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Sample records for alder-winter theory

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.
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
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.
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.
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.
Red alder potential in Alaska

Science.gov (United States)

Allen Brackley; David Nicholls; Mike Hannan

2010-01-01

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

Science.gov (United States)

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

1978-01-01

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

Science.gov (United States)

Robert L. Deal; Constance A. Harrington

2006-01-01

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

Science.gov (United States)

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

1949-01-01

The increasing importance of red alder as a commercial species in the Pacific Northwest has prompted the three agencies listed above to pool their tree measurement data for the construction of standard regional red alder volume tables. The tables included here were based on trees from a variety of sites and form classes. Approximately one quarter of the total number of...
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).
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.
Quantitative structure-activation barrier relationship modeling for Diels-Alder ligations utilizing quantum chemical structural descriptors.

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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.
The pentadehydro-Diels-Alder reaction.

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

Directory of Open Access Journals (Sweden)

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.
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…
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.

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

Directory of Open Access Journals (Sweden)

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.
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.

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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

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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.

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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.
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
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.
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)
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
Germination of red alder seed.

Science.gov (United States)

M.A. Radwan; D.S. DeBell

1981-01-01

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

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.
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.
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.
CERN Winter School on Supergravity, Strings, and Gauge Theory 2010

CERN Multimedia

CERN. Geneva

2010-01-01

The CERN Winter School on Supergravity, Strings, and Gauge Theory is the analytic continuation of the yearly training school of the former EC-RTN string network "Constituents, Fundamental Forces and Symmetries of the Universe". The 2010 edition of the school is supported and organized by the CERN Theory Divison, and will take place from Monday January 25 to Friday January 29, at CERN. As its predecessors, this school is meant primarily for training of doctoral students and young postdoctoral researchers in recent developments in theoretical high-energy physics and string theory. The programme of the school will consist of five series of pedagogical lectures, complemented by tutorial discussion sessions in the afternoons. Previous schools in this series were organized in 2005 at SISSA in Trieste, and in 2006, 2007, 2008, and 2009 at CERN, Geneva. Other similar schools have been organized in the past by the former related RTN network "The Quantum Structure of Spacetime and the Geometric Nature of Fundamenta...
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 JosÃƒÂ© 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.
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.
A Tri-O-Bridged Diels-Alder Adduct from Cortex Mori Radicis

Directory of Open Access Journals (Sweden)

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.
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.
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.
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.
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)
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.
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.

Science.gov (United States)

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.
Red alder: A bibliography with abstracts

Science.gov (United States)

Charles F. Heebner; Mary Jane Bergener

1983-01-01

This bibliography lists 661 references to world literature through Hay 1978 containing information about red alder (Alnus rubra Bong.). Included are publications about its taxonomy, biology and silvics, chemical and physical information about its wood and fiber, studies on its nitrogen fixing properties, and reports on industrial uses and economic...
N2-fixing red alder indirectly accelerates ecosystem nitrogen cycling

Science.gov (United States)

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

2012-01-01

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

Science.gov (United States)

David Nicholls; Joseph. Roos

2007-01-01

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

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

Directory of Open Access Journals (Sweden)

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.
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.
Biology and ecology of red alder.

Science.gov (United States)

Constance A. Harrington

2006-01-01

Red alder is the most common hardwood in the Pacific Northwest with a range stretching from coastal southeast Alaska to southern California and east to isolated populations in Idaho. Soil moisture during the growing season influences where it grows and its growth rates; it can tolerate poor drainage but not droughty, hot sites. Due to its tolerance of wet soil...
Growth and development of red alder compared with conifers in 30-year-old stands.

Science.gov (United States)

Carl M. Berntsen

1961-01-01

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

Science.gov (United States)

Robert H. Ruth; Carl M. Berntsen

1956-01-01

A key to better restocking of conifers on recently cutover forest land in the Oregon Coast Range is the elimination of competition from red alder (Alnus rubra Bong.). This can be readily accomplished with a foliage spray containing 2,4-dichlorophenoxyacetic acid (2.4-D). Tests in 1954 and 1955 on the Cascade Head Experimental Forest have shown that...
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?;.
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...

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

Science.gov (United States)

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

Science.gov (United States)

Marshall D. Murray; Richard E. Miller

1986-01-01

To quantify between-species interactions, we measured and compared survival and growth of planted Douglas-fir and associated planted and volunteer red alder at a location on the west side of the Cascade Range in Washington. The planted alder were wildlings dug either from a nearby area or from a distant, coastal site and interplanted into a 3-year-old Douglas-fir...
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.
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.
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)
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.
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
Character-marked furniture made from red alder harvested in southeast Alaska: product perspectives from consumers and retailers

Science.gov (United States)

Matthew Bumgardner; David Nicholls; Valerie Barber

2009-01-01

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

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

Science.gov (United States)

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

2005-01-01

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

Science.gov (United States)

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.
Winter-to-winter variations in indoor radon

International Nuclear Information System (INIS)

Mose, D.G.; Mushrush, G.W.; Kline, S.W.

1989-01-01

Indoor radon concentrations in northern Virginia and central Maryland show a strong dependence on weather. Winter tends to be associated with higher than average indoor radon, and summer with lower than average. However, compared to the winter of 1986-1987, the winter of 1987-1988 was warmer and drier. Consequently, winter-to-winter indoor radon decreased by about 25%. This winter-to-winter decrease is unexpectedly large, and simulates winter-to-summer variations that have been reported
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
Computational Investigation of the Competition between the Concerted Diels-Alder Reaction and Formation of Diradicals in Reactions of Acrylonitrile with Non-Polar Dienes

Science.gov (United States)

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
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.

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

Science.gov (United States)

Krishna Poudel; Hailemariam Temesgen

2016-01-01

Biomass estimates are required for reporting carbon, assessing feedstock availability, and assessing forest fire threat. We developed diameter- and height-based biomass equations for Western hemlock (Tsuga heterophylla (Raf.) Sarg.) and red alder (Alnus rubra Bong.) trees in Western Oregon. A system of component biomass...
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
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 Alder-Conifer Stands in Alaska: An Example of Mixed Species Management to Enhance Structural and Biological Complexity

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Robert L. Deal

2017-04-01

Full Text Available There is worldwide interest in managing forests to improve biodiversity, enhance ecosystem services and assure long-term sustainability of forest resources. An increasingly important goal of forest management is to increase stand diversity and improve wildlife and aquatic habitat. Well-planned silvicultural systems containing a mixture of broadleaf-conifer species have potential to enhance stand diversity and provide other ecosystem services earlier than typical even-aged conifer plantations. Here, we use the example of mixed Sitka spruce/western hemlock and red alder in young, managed stands in southeast Alaska to achieve these goals. We briefly describe the silvics of Sitka spruce, western hemlock and red alder plantations as pure conifer stands or pure broadleaf stands. Then, we synthesize studies of mixed red alder-Sitka spruce/western hemlock stands in southeast Alaska and present their potential for improving stand structural complexity, biodiversity and other ecosystem services over pure conifer forests. Finally, we discuss some of the opportunities and potential tradeoffs for managing mixed broadleaf-conifer stands for providing a number of natural resources and the influence of these broadleaf-conifer forests on ecosystem linkages and processes.
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.
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...
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.
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
Consumer preferences for kitchen cabinets made from red alder: a comparison to other hardwoods.

Science.gov (United States)

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

2004-01-01

In Alaska, red alder (Alnus rubra Bong.) is an abundant but commercially underutilized species despite having properties suitable for higher value products, including furniture and cabinetry. However, it laces the name recognition of mote traditional hardwoods. Our research measured the effect of this lack of familiarity on consumer preferences...
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
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-ÃÂ€-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.
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.
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.
Variation in damage from growing-season frosts among open-pollinated families of red alder.

Science.gov (United States)

Kevin C. Peeler; Dean S. DeBell

1987-01-01

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

Science.gov (United States)

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

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

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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
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.
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
Size of Douglas-fir trees in relation to distance from a mixed red alder - Douglas-fir stand

Science.gov (United States)

R.E. Miller; D.L. Reukema; T.A. Max

1993-01-01

Variation in diameter, height, and stem volume of 57-year-old Douglas-fir(Pseudotsuga menziesii var. menziesii (Mirb.) Franco) was related to distance of these trees from a 27 m wide strip in the same Douglas-fir plantation that had been interplanted with red alder (Alnus rubra Bong.). Within the...
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.
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.
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.
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.
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

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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.
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.
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
Theoretical Study on the Aza-Diels-Alder Reaction Catalyzed by PHCl2 Lewis Acid via Pnicogen Bonding.

Science.gov (United States)

Yaghoobi, Fereshteh; Sohrabi Mahboub, Mahdi

2018-03-15

The reaction mechanism of the Aza-Diels-Alder (A-D-A) cycloaddition reaction between X 2 C═NNH 2 , where X = H, F, Cl, Br, and 1,3-butadiene catalyzed by a PHCl 2 Lewis acid was characterized using density functional theory calculations. The influences of various substituents of X on the studied reaction were analyzed using the activation strain model (ASM), which is also termed as the distortion-interaction model. Calculations showed that the smallest and largest values of the activation energies belong to the substituents of F and Br, respectively. The activation energy of the studied reactions was decreased within 8.6 kcal·mol -1 in the presence of PHCl 2 catalyst. Investigations showed that the pnicogen bonding is adequately capable of activating the A-D-A reaction. The quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis were implemented to understand the nature of C 4,Cbut ···C XIm and C 1,Cbut ···N XIm bonds at the TS structures. Additionally, the energy decomposition analysis (EDA) based on the ETS-NOCV scheme was used to characterize the nature of C 4,Cbut ···C XIm and C 1,Cbut ···N XIm bond. The results of the study mirror the fact that the PHCl 2 Lewis acid may be suggested as a simple suitable catalyst for experimental studies on the A-D-A reactions.
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)
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.

Science.gov (United States)

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

Science.gov (United States)

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
PREFACE: Lectures from the CERN Winter School on Strings, Supergravity and Gauge Theories, CERN, 9-13 February 2009 Lectures from the CERN Winter School on Strings, Supergravity and Gauge Theories, CERN, 9-13 February 2009

Science.gov (United States)

Uranga, A. M.

2009-11-01

This special section is devoted to the proceedings of the conference `Winter School on Strings, Supergravity and Gauge Theories', which took place at CERN, the European Centre for Nuclear Research, in Geneva, Switzerland 9-13 February 2009. This event is part of a yearly series of scientific schools, which represents a well established tradition. Previous events have been held at SISSA, in Trieste, Italy, in February 2005 and at CERN in January 2006, January 2007 and January 2008, and were funded by the European Mobility Research and Training Network `Constituents, Fundamental Forces and Symmetries of the Universe'. The next event will take place again at CERN, in January 2010. The school was primarily meant for young doctoral students and postdoctoral researchers working in the area of string theory. It consisted of several general lectures of four hours each, whose notes are published in this special section, and six working group discussion sessions, focused on specific topics of the network research program. It was well attended by over 200 participants. The topics of the lectures were chosen to provide an introduction to some of the areas of recent progress, and to the open problems, in string theory. One of the most active areas in string theory in recent years has been the AdS/CFT or gauge/gravity correspondence, which proposes the complete equivalence of string theory on (asymptotically) anti de Sitter spacetimes with certain quantum (gauge) field theories. The duality has recently been applied to understanding the hydrodynamical properties of a hot plasma in gauge theories (like the quark-gluon plasma created in heavy ion collisions at the RHIC experiment at Brookhaven, and soon at the LHC at CERN) in terms of a dual gravitational AdS theory in the presence of a black hole. These developments were reviewed in the lecture notes by M Rangamani. In addition, the AdS/CFT duality has been proposed as a tool to study interesting physical properties in other
Winters fuels report

International Nuclear Information System (INIS)

1995-01-01

The outlook for distillate fuel oil this winter is for increased demand and a return to normal inventory patterns, assuming a resumption of normal, cooler weather than last winter. With industrial production expected to grow slightly from last winter's pace, overall consumption is projected to increase 3 percent from last winter, to 3.4 million barrels per day during the heating season (October 1, 1995-March 31, 1996). Much of the supply win come from stock drawdowns and refinery production. Estimates for the winter are from the Energy Information Administration's (EIA) 4th Quarter 1995 Short-Tenn Energy Outlook (STEO) Mid-World Oil Price Case forecast. Inventories in place on September 30, 1995, of 132 million barrels were 9 percent below the unusually high year-earlier level. Inventories of high-sulfur distillate fuel oil, the principal type used for heating, were 13 percent lower than a year earlier. Supply problems are not anticipated because refinery production and the ready availability of imports should be adequate to meet demand. Residential heating off prices are expected to be somewhat higher than last winter's, as the effects of lower crude oil prices are offset by lower distillate inventories. Heating oil is forecast to average $0.92 per gallon, the highest price since the winter of 1992-93. Diesel fuel (including tax) is predicted to be slightly higher than last year at $1.13 per gallon. This article focuses on the winter assessment for distillate fuel oil, how well last year's STEO winter outlook compared to actual events, and expectations for the coming winter. Additional analyses include regional low-sulfur and high-sulfur distillate supply, demand, and prices, and recent trends in distillate fuel oil inventories
Illustrating the Utility of X-Ray Crystallography for Structure Elucidation through a Tandem Aldol Condensation/Diels-Alder Reaction Sequence

Science.gov (United States)

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

Science.gov (United States)

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.

Science.gov (United States)

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.

Science.gov (United States)

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.
Winter to winter recurrence of atmospheric circulation anomalies over East Asia and its impact on winter surface air temperature anomalies.

Science.gov (United States)

Zhao, Xia; Yang, Guang

2017-01-01

The persistence of atmospheric circulation anomalies over East Asia shows a winter to winter recurrence (WTWR) phenomenon. Seasonal variations in sea level pressure anomalies and surface wind anomalies display significantly different characteristics between WTWR and non-WTWR years. The WTWR years are characterized by the recurrence of both a strong (weak) anomalous Siberian High and an East Asian winter monsoon over two successive winters without persistence through the intervening summer. However, anomalies during the non-WTWR years have the opposite sign between the current and ensuing winters. The WTWR of circulation anomalies contributes to that of surface air temperature anomalies (SATAs), which is useful information for improving seasonal and interannual climate predictions over East Asia and China. In the positive (negative) WTWR years, SATAs are cooler (warmer) over East Asia in two successive winters, but the signs of the SATAs are opposite in the preceding and subsequent winters during the non-WTWR years.
C2-symmetric bisamidines: Chiral Brønsted bases catalysing the Diels-Alder reaction of anthrones

Directory of Open Access Journals (Sweden)

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.

Science.gov (United States)

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

Science.gov (United States)

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.
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
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.

Science.gov (United States)

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.

Science.gov (United States)

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.
Winter is losing its cool

Science.gov (United States)

Feng, S.

2017-12-01

Winter seasons have significant societal impacts across all sectors ranging from direct human health to ecosystems, transportation, and recreation. This study quantifies the severity of winter and its spatial-temporal variations using a newly developed winter severity index and daily temperature, snowfall and snow depth. The winter severity and the number of extreme winter days are decreasing across the global terrestrial areas during 1901-2015 except the southeast United States and isolated regions in the Southern Hemisphere. These changes are dominated by winter warming, while the changes in daily snowfall and snow depth played a secondary role. The simulations of multiple CMIP5 climate models can well capture the spatial and temporal variations of the observed changes in winter severity and extremes during 1951-2005. The models are consistent in projecting a future milder winter under various scenarios. The winter severity is projected to decrease 60-80% in the middle-latitude Northern Hemisphere under the business-as-usual scenario. The winter arrives later, ends earlier and the length of winter season will be notably shorter. The changes in harsh winter in the polar regions are weak, mainly because the warming leads to more snowfall in the high latitudes.
On the Catalytic Effect of Water in the Intramolecular Diels–Alder Reaction of Quinone Systems: A Theoretical Study

Directory of Open Access Journals (Sweden)

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

Science.gov (United States)

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

2012-01-01

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

Science.gov (United States)

Pressman, Norman E. P.

Attempts to generate a "climate-responsive" northern urban form are part of a relatively recent phenomenon and field of investigation. In conjunction with the international "winter cities" movement, the need has been established for explicit, systematic inquiry directed toward national and local action to improve the comfort and lifestyles of all northern inhabitants. It is important to recognize that winter-induced discomforts exist and that they must be acknowledged in planning theory and practice. For northern cities to function more satisfactorily, the negative impacts of winter must be reduced while its beneficial characteristics are enhanced. While not all summer activities can or should be abandoned during winter, proper micro-climatic control is essential if human life is to be retained outside. The outdoor season should be extended since so much indoor isolation occurs. The main principles to be incorporated in exemplary "winter city" design should be contact with nature, year-round usability, user participation, cultural continuity, and the creation of comfortable micro-climatic conditions throughout much of the city's open spaces. All valuable sources of inspiration must be harnessed in the attempt to mediate between organic regionalism and internationalism, on the one hand, and romanticism and pragmatic realism, on the other. Creating optimum conditions for human well-being, habitation, work and intellectual development in each of the four seasons is vital under harsh environments. Adopting a climate-sensitive approach to planning policy and urban design can render everyday life less stressful, especially during the lengthy winter periods found in many northern latitude and high altitude settings.
Resilience of roof-top Plant-Microbial Fuel Cells during Dutch winter

NARCIS (Netherlands)

Helder, M.; Strik, D.P.B.T.B.; Timmers, R.A.; Reas, S.M.T.; Hamelers, H.V.M.; Buisman, C.J.N.

2013-01-01

The Plant-Microbial Fuel Cell (P-MFC) is in theory a technology that could produce sustainable electricity continuously. We operated two designs of the P-MFC under natural roof-top conditions in the Netherlands for 221 days, including winter, to test its resilience. Current and power densities are
Highly enantioselective access to cannabinoid-type tricyles by organocatalytic Diels–Alder reactions

Directory of Open Access Journals (Sweden)

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

Directory of Open Access Journals (Sweden)

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

Science.gov (United States)

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.
New winter hardy winter bread wheat cultivar (Triticum aestivum L. Voloshkova

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Л. М. Голик

2007-12-01

Full Text Available Creation of Initial raw for breeding of winter wheat by change of the development type under low temperatures influence was described. Seeds of spring wheat were vernalized in aluminum weighting bottle. By using low temperatures at sawing of M2-6 at the begin ind of optimal terms of sawing of winter wheat, new winter-hardy variety of Voloshkova was bred.
33 CFR 100.109 - Winter Harbor Lobster Boat Race, Winter Harbor, ME.

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 1 2010-07-01 2010-07-01 false Winter Harbor Lobster Boat Race, Winter Harbor, ME. 100.109 Section 100.109 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY REGATTAS AND MARINE PARADES SAFETY OF LIFE ON NAVIGABLE WATERS § 100.109 Winter Harbor...
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.
Polar-Tropical Coupling in the Winter Stratosphere

Science.gov (United States)

Scott, R.

2017-12-01

A distinct pattern of enhanced equatorial potential vorticitygradients during QBO westerly anomalies, enhanced subtropicalgradients during QBO easterlies, is used to motivate a new formulationof dynamical coupling between the tropics and winter polar vortexbased on remote transfer of finite amplitude wave activity defined interms of lateral potential vorticity displacements. While the weakpotential vorticity gradients in the surf zone imply laterallyevanescent Rossby waves, transfer of wave activity from the polarvortex edge to the subtropical barrier or to the QBO westerly phaseequatorial gradients arises from nonlocality of potential vorticityinversion and the large horizontal displacements of the vortex edge.Our approach goes beyond the traditional description of the effect ofQBO wind anomalies on linear wave propagation through the stratospherevia wave reflection at the zero wind line; linear wave theory isappealing but neglects the long horizontal and vertical wavelengthsinvolved and the inhomogeneous background potential vorticity. Aparticular issue of outstanding interest is whether and how therelatively shallow QBO anomalies can influence the deep verticallypropagating waves on the edge of the winter stratospheric polarvortex. Process studies with a mechanistic model with prescribed QBOand carefully controlled high-latitude wave forcing are analyzed,guided by a reexamination of meteorological reanalysis, to address howsuch a dynamical linkage may influence in particular the resonantexcitation of the winter vortex, and the occurrence ofvortex-splitting sudden warming events. We quantify the associatedtransfer of wave activity from vortex edge to the tropics, considerunder what conditions this becomes a significant source of easterlymomentum in the driving of the QBO itself, and how the structure ofthe Brewer-Dobson circulation varies in response to the location ofthe QBO westerly winds in any given winter.
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.

