Parasitism, productivity, and population growth: response of Least Bell's Vireos (Vireo bellii pusillus) and Southwestern Willow Flycatchers (Empidonax traillii extimus) to cowbird (Molothrus spp.) control

USGS Publications Warehouse

Kus, Barbara E.; Whitfield, Mary J.

2005-01-01

Cowbird (Molothrus spp.) control is a major focus of recovery-oriented management of two endangered riparian bird species,the Least Bell's Vireo (Vireo bellii pusillus) and Southwestern Willow Flycatcher (Empidonax traillii extimus). During the past 20 years, annual trapping of cowbirds at Least Bell's Vireo and Southwestern Willow Flycatcher breeding sites has eliminated or reduced parasitism in comparison with pretrapping rates and, thereby, significantly increased seasonal productivity of nesting pairs. Enhanced productivity, in turn, has resulted in an 8-fold increase in numbers of Least Bell's Vireos; Southwestern Willow Flycatcher abundance, however, has changed little, and at some sites has declined despite cowbird control. Although generally successful by these short-term measures of host population response, cowbird control poses potential negative consequences for long-term recovery of endangered species. As currently employed, cowbird control lacks predetermined biological criteria to trigger an end to the control, making these species' dependence on human intervention open-ended. Prolonged reliance on cowbird control to manage endangered species can shift attention from identifying and managing other factors that limit populations--in particular, habitat availability. On the basis of our analysis of these long-term programs, we suggest that cowbird control be reserved for short-term crisis management and be replaced, when appropriate, by practices emphasizing restoration and maintenance of natural processes on which species depend. /// El manejo orientado hacia la recuperación de dos especies de aves ribereñas Vireo belli pusillus y Empidonax trailli extimus se ha focalizado principalmente en el control de los Molothrus spp parásitos. Durante los pasados 20 años, la captura anual de los Molothrus en las áreas de nidificación de Vireo belli pusillus y Empidonax trailli extimus ha eliminado o reducido el parasitismo en comparación con las tasas

Nest site characteristics of Hammond's and Pacific-slope flycatchers in northwest California

Treesearch

H.F. Sakai; B.R. Noon

1991-01-01

Thirty nests of Hammond’s (Empidonax hammondii) and 88 nests of Pacificslope (E. difficilis) Flycatchers were located in different-aged Douglas-fir (Pseudotsuga menziesii)/ tanoak (Lithocarpus densiflorus) dominated forests at 12 study sites in northwestern California during the...

Recovering southwestern willow flycatcher populations will benefit riparian health

Treesearch

Deborah M. Finch

1999-01-01

When the U.S. Fish and Wildlife Service (USFWS) listed the southwestern willow flycatcher (Empidonax traillii exigua) as federally endangered in 1995, new incentives, controversies and energy were generated to conserve and restore southwestern riparian ecosystems. Close attention has been focused on river and stream conservation in the Southwest since at least 1977,...

Sex determination of the Acadian Flycatcher using discriminant analysis

USGS Publications Warehouse

Wilson, R.R.

1999-01-01

I used five morphometric variables from 114 individuals captured in Arkansas to develop a discriminant model to predict the sex of Acadian Flycatchers (Empidonax virescens). Stepwise discriminant function analyses selected wing chord and tail length as the most parsimonious subset of variables for discriminating sex. This two-variable model correctly classified 80% of females and 97% of males used to develop the model. Validation of the model using 19 individuals from Louisiana and Virginia resulted in 100% correct classification of males and females. This model provides criteria for sexing monomorphic Acadian Flycatchers during the breeding season and possibly during the winter.

Willow Flycatcher nonbreeding territory defense behavior in Costa Rica

USGS Publications Warehouse

Sogge, M.K.; Koronkiewicz, T.J.; van Riper, Charles; Durst, S.L.

2007-01-01

We studied the intraspecific territorial defense behavior of wintering Willow Flycatchers (Empidonax traillii) in Costa Rica using a randomized playback experiment that exposed male and female birds to recordings of Willow Flycatcher songs and calls, Lesser Ground Cuckoo (Morococcyx erythropygius) vocalizations, and random noise. Flycatchers of both sexes responded most strongly to simulated conspecific territory intrusion, and the agonistic behaviors that we observed were similar to those seen during natural intraspecific encounters in winter. Both males and females engaged in song and aggressive behaviors in defense of territories, and there was no significant difference between the sexes in scored agonistic responses. The similarity between the sexes in intraspecific territorial defense behaviors and aggressiveness may account for both sexes of flycatchers using the same habitats at our study sites in Costa Rica, and wintering females defending territories against males. The Willow Flycatcher, a sexually monomorphic species, differs in this way from a number of sexually dimorphic passerines, in which behaviorally dominant males occur in more optimal winter habitats. ?? The Cooper Ornithological Society 2007.

Breeding biology and behavior of Hammond's and western flycatchers in northwestern California

Treesearch

H.F. Sakai

1988-01-01

The Hammond's (Empidonax hammondii) and Western (E. difficilis) flycatchers are sympatric within portions of their breeding ranges in north- western California. Westerns are common in a variety of habitats (Bent 1942:247, Johnson 1980:11-23); Hammond's are more abundant at higher elevations (Bent 1942:226, Johnson...

Migration of the Willow Flycatcher along the Middle Rio Grande

Treesearch

Wang Yong; Deborah M. Finch

1997-01-01

We studied timing, abundance, subspecies composition, fat stores, stopover length, and habitat use of Willow Flycatchers (Empidonax traillii) during spring and fall stopover along the Middle Rio Grande, New Mexico. Spring migration started in mid-May and lasted about a month. Fall migration started in early-August and also lasted about a month. The most abundant...

Geographic variation in the song of Willow Flycatchers: Differentiation between Empidonax traillii adastus and E. t. extimus

USGS Publications Warehouse

Sedgwick, J.A.

