative direct textile dyes. A patent on Congo red was filed by the AGFA Corporation of Berlin 3 weeks after the conclusion of the well-publicized Berlin West Africa Conference. During these important diplomatic talks, German Chancellor Otto von Bismarck presided over a discussion of free trade issues in the Congo River basin. A challenge to AGFA's Congo red patent led to a precedent-setting decision in intellectual property law. The Congo red stain was named "Congo" for marketing purposes by a German textile dyestuff company in 1885, reflecting geopolitical current events of that time.

White dwarf-red dwarf binaries in the Galaxy

NARCIS (Netherlands)

Besselaar, E.J.M. van den

2007-01-01

This PhD thesis shows several studies on white dwarf - red dwarf binaries. White dwarfs are the end products of most stars and red dwarfs are normal hydrogen burning low-mass stars. White dwarf - red dwarf binaries are both blue (white dwarf) and red (red dwarf). Together with the fact that they are

Decadal Stability of Red Sea Mangroves

KAUST Repository

Almahasheer, Hanan; Aljowair, Abdulaziz; Duarte, Carlos M.; Irigoien, Xabier

2015-01-01

Across the Earth, mangroves play an important role in coastal protection, both as nurseries and carbon sinks. However, due to various human and environmental impacts, the coverage of mangroves is declining on a global scale. The Red Sea is in the northern-most area of the distribution range of mangroves. Little is known about the surface covered by mangroves at this northern limit or about the changes experienced by Red Sea mangroves. We sought to study changes in the coverage of Red Sea mangroves by using multi-temporal Landsat data (1972, 2000 and 2013). Interestingly, our results show that there has been no decline in mangrove stands in the Red Sea but rather a slight increase. The area covered by mangroves is about 69 Km2 along the African shore and 51 Km2 along the Arabian Peninsula shore. From 1972 to 2013, the area covered by mangroves increased by about 0.29% y-1. We conclude that the trend exhibited by Red Sea mangroves departs from the general global decline of mangroves. Along the Red Sea, mangroves expanded by 12% over the 41 years from 1972 to 2013. Losses to Red Sea mangroves, mostly due to coastal development, have been compensated by afforestation projects.

Decadal Stability of Red Sea Mangroves

KAUST Repository

Almahasheer, Hanan

2015-12-15

Across the Earth, mangroves play an important role in coastal protection, both as nurseries and carbon sinks. However, due to various human and environmental impacts, the coverage of mangroves is declining on a global scale. The Red Sea is in the northern-most area of the distribution range of mangroves. Little is known about the surface covered by mangroves at this northern limit or about the changes experienced by Red Sea mangroves. We sought to study changes in the coverage of Red Sea mangroves by using multi-temporal Landsat data (1972, 2000 and 2013). Interestingly, our results show that there has been no decline in mangrove stands in the Red Sea but rather a slight increase. The area covered by mangroves is about 69 Km2 along the African shore and 51 Km2 along the Arabian Peninsula shore. From 1972 to 2013, the area covered by mangroves increased by about 0.29% y-1. We conclude that the trend exhibited by Red Sea mangroves departs from the general global decline of mangroves. Along the Red Sea, mangroves expanded by 12% over the 41 years from 1972 to 2013. Losses to Red Sea mangroves, mostly due to coastal development, have been compensated by afforestation projects.

From red giants to planetary nebulae

International Nuclear Information System (INIS)

Kwok, S.

1982-01-01

The transition from red giants to planetary nebulae is studied by comparing the spectral characteristics of red giant envelopes and planetary nebulae. Observational and theoretical evidence both suggest that remnants of red giant envelopes may still be present in planetary nebula systems and should have significant effects on their formation. The dynamical effects of the interaction of stellar winds from central stars of planetary nebulae with the remnant red giant envelopes are evaluated and the mechanism found to be capable of producing the observed masses and momenta of planetary nebulae. The observed mass-radii relation of planetary nebulae may also be best explained by the interacting winds model. The possibility that red giant mass loss, and therefore the production of planetary nebulae, is different between Population I and II systems is also discussed

red - an R package to facilitate species red list assessments according to the IUCN criteria

Directory of Open Access Journals (Sweden)

Pedro Cardoso

2017-10-01

Full Text Available The International Union for the Conservation of Nature Red List is the most useful database of species that are at risk of extinction worldwide, as it relies on a number of objective criteria and is now widely adopted. The R package red – IUCN Redlisting Tools - performs a number of spatial analyses based on either observed occurrences or estimated ranges. Functions include calculating Extent of Occurrence (EOO, Area of Occupancy (AOO, mapping species ranges, species distribution modelling using climate and land cover and calculating the Red List Index for groups of species. The package allows the calculation of confidence limits for all measures. Spatial data of species occurrences, environmental or land cover variables can be either given by the user or automatically extracted from several online databases. It outputs geographical range, elevation and country values, maps in several formats and vectorial data for visualization in Google Earth. Several examples are shown demonstrating the usefulness of the different methods. The red package constitutes an open platform for further development of new tools to facilitate red list assessments.

red - an R package to facilitate species red list assessments according to the IUCN criteria.

Science.gov (United States)

Cardoso, Pedro

2017-01-01

The International Union for the Conservation of Nature Red List is the most useful database of species that are at risk of extinction worldwide, as it relies on a number of objective criteria and is now widely adopted. The R package red - IUCN Redlisting Tools - performs a number of spatial analyses based on either observed occurrences or estimated ranges. Functions include calculating Extent of Occurrence (EOO), Area of Occupancy (AOO), mapping species ranges, species distribution modelling using climate and land cover and calculating the Red List Index for groups of species. The package allows the calculation of confidence limits for all measures. Spatial data of species occurrences, environmental or land cover variables can be either given by the user or automatically extracted from several online databases. It outputs geographical range, elevation and country values, maps in several formats and vectorial data for visualization in Google Earth. Several examples are shown demonstrating the usefulness of the different methods. The red package constitutes an open platform for further development of new tools to facilitate red list assessments.