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

Directory of Open Access Journals (Sweden)

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.
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…
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

Directory of Open Access Journals (Sweden)

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.
Winter Weather Emergencies

Science.gov (United States)

Severe winter weather can lead to health and safety challenges. You may have to cope with Cold related health problems, including ... there are no guarantees of safety during winter weather emergencies, you can take actions to protect yourself. ...
WINTER SAECULUM

Directory of Open Access Journals (Sweden)

Emil Mihalina

2017-03-01

Full Text Available Accumulated imbalances in the economy and on the markets cause specific financial market dynamics that have formed characteristic patterns kept throughout long financial history. In 2008 Authors presented their expectations of key macroeconomic and selected asset class markets developments for period ahead based on Saeculum theory. Use of term Secular describes a specific valuation environment during prolonged period. If valuations as well as selected macro variables are considered as a tool for understanding business cycles then market cycles become much more obvious and easily understandable. Therefore over the long run, certain asset classes do better in terms of risk reward profile than others. Further on, there is no need for frequent portfolio rebalancing and timing of specific investment positions within a particular asset class market. Current stage in cycle development suggests a need for reassessment of trends and prevailing phenomena due to cyclical nture of long lasting Saeculums. Paper reviews developments in recognizable patterns of selected metrics in current Winter Saeculum dominated with prevailing forces of delivering, deflation and decrease in velocity of money.
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.
Economic Selection Theory

DEFF Research Database (Denmark)

Knudsen, Thorbjørn

2003-01-01

principles of variation, continuity and selection, it is argued that economic selection theory should mimic the causal structure of neo-Darwinian theory. Two of the most influential explanations of economic evolution, Alchian's and Nelson and Winter's, are used to illustrate how this could be achieved.......The present article provides a minimal description of the causal structure of economic selection theory and outlines how the internal selection dynamics of business organisations can be reconciled with selection in competitive markets. In addition to generic similarity in terms of the Darwinian...
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
Lectures from the European RTN Winter School on Strings, Supergravity and Gauge Theories, CERN, 16 20 January, 2006

Science.gov (United States)

Derendinger, J.-P.; Scrucca, C. A.; Uranga, A. M.

2006-11-01

This special issue is devoted to the proceedings of the conference 'Winter School on Strings, Supergravity and Gauge Theories', which took place at CERN, the European Centre for Nuclear Research, in Geneva, Switzerland, from the 16 to the 20 of January 2006. This event was organized in the framework of the European Mobility Research and Training Network entitled 'Constituents, Fundamental Forces and Symmetries of the Universe'. It is part of a yearly series of scientific schools which have become a traditional rendezvous for young researchers of the community. The previous one was held at SISSA, in Trieste, Italy, in February 2005, and the next one will take place again at CERN, in January 2007. The school was primarily meant for young doctoral students and postdoctoral researchers working in the area of string theory. It consisted of five general lectures of four hours each, whose notes are published in the present proceedings, and five working group discussion sessions, focused on specific topics of the network research program. It was attended by approximately 250 participants. The topics of the lectures were chosen to provide an introduction to some of the areas of recent progress and to the open problems in string theory. String theory is expected to provide insights into the description of systems where the role of gravity is crucial. One prominent example of such systems are time-dependent backgrounds with big bang singularities, whose status in string theory is reviewed in the lecture notes by Ben Craps. In another main problem in quantum gravity, string theory gives a fascinating microscopic description of black holes and their properties. The lectures by Shiraz Minwalla review the thermal properties of black holes from their microscopic description in terms of a holographically dual large N field theory. Progress in the description of black hole microstates, and its interplay with the macroscopic description in terms of supergravity solutions via the
Insight into the informational-structure behavior of the Diels-Alder reaction of cyclopentadiene and maleic anhydride.

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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.
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

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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.
The politics of atmospheric sciences: "nuclear winter" and global climate change.

Science.gov (United States)

Dörries, Matthias

2011-01-01

This article, by exploring the individual and collective trajectories that led to the "nuclear winter" debate, examines what originally drew scientists on both sides of the controversy to this research. Stepping back from the day-to-day action and looking at the larger cultural and political context of nuclear winter reveals sometimes surprising commonalities among actors who found themselves on opposing sides, as well as differences within the apparently coherent TTAPS group (the theory's originators: Richard P. Turco, Owen Brian Toon, Thomas P. Ackerman, James B. Pollack, and Carl Sagan). This story foreshadows that of recent research on anthropogenic climate change, which was substantially shaped during this--apparently tangential--cold war debate of the 1980s about research on the global effects of nuclear weapons.
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.
EVOLUTIONARY THEORY AND THE MARKET COMPETITION

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SIRGHI Nicoleta

2014-12-01

Full Text Available Evolutionary theory study of processes that transform economy for firms, institutions, industries, employment, production, trade and growth within, through the actions of diverse agents from experience and interactions, using evolutionary methodology. Evolutionary theory analyses the unleashing of a process of technological and institutional innovation by generating and testing a diversity of ideas which discover and accumulate more survival value for the costs incurred than competing alternatives.This paper presents study the behavior of the firms on the market used the evolutionary theory.The paper is to present in full the developments that have led to the re-assessment of theories of firms starting from the criticism on Coase's theory based on the lack of testable hypotheses and on non-operative definition of transaction costs. In the literature in the field studies on firms were allotted a secondary place for a long period of time, to date the new theories of the firm hold a dominant place in the firms’ economic analysis. In an article, published in 1937, Ronald H. Coase identified the main sources of the cost of using the market mechanism. The firms theory represent a issue intensively studied in the literature in the field, regarding the survival, competitiveness and innovation of firm on the market. The research of Nelson and Winter, “An Evolutionary Theory of Economic Change” (1982 is the starting point for a modern literature in the field which considers the approach of the theory of the firm from an evolutionary perspective. Nelson and Winter have shown that the “orthodox” theory, is objectionable primarily by the fact that the hypothesis regarding profit maximization has a normative character and is not valid in any situation. Nelson and Winter reconsidered their microeconomic analysis showing that excessive attention should not be paid to market equilibrium but rather to dynamic processes resulting from irreversible
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

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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
Winter maintenance performance measure.

Science.gov (United States)

2016-01-01

The Winter Performance Index is a method of quantifying winter storm events and the DOTs response to them. : It is a valuable tool for evaluating the States maintenance practices, performing post-storm analysis, training : maintenance personnel...
Winter Survival of Individual Honey Bees and Honey Bee Colonies Depends on Level of Varroa destructor Infestation

Science.gov (United States)

van Dooremalen, Coby; Gerritsen, Lonne; Cornelissen, Bram; van der Steen, Jozef J. M.; van Langevelde, Frank; Blacquière, Tjeerd

2012-01-01

Background Recent elevated winter loss of honey bee colonies is a major concern. The presence of the mite Varroa destructor in colonies places an important pressure on bee health. V. destructor shortens the lifespan of individual bees, while long lifespan during winter is a primary requirement to survive until the next spring. We investigated in two subsequent years the effects of different levels of V. destructor infestation during the transition from short-lived summer bees to long-lived winter bees on the lifespan of individual bees and the survival of bee colonies during winter. Colonies treated earlier in the season to reduce V. destructor infestation during the development of winter bees were expected to have longer bee lifespan and higher colony survival after winter. Methodology/Principal Findings Mite infestation was reduced using acaricide treatments during different months (July, August, September, or not treated). We found that the number of capped brood cells decreased drastically between August and November, while at the same time, the lifespan of the bees (marked cohorts) increased indicating the transition to winter bees. Low V. destructor infestation levels before and during the transition to winter bees resulted in an increase in lifespan of bees and higher colony survival compared to colonies that were not treated and that had higher infestation levels. A variety of stress-related factors could have contributed to the variation in longevity and winter survival that we found between years. Conclusions/Significance This study contributes to theory about the multiple causes for the recent elevated colony losses in honey bees. Our study shows the correlation between long lifespan of winter bees and colony loss in spring. Moreover, we show that colonies treated earlier in the season had reduced V. destructor infestation during the development of winter bees resulting in longer bee lifespan and higher colony survival after winter. PMID:22558421
Estimating winter survival of winter wheat by simulations of plant frost tolerance

NARCIS (Netherlands)

Bergjord Olsen, A.K.; Persson, T.; Wit, de A.; Nkurunziza, L.; Sindhøj, E.; Eckersten, H.

2018-01-01

Based on soil temperature, snow depth and the grown cultivar's maximum attainable level of frost tolerance (LT50c), the FROSTOL model simulates development of frost tolerance (LT50) and winter damage, thereby enabling risk calculations for winter wheat survival. To explore the accuracy of this
Incorporating Yearly Derived Winter Wheat Maps Into Winter Wheat Yield Forecasting Model

Science.gov (United States)

Skakun, S.; Franch, B.; Roger, J.-C.; Vermote, E.; Becker-Reshef, I.; Justice, C.; Santamaría-Artigas, A.

2016-01-01

Wheat is one of the most important cereal crops in the world. Timely and accurate forecast of wheat yield and production at global scale is vital in implementing food security policy. Becker-Reshef et al. (2010) developed a generalized empirical model for forecasting winter wheat production using remote sensing data and official statistics. This model was implemented using static wheat maps. In this paper, we analyze the impact of incorporating yearly wheat masks into the forecasting model. We propose a new approach of producing in season winter wheat maps exploiting satellite data and official statistics on crop area only. Validation on independent data showed that the proposed approach reached 6% to 23% of omission error and 10% to 16% of commission error when mapping winter wheat 2-3 months before harvest. In general, we found a limited impact of using yearly winter wheat masks over a static mask for the study regions.
Winter weather demand considerations.

Science.gov (United States)

2015-04-01

Winter weather has varied effects on travel behavior. Using 418 survey responses from the Northern Virginia : commuting area of Washington, D.C. and binary logit models, this study examines travel related changes under : different types of winter wea...
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
The influence of sowing period and seeding norm on autumn vegetation, winter hardiness and yield of winter cereal crops

Directory of Open Access Journals (Sweden)

Potapova G. N.

2017-10-01

Full Text Available the winter wheat and triticale in the middle part of the Ural Mountains haven’t been seeded before. The technology of winter crop cultivation should be improved due to the production of new varieties of winter rye. Winter hardiness and yield of winter rye are higher in comparison with winter triticale and especially with winter wheat. The sowing period and the seeding rate influence the amount of yield and winter hardiness. The winter hardiness of winter cereals and the yield of the rye variety Iset sowed on August 25 and the yield of the triticale variety Bashkir short-stalked and wheat Kazanskaya 560 sowed on August 15 were higher. It is important to sow winter grain in local conditions in the second half of August. The sowing this period allows to provide plants with the necessary amount of positive temperatures (450–500 °C. This helps the plants to form 3–4 shoots of tillering and a mass of 10 dry plants reaching 3–5 grams. The winter grain crops in the middle part of the Ural Mountains should be sown with seeding rates of 6 and 7 million of sprouting grains per 1 ha, and the seeds must be cultivated with fungicidal preparation before seeding.
The Promotion of HAMK Winter and Summer Camps: Case China

OpenAIRE

Lin, Yulu

2017-01-01

The main purpose of this thesis is to promote HAMK winter and summer camps in China and maintain its competitive advantages by figuring out more effective marketing activities to attract students. The theories used to support and give references to this thesis were based on the research and studies from Philip Kotler, Kevin Keller and Armstrong. Some marketing related books such as Principles of Marketing or Marketing Management proved to be professional sources and explanations for conce...
The nuclear winter

International Nuclear Information System (INIS)

Velikhow, Y.P.

1986-01-01

Nuclear winter is an example of possible secondary effects, and if we speak of secondary we are thinking of small-scale second-order effects, but a nuclear winter is not a second-order effect. If you calculate the amount of heat produced by a nuclear explosion, it is a very small amount which does not have any chance of changing the Earth's climate, but a nuclear explosion drives or stars some new mechanism - the mechanism of nuclear winter - after 100 megatons of dust are transferred to the upper atmosphere. Another example of such amplification is radioactive fall-out, especially long-life radioactive fall-out after the possible elimination of the nuclear power industry, nuclear storage and distribution of storage waste around the globe. This is a very powerful amplification mechanism
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.
Prevalence of operator fatigue in winter maintenance operations.

Science.gov (United States)

Camden, Matthew C; Medina-Flintsch, Alejandra; Hickman, Jeffrey S; Bryce, James; Flintsch, Gerardo; Hanowski, Richard J

2018-02-02

Similar to commercial motor vehicle drivers, winter maintenance operators are likely to be at an increased risk of becoming fatigued while driving due to long, inconsistent shifts, environmental stressors, and limited opportunities for sleep. Despite this risk, there is little research concerning the prevalence of winter maintenance operator fatigue during winter emergencies. The purpose of this research was to investigate the prevalence, sources, and countermeasures of fatigue in winter maintenance operations. Questionnaires from 1043 winter maintenance operators and 453 managers were received from 29 Clear Road member states. Results confirmed that fatigue was prevalent in winter maintenance operations. Over 70% of the operators and managers believed that fatigue has a moderate to significant impact on winter maintenance operations. Approximately 75% of winter maintenance operators reported to at least sometimes drive while fatigued, and 96% of managers believed their winter maintenance operators drove while fatigued at least some of the time. Furthermore, winter maintenance operators and managers identified fatigue countermeasures and sources of fatigue related to winter maintenance equipment. However, the countermeasures believed to be the most effective at reducing fatigue during winter emergencies (i.e., naps) were underutilized. For example, winter maintenance operators reported to never use naps to eliminate fatigue. These results indicated winter maintenance operations are impacted by operator fatigue. These results support the increased need for research and effective countermeasures targeting winter maintenance operator fatigue. Copyright © 2018 Elsevier Ltd. All rights reserved.
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.
On the importance of hydrogen bonding in the promotion of Diels-Alder reactions of unactivated aldehydes: a computational study

Science.gov (United States)

Chemouri, Hafida; Mekelleche, Sidi Mohamed

2014-03-01

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

Energy Technology Data Exchange (ETDEWEB)

Craps, Ben [Theoretische Natuurkunde, Vrije Universiteit Brussel and The International Solvay Institutes Pleinlaan 2, B-1050 Brussels (Belgium)

2006-11-07

These proceedings are based on lectures delivered at the 'RTN Winter School on Strings, Supergravity and Gauge Theories', CERN, 16-20 January 2006. The school was mainly aimed at PhD students and young postdocs. The lectures start with a brief introduction to spacetime singularities and the string theory resolution of certain static singularities. Then they discuss attempts to resolve cosmological singularities in string theory, mainly focusing on two specific examples: the Milne orbifold and the matrix big bang.
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.…
Hidden simplicity of gauge theory amplitudes

Energy Technology Data Exchange (ETDEWEB)

Drummond, J M, E-mail: drummond@lapp.in2p3.f [LAPTH, Universite de Savoie, CNRS, B.P. 110, F-74941 Annecy-le-Vieux, Cedex (France)

2010-11-07

These notes were given as lectures at the CERN Winter School on Supergravity, Strings and Gauge Theory 2010. We describe the structure of scattering amplitudes in gauge theories, focussing on the maximally supersymmetric theory to highlight the hidden symmetries which appear. Using the Britto, Cachzo, Feng and Witten (BCFW) recursion relations we solve the tree-level S-matrix in N=4 super Yang-Mills theory and describe how it produces a sum of invariants of a large symmetry algebra. We review amplitudes in the planar theory beyond tree level, describing the connection between amplitudes and Wilson loops, and discuss the implications of the hidden symmetries.
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
46 CFR 45.73 - Winter freeboard.

Science.gov (United States)

2010-10-01

... 46 Shipping 2 2010-10-01 2010-10-01 false Winter freeboard. 45.73 Section 45.73 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) LOAD LINES GREAT LAKES LOAD LINES Freeboards § 45.73 Winter freeboard. The minimum winter freeboard (fw) in inches is obtained by the formula: fw=f(s)+T s...
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.
EDITORIAL: Lectures from the European RTN Winter School on Strings, Supergravity and Gauge Theories, CERN, 21 25 January 2008

Science.gov (United States)

Derendinger, J.-P.; Orlando, D.; Uranga, A.

2008-11-01

This special issue is devoted to the proceedings of the conference 'RTN Winter School on Strings, Supergravity and Gauge Theories', which took place at CERN, the European Centre for Nuclear Research, in Geneva, Switzerland, on the 21 25 January 2008. This event was organized in the framework of the European Mobility Research and Training Network entitled 'Constituents, Fundamental Forces and Symmetries of the Universe'. It is part of a yearly series of scientific schools, which represents what is by now a well established tradition. The previous ones have been held at SISSA, in Trieste, Italy, in February 2005 and at CERN in January 2006. The next one will again take place at CERN, in February 2009. The school was primarily meant for young doctoral students and postdoctoral researchers working in the area of string theory. It consisted of several general lectures of four hours each, whose notes are published in the present proceedings, and five working group discussion sessions, focused on specific topics of the network research program. It was attended by approximatively 250 participants. The topics of the lectures were chosen to provide an introduction to some of the areas of recent progress, and to the open problems, in string theory. One of the most active areas in string theory in recent years is the AdS/CFT or gauge/gravity correspondence, which proposes the complete equivalence of string theory on (asymptotically) anti-de Sitter spacetimes with gauge theories. The duality relates the weak coupling regime of one system to the strongly coupled regime of the other, and is therefore very non-trivial to test beyond the supersymmetry-protected BPS sector. One of the key ideas to quantitatively match several quantities on both sides is the use of integrability, both in the gauge theory and the string side. The lecture notes by Nick Dorey provide a pedagogical introduction to the fascinating topic of integrability in AdS/CFT. On the string theory side, progress has
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.
Winter warming from large volcanic eruptions

Science.gov (United States)

Robock, Alan; Mao, Jianping

1992-01-01

An examination of the Northern Hemisphere winter surface temperature patterns after the 12 largest volcanic eruptions from 1883-1992 shows warming over Eurasia and North America and cooling over the Middle East which are significant at the 95-percent level. This pattern is found in the first winter after tropical eruptions, in the first or second winter after midlatitude eruptions, and in the second winter after high latitude eruptions. The effects are independent of the hemisphere of the volcanoes. An enhanced zonal wind driven by heating of the tropical stratosphere by the volcanic aerosols is responsible for the regions of warming, while the cooling is caused by blocking of incoming sunlight.
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.
An Active Alkali-Exchanged Faujasite Catalyst for p-Xylene Production via the One-Pot Diels-Alder Cycloaddition/Dehydration Reaction of 2,5-Dimethylfuran with Ethylene.

Science.gov (United States)

Rohling, Roderigh Y; Uslamin, Evgeny; Zijlstra, Bart; Tranca, Ionut C; Filot, Ivo A W; Hensen, Emiel J M; Pidko, Evgeny A

2018-02-02

The one-pot Diels-Alder cycloaddition (DAC)/dehydration (D) tandem reaction between 2,5-dimethylfuran and ethylene is a potent pathway toward biomass-derived p -xylene. In this work, we present a cheap and active low-silica potassium-exchanged faujasite (KY, Si/Al = 2.6) catalyst. Catalyst optimization was guided by a computational study of the DAC/D reaction mechanism over different alkali-exchanged faujasites using periodic density functional theory calculations complemented by microkinetic modeling. Two types of faujasite models were compared, i.e., a high-silica alkali-exchanged faujasite model representing isolated active cation sites and a low-silica alkali-exchanged faujasite in which the reaction involves several cations in the proximity. The mechanistic study points to a significant synergetic cooperative effect of the ensemble of cations in the faujasite supercage on the DAC/D reaction. Alignment of the reactants by their interactions with the cationic sites and stabilization of reaction intermediates contribute to the high catalytic performance. Experiments confirmed the prediction that KY is the most active catalyst among low-silica alkali-exchanged faujasites. This work is an example of how the catalytic reactivity of zeolites depends on multiple interactions between the zeolite and reagents.

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.

Science.gov (United States)

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.
Titan's Emergence from Winter

Science.gov (United States)

Flasar, F. Michael; Achterberg, Richard; Jennings, Donald; Schinder, Paul

2011-01-01

We summarize the changes in Titans thermal structure derived from Cassini CIRS and radio-occultation data during the transition from winter to early spring. Titan's surface, and middle atmosphere show noticeable seasonal change, whereas that in most of the troposphere is mated. This can be understood in terms of the relatively small radiative relaxation time in the middle atmosphere and much larger time scale in the troposphere. The surface exhibits seasonal change because the heat capacity in an annual skin depth is much smaller than that in the lowest scale height of the troposphere. Surface temperatures rise 1 K at raid and high latitudes in the winter northern hemisphere and cool in the southern hemisphere. Changes in in the middle atmosphere are more complicated. Temperatures in the middle stratosphere (approximately 1 mbar) increase by a few kelvin at mid northern latitudes, but those at high latitudes first increase as that region moves out of winter shadow, and then decrease. This probably results from the combined effect of increased solar heating as the suit moves higher in the sky and the decreased adiabatic warming as the sinking motions associated with the cross-equatorial meridional cell weaken. Consistent with this interpretation, the warm temperatures observed higher up at the winter polar stratopause cool significantly.
36 CFR 1002.19 - Winter activities.

Science.gov (United States)

2010-07-01

... RECREATION § 1002.19 Winter activities. (a) Skiing, snowshoeing, ice skating, sledding, innertubing, tobogganing and similar winter sports are prohibited on Presidio Trust roads and in parking areas open to...
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.

Science.gov (United States)

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.