2001-01-01

The vocal signatures of the primary song form (“fitz-bew”) of the endangered Southwestern Willow Flycatcher (Empidonax traillii extimus) and its northern counterpart, E. t. adastus, are distinctive. Songs of the extimus subspecies are longer (total song, note, internote) and frequencies at maximum amplitude are lower than those of adastus. I used vocal evidence to clarify the distributional limits of the Southwestern Willow Flycatcher and that of the geographically adjacent subspecies, E. t. adastus. Unweighted pair-group method using averaging (UPGMA) cluster analysis and canonical discriminant analysis revealed that (1) low elevation, southerly desert populations (Arizona, New Mexico, and southern Utah) have a unique vocal identity corresponding to populations in the range of E. t. extimus; (2) northerly song groups (Oregon, Colorado, and northern Utah) share a different song type corresponding to populations in the range of E. t. adastus; and (3) a departure from vocal and morphological congruence occurs for a population of high-elevation Arizona birds that, although in the currently accepted range of E. t. extimus, sings songs acoustically similar to more northern populations (E. t. adastus). Multiple regression of song distance on latitude and elevation, and a comparison of a matrix of song distances with a matrix of latitude and elevation dissimilarities, demonstrated that song populations sort out by both latitude and elevation: birds with the vocal identity of extimus occur as far north as 37°N if at low elevation, and those acoustically similar to adastus occur as far south as 33.7°N if at high elevation. The vocal background of northern New Mexico birds appears to be intermediate between that of extimus and adastus, suggesting that northern New Mexico is a zone of intermixing and intergradation between the subspecies. Pure forms of E. t. extimus apparently do not occur in Colorado because even the southernmost populations are acoustically similar to

Winter distribution of willow flycatcher subspecies

USGS Publications Warehouse

Paxton, E.H.; Unitt, P.; Sogge, M.K.; Whitfield, M.; Keim, P.

2011-01-01

Documenting how different regions across a species' breeding and nonbreeding range are linked via migratory movements is the first step in understanding how events in one region can influence events in others and is critical to identifying conservation threats throughout a migratory animal's annual cycle. We combined two studies that evaluated migratory connectivity in the Willow Flycatcher (Empidonax traillii), one using mitochondrial DNA sequences from 172 flycatchers sampled throughout their winter range, and another which examined morphological characteristics of 68 museum specimens collected in the winter range. Our results indicate that the four subspecies occupy distinct but overlapping regions of the winter range. Connectivity between specific breeding and winter grounds appears to be moderate to strong, with distributions that suggest migration patterns of both the chain and leap-frog types connecting the breeding and nonbreeding grounds. The Pacific lowlands of Costa Rica appear to be a key winter location for the endangered Southwestern Willow Flycatcher (E. t. extimus), although other countries in Central America may also be important for the subspecies. ?? The Cooper Ornithological Society 2011.

Reproductive ecology of Dusky Flycatchers in western Montana

USGS Publications Warehouse

Sedgwick, James A.

1993-01-01

Breeding ecology of Dusky Flycatchers (Empidonax oberholseri) was studied in western Montana from May-August 1974. Dusky Flycatchers were monogamous and single-brooded although some pairs made renesting attempts after first nests failed. Length of the reproductive cycle for first nesting attempts, from arrival on the breeding grounds to fledging, was about 70 days. All nests were placed in shrubs, primarily ninebark (Physocarpus malvaceus) and Rocky Mountain maple (Acer glabrum), and were an average of 150 cm above the ground. Females incubated a clutch with an average of 4.0 eggs for 15-16 days, and the average nestling period was 17.5 days. Both sexes fed nestlings and fledglings, but only females brooded nestlings. Egg survival was 63.8%, hatching success was 95.4%, and nestling survival was 61.9% for an overall probability of 0.376 percent that an egg produced a fledgling. Predation was the major cause of nest failure. Dusky Flycatchers reared an average of 1.9 fledglings/pair.

The status of the Willow and Pacific-slope flycatchers in northwestern California and southern Oregon

Treesearch

C. John Ralph; K. Hollinger

2003-01-01

The Willow (Empidonax traillii) and Pacific-slope (E. dificilis) flycatchers are generally similar in their morphology and foraging, but differ in their habitat and population dynamics. Through a concentration of constant-effort mist-netting stations, we documented the movements and composition of populations over a relatively...

A satellite model of Southwestern Willow Flycatcher (Empidonax traillii extimus) breeding habitat and a simulation of potential effects of tamarisk leaf beetles (Diorhabda spp.), southwestern United States

USGS Publications Warehouse

Hatten, James R.

2016-08-08

The study described in this report represents the first time that a satellite model has been used to identify potential Southwestern Willow Flycatcher (Empidonax traillii extimus) (hereinafter referred to as “flycatcher”) breeding habitat rangewide for 2013–15. Fifty-seven Landsat scenes were required to map the entire range of the flycatcher, encompassing parts of six States and more than 1 billion 30-meter pixels. Predicted flycatcher habitat was summarized in a hierarchical fashion from largest to smallest: regionwide, State, U.S. Fish and Wildlife Service (FWS) management unit, 7.5-minute quadrangle, and critical-habitat reach. The term “predicted habitat” is used throughout this report to distinguish areas the satellite model predicts as suitable flycatcher habitat from what may actually exist on the ground. A rangewide accuracy assessment was done with 758 territories collected in 2014, and change detection was done with yearly habitat maps to identify how and where habitat changed over time. Additionally, effects of tamarisk leaf beetles (Diorhabda spp.) on flycatcher habitat were summarized for the lower Virgin River from 2010 to 2015, and simulations of how tamarisk leaf beetles may affect flycatcher habitat in the lower Colorado and upper Gila Rivers were done for 2015. Model results indicated that the largest areas of predicted flycatcher habitat at elevations below 1,524 meters were in New Mexico and Arizona, areas followed in descending order by California, Texas, Nevada, Utah, and Colorado. By FWS management unit, the largest area of flycatcher habitat during all 3 years were the Middle Rio Grande (New Mexico), followed by the Upper Gila (Arizona and New Mexico) and Middle Gila/San Pedro (Arizona) management units. The area of predicted flycatcher habitat varied considerably in 7.5-minute quadrangles, ranging from 0 to1,398 hectares (ha). Averaged across 3 years, the top three producing quadrangles were Paraje Well (New Mexico), San Marcial

A habitat overlap analysis derived from Maxent for Tamarisk and the South-western Willow Flycatcher

Treesearch

Patricia York; Paul Evangelista; Sunil Kumar; James Graham; Curtis Flather; Thomas Stohlgren

2011-01-01

Biologic control of the introduced and invasive, woody plant tamarisk (Tamarix spp, saltcedar) in south-western states is controversial because it affects habitat of the federally endangered South-western Willow Flycatcher (Empidonax traillii extimus). These songbirds sometimes nest in tamarisk where floodplain-level invasion replaces native habitats. Biologic control...