Habitability of planets around red dwarf stars.

Science.gov (United States)

Heath, M J; Doyle, L R; Joshi, M M; Haberle, R M

1999-08-01

Recent models indicate that relatively moderate climates could exist on Earth-sized planets in synchronous rotation around red dwarf stars. Investigation of the global water cycle, availability of photosynthetically active radiation in red dwarf sunlight, and the biological implications of stellar flares, which can be frequent for red dwarfs, suggests that higher plant habitability of red dwarf planets may be possible.

The effect of gamma irradiation on crude fibre NDF, ADF, and ADL of some Syrian agricultural residues

International Nuclear Information System (INIS)

Al-Masri, M.R.; Zarkawi, M.

1992-07-01

The effects of 150 KGy of gamma irradiation on crude fibre and its main components (cellulose, hemicellulose-cellulose and lignin) and on neutral detergent fibre (NDF), acid detergent lignin (ADL), and acid detergent fibre (ADF) were investigated. The results indicate that gamma irradiation decreased Cf content by 30%, 28%, 29%, and 17% for cottonwood, lentils straw, apple-tree pruning products and olive-oil cake, respectively. NDF values also decreased by 5%, 23%, 13% and 3% for, cottonwood, lentils straw, olive-oil cake and apple-tree pruning products respectively. Gamma irradiation (150 KGy) had no effects on ADF and ADL for lentils straw, apple-tree pruning products and olive-oil cake whereas, ADF decreased by 8.5% and ADL by 8.3 for cottonwood. Hemicellulose content increased by 12% for cottonwood while decreased by 54% for lentils straw and by 33% for apple-tree pruning products with no effects for olive-oil cake. Cellulose content decreased by 8.6% for cottonwood whereas no effects for the remaining residues were seen. Gamma irradiation treatment improved the nutritive value of the agriculture residues examined. The reduction in crude fibre content varies with the residue. (author). 15 refs., 5 tabs

Infra Red 3D Computer Mouse

DEFF Research Database (Denmark)

Harbo, Anders La-Cour; Stoustrup, Jakob

2000-01-01

The infra red 3D mouse is a three dimensional input device to a computer. It works by determining the position of an arbitrary object (like a hand) by emitting infra red signals from a number of locations and measuring the reflected intensities. To maximize stability, robustness, and use of bandw......The infra red 3D mouse is a three dimensional input device to a computer. It works by determining the position of an arbitrary object (like a hand) by emitting infra red signals from a number of locations and measuring the reflected intensities. To maximize stability, robustness, and use...

Mechanisms of immune red cell destruction, and red cell compatibility testing

International Nuclear Information System (INIS)

Garratty, G.

1983-01-01

The immune destruction of red cells can occur as a complement-mediated intravascular process, or extravascularly, where the red cells are destroyed by macrophages following interaction with cell-bound IgG1, IgG3, and/or C3b. Many of the factors that affect this in vivo destruction are not taken into account during in vitro pretransfusion compatibility testing. At present, even by use of more elaborate tests, it is difficult to accurately predict the fate of a transfused unit of blood. By using some simple information, such as antibody specificity and thermal range, it is sometimes possible to predict the outcome of transfusing a unit of blood that is incompatible in vitro. At other times it may be necessary to utilize 51 Cr-labeled red cells to determine the risk of transfusing such units. Because of the paucity of reported clinical correlations, macrophage/monocyte monolayer assays are of little practical value at present

Combined effects of blue light and supplemental far-red light and effects of increasing red light with constant far-red light on growth of kidney bean [Phaseolus vulgaris] under mixtures of narrow-band light sources

International Nuclear Information System (INIS)

Hanyu, H.; Shoji, K.

2000-01-01

Increasing blue light and decreasing R: FR with supplementary far-red light affect morphogenesis, dry matter production and dry matter partitioning to leaves, stems and roots. In this study, the combined effects of the two spectral treatments were examined in kidney bean (Phaseolus vulgaris L.) grown under the mixture of four different narrow-band light sources. In addition, because the leaf and stem growth are accelerated by increasing red light (600-700 nm) in proportion to far-red light (700-800 nm) while keeping R : FR constant, this study was conducted to determine whether red light or far-red light causes the acceleration of growth. Increasing blue light (400-500 nm) and decreasing R : FR only interacted on stem extension. The results illustrated with figures suggest that blue light amplifies or attenuates the acceleration of stem extension caused by decreasing R : FR. On the other hand, increasing red light with constant far-red light had no influence on leaf expansion or stem extension while R : FR increased. Because the acceleration of leaf and stem growth is caused by increasing either far-red light or both red and far-red light in our environmental conditions, the stimulative effects on leaves and stems seem to require increases in far-red light rather than red light

Diseño de una red WAN

OpenAIRE

Labella Sanz, Gabriel

2010-01-01

Disseny d'una xarxa WAN, formada per una xarxa d'Accés HFC, una xarxa de Commutació ATM i una xarxa de Transport SDH. Diseño de una red WAN, formada por una red de Acceso HFC, una red de Conmutación ATM y una red de Transporte SDH. WAN network design consisting of a HFC access network, an ATM switching network and a SDH transport network.