Science.gov (United States)

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.

Science.gov (United States)

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.
Examining winter visitor use in Yellowstone National Park

Science.gov (United States)

Mae A. Davenport; Wayne A. Freimund; William T. Borrie; Robert E. Manning; William A. Valliere; Benjamin Wang

2000-01-01

This research was designed to assist the managers of Yellowstone National Park (YNP) in their decision making about winter visitation. The focus of this report is on winter use patterns and winter visitor preferences. It is the authorâs hope that this information will benefit both the quality of winter experiences and the stewardship of the park resources. This report...
Winter Dew Harvest in Mexico City

Directory of Open Access Journals (Sweden)

Arias-Torres Jorge Ernesto

2015-12-01

Full Text Available This study presents experimental and theoretical results of winter dew harvest in México City in terms of condensation rate. A simplified theoretical model based on a steady-state energy balance on a radiator-condenser was fitted, as a function of the ambient temperature, the relative humidity and the wind velocity. A glass sheet and aluminum sheet white-painted were used as samples over the outdoor experiments. A good correlation was obtained between the theoretical and experimental data. The experimental results show that there was condensation in 68% of the winter nights on both condensers. The total winter condensed mass was 2977 g/m2 and 2888 g/m2 on the glass sheet and aluminum sheet white-painted, respectively. Thus, the condensed mass on the glass was only 3% higher than that on the painted surface. The maximum nightly dew harvests occurred during December, which linearly reduced from 50 g/m2 night to 22 g/m2 night as the winter months went by. The condensation occurred from 1:00 a.m. to 9:00 a.m., with maximum condensation rates between 6:00 a.m. and 7:00 a.m. The dew harvest can provide a partial alternative to the winter water shortage in certain locations with similar climates to the winter in Mexico City, as long as pollution is not significant.
Leadership in American Indian Communities: Winter Lessons

Science.gov (United States)

Metoyer, Cheryl A.

2010-01-01

Winter lessons, or stories told in the winter, were one of the ways in which tribal elders instructed and directed young men and women in the proper ways to assume leadership responsibilities. Winter lessons stressed the appropriate relationship between the leader and the community. The intent was to remember the power and purpose of that…
Testing Optimal Foraging Theory Using Bird Predation on Goldenrod Galls

Science.gov (United States)

Yahnke, Christopher J.

2006-01-01

All animals must make choices regarding what foods to eat, where to eat, and how much time to spend feeding. Optimal foraging theory explains these behaviors in terms of costs and benefits. This laboratory exercise focuses on optimal foraging theory by investigating the winter feeding behavior of birds on the goldenrod gall fly by comparing…
Resilience of roof-top Plant-Microbial Fuel Cells during Dutch winter

International Nuclear Information System (INIS)

Helder, Marjolein; Strik, David P.B.T.B.; Timmers, Ruud A.; Raes, Sanne M.T.; Hamelers, Hubertus V.M.; Buisman, Cees J.N.

2013-01-01

The Plant-Microbial Fuel Cell (P-MFC) is in theory a technology that could produce sustainable electricity continuously. We operated two designs of the P-MFC under natural roof-top conditions in the Netherlands for 221 days, including winter, to test its resilience. Current and power densities are not stable under outdoor conditions. Highest obtained power density was 88 mW m −2 , which is lower than was achieved under lab-conditions (440 mW m −2 ). Cathode potential was in our case dependent on solar radiation, due to algae growth, making the power output dependent on a diurnal cycle. The anode potential of the P-MFC is influenced by temperature, leading to a decrease in electricity production during low temperature periods and no electricity production during frost periods. Due to freezing of the roots, plants did not survive winter and therefore did not regrow in spring. In order to make a sustainable, stable and weather independent electricity production system of the P-MFC attention should be paid to improving cathode stability and cold insulation of anode and cathode. Only when power output of the Plant-Microbial Fuel Cell can be increased under outdoor conditions and plant-vitality can be sustained over winter, it can be a promising sustainable electricity technology for the future. -- Highlights: ► Plant-Microbial Fuel Cells (P-MFCs) produce sustainable electricity under outdoor conditions. ► During frost periods no electricity is produced in P-MFCs. ► Cathodes limit performance of P-MFCs under outdoor conditions. ► Spartina anglica in P-MFCs does not survive on a roof-top during Dutch winter. ► The P-MFC needs optimization of power output to be a promising sustainable electricity technology
A Pyrene-Linked Cavity within a β-Barrel Protein Promotes an Asymmetric Diels-Alder Reaction.

Science.gov (United States)

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.
Body-mass, survival, and pairing consequences of winter-diet restriction in wood ducks

Science.gov (United States)

Demarest, D.W.; Kaminski, R.M.; Brennan, L.A.; Boyle, C.R.

1997-01-01

We conducted feeding experiments with captive, wild-strain wood ducks (Aix sponsa) during winters 1990-91 and 1991-92 to test effects of increasing levels of food restriction on body mass dynamics, mortality, and pair formation. Male and female wood ducks fed restricted diets (i.e., 5, 10, 15, or 20% less food [g] than consumed on the previous day by a control group fed ad libitum) weighed less (P ??? 0.037) than birds fed ad libitum; those on 15 and 20% restricted diets weighed least. Increased mortality and decreased pair formation occurred only within the 20% restricted group (P ??? 0.049). We concluded that food restriction ranging between 15 and 20% of ad libitum intake may signify a threshold above which survival and reproduction of captive wood ducks may be impaired. Because energy costs of free living are greater than in captivity, a lower threshold may exist for wild wood ducks. Research is needed to validate the threshold theory for free-ranging wood ducks and other waterfowl, and to evaluate its potential application for conservation of winter foraging habitat. Conservation of bottomland hardwood ecosystems, which provide important foraging habitat for migrating and wintering wood ducks, should be encouraged to prevent potential negative effects on wood duck life-cycle events.
Barriers to wheelchair use in the winter.

Science.gov (United States)

Ripat, Jacquie D; Brown, Cara L; Ethans, Karen D

2015-06-01

To test the hypothesis that challenges to community participation posed by winter weather are greater for individuals who use scooters, manual and power wheelchairs (wheeled mobility devices [WMDs]) than for the general ambulatory population, and to determine what WMD users identify as the most salient environmental barriers to community participation during the winter. Cross-sectional survey organized around 5 environmental domains: technological, natural, physical, social/attitudinal, and policy. Urban community in Canada. Convenience sample of WMD users or their proxy (N=99). Not applicable. Not applicable. Forty-two percent identified reduced outing frequency in winter months, associated with increased age (χ(3)=6.4, P=.04), lack of access to family/friends for transportation (χ(2)=8.1, P=.04), and primary type of WMD used in the winter (scooter χ(2)=8.8, P=.003). Most reported tires/casters becoming stuck in the snow (95%) or slipping on the ice (91%), difficulty ascending inclines/ramps (92%), and cold hands while using controls or pushing rims (85%); fewer identified frozen wheelchair/scooter batteries, seat cushions/backrests, or electronics. Sidewalks/roads were reported to be problematic by 99%. Eighty percent reported needing additional help in the winter. Limited community access in winter led to a sense of loneliness/isolation, and fear/anxiety related to safety. Respondents identified policies that limited participation during winter. People who use WMDs decrease their community participation in cold weather because of multiple environmental barriers. Clinicians, researchers, and policymakers can take a multidimensional approach to mitigate these barriers in order to enhance community participation by WMD users in winter. Copyright © 2015 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.
AGA predicts winter jump in residential gas price

International Nuclear Information System (INIS)

Anon.

1992-01-01

The American Gas Association predicts the average heating bill for residential gas consumers could increase by as much as 18% this winter. AGA Pres. Mike Baly said, Last year's winter was warmer than normal. If the 1992-93 winter is similar, AGA projects that residential natural gas heating bills will go up about 6%. If we see a return to normal winter weather, our projection show the average bill could rise by almost 18%
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
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
Diels-Alder Reactions of 12-Hydroxy-9(10®20-5aH-abeo-abieta-1(10,8(9,12(13-triene-11,14-dione

Directory of Open Access Journals (Sweden)

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.

Root development of fodder radish and winter wheat before winter in relation to uptake of nitrogen

DEFF Research Database (Denmark)

Wahlström, Ellen Margrethe; Hansen, Elly Møller; Mandel, A.

2015-01-01

occurred. Quantitative data is missing on N leaching of a catch crop compared to a winter cereal in a conventional cereal-based cropping system. The aim of the study was to investigate whether fodder radish (Raphanus sativus L.) (FR) would be more efficient than winter wheat (Triticum aestivum L.) (WW...
Artificial Metalloenzymes with the Neocarzinostatin Scaffold: Toward a Biocatalyst for the Diels-Alder Reaction.

Science.gov (United States)

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.
The meaning of nuclear winter

International Nuclear Information System (INIS)

Geiger, H.J.

1987-01-01

In this paper the author reviews the history and origins of the basic ideas underlying nuclear winter; and findings and predictions of several groups regarding this topic. The author reviews some of the further developments and scientific analyses regarding nuclear winter since the initial announcements of 1983, touching on some of the revisions and controversies and trying to indicate the current status of the field
Winter climate limits subantarctic low forest growth and establishment.

Science.gov (United States)

Harsch, Melanie A; McGlone, Matt S; Wilmshurst, Janet M

2014-01-01

Campbell Island, an isolated island 600 km south of New Zealand mainland (52 °S, 169 °E) is oceanic (Conrad Index of Continentality = -5) with small differences between mean summer and winter temperatures. Previous work established the unexpected result that a mean annual climate warming of c. 0.6 °C since the 1940's has not led to upward movement of the forest limit. Here we explore the relative importance of summer and winter climatic conditions on growth and age-class structure of the treeline forming species, Dracophyllum longifolium and Dracophyllum scoparium over the second half of the 20th century. The relationship between climate and growth and establishment were evaluated using standard dendroecological methods and local climate data from a meteorological station on the island. Growth and establishment were correlated against climate variables and further evaluated within hierarchical regression models to take into account the effect of plot level variables. Winter climatic conditions exerted a greater effect on growth and establishment than summer climatic conditions. Establishment is maximized under warm (mean winter temperatures >7 °C), dry winters (total winter precipitation <400 mm). Growth, on the other hand, is adversely affected by wide winter temperature ranges and increased rainfall. The contrasting effect of winter warmth on growth and establishment suggests that winter temperature affects growth and establishment through differing mechanisms. We propose that milder winters enhance survival of seedlings and, therefore, recruitment, but increases metabolic stress on established plants, resulting in lower growth rates. Future winter warming may therefore have complex effects on plant growth and establishment globally.
Sage-grouse habitat selection during winter in Alberta

Science.gov (United States)

Carpenter, Jennifer L.; Aldridge, Cameron L.; Boyce, Mark S.

2010-01-01

Greater sage-grouse (Centrocercus urophasianus) are dependent on sagebrush (Artemisia spp.) for food and shelter during winter, yet few studies have assessed winter habitat selection, particularly at scales applicable to conservation planning. Small changes to availability of winter habitats have caused drastic reductions in some sage-grouse populations. We modeled winter habitat selection by sage-grouse in Alberta, Canada, by using a resource selection function. Our purpose was to 1) generate a robust winter habitat-selection model for Alberta sage-grouse; 2) spatially depict habitat suitability in a Geographic Information System to identify areas with a high probability of selection and thus, conservation importance; and 3) assess the relative influence of human development, including oil and gas wells, in landscape models of winter habitat selection. Terrain and vegetation characteristics, sagebrush cover, anthropogenic landscape features, and energy development were important in top Akaike's Information Criterionselected models. During winter, sage-grouse selected dense sagebrush cover and homogenous less rugged areas, and avoided energy development and 2-track truck trails. Sage-grouse avoidance of energy development highlights the need for comprehensive management strategies that maintain suitable habitats across all seasons. ?? 2010 The Wildlife Society.
The Unusual Southern Hemisphere Stratosphere Winter of 2002

Science.gov (United States)

Newman, Paul A.; Nash, Eric R.

2003-01-01

The southern hemisphere stratospheric winter of 2002 was the most unusual winter yet observed in the southern hemisphere climate record. Temperatures near the edge of the Antarctic polar vortex were considerably warmer than normal over the entire course of the winter. The polar night jet was considerably weaker than normal, and was displaced more poleward than has been observed in previous winters. These record high temperatures and weak jet resulted from a series of wave events that took place over the course of the winter. The first large event occurred on 15 May, and the final warming occurred on 25 October. The propagation of these wave events from the troposphere is diagnosed from time series of Eliassen-Palm flux vectors. The wave events tended to occur irregularly over the course of the winter, and pre-conditioned the polar night jet for the extremely large wave event of 22 September. This large wave event resulted in the first ever observed major stratospheric warming in the southern hemisphere. This wave event split the Antarctic ozone hole. The combined effect of the wave events of the 2002 winter resulted in the smallest ozone hole observed since 1988.
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
Deer Wintering Areas

Data.gov (United States)

Vermont Center for Geographic Information — Deer winter habitat is critical to the long term survival of white-tailed deer (Odocoileus virginianus) in Vermont. Being near the northern extreme of the...
C—C bond formation in the intramolecular Diels-Alder reaction of triene amides

Directory of Open Access Journals (Sweden)

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.

Science.gov (United States)

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.
Winter climate limits subantarctic low forest growth and establishment.

Directory of Open Access Journals (Sweden)

Melanie A Harsch

Full Text Available Campbell Island, an isolated island 600 km south of New Zealand mainland (52 °S, 169 °E is oceanic (Conrad Index of Continentality = -5 with small differences between mean summer and winter temperatures. Previous work established the unexpected result that a mean annual climate warming of c. 0.6 °C since the 1940's has not led to upward movement of the forest limit. Here we explore the relative importance of summer and winter climatic conditions on growth and age-class structure of the treeline forming species, Dracophyllum longifolium and Dracophyllum scoparium over the second half of the 20th century. The relationship between climate and growth and establishment were evaluated using standard dendroecological methods and local climate data from a meteorological station on the island. Growth and establishment were correlated against climate variables and further evaluated within hierarchical regression models to take into account the effect of plot level variables. Winter climatic conditions exerted a greater effect on growth and establishment than summer climatic conditions. Establishment is maximized under warm (mean winter temperatures >7 °C, dry winters (total winter precipitation <400 mm. Growth, on the other hand, is adversely affected by wide winter temperature ranges and increased rainfall. The contrasting effect of winter warmth on growth and establishment suggests that winter temperature affects growth and establishment through differing mechanisms. We propose that milder winters enhance survival of seedlings and, therefore, recruitment, but increases metabolic stress on established plants, resulting in lower growth rates. Future winter warming may therefore have complex effects on plant growth and establishment globally.
Winter Climate Limits Subantarctic Low Forest Growth and Establishment

Science.gov (United States)

Harsch, Melanie A.; McGlone, Matt S.; Wilmshurst, Janet M.

2014-01-01

Campbell Island, an isolated island 600 km south of New Zealand mainland (52°S, 169°E) is oceanic (Conrad Index of Continentality = −5) with small differences between mean summer and winter temperatures. Previous work established the unexpected result that a mean annual climate warming of c. 0.6°C since the 1940's has not led to upward movement of the forest limit. Here we explore the relative importance of summer and winter climatic conditions on growth and age-class structure of the treeline forming species, Dracophyllum longifolium and Dracophyllum scoparium over the second half of the 20th century. The relationship between climate and growth and establishment were evaluated using standard dendroecological methods and local climate data from a meteorological station on the island. Growth and establishment were correlated against climate variables and further evaluated within hierarchical regression models to take into account the effect of plot level variables. Winter climatic conditions exerted a greater effect on growth and establishment than summer climatic conditions. Establishment is maximized under warm (mean winter temperatures >7 °C), dry winters (total winter precipitation <400 mm). Growth, on the other hand, is adversely affected by wide winter temperature ranges and increased rainfall. The contrasting effect of winter warmth on growth and establishment suggests that winter temperature affects growth and establishment through differing mechanisms. We propose that milder winters enhance survival of seedlings and, therefore, recruitment, but increases metabolic stress on established plants, resulting in lower growth rates. Future winter warming may therefore have complex effects on plant growth and establishment globally. PMID:24691026
Chapter 7: Migration and winter ecology

Science.gov (United States)

Deborah M. Finch; Jeffrey F. Kelly; Jean-Luc E. Cartron

2000-01-01

The willow flycatcher (Empidonax traillii) is a Neotropical migrant that breeds in North America, but winters in Central and northern South America. Little specific information is known about migration and wintering ecology of the southwestern willow flycatcher (E. t. extimus) (Yong and Finch 1997). Our report applies principally...
Autumn Weather and Winter Increase in Cerebrovascular Disease Mortality

LENUS (Irish Health Repository)

McDonagh, R

2016-11-01

Mortality from cerebrovascular disease increases in winter but the cause is unclear. Ireland’s oceanic climate means that it infrequently experiences extremes of weather. We examined how weather patterns relate to stroke mortality in Ireland. Seasonal data for Sunshine (% of average), Rainfall (% of average) and Temperature (degrees Celsius above average) were collected for autumn (September-November) and winter (December-February) using official Irish Meteorological Office data. National cerebrovascular mortality data was obtained from Quarterly Vital Statistics. Excess winter deaths were calculated by subtracting (nadir) 3rd quarter mortality data from subsequent 1st quarter data. Data for 12 years were analysed, 2002-2014. Mean winter mortality excess was 24.7%. Winter mortality correlated with temperature (r=.60, p=0.04). Rise in winter mortality correlated strongly with the weather in the preceding autumn (Rainfall: r=-0.19 p=0.53, Temperature: r=-0.60, p=0.03, Sunshine, r=0.58, p=0.04). Winter cerebrovascular disease mortality appears higher following cool, sunny autum
Winter climate variability and classification in the Bulgarian Mountainous Regions

International Nuclear Information System (INIS)

Petkova, Nadezhda; Koleva, Ekaterina

2004-01-01

The problems of snowiness and thermal conditions of winters are of high interest of investigations because of the more frequent droughts, occurred in the region. In the present study an attempt to reveal tendencies existing during the last 70 years of 20 th century in the course winter precipitation and,temperature as well as in some of the snow cover parameters. On the base of mean winter air temperature winters in the Bulgarian mountains were analyzed and classified. The main results of the study show that winter precipitation has decrease tendencies more significant in the highest parts of the mountains. On the other hand winter air temperature increases. It shows a relatively well-established maximum at the end of the studied period. In the Bulgarian mountains normal winters are about 35-40% of all winters. (Author)
Interim Report 'Winter smog and traffic'.

NARCIS (Netherlands)

Bloemen, H.; Blom, T.; Bogaard, van den C.; Boluyt, N.; Bree, van L.; Brunekreef, B.; Hoek, G.; Zee, van der S.

1994-01-01

This report presents a halfway score of the research project "Winter smog and Traffic", one of the themes of the research programme "Air Pollution and Health". A state of the art is presented of the health effects associated with exposure to winter smog and of the toxicological effects caused by the
Home advantage in the Winter Paralympic Games 1976-2014.

Science.gov (United States)

Wilson, Darryl; Ramchandani, Girish

2017-01-01

There is a limited amount of home advantage research concerned with winter sports. There is also a distinct lack of studies that investigate home advantage in the context of para sport events. This paper addresses this gap in the knowledge by examining home advantage in the Winter Paralympic Games. Using a standardised measure of success, we compared the performances of host nations at home with their own performances away from home between 1976 and 2014. Both country level and individual sport level analysis is conducted for this time period. Comparisons are also drawn with the Winter Olympic Games since 1992, the point from which both the Winter Olympic Games and the Winter Paralympic Games have been hosted by the same nations and in the same years. Clear evidence of a home advantage effect in the Winter Paralympic Games was found at country level. When examining individual sports, only alpine skiing and cross country skiing returned a significant home advantage effect. When comparing home advantage in the Winter Paralympic Games with the Winter Olympic Games for the last seven host nations (1992-2014), we found that home advantage was generally more pronounced (although not a statistically significant difference) in the case of the former. The causes of home advantage in the Winter Paralympic Games are unclear and should be investigated further.
Real-time weed detection, decision making and patch spraying in maize, sugarbeet, winter wheat and winter barley

DEFF Research Database (Denmark)

Gerhards, R; Christensen, Svend

2003-01-01

with weed infestation levels higher than the economic weed threshold; a review of such work is provided. This paper presents a system for site-specific weed control in sugarbeet (Beta vulgaris L.), maize (Zea mays L.), winter wheat (Triticum aestivum L.) and winter barley (Hordeum vulgare L.), including...
Warmed Winter Water Temperatures Alter Reproduction in Two Fish Species

Science.gov (United States)

Firkus, Tyler; Rahel, Frank J.; Bergman, Harold L.; Cherrington, Brian D.