The ecology of the Southwestern Willow Flycatcher in central Arizona - A 10-year synthesis report

USGS Publications Warehouse

Paxton, Eben H.; Sogge, Mark K.; Durst, Scott L.; Theimer, Tad C.; Hatten, James R.

2007-01-01

BACKGROUND From 1996 to 2005, the U.S. Geological Survey (USGS) conducted a demographic study of the Southwestern Willow Flycatcher (Empidonax traillii extimus) in Arizona in collaboration with the Arizona Game and Fish Department (AGFD). The study was begun the year following the listing of the Southwestern Willow Flycatcher as an endangered species. At the time of the listing, very little was known about the biology and threats to the flycatcher, and one of the main objectives of the study was to gather detailed long-term information on the biology of the flycatcher. This report is organized into eight chapters. Following the introductory chapter, we deal with specific aspects of flycatcher ecology and habitat use in each of six separate chapters. We end with a concluding chapter that synthesizes information into broad topical themes that address key management issues. Each of the core chapters (chapters 2 through 7) conclude with a list of management considerations derived from the findings of the respective chapter.

Injury due to leg bands in willow flycatchers

USGS Publications Warehouse

Sedgwick, J.A.; Klus, R.J.

1997-01-01

We report an apparently unusually high incidence of leg injury in Willow Flycatchers (Empidonax traillii) as a result of banding and color banding. Color bands and U.S. Fish and Wildlife Service (USFWS) bands applied to Willow Flycatchers from 1988-1995 resulted in an overall leg injury rate of 9.6% to birds returning to our study areas in subsequent years. Most injuries occurred on legs with only color band(s) (58.3%) or on legs with both a USFWS band and a color band (35%); only 6.7% of injuries (4/60) were due to USFWS bands alone, yielding an overall USFWS band injury rate of only 0.6%. Injuries ranged from severe (swollen, bleeding legs; a missing foot) to relatively minor (irritations on the tarsus). Amputation of the foot occurred in 33.9% of the cases. Return rates of adult injured birds in the year(s) following injury were significantly lower than for the population at large.

Nestling sex ratio in the Southwestern Willow Flycatcher

USGS Publications Warehouse

Paxton, E.H.; Sogge, M.K.; McCarthey, T.D.; Keim, P.

2002-01-01

Using molecular-genetic techniques, we determined the gender of 202 Southwestern Willow Flycatcher (Empidonax traillii extimus) nestlings from 95 nests sampled over a five-year period. Overall nestling sex ratio did not vary significantly from 50:50 among years, by clutch order, or by mating strategy (monogamous vs. polygamous pairings). However, we did observe significant differences among the four sites sampled, with sex ratios biased either toward males or females at the different sites. Given the small population sizes and geographic isolation of many of the endangered subspecies' breeding populations, sex-ratio differences may have localized negative impacts. ?? The Cooper Ornithological Society 2002.

Nestling sex ratios in the southwestern willow flycatcher

USGS Publications Warehouse

Paxton, E.H.; Sogge, M.K.; McCarthey, Tracy; Keim, Paul

2002-01-01

Using molecular-genetic techniques, we determined the gender of 202 Southwestern Willow Flycatcher (Empidonax traillii extimus) nestlings from 95 nests sampled over a five-year period. Overall nestling sex ratio did not vary significantly from 50:50 among years, by clutch order, or by mating strategy (monogamous vs. polygamous pairings). However, we did observe significant differences among the four sites sampled, with sex ratios biased either toward males or females at the different sites. Given the small population sizes and geographic isolation of many of the endangered subspecies' breeding populations, sex-ratio differences may have localized negative impacts.

Available data support protection of the Southwestern Willow Flycatcher under the Endangered Species Act

USGS Publications Warehouse

Theimer, Tad C.; Smith, Aaron D.; Mahoney, Sean M.; Ironside, Kirsten E.

2016-01-01

Zink (2015) argued there was no evidence for genetic, morphological, or ecological differentiation between the federally endangered Southwestern Willow Flycatcher (Empidonax traillii extimus) and other Willow Flycatcher subspecies. Using the same data, we show there is a step-cline in both the frequency of a mtDNA haplotype and in plumage variation roughly concordant with the currently recognized boundary between E. t. extimus and E. t adastus, the subspecies with which it shares the longest common boundary. The geographical pattern of plumage variation is also concordant with previous song analyses differentiating those 2 subspecies and identified birds in one low-latitude, high-elevation site in Arizona as the northern subspecies. We also demonstrate that the ecological niche modeling approach used by Zink yields the same result whether applied to the 2 flycatcher subspecies or to 2 unrelated species, E. t. extimus and Yellow Warbler (Setophaga petechia). As a result, any interpretation of those results as evidence for lack of ecological niche differentiation among Willow Flycatcher subspecies would also indicate no differentiation among recognized species and would therefore be an inappropriate standard for delineating subspecies. We agree that many analytical techniques now available to examine genetic, morphological, and ecological differentiation would improve our understanding of the distinctness (or lack thereof) of Willow Flycatcher subspecies, but we argue that currently available evidence supports protection of the Southwestern Willow Flycatcher under the Endangered Species Act.

A Natural History Summary and Survey Protocol for the Southwestern Willow Flycatcher

USGS Publications Warehouse

Sogge, Mark K.; ,; Ahlers, Darrell; ,; Sferra, Susan J.; ,

2010-01-01

The Southwestern Willow Flycatcher (Empidonax traillii extimus) has been the subject of substantial research, monitoring, and management activity since it was listed as an endangered species in 1995. When proposed for listing in 1993, relatively little was known about the flycatcher's natural history, and there were only 30 known breeding sites supporting an estimated 111 territories rangewide (Sogge and others, 2003a). Since that time, thousands of presence/absences surveys have been conducted throughout the historical range of the flycatcher, and many studies of its natural history and ecology have been completed. As a result, the ecology of the flycatcher is much better understood than it was just over a decade ago. In addition, we have learned that the current status of the flycatcher is better than originally thought: as of 2007, the population was estimated at approximately 1,300 territories distributed among approximately 280 breeding sites (Durst and others, 2008a). Concern about the Southwestern Willow Flycatcher on a rangewide scale was brought to focus by Unitt (1987), who described declines in flycatcher abundance and distribution throughout the Southwest. E. t. extimus populations declined during the 20th century, primarily because of habitat loss and modification from activities, such as dam construction and operation, groundwater pumping, water diversions, and flood control. In 1991, the U.S. Fish and Wildlife Service (USFWS) designated the Southwestern Willow Flycatcher as a candidate category 1 species (U.S. Fish and Wildlife Service, 1991). In July 1993, the USFWS proposed to list E. t. extimus as an endangered species and to designate critical habitat under the Act (U.S. Fish and Wildlife Service, 1993). A final rule listing E. t. extimus as endangered was published in February 1995 (U.S. Fish and Wildlife Service, 1995); critical habitat was designated in 1997 (U.S. Fish and Wildlife Service, 1997). The USFWS Service released a Recovery Plan for