2018-02-01

We examined the spawning success of Fathead Minnows ( Pimephales promelas) and Johnny Darters ( Etheostoma nigrum) exposed to elevated winter water temperatures typical of streams characterized by anthropogenic thermal inputs. When Fathead Minnows were exposed to temperature treatments of 12, 16, or 20 °C during the winter, spawning occurred at 16 and 20 °C but not 12 °C. Eggs were deposited over 9 weeks before winter spawning ceased. Fathead Minnows from the three winter temperature treatments were then exposed to a simulated spring transition. Spawning occurred at all three temperature treatments during the spring, but fish from the 16° and 20 °C treatment had delayed egg production indicating a latent effect of warm winter temperatures on spring spawning. mRNA analysis of the egg yolk protein vitellogenin showed elevated expression in female Fathead Minnows at 16 and 20 °C during winter spawning that decreased after winter spawning ceased, whereas Fathead Minnows at 12 °C maintained comparatively low expression during winter. Johnny Darters were exposed to 4 °C to represent winter temperatures in the absence of thermal inputs, and 12, 16, and 20 °C to represent varying degrees of winter thermal pollution. Johnny Darters spawned during winter at 12, 16, and 20 °C but not at 4 °C. Johnny Darters at 4 °C subsequently spawned following a simulated spring period while those at 12, 16, and 20 °C did not. Our results indicate elevated winter water temperatures common in effluent-dominated streams can promote out-of-season spawning and that vitellogenin expression is a useful indicator of spawning readiness for fish exposed to elevated winter temperatures.
Winter barley mutants created in the Ukraine

International Nuclear Information System (INIS)

Zayats, O.M.

2001-01-01

Full text: Increasing fodder and protein production is one of the objectives of the development of agriculture in Ukraine. Higher productivity of fodder crops, due to new highly productive varieties, is the means to meet this aim. Winter barley is an important crop for fodder purposes. The climate of the Ukraine is favourable for growing this crop. The areas used for the growth of winter barley are however, small (500,000-550,000 ha) and there is a shortage of good quality varieties. The main aim of the work was therefore to create new varieties of highly productive winter barley, of good quality. The new varieties and mutation lines of winter barley were created under the influence of water solutions of N-nitroso-N-methylurea (NMH - 0,012, 0,005%), N-nitroso-N-ethylurea (NEH - 0,05; 0.025; 0,012%) ethyleneimine (EI - 0,02; 0,01; 0,005%) on winter barley seeds of the varieties of local and foreign selections. On the basis of many years of investigations (1984-94) the following mutations were described: hard-grained, winter-hardiness, earliness, middle-maturity, late-maturity, wide and large leaves, narrow leaves, multinodal, great number of leaves, great number of flowers, strong stem (lodging resistant), tallness, semi-dwarfness, dwarfness, and high productivity. Particularly valuable are mutants with high productivity of green bulk. Their potential yield is 70 t/ha. As a result of the work two varieties of winter barley 'Shyrokolysty' and 'Kormovy' were released into the State register of plant varieties of the Ukraine. The other valuable mutant genotypes are used in cross breeding programmes. (author)

Impacts of winter NPO on subsequent winter ENSO: sensitivity to the definition of NPO index

Science.gov (United States)

Chen, Shangfeng; Wu, Renguang

2018-01-01

This study investigates the linkage between boreal winter North Pacific Oscillation (NPO) and subsequent winter El Niño-Southern Oscillation (ENSO) based on seven different NPO indices. Results show that the influence of winter NPO on the subsequent winter El Niño is sensitive to how the NPO is defined. A significant NPO-El Niño connection is obtained when the NPO-related anomalous cyclone over the subtropical North Pacific extends to near-equatorial regions. The anomalous cyclone induces warm sea surface temperature (SST) anomalies through modulating surface heat fluxes. These warm SST anomalies are able to maintain into the following spring and summer through an air-sea coupled process and in turn induce significant westerly wind anomalies over the tropical western Pacific. In contrast, the NPO-El Niño relationship is unclear when the NPO-related anomalous cyclone over the subtropical North Pacific is confined to off-equatorial regions and cannot induce significant warm SST anomalies over the subtropical North Pacific. The present study suggests that definitions of NPO should be taken into account when using NPO to predict ENSO. In particular, we recommend defining the NPO index based on the empirical orthogonal function technique over appropriate region that does not extend too far north.
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.
Excess mortality in winter in Finnish intensive care.

Science.gov (United States)

Reinikainen, M; Uusaro, A; Ruokonen, E; Niskanen, M

2006-07-01

In the general population, mortality from acute myocardial infarctions, strokes and respiratory causes is increased in winter. The winter climate in Finland is harsh. The aim of this study was to find out whether there are seasonal variations in mortality rates in Finnish intensive care units (ICUs). We analysed data on 31,040 patients treated in 18 Finnish ICUs. We measured severity of illness with acute physiology and chronic health evaluation II (APACHE II) scores and intensity of care with therapeutic intervention scoring system (TISS) scores. We assessed mortality rates in different months and seasons and used logistic regression analysis to test the independent effect of various seasons on hospital mortality. We defined 'winter' as the period from December to February, inclusive. The crude hospital mortality rate was 17.9% in winter and 16.4% in non-winter, P = 0.003. Even after adjustment for case mix, winter season was an independent risk factor for increased hospital mortality (adjusted odds ratio 1.13, 95% confidence interval 1.04-1.22, P = 0.005). In particular, the risk of respiratory failure was increased in winter. Crude hospital mortality was increased during the main holiday season in July. However, the severity of illness-adjusted risk of death was not higher in July than in other months. An increase in the mean daily TISS score was an independent predictor of increased hospital mortality. Severity of illness-adjusted hospital mortality for Finnish ICU patients is higher in winter than in other seasons.
Essential Outdoor Sun Safety Tips for Winter

Science.gov (United States)

... Weekend Warriors expand/collapse Vitamin D Essential Outdoor Sun Safety Tips for Winter Winter sports enthusiasts are ... skiing! Be Mindful of Time Spent in the Sun, Regardless of the Season If possible, ski early ...
Winter Season Mortality: Will Climate Warming Bring Benefits?

Science.gov (United States)

Kinney, Patrick L; Schwartz, Joel; Pascal, Mathilde; Petkova, Elisaveta; Tertre, Alain Le; Medina, Sylvia; Vautard, Robert

2015-06-01

Extreme heat events are associated with spikes in mortality, yet death rates are on average highest during the coldest months of the year. Under the assumption that most winter excess mortality is due to cold temperature, many previous studies have concluded that winter mortality will substantially decline in a warming climate. We analyzed whether and to what extent cold temperatures are associated with excess winter mortality across multiple cities and over multiple years within individual cities, using daily temperature and mortality data from 36 US cities (1985-2006) and 3 French cities (1971-2007). Comparing across cities, we found that excess winter mortality did not depend on seasonal temperature range, and was no lower in warmer vs. colder cities, suggesting that temperature is not a key driver of winter excess mortality. Using regression models within monthly strata, we found that variability in daily mortality within cities was not strongly influenced by winter temperature. Finally we found that inadequate control for seasonality in analyses of the effects of cold temperatures led to spuriously large assumed cold effects, and erroneous attribution of winter mortality to cold temperatures. Our findings suggest that reductions in cold-related mortality under warming climate may be much smaller than some have assumed. This should be of interest to researchers and policy makers concerned with projecting future health effects of climate change and developing relevant adaptation strategies.
Warmed Winter Water Temperatures Alter Reproduction in Two Fish Species.

Science.gov (United States)

Firkus, Tyler; Rahel, Frank J; Bergman, Harold L; Cherrington, Brian D

2018-02-01

We examined the spawning success of Fathead Minnows (Pimephales promelas) and Johnny Darters (Etheostoma nigrum) exposed to elevated winter water temperatures typical of streams characterized by anthropogenic thermal inputs. When Fathead Minnows were exposed to temperature treatments of 12, 16, or 20 °C during the winter, spawning occurred at 16 and 20 °C but not 12 °C. Eggs were deposited over 9 weeks before winter spawning ceased. Fathead Minnows from the three winter temperature treatments were then exposed to a simulated spring transition. Spawning occurred at all three temperature treatments during the spring, but fish from the 16° and 20 °C treatment had delayed egg production indicating a latent effect of warm winter temperatures on spring spawning. mRNA analysis of the egg yolk protein vitellogenin showed elevated expression in female Fathead Minnows at 16 and 20 °C during winter spawning that decreased after winter spawning ceased, whereas Fathead Minnows at 12 °C maintained comparatively low expression during winter. Johnny Darters were exposed to 4 °C to represent winter temperatures in the absence of thermal inputs, and 12, 16, and 20 °C to represent varying degrees of winter thermal pollution. Johnny Darters spawned during winter at 12, 16, and 20 °C but not at 4 °C. Johnny Darters at 4 °C subsequently spawned following a simulated spring period while those at 12, 16, and 20 °C did not. Our results indicate elevated winter water temperatures common in effluent-dominated streams can promote out-of-season spawning and that vitellogenin expression is a useful indicator of spawning readiness for fish exposed to elevated winter temperatures.
Winter Wonderlands

Science.gov (United States)

Coy, Mary

2011-01-01

Listening to people complain about the hardships of winter and the dreariness of the nearly constant gray sky prompted the author to help her sixth graders recognize and appreciate the beauty that surrounds them for nearly five months of the year in western New York. The author opines that if students could see things more artistically, the winter…
Graph theory favorite conjectures and open problems 1

CERN Document Server

Hedetniemi, Stephen; Larson, Craig

2016-01-01

This is the first in a series of volumes, which provide an extensive overview of conjectures and open problems in graph theory. The readership of each volume is geared toward graduate students who may be searching for research ideas. However, the well-established mathematician will find the overall exposition engaging and enlightening. Each chapter, presented in a story-telling style, includes more than a simple collection of results on a particular topic. Each contribution conveys the history, evolution, and techniques used to solve the authors’ favorite conjectures and open problems, enhancing the reader’s overall comprehension and enthusiasm. The editors were inspired to create these volumes by the popular and well attended special sessions, entitled “My Favorite Graph Theory Conjectures," which were held at the winter AMS/MAA Joint Meeting in Boston (January, 2012), the SIAM Conference on Discrete Mathematics in Halifax (June,2012) and the winter AMS/MAA Joint meeting in Baltimore(January, 2014). In...
Classification guide: Sochi 2014 Paralympic Winter Games

OpenAIRE

2014-01-01

The Sochi 2014 Paralympic Winter Games classification guide is designed to provide National Paralympic Committees (NPCs) and International Federations (IFs) with information about the classification policies and procedures that will apply to the Sochi 2014 Paralympic Winter Games.
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.
Winter chilling speeds spring development of temperate butterflies.

Science.gov (United States)

Stålhandske, Sandra; Gotthard, Karl; Leimar, Olof

2017-07-01

Understanding and predicting phenology has become more important with ongoing climate change and has brought about great research efforts in the recent decades. The majority of studies examining spring phenology of insects have focussed on the effects of spring temperatures alone. Here we use citizen-collected observation data to show that winter cold duration, in addition to spring temperature, can affect the spring emergence of butterflies. Using spatial mixed models, we disentangle the effects of climate variables and reveal impacts of both spring and winter conditions for five butterfly species that overwinter as pupae across the UK, with data from 1976 to 2013 and one butterfly species in Sweden, with data from 2001 to 2013. Warmer springs lead to earlier emergence in all species and milder winters lead to statistically significant delays in three of the five investigated species. We also find that the delaying effect of winter warmth has become more pronounced in the last decade, during which time winter durations have become shorter. For one of the studied species, Anthocharis cardamines (orange tip butterfly), we also make use of parameters determined from previous experiments on pupal development to model the spring phenology. Using daily temperatures in the UK and Sweden, we show that recent variation in spring temperature corresponds to 10-15 day changes in emergence time over UK and Sweden, whereas variation in winter duration corresponds to 20 days variation in the south of the UK versus only 3 days in the south of Sweden. In summary, we show that short winters delay phenology. The effect is most prominent in areas with particularly mild winters, emphasising the importance of winter for the response of ectothermic animals to climate change. With climate change, these effects may become even stronger and apply also at higher latitudes. © 2017 The Authors. Journal of Animal Ecology © 2017 British Ecological Society.
[3+2] Cycloaddition of propargylic alcohols and α-oxo ketene dithioacetals: synthesis of functionalized cyclopentadienes and further application in a Diels-Alder reaction.

Science.gov (United States)

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

Directory of Open Access Journals (Sweden)

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

Science.gov (United States)

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.
AUTOMATIC CONTROL SYSTEM OF WINTER AUTOMOBILE-ROAD MAINTENANCE

Directory of Open Access Journals (Sweden)

I. I. Leonovich

2008-01-01

Full Text Available In order to ensure a rational usage of financial and material resources directed on winter automobile-road maintenance in theRepublicofBelarusan automatic control system of winter maintenance is under its development and introduction. The main purpose of the system is to obtain and use meteorological information on the state of a road network that allows to take necessary organizational and technological solutions ensuring safety and continuity of traffic during winter. This system also presupposes to ensure constant control over the state of roadway covering, expenditure of anti-glazed frost materials at all levels of management.The paper considers main aspects pertaining to introduction of the automatic control system of winter maintenance
Interspecific Plant Interactions Reflected in Soil Bacterial Community Structure and Nitrogen Cycling in Primary Succession.

Science.gov (United States)

Knelman, Joseph E; Graham, Emily B; Prevéy, Janet S; Robeson, Michael S; Kelly, Patrick; Hood, Eran; Schmidt, Steve K

2018-01-01

Past research demonstrating the importance plant-microbe interactions as drivers of ecosystem succession has focused on how plants condition soil microbial communities, impacting subsequent plant performance and plant community assembly. These studies, however, largely treat microbial communities as a black box. In this study, we sought to examine how emblematic shifts from early successional Alnus viridus ssp. sinuata (Sitka alder) to late successional Picea sitchensis (Sitka spruce) in primary succession may be reflected in specific belowground changes in bacterial community structure and nitrogen cycling related to the interaction of these two plants. We examined early successional alder-conditioned soils in a glacial forefield to delineate how alders alter the soil microbial community with increasing dominance. Further, we assessed the impact of late-successional spruce plants on these early successional alder-conditioned microbiomes and related nitrogen cycling through a leachate addition microcosm experiment. We show how increasingly abundant alder select for particular bacterial taxa. Additionally, we found that spruce leachate significantly alters the composition of these microbial communities in large part by driving declines in taxa that are enriched by alder, including bacterial symbionts. We found these effects to be spruce specific, beyond a general leachate effect. Our work also demonstrates a unique influence of spruce on ammonium availability. Such insights bolster theory relating the importance of plant-microbe interactions with late-successional plants and interspecific plant interactions more generally.
Postharvest tillage reduces Downy Brome infestations in winter wheat

Science.gov (United States)

In the Pacific Northwest, downy brome continues to infest winter wheat producing regions especially in low-rainfall areas where the winter wheat-summer fallow rotation is the dominate production system. In Washington, a study was conducted for 2 years at each of two locations in the winter wheat -su...
How to Have a Healthy Winter | Poster

Science.gov (United States)

Without a doubt, winter is here. Between the icy weather and the recent hustle and bustle of the holidays, everyone is at an increased risk of getting sick. With that in mind, Occupational Health Services has a few simple tips for staying healthy this winter.
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.

Risk management model of winter navigation operations

International Nuclear Information System (INIS)

Valdez Banda, Osiris A.; Goerlandt, Floris; Kuzmin, Vladimir; Kujala, Pentti; Montewka, Jakub

2016-01-01

The wintertime maritime traffic operations in the Gulf of Finland are managed through the Finnish–Swedish Winter Navigation System. This establishes the requirements and limitations for the vessels navigating when ice covers this area. During winter navigation in the Gulf of Finland, the largest risk stems from accidental ship collisions which may also trigger oil spills. In this article, a model for managing the risk of winter navigation operations is presented. The model analyses the probability of oil spills derived from collisions involving oil tanker vessels and other vessel types. The model structure is based on the steps provided in the Formal Safety Assessment (FSA) by the International Maritime Organization (IMO) and adapted into a Bayesian Network model. The results indicate that ship independent navigation and convoys are the operations with higher probability of oil spills. Minor spills are most probable, while major oil spills found very unlikely but possible. - Highlights: •A model to assess and manage the risk of winter navigation operations is proposed. •The risks of oil spills in winter navigation in the Gulf of Finland are analysed. •The model assesses and prioritizes actions to control the risk of the operations. •The model suggests navigational training as the most efficient risk control option.
Drought and Winter Drying (Pest Alert)

Science.gov (United States)

USDA Forest Service

Drought and winter drying have periodically caused major damage to trees. Drought reduces the amount of water available in the soil. In the case of winter drying, the water may be in the soil, but freezing of the soil makes the water unavailable to the tree. In both cases, more water is lost through transpiration than is available to the plant. Symptoms of drought and...
Global characteristics of extreme winters from a multi-millennial simulation

Energy Technology Data Exchange (ETDEWEB)

Hunt, B.G. [CSIRO Marine and Atmospheric Research, PO Box 1, Aspendale (Australia)

2011-10-15

Output from a multi-millennial simulation with the CSIRO Mark 2 coupled global climatic model has been analysed to determine the principal characteristics of extreme winters over the globe for ''present conditions''. Thus, this study is not concerned with possible changes in winter conditions associated with anthropogenically induced climatic change. Defining an extreme winter as having a surface temperature anomaly of below -2 standard deviations (sd) revealed a general occurrence rate over the globe of between 100 and 200 over a 6,000-year period of the simulation, with somewhat higher values over northwest North America. For temperature anomalies below -3 sd the corresponding occurrence rate drops to about 10. Spatial correlation studies revealed that extreme winters over regions in Europe, North America or Asia were very limited geographically, with time series of the surface temperature anomalies for these regions having mutual correlation coefficients of about 0.2. The temporal occurrence rates of winters (summers) having sd below -3 (above +3) were very asymmetric and sporadic, suggesting that such events arise from stochastic influences. Multi-year sequences of extreme winters were comparatively rare events. Detailed analysis revealed that the temporal and spatial evolution of the monthly surface temperature anomalies associated with an individual extreme winter were well replicated in the simulation, as were daily time series of such anomalies. Apart from an influence of the North Atlantic Oscillation on extreme winters in Europe, other prominent climatic oscillations were very poorly correlated with such winters. Rather modest winter temperature anomalies were found in the southern hemisphere. (orig.)
On the relation between ionospheric winter anomalies and solar wind

International Nuclear Information System (INIS)

Rumi, G.C.

2001-01-01

There are two different winter anomalies. A small one that appears in connection with ionization at relatively low latitudes in the bottom of the D-region of the ionosphere. There, the electron densities in the winter happen to be less than should be expected. On the other hand, the classic winter anomaly is present when in the winter the upper D-region, again at relatively low latitudes, has more ionization than should be expected. Both these effects are due to the slant compression of the geomagnetic field produced by the solar wind in the wind in the winter season (which is, of course, the summer season when reference is made to events in the other hemisphere). It is shown that the small winter anomaly is a consequence of a hemispheric imbalance in the flux of galactic cosmic rays determined by the obliquely distorted geomagnetic field. It is shown that the standard winter anomaly can be ascribed to the influx of a super solar wind, which penetrates into the Earth's polar atmosphere down to E-region, heights and, duly concentrated through a funneling action at the winter pole of the distorted geomagnetic field, slows down the winter polar vortex. An equatorward motion of the polar air with its content of nitric oxide brings about the excess of ionization in the upper D-region at lower latitudes. The experimentally observed rhythmic recurrence of the upper winter anomaly is correlated to a possible rhythmic recurrence of the super solar wind. The actual detection of the upper winter anomaly could yield some information on the velocity of the basic solar wind. A by-product of the present analysis, the determination of Γ, the coefficient of collisional detachment of the electrons from the O 2 - ions, is presented in the Appendix
On the relation between ionospheric winter anomalies and solar wind

Energy Technology Data Exchange (ETDEWEB)

Rumi, G.C. [Lecco, (Italy)

2001-06-01

There are two different winter anomalies. A small one that appears in connection with ionization at relatively low latitudes in the bottom of the D-region of the ionosphere. There, the electron densities in the winter happen to be less than should be expected. On the other hand, the classic winter anomaly is present when in the winter the upper D-region, again at relatively low latitudes, has more ionization than should be expected. Both these effects are due to the slant compression of the geomagnetic field produced by the solar wind in the wind in the winter season (which is, of course, the summer season when reference is made to events in the other hemisphere). It is shown that the small winter anomaly is a consequence of a hemispheric imbalance in the flux of galactic cosmic rays determined by the obliquely distorted geomagnetic field. It is shown that the standard winter anomaly can be ascribed to the influx of a super solar wind, which penetrates into the Earth's polar atmosphere down to E-region, heights and, duly concentrated through a funneling action at the winter pole of the distorted geomagnetic field, slows down the winter polar vortex. An equatorward motion of the polar air with its content of nitric oxide brings about the excess of ionization in the upper D-region at lower latitudes. The experimentally observed rhythmic recurrence of the upper winter anomaly is correlated to a possible rhythmic recurrence of the super solar wind. The actual detection of the upper winter anomaly could yield some information on the velocity of the basic solar wind. A by-product of the present analysis, the determination of {gamma}, the coefficient of collisional detachment of the electrons from the O{sub 2} {sup -} ions, is presented in the Appendix.
Bridging the gap between Schumpeterian competition and evolutionary game theory

DEFF Research Database (Denmark)

Andersen, Esben Sloth

This paper suggests that the analysis of Schumpeterian competition within the Nelson-Winter model should be complemented with evolutionary game theory. This model and its limitations for density-dependent Schumpeterian strategies are presented in terms of the equations of evolutionary dynamics. F...
Coming to grips with nuclear winter

International Nuclear Information System (INIS)

Scherr, S.J.

1985-01-01

This editorial examines the politics related to the concept of nuclear winter which is a term used to describe temperature changes brought on by the injection of smoke into the atmosphere by the massive fires set off by nuclear explosions. The climate change alone could cause crop failures and lead to massive starvation. The author suggests that the prospect of a nuclear winter should be a deterrent to any nuclear exchange
Synthesis of Unsymmetrical Annulated 2,2Ã¢Â€Â™-Bipyridine Analogues with Attached Cycloalkene and Piperidine Rings via Sequential Diels-Alder Reaction of 5,5Ã¢Â€Â™-bi-1,2,4-triazinesÃ¢Â€

Directory of Open Access Journals (Sweden)

D. Branowska

2005-12-01

Full Text Available Synthesis of bisfunctionalized unsymmetrical 2,2Ã¢Â€Â™-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 3,3Ã¢Â€Â™-bis(methyl- sulfanyl-5,5Ã¢Â€Â™-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 2,2Ã¢Â€Â™-bipyridine derivatives 8, consisting of the two different heterocyclic units: cycloalkeno[c]pyridine and 2,6-naphthyridine.
Winter/Summer Monsoon Experiment

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — The Winter/Summer Monsoon Experiment (MONEX) was conducted during the First Global GARP (Global Atmospheric Research Program) Experiment (FGGE). An international...
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.
我的寒假%My Winter Holidays

Institute of Scientific and Technical Information of China (English)

无

2008-01-01

@@ Winter holidays have about twenty days.During winter holidays, I do all kinds of interesting thing.I like climbing the hill,because it can make me heMthy.I like fishing,it can give me a lot of fun.I like visiting some places of interest, it can enlarge my knowledge.
Combined Use of Landsat-8 and Sentinel-2A Images for Winter Crop Mapping and Winter Wheat Yield Assessment at Regional Scale

Science.gov (United States)

Skakun, Sergii; Vermote, Eric; Roger, Jean-Claude; Franch, Belen

2017-01-01

Timely and accurate information on crop yield and production is critical to many applications within agriculture monitoring. Thanks to its coverage and temporal resolution, coarse spatial resolution satellite imagery has always been a source of valuable information for yield forecasting and assessment at national and regional scales. With availability of free images acquired by Landsat-8 and Sentinel-2 remote sensing satellites, it becomes possible to provide temporal resolution of an image every 3-5 days, and therefore, to develop next generation agriculture products at higher spatial resolution (10-30 m). This paper explores the combined use of Landsat-8 and Sentinel-2A for winter crop mapping and winter wheat yield assessment at regional scale. For the former, we adapt a previously developed approach for the Moderate Resolution Imaging Spectroradiometer (MODIS) instrument at 250 m resolution that allows automatic mapping of winter crops taking into account a priori knowledge on crop calendar. For the latter, we use a generalized winter wheat yield forecasting model that is based on estimation of the peak Normalized Difference Vegetation Index (NDVI) from MODIS image time-series, and further downscaled to be applicable at 30 m resolution. We show that integration of Landsat-8 and Sentinel-2A improves both winter crop mapping and winter wheat yield assessment. In particular, the error of winter wheat yield estimates can be reduced up to 1.8 times compared to using a single satellite.
Combined Use of Landsat-8 and Sentinel-2A Images for Winter Crop Mapping and Winter Wheat Yield Assessment at Regional Scale

Directory of Open Access Journals (Sweden)

Sergii Skakun

2017-05-01

Full Text Available Timely and accurate information on crop yield and production is critical to many applications within agriculture monitoring. Thanks to its coverage and temporal resolution, coarse spatial resolution satellite imagery has always been a source of valuable information for yield forecasting and assessment at national and regional scales. With availability of free images acquired by Landsat-8 and Sentinel-2 remote sensing satellites, it becomes possible to provide temporal resolution of 3–5 days, and therefore, to develop next generation agriculture products at higher spatial resolution (10–30 m. This paper explores the combined use of Landsat-8 and Sentinel-2A for winter crop mapping and winter wheat yield assessment at regional scale. For the former, we adapt a previously developed approach for the Moderate Resolution Imaging Spectroradiometer (MODIS instrument at 250 m resolution that allows automatic mapping of winter crops taking into account a priori knowledge on crop calendar. For the latter, we use a generalized winter wheat yield forecasting model that is based on estimation of the peak Normalized Difference Vegetation Index (NDVI from MODIS image time-series, and further downscaled to be applicable at 30 m resolution. We show that integration of Landsat-8 and Sentinel-2A improves both winter crop mapping and winter wheat yield assessment. In particular, the error of winter wheat yield estimates can be reduced up to 1.8 times compared to using a single satellite.
Payment mechanisms for winter road maintenance services

Directory of Open Access Journals (Sweden)

Adel Abdi

2013-12-01

Full Text Available In countries with severe winters a major part of the annual budget for road maintenance is allocated on performance of winter road maintenance tasks. Finding appropriate remuneration forms to compensate entrepreneurs for performed road measures during winter is not an easy task in order to minimise or eliminate disputes and satisfy both client organisations and contractors. On the other hand improper reimbursement models lead either to the client’s annual budget imbalance due to unnecessary cost overruns or affect contractor’s cash-flow. Such cases in turn affect just-in-time winter road maintenance and then traffic safety. To solve such problems, a number of countries in cold regions like Sweden have developed different remuneration models based more on weather data called Weather Index. Therefore the objective of this paper is to investigate and evaluate the payment models applied in Sweden. The study uses a number of approaches namely; domestic questionnaire survey, analysis of a number of contract documents, a series of meetings with the project managers and an international benchmarking. The study recognised four remuneration models for winter maintenance service of which one based on weather data statistics. The study reveals the payment model based on weather data statistics is only applied for the roads with higher traffic flow and the model generates most uncertainty.
Wintering bald eagle trends in northern Arizona, 1975-2000

Science.gov (United States)

Teryl G. Grubb

2003-01-01

Between 1975 and 2000, 4,525 sightings of wintering bald eagles (Haliaeetus leucocephalus) were recorded at Mormon Lake in northern Arizona. Numbers of wintering eagles fluctuated little in the 20 years from 1975 through 1994 (5.5 Â± 3.0 mean sightings per day). However, during the winters of 1995 through 1997 local record highs of 59 to 118 eagles...
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.
Effects of sowing time on pink snow mould, leaf rust and winter damage in winter rye varieties in Finland

Directory of Open Access Journals (Sweden)

M. SERENIUS

2008-12-01

Full Text Available Disease infection in relation to sowing time of winter rye (Secale cereale was studied in southern Finland in order to compare overwintering capacity of modern rye varieties and to give recommendations for rye cultivation. This was done by using three sowing times and four rye varieties in field trials conducted at three locations in 19992001. The early sown rye (beginning of August was severely affected by diseases caused by Puccinia recondita and Microdochium nivale, whereas postponing sowing for two weeks after the recommended sowing time resulted in considerably less infection. The infection levels of diseases differed among rye varieties. Finnish rye varieties Anna and Bor 7068 were more resistant to snow mould and more winter hardy than the Polish variety Amilo, or the German hybrid varieties Picasso and Esprit. However, Amilo was the most resistant to leaf rust. In the first year snow mould appeared to be the primary cause of winter damage, but in the second year the winter damage was positively correlated with leaf rust. No significant correlation between frit fly infestation and winter damage or disease incidence of snow mould or leaf rust was established. The late sowing of rye (in the beginning of September is recommended in Finland, particularly with hybrid varieties, to minimize the need for chemical plant protection in autumn.;
Mapping of QTLs for leaf area and the association with winter ...

African Journals Online (AJOL)

Variations in plant architecture are often associated with the ability of plants to survive cold stress during winter. In studies of winter hardiness in lentil, it appeared that small leaf area was associated with improved winter survival. Based on this observation, the inheritance of leaf area and the relationship with winter ...
The Anomalous Winter of 1783-1784: Was the Laki Eruption or an Analog of the 2009-2010 Winter to Blame?

Science.gov (United States)

D'Arrigo, Rosanne; Seager, Richard; Smerdon, Jason E.; LeGrande, Allegra N.; Cook, Edward R.

2011-01-01

The multi ]stage eruption of the Icelandic volcano Laki beginning in June, 1783 is speculated to have caused unusual dry fog and heat in western Europe and cold in North America during the 1783 summer, and record cold and snow the subsequent winter across the circum-North Atlantic. Despite the many indisputable impacts of the Laki eruption, however, its effect on climate, particularly during the 1783.1784 winter, may be the most poorly constrained. Here we test an alternative explanation for the unusual conditions during this time: that they were caused primarily by a combined negative phase of the North Atlantic Oscillation (NAO) and an El Nino ]Southern Oscillation (ENSO) warm event. A similar combination of NAO ]ENSO phases was identified as the cause of record cold and snowy conditions during the 2009.2010 winter in Europe and eastern North America. 600-year tree-ring reconstructions of NAO and ENSO indices reveal values in the 1783.1784 winter second only to their combined severity in 2009.2010. Data sources and model simulations support our hypothesis that a combined, negative NAO ]ENSO warm phase was the dominant cause of the anomalous winter of 1783.1784, and that these events likely resulted from natural variability unconnected to Laki.
Nuclear Winter: Scientists in the Political Arena

Science.gov (United States)

Badash, Lawrence

2001-03-01

The nuclear winter phenomenon is used to illustrate the many paths by which scientific advice reaches decision makers in the United States government. Because the Reagan administration was hostile to the strategic policy that the scientific discovery seemed to demand, the leading proponent of nuclear winter, Carl Sagan, used his formidable talent for popularization to reach a larger audience.

The engineering approach to winter sports

CERN Document Server

Cheli, Federico; Maldifassi, Stefano; Melzi, Stefano; Sabbioni, Edoardo

2016-01-01

The Engineering Approach to Winter Sports presents the state-of-the-art research in the field of winter sports in a harmonized and comprehensive way for a diverse audience of engineers, equipment and facilities designers, and materials scientists. The book examines the physics and chemistry of snow and ice with particular focus on the interaction (friction) between sports equipment and snow/ice, how it is influenced by environmental factors, such as temperature and pressure, as well as by contaminants and how it can be modified through the use of ski waxes or the microtextures of blades or ski soles. The authors also cover, in turn, the different disciplines in winter sports: skiing (both alpine and cross country), skating and jumping, bob sledding and skeleton, hockey and curling, with attention given to both equipment design and on the simulation of gesture and track optimization.
Nuclear Winter: Implications for civil defense

Energy Technology Data Exchange (ETDEWEB)

Chester, C.V.; Perry, A.M.; Hobbs, B.F.

1988-05-01

''Nuclear Winter'' is the term given to the cooling hypothesized to occur in the Northern Hemisphere following a nuclear war as the result of the injection of smoke from burning cities into the atmosphere. The voluminous literature on this subject produced since the paper was published in 1983 by Turco, Toon, Ackerman, Pollack, and Sagen (TTAPS) has been reviewed. Three-dimensional global circulation models have resulted in reduced estimates of cooling---15 to 25/degree/C for a summer war and a few degrees for a winter war. More serious may be the possibility of suppression of convective precipitation by the altered temperature profiles in the atmosphere. However, very large uncertainties remain in input parameters, the models, and the results of calculations. We believe the state of knowledge about nuclear winter is sufficiently developed to conclude: Neither cold nor drought is likely to be a direct threat to human survival for populations with the wherewithal to survive normal January temperatures. The principal threat from nuclear winter is to food production, and this could present problems to third parties who are without food reserves. Loss of a crop year is neither a new nor an unexpected threat from nuclear war to the United States and the Soviet Union. Both have at least a year's food reserve at all times. Both face formidable organizational problems in distributing their reserves in a war-damaged environment. The consequences of nuclear winter could be expected to fall more heavily on the Soviet Union than the United States due to its higher latitude and less productive agriculture. This may be especially true if disturbances of rainfall amounts and distribution persist for more than a year.
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.
Winter precipitation and fire in the Sonoran Desert

Energy Technology Data Exchange (ETDEWEB)

Rogers, G.F.; Vint, M.K.

1987-01-01

Historical fire and climate records from the Arizona Upland portion of the Tonto National forest were used to test the hypothesis that fires burn larger areas in the Sonoran Desert after two wet winters than after one. We found that many more hectares burn in years following two winters that are wetter than normal, than during any other years. We agree with other ecologists, that desert fire occurrence is probably related to increased production of winter annual plants, and we suggest ways that the relationship may be clarified.
Relationship of deer and moose populations to previous winters' snow

Science.gov (United States)

Mech, L.D.; McRoberts, R.E.; Peterson, R.O.; Page, R.E.

1987-01-01

(1) Linear regression was used to relate snow accumulation during single and consecutive winters with white-tailed deer (Odocoileus virginianus) fawn:doe ratios, mosse (Alces alces) twinning rates and calf:cow ratios, and annual changes in deer and moose populations. Significant relationships were found between snow accumulation during individual winters and these dependent variables during the following year. However, the strongest relationships were between the dependent variables and the sums of the snow accumulations over the previous three winters. The percentage of the variability explained was 36 to 51. (2) Significant relationships were also found between winter vulnerability of moose calves and the sum of the snow accumulations in the current, and up to seven previous, winters, with about 49% of the variability explained. (3) No relationship was found between wolf numbers and the above dependent variables. (4) These relationships imply that winter influences on maternal nutrition can accumulate for several years and that this cumulative effect strongly determines fecundity and/or calf and fawn survivability. Although wolf (Canis lupus L.) predation is the main direct mortality agent on fawns and calves, wolf density itself appears to be secondary to winter weather in influencing the deer and moose populations.
Novel psychrotolerant picocyanobacteria isolated from Chesapeake Bay in the winter.

Science.gov (United States)

Xu, Yongle; Jiao, Nianzhi; Chen, Feng

2015-08-01

Picocyanobacteria are major primary producers in the ocean, especially in the tropical or subtropical oceans or during warm seasons. Many "warm" picocyanobacterial species have been isolated and characterized. However, picocyanobacteria in cold environments or cold seasons are much less studied. In general, little is known about the taxonomy and ecophysiology of picocyanobacteria living in the winter. In this study, 17 strains of picocyanobacteria were isolated from Chesapeake Bay, a temperate estuarine ecosystem, during the winter months. These winter isolates belong to five distinct phylogenetic lineages, and are distinct from the picocyanobacteria previously isolated from the warm seasons. The vast majority of the winter isolates were closely related to picocyanobacteria isolated from other cold environments like Arctic or subalpine waters. The winter picocyanobacterial isolates were able to maintain slow growth or prolonged dormancy at 4°C. Interestingly, the phycoerythrin-rich strains outperformed the phycocyanin-rich strains at cold temperature. In addition, winter picocyanobacteria changed their morphology when cultivated at 4°C. The close phylogenetic relationship between the winter picocyanobacteria and the picocyanobacteria living in high latitude cold regions indicates that low temperature locations select specific ecotypes of picocyanobacteria. © 2015 Phycological Society of America.
An induced mutant of Coastcross 1 Bermudagrass with improved winter hardiness

International Nuclear Information System (INIS)

Burton, G.W.; Constantin, M.J.; Dobson, J.W. Jr.; Hanna, W.W.; Powell, J.B.

1980-01-01

Coastcross 1 bermudagrass, a sterile F 1 hybrid, (Coastal x PI 255445) establishes faster, yields as much dry matter, is 12% more digestible, and gives 30-35% better daily gains and liveweight gains per ha when fed to cattle than does the Coastal clone but fails to develop rhizomes and lacks the winter hardiness of Coastal. To create a winter hardy mutant, 500,000 green stems were exposed to 7000 rad of 60 -Co rays at Oak Ridge, TN June 21, 1971 and were immediately planted at Blairsville, GA where relatively severe winters occur frequently. One of 4 plants surviving the 1971-72 winter was like Coastcross 1 in yield, in vitro dry matter digestibility and appearance in a 3-yr test during mild winters at Tifton, GA. Following the moderate winter of 1976-77, Coastcross 1-M3 yielded more than Coastcross 1 but only about half as much as Coastal. The severe winter of 1977-78 destroyed about 98% of the plants of Coastcross 1 and Coastcross 1-M3 but reduced the stand of Coastal very little. The small gain in winter hardiness by Coastcross 1-M3 suggests that several genes control the winter hardiness of well-established Coastal bermudagrass. (author)
Winter Bottom Trawl Survey

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — The standardized NEFSC Winter Bottom Trawl Survey was initiated in 1992 and covered offshore areas from the Mid-Atlantic to Georges Bank. Inshore strata were covered...
Severe European winters in a secular perspective

Science.gov (United States)

Hoy, Andreas; Hänsel, Stephanie

2017-04-01

Temperature conditions during the winter time are substantially shaped by a strong year-to-year variability. European winters since the late 1980s - compared to previous decades and centuries - were mainly characterised by a high temperature level, including recent record-warm winters. Yet, comparably cold winters and severe cold spells still occur nowadays, like recently observed from 2009 to 2013 and in early 2017. Central England experienced its second coldest December since start of observations more than 350 years ago in 2010, and some of the lowest temperatures ever measured in northern Europe (below -50 °C in Lapland) were recorded in January 1999. Analysing thermal characteristics and spatial distribution of severe (historical) winters - using early instrumental data - helps expanding and consolidating our knowledge of past weather extremes. This contribution presents efforts towards this direction. We focus on a) compiling and assessing a very long-term instrumental, spatially widespread and well-distributed, high-quality meteorological data set to b) investigate very cold winter temperatures in Europe from early measurements until today. In a first step, we analyse the longest available time series of monthly temperature averages within Europe. Our dataset extends from the Nordic countries up to the Mediterranean and from the British Isles up to Russia. We utilise as much as possible homogenised times series in order to ensure reliable results. Homogenised data derive from the NORDHOM (Scandinavia) and HISTALP (greater alpine region) datasets or were obtained from national weather services and universities. Other (not specifically homogenised) data were derived from the ECA&D dataset or national institutions. The employed time series often start already during the 18th century, with Paris & Central England being the longest datasets (from 1659). In a second step, daily temperature averages are involved. Only some of those series are homogenised, but
Interspecific Plant Interactions Reflected in Soil Bacterial Community Structure and Nitrogen Cycling in Primary Succession

Directory of Open Access Journals (Sweden)

Joseph E. Knelman

2018-02-01

Full Text Available Past research demonstrating the importance plant–microbe interactions as drivers of ecosystem succession has focused on how plants condition soil microbial communities, impacting subsequent plant performance and plant community assembly. These studies, however, largely treat microbial communities as a black box. In this study, we sought to examine how emblematic shifts from early successional Alnus viridus ssp. sinuata (Sitka alder to late successional Picea sitchensis (Sitka spruce in primary succession may be reflected in specific belowground changes in bacterial community structure and nitrogen cycling related to the interaction of these two plants. We examined early successional alder-conditioned soils in a glacial forefield to delineate how alders alter the soil microbial community with increasing dominance. Further, we assessed the impact of late-successional spruce plants on these early successional alder-conditioned microbiomes and related nitrogen cycling through a leachate addition microcosm experiment. We show how increasingly abundant alder select for particular bacterial taxa. Additionally, we found that spruce leachate significantly alters the composition of these microbial communities in large part by driving declines in taxa that are enriched by alder, including bacterial symbionts. We found these effects to be spruce specific, beyond a general leachate effect. Our work also demonstrates a unique influence of spruce on ammonium availability. Such insights bolster theory relating the importance of plant–microbe interactions with late-successional plants and interspecific plant interactions more generally.
Regional greenhouse gas emissions from cultivation of winter wheat and winter rapeseed for biofuels in Denmark

DEFF Research Database (Denmark)

Elsgaard, Lars; Olesen, Jørgen E; Hermansen, John Erik

2013-01-01

Biofuels from bioenergy crops may substitute a significant part of fossil fuels in the transport sector where, e.g., the European Union has set a target of using 10% renewable energy by 2020. Savings of greenhouse gas emissions by biofuels vary according to cropping systems and are influenced...... by such regional factors as soil conditions, climate and input of agrochemicals. Here we analysed at a regional scale the greenhouse gas (GHG) emissions associated with cultivation of winter wheat for bioethanol and winter rapeseed for rapeseed methyl ester (RME) under Danish conditions. Emitted CO2 equivalents...
Synthesis of Hydroxynaphtharines; Sintesis de naftazarinas hidroxiladas

Energy Technology Data Exchange (ETDEWEB)

Farina, F.; Fernandez, E.; Gimeno, V.; Valderrama, J.A. [Instituto de Quimica Organica General, CSIC, Madrid (Spain)

1995-12-01

A variety of naththazarines type 4 and 8 were prepared through Diels-Alder reactions of substituted 1,4-benzoquinones with 1,3-dienes. Thiele-Winter reaction of 5 afforded 6 which by chromic oxidation yielded naththazarines 7 and/or naphthoquinones 9. Hydroxynaphthazarines of type 8 were synthesized from 5 through 2,3-epoxides of the type 14. The structural study of the products, by H-NMR, showed the typical tautomerism of the naphthazarine system. 23 refs.
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.
The influence of winter swimming on the rheological properties of blood.