Vocal frequency change reflects different responses to anthropogenic noise in two suboscine tyrant flycatchers

PubMed Central

Francis, Clinton D.; Ortega, Catherine P.; Cruz, Alexander

2011-01-01

Anthropogenic noise is prevalent across the globe and can exclude birds from otherwise suitable habitat and negatively influence fitness; however, the mechanisms responsible for species' responses to noise are not always clear. One effect of noise is a reduction in effective acoustic communication through acoustic masking, yet some urban songbirds may compensate for masking by noise through altering their songs. Whether this vocal flexibility accounts for species persistence in noisy areas is unknown. Here, we investigated the influence of noise on habitat use and vocal frequency in two suboscine flycatchers using a natural experiment that isolated effects of noise from confounding stimuli common to urban habitats. With increased noise exposure, grey flycatcher (Empidonax wrightii) occupancy declined, but vocal frequency did not change. By contrast, ash-throated flycatcher (Myiarchus cinerascens) occupancy was uninfluenced by noise, but individuals in areas with greater noise amplitudes vocalized at a higher frequency, although the increase (≈200 kHz) may only marginally improve communication and may represent a secondary effect from increased vocal amplitude. Even so, the different flycatcher behavioural responses suggest that signal change may help some species persist in noisy areas and prompt important questions regarding which species will cope with an increasingly noisy world. PMID:21123268

Survivorship across the annual cycle of a migratory passerine, the willow flycatcher

USGS Publications Warehouse

Paxton, Eben H.; Durst, Scott L.; Sogge, Mark K.; Koronkiewicz, Thomas J.; Paxton, Kristina L.

2017-01-01

Annual survivorship in migratory birds is a product of survival across the different periods of the annual cycle (i.e. breeding, wintering, and migration), and may vary substantially among these periods. Determining which periods have the highest mortality, and thus are potentially limiting a population, is important especially for species of conservation concern. To estimate survival probabilities of the willow flycatcher Empidonax traillii in each of the different periods, we combined demographic data from a 10-year breeding season study with that from a 5-year wintering grounds study. Estimates of annual apparent survival for breeding and wintering periods were nearly identical (65–66%), as were estimates of monthly apparent survival for both breeding and wintering stationary periods (98–99%). Because flycatchers spend at least half the year on the wintering grounds, overall apparent survivorship was lower (88%) on the wintering grounds than on the breeding grounds (97%). The migratory period had the highest mortality rate, accounting for 62% of the estimated annual mortality even though it comprises only one quarter or less of the annual cycle. The migratory period in the willow flycatcher and many other neotropical migrants is poorly understood, and further research is needed to identify sources of mortality during this crucial period.

77 FR 43107 - Endangered and Threatened Species Permit Applications

Federal Register 2010, 2011, 2012, 2013, 2014

2012-07-23

... presence/absence surveys for southwestern willow flycatcher (Empidonax traillii extimus) within Arizona...), southwestern willow flycatcher (Empidonax trailii extimus), and Yuma clapper rail (Rallus longirostris... conduct presence/absence surveys and collect plant material (leaves, flowers) of white bladderpod...

Describing Willow Flycatcher habitats: scale perspectives and gender differences

USGS Publications Warehouse

Sedgwick, James A.; Knopf, Fritz L.

1992-01-01

We compared habitat characteristics of nest sites (female-selected sites) and song perch sites (male-selected sites) with those of sites unused by Willow Flycatchers (Empidonax traillii) at three different scales of vegetation measurement: (1) microplot (central willow [Salix spp.] bush and four adjacent bushes); (2) mesoplot (0.07 ha); and, (3) macroplot (flycatcher territory size). Willow Flycatchers exhibited vegetation preferences at all three scales. Nest sites were distinguished by high willow density and low variability in willow patch size and bush height. Song perch sites were characterized by large central shrubs, low central shrub vigor, and high variability in shrub size. Unused sites were characterized by greater distances between willows and willow patches, less willow coverage, and a smaller riparian zone width than either nest or song perch sites. At all scales, nest sites were situated farther from unused sites in multivariate habitat space than were song perch sites, suggesting (1) a correspondence among scales in their ability to describe Willow Flycatcher habitat, and (2) females are more discriminating in habitat selection than males. Microhabitat differences between male-selected (song perch) and female-selected (nest) sites were evident at the two smaller scales; at the finest scale, the segregation in habitat space between male-selected and female-selected sites was greater than that between male-selected and unused sites. Differences between song perch and nest sites were not apparent at the scale of flycatcher territory size, possibly due to inclusion of (1) both nest and song perch sites, (2) defended, but unused habitat, and/or (3) habitat outside of the territory, in larger scale analyses. The differences between nest and song perch sites at the finer scales reflect their different functions (e.g., nest concealment and microclimatic requirements vs. advertising and territorial defense, respectively), and suggest that the exclusive use

Elucidating spatially explicit behavioral landscapes in the Willow Flycatcher

USGS Publications Warehouse

Bakian, Amanda V.; Sullivan, Kimberly A.; Paxton, Eben H.