Science.gov (United States)

Teległów, Aneta; Dąbrowski, Zbigniew; Marchewka, Anna; Tyka, Aleksander; Krawczyk, Marcin; Głodzik, Jacek; Szyguła, Zbigniew; Mleczko, Edward; Bilski, Jan; Tyka, Anna; Tabarowski, Zbigniew; Czepiel, Jacek; Filar-Mierzwa, Katarzyna

2014-01-01

The aim of this study was to analyze the changes in blood rheology resulting from regular winter swimming. The study was carried out on 12 male winter swimmers. Venous blood for morphological, biochemical and rheological analysis was sampled twice from each winter swimmer - at the beginning of the season and after its completion. There were no significant changes detected in the median values of most blood morphological parameters. The only exception pertained to MCHC which was significantly lower after the season. Winter swimming entailed significant decrease in median elongation index values at shear stress levels of 0.30 Pa and 0.58 Pa, and significant increase in median values of this parameter at shear stress levels ≥1.13 Pa. No significant changes were observed in winter swimmers' median values of aggregation indices and plasma viscosity. The median level of glucose was lower post winter swimming in comparison to the pre-seasonal values. In contrast, one season of winter swimming did not influence swimmers' median value of fibrinogen concentration. In summary, this study revealed positive effects of winter swimming on the rheological properties of blood, manifested by an increase in erythrocyte deformability without accompanying changes in erythrocyte aggregation.
Mortality impact of extreme winter temperatures

Science.gov (United States)

Díaz, Julio; García, Ricardo; López, César; Linares, Cristina; Tobías, Aurelio; Prieto, Luis

2005-01-01

During the last few years great attention has been paid to the evaluation of the impact of extreme temperatures on human health. This paper examines the effect of extreme winter temperature on mortality in Madrid for people older than 65, using ARIMA and GAM models. Data correspond to 1,815 winter days over the period 1986 1997, during which time a total of 133,000 deaths occurred. The daily maximum temperature (Tmax) was shown to be the best thermal indicator of the impact of climate on mortality. When total mortality was considered, the maximum impact occured 7 8 days after a temperature extreme; for circulatory diseases the lag was between 7 and 14 days. When respiratory causes were considered, two mortality peaks were evident at 4 5 and 11 days. When the impact of winter extreme temperatures was compared with that associated with summer extremes, it was found to occur over a longer term, and appeared to be more indirect.
Increasing Winter Maximal Metabolic Rate Improves Intrawinter Survival in Small Birds.

Science.gov (United States)

Petit, Magali; Clavijo-Baquet, Sabrina; Vézina, François

Small resident bird species living at northern latitudes increase their metabolism in winter, and this is widely assumed to improve their chances of survival. However, the relationship between winter metabolic performance and survival has yet to be demonstrated. Using capture-mark-recapture, we followed a population of free-living black-capped chickadees (Poecile atricapillus) over 3 yr and evaluated their survival probability within and among winters. We also measured the size-independent body mass (M s ), hematocrit (Hct), basal metabolic rate (BMR), and maximal thermogenic capacity (Msum) and investigated how these parameters influenced survival within and among winters. Results showed that survival probability was high and constant both within (0.92) and among (0.96) winters. They also showed that while M s , Hct, and BMR had no significant influence, survival was positively related to Msum-following a sigmoid relationship-within but not among winter. Birds expressing an Msum below 1.26 W (i.e., similar to summer levels) had a winter. Our data therefore suggest that black-capped chickadees that are either too slow or unable to adjust their phenotype from summer to winter have little chances of survival and thus that seasonal upregulation of metabolic performance is highly beneficial. This study is the first to document in an avian system the relationship between thermogenic capacity and winter survival, a proxy of fitness.
Winter cover crop effect on corn seedling pathogens

Science.gov (United States)

Cover crops are an excellent management tool to improve the sustainability of agriculture. Winter rye cover crops have been used successfully in Iowa corn-soybean rotations. Unfortunately, winter rye cover crops occasionally reduce yields of the following corn crop. We hypothesize that one potential...
Reindeer (Rangifer tarandus and climate change: Importance of winter forage

Directory of Open Access Journals (Sweden)

Thrine Moen Heggberget

2002-06-01

Full Text Available As a consequence of increasing greenhouse gas concentrations, climate change is predicted to be particularly pronounced, although regionally variable, in the vast arctic, sub-arctic and alpine tundra areas of the northern hemisphere. Here, we review winter foraging conditions for reindeer and caribou (Rangifer tarandus living in these areas, and consider diet, forage quality and distribution, accessibility due to snow variation, and effects of snow condition on reindeer and caribou populations. Finally, we hypothesise how global warming may affect wild mountain reindeer herds in South Norway. Energy-rich lichens often dominate reindeer and caribou diets. The animals also prefer lichens, and their productivity has been shown to be higher on lichen-rich than on lichen-poor ranges. Nevertheless, this energy source appears to be neither sufficient as winter diet for reindeer or caribou (at least for pregnant females nor necessary. Some reindeer and caribou populations seem to be better adapted to a non-lichen winter diet, e.g. by a larger alimentary tract. Shrubs appear to be the most common alternative winter forage, while some grasses appear to represent a good, nutritionally-balanced winter diet. Reindeer/caribou make good use of a wide variety of plants in winter, including dead and dry parts that are digested more than expected based on their fibre content. The diversity of winter forage is probably important for the mineral content of the diet. A lichen-dominated winter diet may be deficient in essential dietary elements, e.g. minerals. Sodium in particular may be marginal in inland winter ranges. Our review indicates that most Rangifer populations with lichen-dominated winter diets are either periodically or continuously heavily harvested by humans or predators. However, when population size is mainly limited by food, accessible lichen resources are often depleted. Plant studies simulating climatic change indicate that a warmer, wetter
Planning of traumatological hospital resources for a major winter sporting event as illustrated by the 2005 Winter Universiad.

Science.gov (United States)

Oberladstaetter, J; Kamelger, F S; Rosenberger, R; Dallapozza, Ch; Struve, P; Luger, T; Fink, Ch; Attal, R

2009-03-01

The 22nd Student World Winter Games took place in January 2005 in Innsbruck and Seefeld, Austria. Exactly 1,500 athletes of 50 nationalities competed in 69 events in ten winter sports. A total number of 750 functionaries, 800 volunteers and 85,000 spectators participated in the second largest winter sports event behind the Olympic winter games. The aim of this study was to evaluate the needed resources to ensure traumatological care for an event of that size. At the medical "call-center" all consultations, as well as patient data, diagnosis, and medical treatment were recorded using a preset protocol. Further, all patients treated in the University Hospital Innsbruck were registered with an emphasis on trauma patients. Forty-eight of 65 patients transported to the hospital as a result of the Universiade were trauma patients, 37 of whom were athletes. The gender distribution was 34:14 (m:f). Ice hockey players had the highest rate of injury (25% of all injured athletes), followed by alpine skiers (20.8% of injured athletes). The highest ISS was nine. Forty-three patients got ambulatory treatment, five were admitted to the hospital and surgical treatment was conducted in three cases. Mean patient number was 4.8 per day. No additional personnel, structural, or technical hospital resources were needed to accommodate a large winter sports event like the Universiad. Thus, a level-B trauma center with an emergency room and independent traumatological department with around the clock surgical capability seems to be sufficient to provide traumatological care for an event of this size if the possibility of patient transport to a larger facility exists in the case of catastrophic events.

Aircraft measurements to characterize polluted winter boundary layers: Overview of twin otter flights during the Utah Winter Fine Particulate Matter Study

Science.gov (United States)

Brown, S. S.; Baasandorj, M.; Franchin, A.; Middlebrook, A. M.; Goldberger, L.; Thornton, J. A.; Dube, W. P.; McDuffie, E. E.; Womack, C.; Fibiger, D. L.; Moravek, A.; Clark, J. C.; Murphy, J. G.; Mitchell, R.

2017-12-01

Winter air pollution is a significant public health concern. In many regions of the U.S., Europe and Asia, wintertime particulate matter concentrations exceed national and / or international air quality standards. Winter air pollution also represents a scientific challenge because these events occur during stagnation events in shallow, vertically stratified boundary layers whose composition is difficult to probe from surface level measurements. Chemical processes responsible for the conversion of primary emissions to secondary pollutants such as ammonium nitrate aerosol vary with height above ground level. Sources of oxidants are poorly understood and may result from both local chemical production and mixing between shallow inversion layers and background air. During the Utah Winter Fine Particulate Study (UWFPS) in January - February 2017, the NOAA twin otter executed 23 research flights with a payload designed to characterize the formation of ammonium nitrate aerosol in three mountain valleys of northern Utah (Salt Lake, Cache, and Utah). These valleys are subject to periodic episodes of winter aerosol pollution well in excess of U.S. national ambient air quality standards. This presentation will describe the measurement strategy of the twin otter flights to address the specific features of aerosol pollution within winter boundary layer of this region. This strategy is relevant to understanding the broader issue of winter air pollution in other regions and potentially to the design of future studies. The presentation will summarize findings from UWFPS related to boundary layer structure, emissions and chemical processes responsible for ammonium nitrate aerosol in this region.
Zimbabwean fourth social workers conference and winter school ...

African Journals Online (AJOL)

Such steps include running the Annual Social Workers Conference & Winter School. This annual observance creates a platform to showcase the goals and accomplishments of diverse social work professionals in the country, give a report on progress and convening a social work winter school for exchanging professional ...
Winter-APK voor bijen : Helpt u deze winter mee bij het praktijkonderzoek?

NARCIS (Netherlands)

Som de Cerff, B.; Cornelissen, B.; Moens, F.

2013-01-01

Om de risico’s van een aanrijding bij sneeuw en gladheid te verminderen, laten steeds meer automobilisten bij het monteren van winterbanden ook een wintercontrole uitvoeren. Zou een dergelijke controle voor de winter ook schade aan onze volken in de vorm van wintersterfte kunnen verminderen? Dat zou
STIMULATION OF RESISTANCE OF BEE FAMILIES DURING WINTERING

Directory of Open Access Journals (Sweden)

nicolae eremia

2013-10-01

Full Text Available Honey bees use as food nectar, honey, pollen and bee bread. They collect nectar and pollen on flowers, that process in food - honey and bee bread. Food provides the bees body with energy due to carbohydrates, proteins, enzymes, lipids, vitamins, minerals. The goal of the studies was to stimulate the bees’ resistance during wintering against nesemosa disease in bee families’ survival after winter time and productivity increasing. There was established that the optimal dose of feed additive Pramix Bionorm P (symbiotic complex, in reserves supplementing of food of bee families during autumn is 150 mg of sugar syrup. There was revealed that using of the feed additive Pramix Bionorm P (symbiotic complex, in bees feeding for reserves supplementing of bees food ensures a stimulating of resistance at wintering of bees, decreases the quantity of used honey during wintering at one space between honey combs populated with bees, as well increases the productivity.
RTN Winter School on Strings, Supergravity and Gauge Theories (3/5)

CERN Multimedia

CERN. Geneva

2006-01-01

9.30-10.30 B. Pioline Black Hole Degeneracies, Topological Strings and Quantum Attractor Flow (2/4) 10.30-11.30 S. Minwalla Large N Thermal Phase Transitions (2/4) 12.15-13.15 B. Craps Big Bang Models in String Theory (3/4) 14.00 CERN presentation and visit Organiser(s): CERN and Neuchâtel UniversityMore information: http://www.unine.ch/phys/string/rtn-school/index.php
On the effect of tether composition on cis/trans selectivity in intramolecular Diels-Alder reactions.

Science.gov (United States)

Paddon-Row, Michael N; Longshaw, Alistair I; Willis, Anthony C; Sherburn, Michael S

2009-01-05

Intramolecular Diels-Alder (IMDA) transition structures (TSs) and energies have been computed at the B3LYP/6-31+G(d) and CBS-QB3 levels of theory for a series of 1,3,8-nonatrienes, H(2)C=CH-CH=CH-CH(2)-X-Z-CH=CH(2) [-X-Z- = -CH(2)-CH(2)- (1); -O-C(=O)- (2); -CH(2)-C(=O)- (3); -O-CH(2)- (4); -NH-C(=O)- (5); -S-C(=O)- (6); -O-C(=S)- (7); -NH-C(=S)- (8); -S-C(=S)- (9)]. For each system studied (1-9), cis- and trans-TS isomers, corresponding, respectively, to endo- and exo-positioning of the -C-X-Z- tether with respect to the diene, have been located and their relative energies (E(rel) (TS)) employed to predict the cis/trans IMDA product ratio. Although the E(rel) (TS) values are modest (typically NH or S), the IMDA cis stereoselectivity diminishes. The predicted stereochemical reaction preferences are explained in terms of two opposing effects operating in the cis-TS, namely (1) unfavorable torsional (eclipsing) strain about the C4-C5 bond, that is caused by the -C-X-C(=Y)- group's strong tendency to maintain local planarity; and (2) attractive electrostatic and secondary orbital interactions between the endo-(thio)carbonyl group, C=Y, and the diene. The former interaction predominates when X is weakly electronegative (X=N, S), while the latter is dominant when X is more strongly electronegative (X=O), or a methylene group (X=CH(2)) which increases tether flexibility. These predictions hold up to experimental scrutiny, with synthetic IMDA reactions of 1, 2, 3, and 4 (published work) and 5, 6, and 8 (this work) delivering ratios close to those calculated. The reactions of thiolacrylate 5 and thioamide 8 represent the first examples of IMDA reactions with tethers of these types. Our results point to strategies for designing tethers, which lead to improved cis/trans-selectivities in IMDAs that are normally only weakly selective. Experimental verification of the validity of this claim comes in the form of fumaramide 14, which undergoes a more trans-selective IMDA reaction
European seasonal mortality and influenza incidence due to winter temperature variability

Science.gov (United States)

Rodó, X.; Ballester, J.; Robine, J. M.; Herrmann, F. R.

2017-12-01

Recent studies have vividly emphasized the lack of consensus on the degree of vulnerability (sensu IPCC) of European societies to current and future winter temperatures. Here we consider several climate factors, influenza incidence and daily numbers of deaths to characterize the relationship between winter temperature and mortality in a very large ensemble of European regions representing more than 400 million people. Analyses highlight the strong association between the year-to-year fluctuations in winter mean temperature and mortality, with higher seasonal cases during harsh winters, in all of the countries except the United Kingdom, the Netherlands and Belgium. This spatial distribution contrasts with the well-documented latitudinal orientation of the dependency between daily temperature and mortality within the season. A theoretical framework is proposed to reconcile the apparent contradictions between recent studies, offering an interpretation to regional differences in the vulnerability to daily, seasonal and long-term winter temperature variability. Despite the lack of a strong year-to-year association between winter mean values in some countries, it can be concluded that warmer winters will contribute to the decrease in winter mortality everywhere in Europe. More information in Ballester J, et al. (2016) Nature Climate Change 6, 927-930, doi:10.1038/NCLIMATE3070.
Migration and wintering sites of Pelagic Cormorants determined by satellite telemetry

Science.gov (United States)

Hatch, Shyla A.; Gill, V.A.; Mulcahy, D.M.

2011-01-01

Factors affecting winter survival may be key determinants of status and population trends of seabirds, but connections between breeding sites and wintering areas of most populations are poorly known. Pelagic Cormorants (Phalacrocorax pelagicus; N= 6) surgically implanted with satellite transmitters migrated from a breeding colony on Middleton Island, northern Gulf of Alaska, to wintering sites in southeast Alaska and northern British Columbia. Winter locations averaged 920 km (range = 600-1190 km) from the breeding site. Migration flights in fall and spring lasted ???5 d in four instances. After reaching wintering areas, cormorants settled in narrowly circumscribed inshore locations (~10-km radius) and remained there throughout the nonbreeding period (September- March). Two juveniles tagged at the breeding colony as fledglings remained at their wintering sites for the duration of the tracking interval (14 and 22 mo, respectively). Most cormorants used multiple sites within their winter ranges for roosting and foraging. Band recoveries show that Pelagic Cormorants in southern British Columbia and Washington disperse locally in winter, rather than migrating like the cormorants in our study. Radio-tagging and monitoring cormorants and other seabirds from known breeding sites are vital for understanding migratory connectivity and improving conservation strategies for local populations. ?? 2011 The Authors. Journal of Field Ornithology ?? 2011 Association of Field Ornithologists.
Comparison of Selected Morphological, Rheological and Biochemical Parameters of Winter Swimmers' Blood at the End of One Winter Swimming Season and at the Beginning of Another.

Science.gov (United States)

Teległów, Aneta; Marchewka, Jakub; Tabarowski, Zbigniew; Rembiasz, Konrad; Głodzik, Jacek; Scisłowska-Czarnecka, Anna

2015-01-01

The aim of the study was to examine potential differences in the morphological, rheological and biochemical blood parameters of winter swimmers who remained physically active during the period between the end of one winter swimming season and the beginning of another. The study included a group of healthy winter swimmers (n = 17, all between 30 and 60 years of age). Six months following the end of winter season, the levels of mean corpuscular hemoglobin concentration and mean corpuscular hemoglobin turned out to be significantly higher, while erythrocyte count and hematocrit level significantly lower than at the baseline. Moreover, the break in winter swimming was reflected by a significant increase in median erythrocyte elongation index at all shear stress levels ≥ 1.13 Pa. The only significant changes in biochemical parameters of the blood pertained to an increase in the concentration of transferrin and to a decrease in the total protein, albumin and beta-1 globulin concentrations. Seasonal effort of winter swimmers between the end of one winter swimming season and the beginning of another has a positive influence on morphological, rheological and biochemical blood parameters.
Polar vortex evolution during Northern Hemispheric winter 2004/05

Directory of Open Access Journals (Sweden)

T. Chshyolkova

2007-06-01

Full Text Available As a part of the project "Atmospheric Wave Influences upon the Winter Polar Vortices (0–100 km" of the CAWSES program, data from meteor and Medium Frequency radars at 12 locations and MetO (UK Meteorological Office global assimilated fields have been analyzed for the first campaign during the Northern Hemispheric winter of 2004/05. The stratospheric state has been described using the conventional zonal mean parameters as well as Q-diagnostic, which allows consideration of the longitudinal variability. The stratosphere was cold during winter of 2004/05, and the polar vortex was relatively strong during most of the winter with relatively weak disturbances occurring at the end of December and the end of January. For this winter the strongest deformation with the splitting of the polar vortex in the lower stratosphere was observed at the end of February. Here the results show strong latitudinal and longitudinal differences that are evident in the stratospheric and mesospheric data sets at different stations. Eastward winds are weaker and oscillations with planetary wave periods have smaller amplitudes at more poleward stations. Accordingly, the occurrence, time and magnitude of the observed reversal of the zonal mesospheric winds associated with stratospheric disturbances depend on the local stratospheric conditions. In general, compared to previous years, the winter of 2004/05 could be characterized by weak planetary wave activity at stratospheric and mesospheric heights.
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

Directory of Open Access Journals (Sweden)

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.
Overhead irrigation increased winter chilling and floral bud ...

African Journals Online (AJOL)

Eucalyptus nitens requires a sufficiently cold winter to produce flower buds. In areas in South Africa where E. nitens commercial plantations as well as breeding and production seed orchards are located, winter chilling is often insufficient for floral bud initiation. Hence, under such conditions, E. nitens floral bud and seed ...
Does Wyoming's Core Area Policy Protect Winter Habitats for Greater Sage-Grouse?

Science.gov (United States)

Smith, Kurt T.; Beck, Jeffrey L.; Pratt, Aaron C.

2016-10-01

Conservation reserves established to protect important habitat for wildlife species are used world-wide as a wildlife conservation measure. Effective reserves must adequately protect year-round habitats to maintain wildlife populations. Wyoming's Sage-Grouse Core Area policy was established to protect breeding habitats for greater sage-grouse ( Centrocercus urophasianus). Protecting only one important seasonal habitat could result in loss or degradation of other important habitats and potential declines in local populations. The purpose of our study was to identify the timing of winter habitat use, the extent which individuals breeding in Core Areas used winter habitats, and develop resource selection functions to assess effectiveness of Core Areas in conserving sage-grouse winter habitats in portions of 5 Core Areas in central and north-central Wyoming during winters 2011-2015. We found that use of winter habitats occured over a longer period than current Core Area winter timing stipulations and a substantial amount of winter habitat outside of Core Areas was used by individuals that bred in Core Areas, particularly in smaller Core Areas. Resource selection functions for each study area indicated that sage-grouse were selecting habitats in response to landscapes dominated by big sagebrush and flatter topography similar to other research on sage-grouse winter habitat selection. The substantial portion of sage-grouse locations and predicted probability of selection during winter outside small Core Areas illustrate that winter requirements for sage-grouse are not adequately met by existing Core Areas. Consequently, further considerations for identifying and managing important winter sage-grouse habitats under Wyoming's Core Area Policy are warranted.
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
Perspectives in Winter Limnology: Closing the annual cycle of freezing lakes

NARCIS (Netherlands)

Salonen, K.; Leppäranta, M.; Viljanen, M.; Gulati, R.D.

2009-01-01

Winter has traditionally been considered as an ecologically insignificant season and, together with technical difficulties, this has led winter limnology to lag behind summer limnology. Recently, rapidly expanding interest in climate warming has increased water research in winter. It has also become
Migration and winter distribution of the Chestnutcollared Longspur

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Ellison Kevin

2017-12-01

Full Text Available The Chestnut-collared Longspur (Calcarius ornatus is one of five grassland songbirds, endemic within North America, with populations that have declined >65% since the 1960s. These species breed and winter in the northern and southern Great Plains, respectively. Identifying migration routes, wintering sites, and the timing of their habitat use is key for understanding the relative magnitude of threats across the annual cycle and effectively targeting habitats for conservation. We tracked migratory movements of seven Chestnut-collared Longspurs with light-level geolocators deployed in Canada. Individuals wintered up to 112-1,200km apart. All followed the Central Flyway, circumvented high-elevation terrain, and traveled east of the breeding location. Unlike most songbirds, the durations of spring and fall migrations were similar; on average 42 ± 7d and 41 ± 5d during fall and spring migrations, respectively, for an approximately 2,000km migration; this highlights the need to better understand habitat requirements during migration for grassland songbirds. Using geospatial habitat data, we assessed winter distribution overlap with four other endemic grassland songbirds; wintering range overlapped 63-99%. Future studies should use more precise devices (e.g., archival GPS units, programmed for data collection dates from this study, to identify specific migratory sites for better conserving this and associated grassland species.
Neurotic psychopathology and alexithymia among winter swimmers and controls--a prospective study.

Science.gov (United States)

Lindeman, Sari; Hirvonen, Jorma; Joukamaa, Matti

2002-05-01

Random samples of 25 voluntary Finnish winter swimmers (7 males, 18 females) and 11 controls (3 males, 8 females were followed prospectively during the winter season from October 1999 to May 2000 to (determine whether winter swimming is beneficial for mental well-being, as many of its practitioners claim. The Crown-Crisp Experimental Index (CCEI) was used for measuring free-floating anxiety, phobic anxiety, obsessionality, depression, somatic anxiety and hysteria, and the 20-item version of the Toronto Alexithymia Scale (TAS-20) for measuring alexithymia. Self-reported somatic and mental health and the reasons for and the frequency of winter-swimming were asked, too. As resealed by open questions, the winter swimmers reported positive effects of winter swimming. Several of the swimmers also told that they had started winter swimming to improve their physical and mental health. Their experience was that the swimming had relieved physical symptoms and made their mood more positive. However, we found no major differences between winter swimmers and controls in any CCEI or TAS variables. The structured questionnaires do not necessarily, however, reach subjective feelings and experiences.
Nuclear Winter: The implications for civil defense

International Nuclear Information System (INIS)

Chester, C.V.; Perry, A.M.; Hobbs, B.F.

1987-01-01

''Nuclear Winter'' is the term given to hypothesized cooling in the northern hemisphere following a nuclear war due to injection of smoke from burning cities into the atmosphere. The voluminous literature on this subject produced since the original paper in 1983 by Turco, Toon, Ackerman, Pollack, and Sagen (TTAPS) has been reviewed. The widespread use of 3-dimensional global circulation models have resulted in reduced estimates of cooling; 15 to 25 0 C for a summer war and a few degrees for a winter war. More serious may be the possibility of suppression of convective precipitation by the altered temperature profiles in the atmosphere. However, very large uncertainties remain in input parameters, the models, and the results of calculations. We believe the state of knowledge about nuclear winter is sufficiently developed to conclude: Neither cold nor drought are likely to be direct threats to human survival for populations with the wherewithal to survive normal January temperatures; The principal threat from nuclear winter is to food production, and could present problems to third parties without food reserves; and Loss of a crop year is neither a new nor unexpected threat from nuclear war to the US and the Soviet Union. Both have at least a year's food reserve at all times. Both face formidable organizational problems in distributing their reserves in a war-damaged environment. The consequences of nuclear winter could be expected to fall more heavily on the Soviet Union than the US due to its higher latitude and less productive agriculture. This may be especially true if disturbances of rainfall amounts and distribution persist for more than a year. 6 refs
CAN WINTER DEPRESSION BE PREVENTED BY LIGHT TREATMENT

NARCIS (Netherlands)

MEESTERS, Y; LAMBERS, PA; JANSEN, JHC; BOUHUYS, AL; BEERSMA, DGM; VANDENHOOFDAKKER, RH

1991-01-01

The administration of light at the development of the first signs of a winter depression appears to prevent it from developing into a full-blown depression. No patient from a group of 10 treated in this way developed any signs of depression during the rest of the winter season, while five of seven
Can winter depression be prevented by light treatment?

NARCIS (Netherlands)

Meesters, Ybe; Lambers, Petrus A.; Jansen, Jacob; Bouhuys, Antoinette L.; Beersma, Domien G.M.; Hoofdakker, Rutger H. van den

1991-01-01

The administration of light at the development of the first signs of a winter depression appears to prevent it from developing into a full-blown depression. No patient from a group of 10 treated in this way developed any signs of depression during the rest of the winter season, while five of seven

Are cold winters in Europe associated with low solar activity?

International Nuclear Information System (INIS)

Lockwood, M; Harrison, R G; Woollings, T; Solanki, S K

2010-01-01

Solar activity during the current sunspot minimum has fallen to levels unknown since the start of the 20th century. The Maunder minimum (about 1650-1700) was a prolonged episode of low solar activity which coincided with more severe winters in the United Kingdom and continental Europe. Motivated by recent relatively cold winters in the UK, we investigate the possible connection with solar activity. We identify regionally anomalous cold winters by detrending the Central England temperature (CET) record using reconstructions of the northern hemisphere mean temperature. We show that cold winter excursions from the hemispheric trend occur more commonly in the UK during low solar activity, consistent with the solar influence on the occurrence of persistent blocking events in the eastern Atlantic. We stress that this is a regional and seasonal effect relating to European winters and not a global effect. Average solar activity has declined rapidly since 1985 and cosmogenic isotopes suggest an 8% chance of a return to Maunder minimum conditions within the next 50 years (Lockwood 2010 Proc. R. Soc. A 466 303-29): the results presented here indicate that, despite hemispheric warming, the UK and Europe could experience more cold winters than during recent decades.
Going outside in Winter: A Qualitative Study of Preschool Dressing Routines

Science.gov (United States)

Hatcher, Beth; Squibb, Betsy

2011-01-01

The exploratory study focused on describing typical routines of preparing for winter outdoor play with preschool children and their teachers. Naturalistic observations, interviews and photographs resulted in extensive examples of children's development in cognitive understanding of winter and winter-related concepts. Observations of teachers and…
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.
Genetic differentiation between sympatric and allopatric wintering populations of Snow Geese

Science.gov (United States)

Humphries, E.M.; Peters, J.L.; Jonsson, J.E.; Stone, R.; Afton, A.D.; Omland, K.E.

2009-01-01

Blackwater National Wildlife Refuge on the Delmarva Peninsula, Maryland, USA has been the wintering area of a small population of Lesser Snow Geese (Chen caerulescens caerulescens; LSGO) since the 1930s. Snow Geese primarily pair in wintering areas and gene flow could be restricted between this and other LSGO wintering populations. Winter pair formation also could facilitate interbreeding with sympatric but morphologically differentiated Greater Snow Geese (C. c. atlantica; GSGO).We sequenced 658 bp of the mitochondrial DNA control region for 68 Snow Geese from East Coast and Louisiana wintering populations to examine the level of genetic differentiation among populations and subspecies. We found no evidence for genetic differentiation between LSGO populations but, consistent with morphological differences, LSGO and GSGO were significantly differentiated. We also found a lack of genetic differentiation between different LSGO morphotypes from Louisiana. We examined available banding data and found the breeding range of Delmarva LSGO overlaps extensively with LSGO that winter in Louisiana, and documented movements between wintering populations. Our results suggest the Delmarva population of LSGO is not a unique population unit apart from Mid-Continent Snow Geese. ?? 2009 by the Wilson Ornithological Society.
Downtown People Mover (DPM) Winterization Test Demonstration : Otis Elevator

Science.gov (United States)

1982-01-01

The Otis Elevator Company Transportation Technology Division (OTIS-TTD) Downtown People Mover (DPM) Winterization Test Demonstration Final Report covers the 1978-79 and 1979-80 winter periods. Tests were performed at the Otis test track in Denver, Co...
Small Winter Thunderstorm with Sprites and Strong Positive Discharge

Science.gov (United States)

Suzuki, Tomoyuki; Hayakawa, Masashi; Michimoto, Koichiro

A sprite campaign was conducted in the Hokuriku area of Japan during a winter of 2004/2005. On the basis of a combined analysis of the data from various instruments (CCD cameras, radar, VHF/LF∼MF lightning mapping system, field mill network, and ELF detector), we studied meteorological and electrical structures for winter thunderstorms and sprite-producing positive discharge. Typical winter sprite parent thunderstorms had a meso-scale cloud area with embedded small convective cells. Some small winter thunderstorms accompanied by the most frequent sprite events were found to cause 2∼3 sprite events during a short interval of about 3∼5 min. When the sprites were observed, the extent of the convective cells at 20 dBZ counter was atmost ∼20 × 20 km. The VHF sources associated with sprites were located near south of the convective cell and were mapped within very small areas of at most ∼10 × 10 km. This fact shows that some small winter thunderstorms can generate large positive charge associated with sprites. We will present the analysis of such a small thunderstorms with sprites and positive lightning discharges.
Controls on winter ecosystem respiration in temperate and boreal ecosystems

Directory of Open Access Journals (Sweden)

T. Wang

2011-07-01

Full Text Available Winter CO₂ fluxes represent an important component of the annual carbon budget in northern ecosystems. Understanding winter respiration processes and their responses to climate change is also central to our ability to assess terrestrial carbon cycle and climate feedbacks in the future. However, the factors influencing the spatial and temporal patterns of winter ecosystem respiration (R_eco of northern ecosystems are poorly understood. For this reason, we analyzed eddy covariance flux data from 57 ecosystem sites ranging from ~35° N to ~70° N. Deciduous forests were characterized by the highest winter R_eco rates (0.90 ± 0.39 g C m⁻² d⁻¹, when winter is defined as the period during which daily air temperature remains below 0 °C. By contrast, arctic wetlands had the lowest winter R_eco rates (0.02 ± 0.02 g C m⁻² d⁻¹. Mixed forests, evergreen needle-leaved forests, grasslands, croplands and boreal wetlands were characterized by intermediate winter R_eco rates (g C m⁻² d⁻¹ of 0.70(±0.33, 0.60(±0.38, 0.62(±0.43, 0.49(±0.22 and 0.27(±0.08, respectively. Our cross site analysis showed that winter air (T_air and soil (T_soil temperature played a dominating role in determining the spatial patterns of winter R_eco in both forest and managed ecosystems (grasslands and croplands. Besides temperature, the seasonal amplitude of the leaf area index (LAI, inferred from satellite observation, or growing season gross primary productivity, which we use here as a proxy for the amount of recent carbon available for R_eco in the subsequent winter, played a marginal role in winter CO₂ emissions from forest ecosystems. We found that winter R_eco sensitivity to temperature variation across space (
Kleptoparasitism by bald eagles wintering in south-central Nebraska

Science.gov (United States)

Jorde, Dennis G.; Lingle, G.R.

1988-01-01

Kleptoparasitism on other raptors was one means by which Bald Eagles (Haliaeetus leucocephalus) secured food along the North Platte and Platte rivers during the winters of 1978-1980. Species kelptoparasitized were Ferruginous Hawk (Buteo regalis), Red-tailed Hawk (B. jamaicensis), Rough-legged Hawk (B. lagopus), Golden Eagle (Aquila chrysaetos), and Bald Eagle. Stealing of prey occurred more often during the severe winter of 1978-1979 when ice cover restricted eagles from feeding on fish than during the milder winter of 1979-1980. Kleptoparasitism occurred principally in agricultural habitats where large numbers of Mallards (Anas platyrhynchos) were foraging. Subadults watched adults steal food and participated in food-stealing with adults, which indicated interspecific kleptoparasitism may be a learned behavior. We suggest factors that may favor interspecific kleptoparasitism as a foraging strategy of Bald Eagles in obtaining waterfowl during severe winters.
Winter severity determines functional trait composition of phytoplankton in seasonally ice-covered lakes.

Science.gov (United States)

Özkundakci, Deniz; Gsell, Alena S; Hintze, Thomas; Täuscher, Helgard; Adrian, Rita

2016-01-01

How climate change will affect the community dynamics and functionality of lake ecosystems during winter is still little understood. This is also true for phytoplankton in seasonally ice-covered temperate lakes which are particularly vulnerable to the presence or absence of ice. We examined changes in pelagic phytoplankton winter community structure in a north temperate lake (Müggelsee, Germany), covering 18 winters between 1995 and 2013. We tested how phytoplankton taxa composition varied along a winter-severity gradient and to what extent winter severity shaped the functional trait composition of overwintering phytoplankton communities using multivariate statistical analyses and a functional trait-based approach. We hypothesized that overwintering phytoplankton communities are dominated by taxa with trait combinations corresponding to the prevailing winter water column conditions, using ice thickness measurements as a winter-severity indicator. Winter severity had little effect on univariate diversity indicators (taxon richness and evenness), but a strong relationship was found between the phytoplankton community structure and winter severity when taxon trait identity was taken into account. Species responses to winter severity were mediated by the key functional traits: motility, nutritional mode, and the ability to form resting stages. Accordingly, one or the other of two functional groups dominated the phytoplankton biomass during mild winters (i.e., thin or no ice cover; phototrophic taxa) or severe winters (i.e., thick ice cover; exclusively motile taxa). Based on predicted milder winters for temperate regions and a reduction in ice-cover durations, phytoplankton communities during winter can be expected to comprise taxa that have a relative advantage when the water column is well mixed (i.e., need not be motile) and light is less limiting (i.e., need not be mixotrophic). A potential implication of this result is that winter severity promotes different
Winter School Les Houches

CERN Document Server

Lannoo, Michel; Bastard, Gérald; Voos, Michel; Boccara, Nino

1986-01-01

The Winter School held in Les Houches on March 12-21, 1985 was devoted to Semiconductor Heterojunctions and Superlattices, a topic which is recognized as being now one of the most interesting and active fields in semiconductor physics. In fact, following the pioneering work of Esaki and Tsu in 1970, the study of these two-dimensional semiconductor heterostructures has developed rapidly, both from the point of view of basic physics and of applications. For instance, modulation-doped heterojunctions are nowadays currently used to investigate the quantum Hall effect and to make very fast transistors. This book contains the lectures presented at this Winter School, showing in particular that many aspects of semiconductor heterojunctions and super lattices were treated, extending from the fabrication of these two-dimensional systems to their basic properties and applications in micro-and opto-electron ics. Among the subjects which were covered, one can quote as examples: molecular beam epitaxy and metallorgani...
Editorial - The winter Atomiades

CERN Multimedia

Staff Association

2011-01-01

As we wrote in our previous editorial, the Staff Association gives direct support to sports events, such as the Atomiades, a section of the Association of Sports Communities of European Research Institutes, which brings together sportsmen and women from 38 European research centres in 13 countries (Austria, Belgium, Czech Republic, United Kingdom, Finland, France, Germany, Hungary, Italy, Luxemburg, the Netherlands, Russia, and Switzerland). The summer Atomiades take place between the months of June and September every three years. Thirteen such events have taken place since 1973, the last one in June 2009 in Berlin. As far as the winter Atomiades are concerned, also organized every three years, and alternating with the summer Atomiades, there have been eleven since 1981, the last one at the end of January this year in neighbouring France. The following article tells the wonderful adventure of the CERN staff who took part in this event. A positive outcome for CERN skiers at the winter Atomiades The 11t...
Impact of warm winters on microbial growth

Science.gov (United States)

Birgander, Johanna; Rousk, Johannes; Axel Olsson, Pål

2014-05-01

Growth of soil bacteria has an asymmetrical response to higher temperature with a gradual increase with increasing temperatures until an optimum after which a steep decline occurs. In laboratory studies it has been shown that by exposing a soil bacterial community to a temperature above the community's optimum temperature for two months, the bacterial community grows warm-adapted, and the optimum temperature of bacterial growth shifts towards higher temperatures. This result suggests a change in the intrinsic temperature dependence of bacterial growth, as temperature influenced the bacterial growth even though all other factors were kept constant. An intrinsic temperature dependence could be explained by either a change in the bacterial community composition, exchanging less tolerant bacteria towards more tolerant ones, or it could be due to adaptation within the bacteria present. No matter what the shift in temperature tolerance is due to, the shift could have ecosystem scale implications, as winters in northern Europe are getting warmer. To address the question of how microbes and plants are affected by warmer winters, a winter-warming experiment was established in a South Swedish grassland. Results suggest a positive response in microbial growth rate in plots where winter soil temperatures were around 6 °C above ambient. Both bacterial and fungal growth (leucine incorporation, and acetate into ergosterol incorporation, respectively) appeared stimulated, and there are two candidate explanations for these results. Either (i) warming directly influence microbial communities by modulating their temperature adaptation, or (ii) warming indirectly affected the microbial communities via temperature induced changes in bacterial growth conditions. The first explanation is in accordance with what has been shown in laboratory conditions (explained above), where the differences in the intrinsic temperature relationships were examined. To test this explanation the
A winter severity index for the state of Maine.

Science.gov (United States)

2009-01-01

Winter maintenance in the Sate of Maine consumes around twenty percent of the Bureau of : Maintenance and Operations budget each year. Costs are directly related to the length and severity : of a winter season. In addition, the cost of materials and ...
Marine assemblages respond rapidly to winter climate variability.

Science.gov (United States)

Morley, James W; Batt, Ryan D; Pinsky, Malin L

2017-07-01

Even species within the same assemblage have varied responses to climate change, and there is a poor understanding for why some taxa are more sensitive to climate than others. In addition, multiple mechanisms can drive species' responses, and responses may be specific to certain life stages or times of year. To test how marine species respond to climate variability, we analyzed 73 diverse taxa off the southeast US coast in 26 years of scientific trawl survey data and determined how changes in distribution and biomass relate to temperature. We found that winter temperatures were particularly useful for explaining interannual variation in species' distribution and biomass, although the direction and magnitude of the response varied among species from strongly negative, to little response, to strongly positive. Across species, the response to winter temperature varied greatly, with much of this variation being explained by thermal preference. A separate analysis of annual commercial fishery landings revealed that winter temperatures may also impact several important fisheries in the southeast United States. Based on the life stages of the species surveyed, winter temperature appears to act through overwinter mortality of juveniles or as a cue for migration timing. We predict that this assemblage will be responsive to projected increases in temperature and that winter temperature may be broadly important for species relationships with climate on a global scale. © The Authors Global Change Biology Published by John Wiley & Sons Ltd.
Excess winter mortality and cold temperatures in a subtropical city, Guangzhou, China.