2012-01-01

Animal resource selection is a complex, hierarchical decision-making process, yet resource selection studies often focus on the presence and absence of an animal rather than the animal's behavior at resource use locations. In this study, we investigate foraging and vocalization resource selection in a population of Willow Flycatchers, Empidonax traillii adastus, using Bayesian spatial generalized linear models. These models produce “behavioral landscapes” in which space use and resource selection is linked through behavior. Radio telemetry locations were collected from 35 adult Willow Flycatchers (n = 14 males, n = 13 females, and n = 8 unknown sex) over the 2003 and 2004 breeding seasons at Fish Creek, Utah. Results from the 2-stage modeling approach showed that habitat type, perch position, and distance from the arithmetic mean of the home range (in males) or nest site (in females) were important factors influencing foraging and vocalization resource selection. Parameter estimates from the individual-level models indicated high intraspecific variation in the use of the various habitat types and perch heights for foraging and vocalization. On the population level, Willow Flycatchers selected riparian habitat over other habitat types for vocalizing but used multiple habitat types for foraging including mountain shrub, young riparian, and upland forest. Mapping of observed and predicted foraging and vocalization resource selection indicated that the behavior often occurred in disparate areas of the home range. This suggests that multiple core areas may exist in the home ranges of individual flycatchers, and demonstrates that the behavioral landscape modeling approach can be applied to identify spatially and behaviorally distinct core areas. The behavioral landscape approach is applicable to a wide range of animal taxa and can be used to improve our understanding of the spatial context of behavior and resource selection.

Territoriality, site fidelity, and survivorship of willow flycatchers wintering in Costa Rica

USGS Publications Warehouse

Koronkiewicz, T.J.; Sogge, M.K.; van Riper, Charles; Paxton, E.H.

2006-01-01

We studied wintering Willow Flycatchers (Empidonax traillii) in two seasonal freshwater wetland habitats in northwestern Costa Rica during five boreal winters, to determine habitat occupancy, overwinter and between-year site and territory fidelity, and the degree to which the sexes maintain and defend winter territories. Both males and females used agonistic displays, song, and other vocalizations to maintain and defend mutually exclusive winter territories. Males were generally more abundant than females, but this varied by site and year. There was no significant difference in male and female territory size, nor any indication of sexual habitat segregation. Similarity in morphology and aggressiveness between the sexes may account for the lack of habitat segregation and the ability of females to maintain territories at wintering sites. Each year, 80%-92% of banded flycatchers that were present in midwinter remained at the site until late winter; of these, 86%-100% of individuals maintained the same territories throughout the entire period. We also observed nonterritorial floaters that subsequently established and held winter territories. Between-year site fidelity averaged 68%, and almost all returning birds established territories with boundaries similar to the previous year. Between-year apparent survivorship estimates ranged annually from 54%-72%, with no difference between sites but weak support for higher survivorship of males compared to females. Values for winter site and territory fidelity were generally higher than those reported for other species and for Willow Flycatchers on the breeding grounds; between-year survivorship estimates were similar to those reported for breeding flycatchers. ?? The Cooper Ornithological Society 2006.

Food habits of the southwestern willow flycatcher during the nesting season

USGS Publications Warehouse

Drost, Charles A.; Paxton, Eben H.; Sogge, Mark K.; Whitfield, Mary J.

2003-01-01

The food habits and prey base of the endangered Southwestern Willow Flycatcher (Empidonax traillii extimus) are not well known. We analyzed prey remains in 59 fecal samples from an intensively-studied population of this flycatcher at the Kern River Preserve in southern California. These samples were collected during the nesting season in 1996 and 1997 from adults caught in mist nets, and from nestlings temporarily removed from the nest for banding. A total of 379 prey individuals were identified in the samples. Dominant prey taxa, both in total numbers and in percent occurrence, were true bugs (Hemiptera), flies (Diptera), and beetles (Coleoptera). Leafhoppers (Homoptera: Cicadellidae), spiders (Araneae), bees and wasps (Hymenoptera), and dragonflies and damselflies (Odonata) were also common items. Diet composition was significantly different between years, due to a large difference in the numbers of spiders between 1996 and 1997. There was also a significant difference between the diet of young and adults, with the diet of young birds having significantly higher numbers of odonates and beetles. There was a trend toward diet differences between males and females, but this was not significant at the P = 0.05 level.

Southwestern Willow Flycatcher Breeding Site and Territory Summary - 2007

USGS Publications Warehouse

Durst, Scott L.; Sogge, Mark K.; Stump, Shay D.; Walker, Hira A.; Kus, Barbara E.; Sferra, Susan J.

2008-01-01

The Southwestern willow flycatcher (Empidonax traillii extimus; hereafter references to willow flycatcher and flycatcher refer to E.t. extimus, except where specifically noted) is an endangered bird that breeds only in dense riparian habitats in parts of six Southwestern states (Arizona, New Mexico, southern California, extreme southern Nevada, southern Utah, and southwestern Colorado). Since 1993, hundreds of Southwestern willow flycatcher surveys have been conducted each year, and many new flycatcher breeding sites located. This document synthesizes the most current information available on all known Southwestern willow flycatcher breeding sites. This rangewide data synthesis was designed to meet two objectives: (1) identify all known Southwestern willow flycatcher breeding sites and (2) assemble data to estimate population size, location, habitat, and other information for all breeding sites, for as many years as possible, from 1993 through 2007. This report provides data summaries in terms of the number of flycatcher sites and the number of territories. When interpreting and using this information, it must be kept in mind that a 'site' is a geographic location where one or more willow flycatchers establishes a territory. Sites with unpaired territorial males are considered breeding sites, even if no nesting attempts were documented. A site is often a discrete patch of riparian habitat but may also be a cluster of riparian patches; there is no standardized definition for site, and its use varies within and among states. For example, five occupied habitat patches along a 10-km stretch of river might be considered five different sites in one state but only a single site in another state. This lack of standardization makes comparisons based on site numbers problematic. Researchers for this report generally deferred to statewide summary documents or to local managers and researchers when delineating a site for inclusion in the database. However, to avoid inflating

Genetic variation in the endangered Southwestern Willow Flycatcher

USGS Publications Warehouse

Busch, Joseph; Miller, Mark P.; Paxton, E.H.; Sogge, M.K.; Keim, Paul

2000-01-01

The Southwestern Willow Flycatcher (Empidonax traillii extimus) is an endangered Neotropical migrant that breeds in isolated remnants of dense riparian habitat in the southwestern United States. We estimated genetic variation at 20 breeding sites of the Southwestern Willow Flycatcher (290 individuals) using 38 amplified fragment length polymorphisms (AFLPs). Our results suggest that considerable genetic diversity exists within the subspecies and within local breeding sites. Statistical analyses of genetic variation revealed only slight, although significant, differentiation among breeding sites (Mantel's r = 0.0705, P < 0.0005; θ = 0.0816, 95% CI = 0.0608 to 0.1034; ΦST = 0.0458, P < 0.001). UPGMA cluster analysis of the AFLP markers indicates that extensive gene flow has occurred among breeding sites. No one site stood out as being genetically unique or isolated. Therefore, the small level of genetic structure that we detected may not be biologically significant. Ongoing field studies are consistent with this conclusion. Of the banded birds that were resighted or recaptured in Arizona during the 1996 to 1998 breeding seasons, one-third moved between breeding sites and two-thirds were philopatric. Low differentiation may be the result of historically high rangewide diversity followed by recent geographic isolation of breeding sites, although observational data indicate that gene flow is a current phenomenon. Our data suggest that breeding groups of E. t. extimus act as a metapopulation.

A habitat overlap analysis derived from maxent for tamarisk and the south-western willow flycatcher

NASA Astrophysics Data System (ADS)

York, Patricia; Evangelista, Paul; Kumar, Sunil; Graham, James; Flather, Curtis; Stohlgren, Thomas

2011-06-01

Biologic control of the introduced and invasive, woody plant tamarisk ( Tamarix spp, saltcedar) in south-western states is controversial because it affects habitat of the federally endangered South-western Willow Flycatcher ( Empidonax traillii extimus). These songbirds sometimes nest in tamarisk where floodplain-level invasion replaces native habitats. Biologic control, with the saltcedar leaf beetle ( Diorhabda elongate), began along the Virgin River, Utah, in 2006, enhancing the need for comprehensive understanding of the tamarisk-flycatcher relationship. We used maximum entropy (Maxent) modeling to separately quantify the current extent of dense tamarisk habitat (>50% cover) and the potential extent of habitat available for E. traillii extimus within the studied watersheds. We used transformations of 2008 Landsat Thematic Mapper images and a digital elevation model as environmental input variables. Maxent models performed well for the flycatcher and tamarisk with Area Under the ROC Curve (AUC) values of 0.960 and 0.982, respectively. Classification of thresholds and comparison of the two Maxent outputs indicated moderate spatial overlap between predicted suitable habitat for E. traillii extimus and predicted locations with dense tamarisk stands, where flycatcher habitat will potentially change flycatcher habitats. Dense tamarisk habitat comprised 500 km2 within the study area, of which 11.4% was also modeled as potential habitat for E. traillii extimus. Potential habitat modeled for the flycatcher constituted 190 km2, of which 30.7% also contained dense tamarisk habitat. Results showed that both native vegetation and dense tamarisk habitats exist in the study area and that most tamarisk infestations do not contain characteristics that satisfy the habitat requirements of E. traillii extimus. Based on this study, effective biologic control of Tamarix spp. may, in the short term, reduce suitable habitat available to E. traillii extimus, but also has the potential

Distribution and abundance of Least Bell’s Vireos (Vireo bellii pusillus) and Southwestern Willow Flycatchers (Empidonax traillii extimus) on the Middle San Luis Rey River, San Diego, southern California—2016 data summary

USGS Publications Warehouse

Allen, Lisa D.; Howell, Scarlett L.; Kus, Barbara E.

2017-09-29

Executive SummaryWe surveyed for Least Bell’s Vireos (LBVI) (Vireo bellii pusillus) and Southwestern Willow Flycatchers (SWFL) (Empidonax traillii extimus) along the San Luis Rey River, between College Boulevard in Oceanside and Interstate 15 in Fallbrook, California (middle San Luis Rey River), in 2016. Surveys were done from March 30 to July 11 (LBVI) and from May 18 to July 30 (SWFL). We found 142 LBVI territories, at least 106 of which were occupied by pairs. Six additional transient LBVIs were detected. Of 20 banded LBVIs detected in the survey area, 9 had been given full color-band combinations prior to 2016, although we were unable to determine the exact color combination of 1 female LBVI. Seven other LBVIs with single (natal) federal bands were recaptured and banded in 2016. Four vireos with single dark blue federal bands indicating that they were banded as nestlings on the lower San Luis Rey River could not be recaptured for identification.Three SFWL territories were observed in the survey area in 2016. Two territories were occupied by pairs and one by a male of unknown breeding status. Both pairs attempted to nest at least once, and both pairs were successful, fledging three young each. Nesting began in early June and continued into July. Brown-Headed Cowbird (Molothrus ater) eggs were not observed in either nest. An additional 12 transient Willow Flycatchers of unknown subspecies were detected in 2016.Two of the five resident SWFLs were originally banded as nestlings on Marine Corps Base Camp Pendleton. One male and one female were banded as nestlings on Camp Pendleton in 2009 and 2011, respectively. One natal male of unknown breeding status, originally banded as a nestling on the middle San Luis Rey River in 2015, was recaptured and given a unique color combination in 2016. This male was later detected on Marine Corps Base Camp Pendleton.

Risky business: Site selection by Acadian Flycatchers under threat of nest predation and brood parasitism

USGS Publications Warehouse

HazIer, K.R.; Cooper, R.J.; Twedt, D.J.

2006-01-01

Habitat quality is determined not only by habitat structure and the availability of resources, but also by competitors, cooperators, predators, and parasites. We hypothesized that, for passerines, minimizing risk from avian nest predators and brood parasites is an important factor in selecting a breeding site. Through the early part of two breeding seasons, we spot-mapped locations of Acadian Flycatchers (Empidonax virescens, territory selectors), Red-bellied Woodpeckers (Melanerpes carolinus, nest predators) and Brown-headed Cowbirds (Molothrus ater, brood parasites) in a 56-ha study area within an extensive bottomland hardwood forest. We were thereby able to determine the order of flycatcher territory settlement and nest initiation in relation to risk of predation and parasitism, while accounting for habitat structure. Male settlement was influenced by both habitat structure and risk avoidance. However, risk trom woodpeckers was relatively more important in the first season and risk from cowbirds in the second, evidently due to differences in the relative abundance of predator and brood-parasite in each year. For male flycatchers, settlement choices appear to be flexible in the face of changing 'risk landscapes.' For females, habitat structure was the most important predictor of nest site selection. Even so, there was evidence that females avoided cowbirds. Surprisingly, nest site selection was positively associated with woodpecker abundance in the first season when woodpeckers were present in greater numbers. Possible explanations for this contradictory result are discussed.