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Chun-Quan Ou

Full Text Available BACKGROUND: A significant increase in mortality was observed during cold winters in many temperate regions. However, there is a lack of evidence from tropical and subtropical regions, and the influence of ambient temperatures on seasonal variation of mortality was not well documented. METHODS: This study included 213,737 registered deaths from January 2003 to December 2011 in Guangzhou, a subtropical city in Southern China. Excess winter mortality was calculated by the excess percentage of monthly mortality in winters over that of non-winter months. A generalized linear model with a quasi-Poisson distribution was applied to analyze the association between monthly mean temperature and mortality, after controlling for other meteorological measures and air pollution. RESULTS: The mortality rate in the winter was 26% higher than the average rate in other seasons. On average, there were 1,848 excess winter deaths annually, with around half (52% from cardiovascular diseases and a quarter (24% from respiratory diseases. Excess winter mortality was higher in the elderly, females and those with low education level than the young, males and those with high education level, respectively. A much larger winter increase was observed in out-of-hospital mortality compared to in-hospital mortality (45% vs. 17%. We found a significant negative correlation of annual excess winter mortality with average winter temperature (rs=-0.738, P=0.037, but not with air pollution levels. A 1 °C decrease in monthly mean temperature was associated with an increase of 1.38% (95% CI:0.34%-2.40% and 0.88% (95% CI:0.11%-1.64% in monthly mortality at lags of 0-1 month, respectively. CONCLUSION: Similar to temperate regions, a subtropical city Guangzhou showed a clear seasonal pattern in mortality, with a sharper spike in winter. Our results highlight the role of cold temperature on the winter mortality even in warm climate. Precautionary measures should be strengthened to mitigate
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

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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 LCâMS/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 LCâMS/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 (100Â mmÃ4.6Â mm, 2.5Â Âµm column using acetonitrile and 0.1% (v/v formic acid in water containing 0.14% methylamine within 6.0Â 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 LIMSâ¢ software which provided excellent data integrity and high throughput with improved operational efficiency. The major advantage of this method includes higher sensitivity (0.10Â ng/mL, superior extraction efficiency (â¥83% and small sample volume (100Â ÂµL for processing. The method was linear in the concentration range of 0.10â100Â 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 1.25Â mg ergocalciferol capsules in 12 healthy subjects. Keywords: Ergocalciferol, Diels-Alder reaction, 4-phenyl-1,2,4-triazoline-3,5-dione, LCâMS/MS, Human plasma
Latitudinal trends in human primary activities: characterizing the winter day as a synchronizer.

Science.gov (United States)

Martín-Olalla, José María

2018-03-28

This work analyzes time use surveys from 19 countries (17 European and 2 American) in the middle latitude (38-61 degree) accounting for 45% of world population in this range. Time marks for primary activities are contrasted against light/dark conditions. The analysis reveals winter sunrise synchronizes labor start time below 54 degree, occurring within winter civil twilight. Winter sunset is a source of synchronization for labor end times. Winter terminator punctuate meal times in Europe: dinner occurs 3 h after winter sunset time within 1 h; 40% narrower than variability of dinner local times. The sleep-wake cycle of laborers is shown to be related to winter sunrise whereas standard population's appears to be irrespective of latitude. The significance of the winter terminator depends on two competing factors average labor time (~7 h30 m) and the shortest photoperiod. Winter terminator gains significance when both roughly matches. That is within a latitude range from 38 degree to 54 degree. The significance of winter terminator as a source of synchronization is also related to contemporary year round time schedules: the shortest photoperiod represents the worst case scenario the society faces.

RTN Winter School on Strings, Supergravity and Gauge Theories (4/5)

CERN Multimedia

CERN. Geneva

2006-01-01

9.30-10.30 A. Dabholkar Black Holes Entropy and Microstate Counting (4/4) 10.30-11.30 M. Grana Flux Compactifications and Generalized Geometry (3/4) 12.15-13.15 B. Pioline Black Hole Degeneracies, Topological Strings and Quantum Attractor Flow (3/4) 14.00-15.00 S. Minwalla Large N Thermal Phase Transitions (3/4) 15.00-16.00 B. Craps Big Bang Models in String Theory (4/4) 16.30 Workgroups Organiser(s): CERN and Neuchâtel UniversityMore information: http://www.unine.ch/phys/string/rtn-school/index.php
RTN Winter School on Strings, Supergravity and Gauge Theories (1/5)

CERN Multimedia

CERN. Geneva

2006-01-01

9.30-10.30 A. Dabholkar Black Holes Entropy and Microstate Counting (1/4) 10.30-11.30 M. Grana Flux Compactifications and Generalized Geometry (1/4) 12.15-13.15 B. Craps Big Bang Models in String Theory (1/4) 14.30-15.30 A. Dabholkar Black Holes Entropy and Microstate Counting (2/4) 15.30-16.30 S. Minwalla Large N Thermal Phase Transitions (1/4) 17.00 Discussion Organiser(s): CERN and Neuchâtel UniversityMore information: http://www.unine.ch/phys/string/rtn-school/index.php
Winter active bumblebees (Bombus terrestris achieve high foraging rates in urban Britain.

Directory of Open Access Journals (Sweden)

Ralph J Stelzer

2010-03-01

Full Text Available Foraging bumblebees are normally associated with spring and summer in northern Europe. However, there have been sightings of the bumblebee Bombus terrestris during the warmer winters in recent years in southern England. But what floral resources are they relying upon during winter and how much winter forage can they collect?To test if urban areas in the UK provide a rich foraging niche for bees we set up colonies of B. terrestris in the field during two late winter periods (2005/6 & 2006/7 in London, UK, and measured their foraging performance. Fully automatic radio-frequency identification (RFID technology was used in 2006/7 to enable us to record the complete foraging activity of individually tagged bees. The number of bumblebees present during winter (October 2007 to March 2008 and the main plants they visited were also recorded during transect walks. Queens and workers were observed throughout the winter, suggesting a second generation of bee colonies active during the winter months. Mass flowering shrubs such as Mahonia spp. were identified as important food resources. The foraging experiments showed that bees active during the winter can attain nectar and pollen foraging rates that match, and even surpass, those recorded during summer.B. terrestris in the UK are now able to utilise a rich winter foraging resource in urban parks and gardens that might at present still be under-exploited, opening up the possibility of further changes in pollinator phenology.
Winter active bumblebees (Bombus terrestris) achieve high foraging rates in urban Britain.

Science.gov (United States)

Stelzer, Ralph J; Chittka, Lars; Carlton, Marc; Ings, Thomas C

2010-03-05

Foraging bumblebees are normally associated with spring and summer in northern Europe. However, there have been sightings of the bumblebee Bombus terrestris during the warmer winters in recent years in southern England. But what floral resources are they relying upon during winter and how much winter forage can they collect? To test if urban areas in the UK provide a rich foraging niche for bees we set up colonies of B. terrestris in the field during two late winter periods (2005/6 & 2006/7) in London, UK, and measured their foraging performance. Fully automatic radio-frequency identification (RFID) technology was used in 2006/7 to enable us to record the complete foraging activity of individually tagged bees. The number of bumblebees present during winter (October 2007 to March 2008) and the main plants they visited were also recorded during transect walks. Queens and workers were observed throughout the winter, suggesting a second generation of bee colonies active during the winter months. Mass flowering shrubs such as Mahonia spp. were identified as important food resources. The foraging experiments showed that bees active during the winter can attain nectar and pollen foraging rates that match, and even surpass, those recorded during summer. B. terrestris in the UK are now able to utilise a rich winter foraging resource in urban parks and gardens that might at present still be under-exploited, opening up the possibility of further changes in pollinator phenology.
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.
Regional fluxes of momentum and sensible heat over a sub-arctic landscape during late winter

DEFF Research Database (Denmark)

Batchvarova, E.; Gryning, Sven-Erik; Hasager, C.B.

2001-01-01

flux is determined in two ways, both based on blending height theory. One is a parameterised method, the other represents a numerical solution of an aggregation model. The regional sensible heat flux is determined from the theory of mixed-layer growth. At near neutral conditions the regional momentum......Based on measurements at Sodankyla Meteorological Observatory the regional (aggregated) momentum and sensible heat fluxes are estimated for two days over a site in Finnish Lapland during late winter. The forest covers 49% of the area. The study shows that the forest dominates and controls...... the regional fluxes of momentum and sensible heat in different ways. The regional momentum flux is found to be 10-20% smaller than the measured momentum flux over the forest, and the regional sensible heat flux is estimated to be 30-50% of the values measured over a coniferous forest. The regional momentum...
The decline in winter excess mortality in The Netherlands

NARCIS (Netherlands)

Kunst, A. E.; Looman, C. W.; Mackenbach, J. P.

1991-01-01

In most countries, numbers of deaths rise considerably during the winter season. This winter excess in mortality has, however, been declining during recent decades. The causes of this decline are hardly known. This paper attempts to derive a number of hypotheses on the basis of a detailed
Genetic architecture of winter hardiness and frost tolerance in triticale.

Directory of Open Access Journals (Sweden)

Wenxin Liu

Full Text Available Abiotic stress experienced by autumn-sown crops during winter is of great economic importance as it can have a severe negative impact on yield. In this study, we investigated the genetic architecture of winter hardiness and frost tolerance in triticale. To this end, we used a large mapping population of 647 DH lines phenotyped for both traits in combination with genome-wide marker data. Employing multiple-line cross QTL mapping, we identified nine main effect QTL for winter hardiness and frost tolerance of which six were overlapping between both traits. Three major QTL were identified on chromosomes 5A, 1B and 5R. In addition, an epistasis scan revealed the contribution of epistasis to the genetic architecture of winter hardiness and frost tolerance in triticale. Taken together, our results show that winter hardiness and frost tolerance are complex traits that can be improved by phenotypic selection, but also that genomic approaches hold potential for a knowledge-based improvement of these important traits in elite triticale germplasm.
A comparison of pine and spruce in recovery from winter stress; changes in recovery kinetics, and the abundance and phosphorylation status of photosynthetic proteins during winter.

Science.gov (United States)

Merry, Ryan; Jerrard, Jacob; Frebault, Julia; Verhoeven, Amy

2017-09-01

During winter evergreens maintain a sustained form of thermal energy dissipation that results in reduced photochemical efficiency measured using the chlorophyll fluorescence parameter Fv/Fm. Eastern white pine (Pinus strobus L.) and white spruce [Picea glauca (Moench) Voss] have been shown to differ in their rate of recovery of Fv/Fm from winter stress. The goal of this study was to monitor changes in photosynthetic protein abundance and phosphorylation status during winter recovery that accompany these functional changes. An additional goal was to determine whether light-dependent changes in light harvesting complex II (LHCII) phosphorylation occur during winter conditions. We used a combination of field measurements and recovery experiments to monitor chlorophyll fluorescence and photosynthetic protein content and phosphorylation status. We found that pine recovered three times more slowly than spruce, and that the kinetics of recovery in spruce included a rapid and slow component, while in pine there was only a rapid component to recovery. Both species retained relatively high amounts of the light harvesting protein Lhcb5 (CP26) and the PsbS protein during winter, suggesting a role for these proteins in sustained thermal dissipation. Both species maintained high phosphorylation of LHCII and the D1 protein in darkness during winter. Pine and spruce differed in the kinetics of the dephosphorylation of LHCII and D1 upon warming, suggesting the rate of dephosphorylation of LHCII and D1 may be important in the rapid component of recovery from winter stress. Finally, we demonstrated that light-dependent changes in LHII phosphorylation do not continue to occur on subzero winter days and that needles are maintained in a phosphorylation pattern consistent with the high light conditions to which those needles are exposed. Our results suggest a role for retained phosphorylation of both LHCII and D1 in maintenance of the photosynthetic machinery in a winter conformation
The Application of Marketing Theory to Community College Faculty Recruitment: An Empirical Test.

Science.gov (United States)

Winter, Paul A.

1996-01-01

Reviews literature on faculty recruitment at community colleges. Describes a study using job-marketing theory and Winter's educational recruitment model to assess reactions to recruitment advertisements for a business faculty position. Reports that participants responded favorably to emphases on academic transfer program content. Discusses…
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.
75 FR 4842 - Winter Use Plan, Environmental Impact Statement, Yellowstone National Park

Science.gov (United States)

2010-01-29

... DEPARTMENT OF THE INTERIOR National Park Service Winter Use Plan, Environmental Impact Statement... to prepare an Environmental Impact Statement for a Winter Use Plan, Yellowstone National Park... Park Service (NPS) is preparing an Environmental Impact Statement (EIS) for a Winter Use Plan for...
The elusive gene for keratolytic winter erythema | Hull | South ...

African Journals Online (AJOL)

Keratolytic winter erythema (KWE), also known as Oudtshoorn skin disease, is characterised by a cyclical disruption of normal epidermal keratinisation affecting primarily the palmoplantar skin with peeling of the palms and soles, which is worse in the winter. It is a rare monogenic, autosomal dominant condition of unknown ...
Assessing winter cover crop nutrient uptake efficiency using a water quality simulation model

Science.gov (United States)

Yeo, In-Young; Lee, Sangchui; Sadeghi, Ali M.; Beeson, Peter C.; Hively, W. Dean; McCarty, Greg W.; Lang, Megan W.

2013-01-01

Winter cover crops are an effective conservation management practice with potential to improve water quality. Throughout the Chesapeake Bay Watershed (CBW), which is located in the Mid-Atlantic US, winter cover crop use has been emphasized and federal and state cost-share programs are available to farmers to subsidize the cost of winter cover crop establishment. The objective of this study was to assess the long-term effect of planting winter cover crops at the watershed scale and to identify critical source areas of high nitrate export. A physically-based watershed simulation model, Soil and Water Assessment Tool (SWAT), was calibrated and validated using water quality monitoring data and satellite-based estimates of winter cover crop species performance to simulate hydrological processes and nutrient cycling over the period of 1991–2000. Multiple scenarios were developed to obtain baseline information on nitrate loading without winter cover crops planted and to investigate how nitrate loading could change with different winter cover crop planting scenarios, including different species, planting times, and implementation areas. The results indicate that winter cover crops had a negligible impact on water budget, but significantly reduced nitrate leaching to groundwater and delivery to the waterways. Without winter cover crops, annual nitrate loading was approximately 14 kg ha−1, but it decreased to 4.6–10.1 kg ha−1 with winter cover crops resulting in a reduction rate of 27–67% at the watershed scale. Rye was most effective, with a potential to reduce nitrate leaching by up to 93% with early planting at the field scale. Early planting of winter cover crops (~30 days of additional growing days) was crucial, as it lowered nitrate export by an additional ~2 kg ha−1 when compared to late planting scenarios. The effectiveness of cover cropping increased with increasing extent of winter cover crop implementation. Agricultural fields with well-drained soils
Contrasting Seasonal Survivorship of Two Migratory Songbirds Wintering in Threatened Mangrove Forests

Directory of Open Access Journals (Sweden)

Anna M. Calvert

2010-06-01

Full Text Available Long-distance migrants wintering in tropical regions face a number of critical conservation threats throughout their lives, but seasonal estimates of key demographic parameters such as winter survival are rare. Using mist-netting-based mark-recapture data collected in coastal Costa Rica over a six-year period, we examined variation in within- and between-winter survivorship of the Prothonotary Warbler (Protonotaria citrea; 753 young and 376 adults banded, a declining neotropical habitat specialist that depends on threatened mangrove forests during the nonbreeding season. We derived parallel seasonal survivorship estimates for the Northern Waterthrush (Seiurus noveboracensis; 564 young and 93 adults banded, a cohabitant mangrove specialist that has not shown the same population decline in North America, to assess whether contrasting survivorship might contribute to the observed differences in the species’ population trajectories. Although average annual survival probability was relatively similar between the two species for both young and adult birds, monthly estimates indicated that relative to Northern Waterthrush, Prothonotary Warblers exhibited: greater interannual variation in survivorship, especially within winters; greater variation in survivorship among the three study sites; lower average between-winter survivorship, particularly among females, and; a sharp decline in between-winter survivorship from 2003 to 2009 for both age groups and both sexes. Rather than identifying one seasonal vital rate as a causal factor of Prothonotary Warbler population declines, our species comparison suggests that the combination of variable within-winter survival with decreasing between-winter survival demands a multi-seasonal approach to the conservation of this and other tropical-wintering migrants.
Spirit's Winter Work Site

Science.gov (United States)

2006-01-01

[figure removed for brevity, see original site] Annotated Version This portion of an image acquired by the Mars Reconnaissance Orbiter's High Resolution Imaging Science Experiment camera shows the Spirit rover's winter campaign site. Spirit was parked on a slope tilted 11 degrees to the north to maximize sunlight during the southern winter season. 'Tyrone' is an area where the rover's wheels disturbed light-toned soils. Remote sensing and in-situ analyses found the light-toned soil at Tyrone to be sulfate rich and hydrated. The original picture is catalogued as PSP_001513_1655_red and was taken on Sept. 29, 2006. NASA's Jet Propulsion Laboratory, a division of the California Institute of Technology in Pasadena, manages the Mars Reconnaissance Orbiter for NASA's Science Mission Directorate, Washington. Lockheed Martin Space Systems, Denver, is the prime contractor for the project and built the spacecraft. The High Resolution Imaging Science Experiment is operated by the University of Arizona, Tucson, and the instrument was built by Ball Aerospace and Technology Corp., Boulder, Colo.
Comparison of snowpack and winter wet-deposition chemistry in the Rocky Mountains, USA: implications for winter dry deposition

Science.gov (United States)

Clow, David W.; Ingersoll, George P.; Mast, M. Alisa; Turk, John T.; Campbell, Donald H.

Depth-integrated snowpack chemistry was measured just prior to maximum snowpack depth during the winters of 1992-1999 at 12 sites co-located with National Atmospheric Deposition Program/National Trend Network (NADP/NTN) sites in the central and southern Rocky Mountains, USA. Winter volume-weighted mean wet-deposition concentrations were calculated for the NADP/NTN sites, and the data were compared to snowpack concentrations using the paired t-test and the Wilcoxon signed-rank test. No statistically significant differences were indicated in concentrations of SO 42- or NO 3- ( p>0.1). Small, but statistically significant differences ( p⩽0.03) were indicated for all other solutes analyzed. Differences were largest for Ca 2+ concentrations, which on average were 2.3 μeq l -1 (43%) higher in the snowpack than in winter NADP/NTN samples. Eolian carbonate dust appeared to influence snowpack chemistry through both wet and dry deposition, and the effect increased from north to south. Dry deposition of eolian carbonates was estimated to have neutralized an average of 6.9 μeq l -1 and a maximum of 12 μeq l -1 of snowpack acidity at the southernmost sites. The good agreement between snowpack and winter NADP/NTN SO 42- and NO 3- concentrations indicates that for those solutes the two data sets can be combined to increase data density in high-elevation areas, where few NADP/NTN sites exist. This combination of data sets will allow for better estimates of atmospheric deposition of SO 42- and NO 3- across the Rocky Mountain region.
Comparative proteomics reveals the physiological differences between winter tender shoots and spring tender shoots of a novel tea (Camellia sinensis L.) cultivar evergrowing in winter.

Science.gov (United States)

Liu, Shengjie; Gao, Jiadong; Chen, Zhongjian; Qiao, Xiaoyan; Huang, Hualin; Cui, Baiyuan; Zhu, Qingfeng; Dai, Zhangyan; Wu, Hualing; Pan, Yayan; Yang, Chengwei; Liu, Jun

2017-11-20

A recently discovered tea [Camellia sinensis (L.) O. Kuntze] cultivar can generate tender shoots in winter. We performed comparative proteomics to analyze the differentially accumulated proteins between winter and spring tender shoots of this clonal cultivar to reveal the physiological basis of its evergrowing character during winter. We extracted proteins from the winter and spring tender shoots (newly formed two leaves and a bud) of the evergrowing tea cultivar "Dongcha11" respectively. Thirty-three differentially accumulated high-confidence proteins were identified by matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF / TOF MS). Among these, 24 proteins had increased abundance while nine showed were decreased abundance in winter tender shoots as compared with the spring tender shoots. We categorized the differentially accumulated proteins into eight critical biological processes based on protein function annotation including photosynthesis, cell structure, protein synthesis & destination, transporters, metabolism of sugars and polysaccharides, secondary metabolism, disease/defense and proteins with unknown functions. Proteins with increased abundance in winter tender shoots were mainly related to the processes of photosynthesis, cytoskeleton and protein synthesis, whereas those with decreased abundance were correlated to metabolism and the secondary metabolism of polyphenolic flavonoids. Biochemical analysis showed that the total contents of soluble sugar and amino acid were higher in winter tender shoots while tea polyphenols were lower as compared with spring tender shoots. Our study suggested that the simultaneous increase in the abundance of photosynthesis-related proteins rubisco, plastocyanin, and ATP synthase delta chain, metabolism-related proteins eIF4 and protease subunits, and the cytoskeleton-structure associated proteins phosphatidylinositol transfer protein and profilin may be because of the adaptation of the
Learning at old age: a study on winter bees

Directory of Open Access Journals (Sweden)

Andreas Behrends

2010-04-01

Full Text Available Ageing is often accompanied by a decline in learning and memory abilities across the animal kingdom. Understanding age-related changes in cognitive abilities is therefore a major goal of current research. The honey bee is emerging as a novel model organism for age-related changes in brain function, because learning and memory can easily be studied in bees under controlled laboratory conditions. In addition, genetically similar workers naturally display life expectancies from six weeks (summer bees to six months (winter bees. We studied whether in honey bees, extreme longevity leads to a decline in cognitive functions. Six-month-old winter bees were conditioned either to odours or to tactile stimuli. Afterwards, long-term memory and discrimination abilities were analysed. Winter bees were kept under different conditions (flight /no flight opportunity to test for effects of foraging activity on learning performance. Despite their extreme age, winter bees did not display an age-related decline in learning or discrimination abilities, but had a slightly impaired olfactory long-term memory. The opportunity to forage indoors led to a slight decrease in learning performance. This suggests that in honey bees, unlike in most other animals, age per se does not impair associative learning. Future research will show which mechanisms protect winter bees from age-related deficits in learning.
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.

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