Distribution and abundance of Least Bell’s Vireos (Vireo bellii pusillus) and Southwestern Willow Flycatchers (Empidonax traillii extimus) on the Middle San Luis Rey River, San Diego County, southern California—2017 data summary

USGS Publications Warehouse

Allen, Lisa D.; Howell, Scarlett L.; Kus, Barbara E.

2018-04-20

We surveyed for Least Bell’s Vireos (LBVI) (Vireo bellii pusillus) and Southwestern Willow Flycatchers (SWFL) (Empidonax traillii extimus) along the San Luis Rey River, between College Boulevard in Oceanside and Interstate 15 in Fallbrook, California (middle San Luis Rey River), in 2017. Surveys were conducted from April 13 to July 11 (LBVI) and from May 16 to July 28 (SWFL). We found 146 LBVI territories, at least 107 of which were occupied by pairs. Five additional transient LBVIs were detected. LBVIs used five different habitat types in the survey area: mixed willow, willow-cottonwood, willow-sycamore, riparian scrub, and upland scrub. Forty-four percent of the LBVIs occurred in habitat characterized as mixed willow and 89 percent of the LBVI territories occurred in areas with greater than 50 percent native plant cover. Of 16 banded LBVIs detected in the survey area, 8 had been given full color-band combinations prior to 2017. Four other LBVIs with single (natal) federal bands were recaptured and banded in 2017. Three LBVIs with single dark blue federal bands indicating that they were banded as nestlings on the lower San Luis Rey River and one LBVI with a single gold federal band indicating that it was banded as a nestling on Marine Corps Base Camp Pendleton (MCBCP) could not be recaptured for identification. One banded LBVI emigrated from the middle San Luis Rey River to the lower San Luis Rey River in 2017.One resident SWFL territory and one transient Willow Flycatcher of unknown subspecies (WIFL) were observed in the survey area in 2017. The resident SWFL territory, which was comprised of mixed willow habitat (5–50 percent native plant cover), was occupied by a single male from May 22 to June 21, 2017. No evidence of pairing or nesting activity was observed. The SWFL male was banded with a full color-combination indicating that he was originally banded as a nestling on the middle San Luis Rey River in 2014 and successfully bred in the survey area in 2016

Chapter 7: Migration and winter ecology

Treesearch

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...

Chapter 3: Threats

Treesearch

Robert M. Marshall; Scott H. Stoleson

2000-01-01

The continued survival of the southwestern willow flycatcher (Empidonax traillii extimus) is threatened indirectly by the loss, modification, and fragmentation of riparian habitat, and directly by factors that impact the survival and reproductive success of flycatchers. Because the impact of habitat loss on small populations can be particularly...

Chapter 6: Breeding season ecology

Treesearch

Mark K. Sogge

2000-01-01

The willow flycatcher (Empidonax traillii) breeds across much of the conterminous United States and in portions of extreme southern Canada. As might be expected in such a wide-ranging species, willow flycatchers in different portions of the range exhibit differences in appearance, song, and ecological characteristics. The intent of this chapter is to...

Response

Treesearch

Wang Yong; Deborah M. Finch

1999-01-01

Hubbard (1999) criticizes our paper "Migration of the Willow Flycatcher along the middle Rio Grande" (Yong and Finch 1997), where we reported aspects of stopover ecology of the species including timing, abundance, fat stores, stopover length, and habitat use. Hubbard questions our identification of subspecies of the Willow Flycatcher (Empidonax traillii) and...

Archaeological and Historical Reconnaissance and Literature Search of Cultural Resources within the Pembina River Project, Pembina and Cavalier Counties, North Dakota. Volume 1.

DTIC Science & Technology

1982-12-01

SAythya americana Redhead Aythya valisineria Canvasback Aix sponsa Wood Duck Aythya collaris Ring-necked Ducks Aythya affinis Lesser Scaup Lophodytes...Chickadee Vireo olivaceus Red-eyed Vireo Vireo gilvus Warbling Vireo Empidonax Tinimus Least Flycatcher Contopus virens Eastern Wood Pewee Contopus...sordidulus Western Wood Pewee Myiarchus crinitus Great Crested Flycatcher Catharus fuscescens Veery Sejurus aurocapillus Ovenbird Mniotilta varia Black-and

75 FR 19987 - Endangered and Threatened Species Permit Applications

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-16

..., during normal business hours at the U.S. Fish and Wildlife Service, 500 Gold Ave. SW., Room 6034... seminuda), woundfin (Plagopterus argentissimus), Colorado pikeminnow (Ptychocheilus lucius), razorback... southwestern willow flycatcher (Empidonax taillii extimus) within Arizona, Colorado, and Utah. Authority: 16 U...

Inferring the demographic history of European Ficedula flycatcher populations

PubMed Central

2013-01-01

Background Inference of population and species histories and population stratification using genetic data is important for discriminating between different speciation scenarios and for correct interpretation of genome scans for signs of adaptive evolution and trait association. Here we use data from 24 intronic loci re-sequenced in population samples of two closely related species, the pied flycatcher and the collared flycatcher. Results We applied Isolation-Migration models, assignment analyses and estimated the genetic differentiation and diversity between species and between populations within species. The data indicate a divergence time between the species of <1 million years, significantly shorter than previous estimates using mtDNA, point to a scenario with unidirectional gene-flow from the pied flycatcher into the collared flycatcher and imply that barriers to hybridisation are still permeable in a recently established hybrid zone. Furthermore, we detect significant population stratification, predominantly between the Spanish population and other pied flycatcher populations. Conclusions Our results provide further evidence for a divergence process where different genomic regions may be at different stages of speciation. We also conclude that forthcoming analyses of genotype-phenotype relations in these ecological model species should be designed to take population stratification into account. PMID:23282063

Problems in separating species with similar habits and vocalizations

USGS Publications Warehouse

Robbins, C.S.; Stallcup, R.W.; Ralph, C. John; Scott, J. Michael

1981-01-01

The possibilities for species misidentification based on vocalization or habitat association are high. However, the magnitude of the errors actually perpetrated is generally within an acceptable range in most types of bird survey work. Examples of problems discussed are: congeners that are similar in appearance or in song (such as Chimney and Vaux's Swifts, Chaetura pelagica, C. vauxi; Hammond's, Dusky and Gray Flycatchers, Empidonax hammondii, E. oberholseri, E. wrightii; Willow and Alder Flycatchers, E. traillii, E. alnorum; Common and Fish Crows, Corvus brachyrhynchos, C. ossifragus); birds that are misidentified because they are not expected by the observer (House Finches, Carpodacus mexicanus, invading new areas of eastern U.S.); birds that imitate other species (especially Starling, Sturnus vulgaris, and Mockingbird, Mimus polyglottos); birds in mixed flocks; birds with geographic differences in vocalizations (Solitary Vireo, Vireo solitarius); woodpeckers that are only heard drumming; and nests or eggs that are misidentified. Equally serious problems are the errors resulting from undetected species and from careless recording or failure to check manuscripts against original data. The quality of published count work can be improved considerably by (1) recognizing the problems that exist, (2) standardizing techniques for dealing with situations where not all birds can be identified, and (3) routinely applying all appropriate safeguards such as verification by mist netting and measuring, photography, tape recording or playback, additional observations, and careful verification of all entries in the final manuscript.

Parents or predators: Examining intraseasonal variation in nest survival for migratory passerine

Treesearch

Robin Hirsch-Jacobson; W. Andrew Cox; Emily E. Tewes; Frank R., III Thompson; John Faaborg

2012-01-01

For birds, risk of nest predation can vary within a breeding season, but few data exist that explain why such variation occurs. We investigated intraseasonal variation of nest survival of the Acadian Flycatcher (Empidonax virescens) in Midwestern forests and tested whether four of the adults' reproductive strategies (clutch size, nest...

Landscape forest cover and edge effects on songbird nest predation vary by nest predator

Treesearch

W. Andrew Cox; Frank R. III Thompson; John Faaborg

2012-01-01

Rates of nest predation for birds vary between and within species across multiple spatial scales, but we have a poor understanding of which predators drive such patterns. We video-monitored nests and identified predators at 120 nests of the Acadian Flycatcher (Empidonax virescens) and the Indigo Bunting (Passerina cyanea) at eight...

Niche separation in flycatcher-like species in the lowland rainforests of Malaysia.

PubMed

Mansor, Mohammad Saiful; Ramli, Rosli

2017-07-01

Niche theory suggests that sympatric species reduce interspecific competition through segregation of shared resources by adopting different attack manoeuvres. However, the fact that flycatcher-like bird species exclusively use the sally manoeuvre may thus challenge this view. We studied the foraging ecology of three flycatcher-like species (i.e. Paradise-flycatcher Terpsiphone sp., Black-naped Monarch Hypothymis azurea, and Rufous-winged Philentoma Philentoma pyrhoptera) in the Krau Wildlife Reserve in central Peninsular Malaysia. We investigated foraging preferences of each bird species and the potential niche partitioning via spatial or behavioural segregation. Foraging substrate was important parameter that effectively divided paradise-flycatcher from Black-naped Monarch and Rufous-winged Philentoma, where monarch and philentoma foraged mainly on live green leaves, while paradise-flycatcher foraged on the air. They also exhibited different foraging height preferences. Paradise-flycatcher, for instance, preferred the highest studied strata, while Black-naped Monarch foraged mostly in lower strata, and Rufous-winged Philentoma made use of the lowest strata. This study indicates that niche segregation occurs among sympatric species through foraging substrate and attack manoeuvres selection. Copyright © 2017 Elsevier B.V. All rights reserved.

A multiscaled model of southwestern willow flycatcher breeding habitat

USGS Publications Warehouse

Hatten, J.R.; Paradzick, C.E.

2003-01-01

The southwestern willow flycatcher (SWFL; Empidonax traillii extimus) is an endangered songbird whose habitat has declined dramatically over the last century. Understanding habitat selection patterns and the ability to identify potential breeding areas for the SWFL is crucial to the management and conservation of this species. We developed a multiscaled model of SWTL breeding habitat with a Geographic Information System (GIS), survey data, GIS variables, and multiple logistic regressions. We obtained presence and absence survey data from a riverine ecosystem and a reservoir delta in south-central Arizona, USA, in 1999. We extracted the GIS variables from satellite imagery and digital elevation models to characterize vegetation and floodplain within the project area. We used multiple logistic regressions within a cell-based (30 X 30 m) modeling environment to (1) determine associations between GIS variables and breeding-site occurrence at different spatial scales (0.09-72 ha), and (2) construct a predictive model. Our best model explained 54% of the variability in breeding-site occurrence with the following variables: vegetation density at the site (0.09 ha), proportion of dense vegetation and variability in vegetation density within a 4.5-ha neighborhood, and amount of floodplain or flat terrain within a 41-ha neighborhood. The density of breeding sites was highest in areas that the model predicted to be most suitable within the project area and at an external test site 200 km away. Conservation efforts must focus on protecting not only occupied patches, but also surrounding riparian forests and floodplain to ensure long-term viability of SWTL. We will use the multiscaled model to map SWTL breeding habitat in Arizona, prioritize future survey effort, and examine changes in habitat abundance and quality over time.

Extreme drought alters frequency and reproductive success of floaters in Willow Flycatchers

USGS Publications Warehouse

Theimer, Tad; Sogge, Mark K.; Cardinal, Suzanne N.; Durst, Scott L.; Paxton, Eben H.

2018-01-01

Changes in habitat quality, including those caused by extreme events like droughts and floods, could alter costs and benefits of territoriality and thereby the prevalence and reproductive consequences for individuals capable of breeding that do not do so (floaters). We studied floating behavior in a population of Southwestern Willow Flycatchers (Empidonax traillii extimus) in central Arizona during one year of extreme drought, one year of lake inundation, and three years of near average precipitation. In all years, most floaters were second year (SY) males, and most subsequently settled outside of the patch where they were detected in the floating year, suggesting that floaters did not “queue” at high-quality territories in order to achieve higher reproductive success in subsequent years. Instead, cohorts that floated in non-drought years had lower apparent survival and lower reproductive success compared to territorial birds. In the extreme drought year, however, the number of floaters was 1.5 times greater than in all other years combined, more females floated, and apparent survival and mean annual productivity in subsequent years was higher for males that floated in that year than for those that were territorial. Inundation of habitat due to rising reservoir levels did not result in an increase in floaters because many birds nested in inundated areas where trees projected above the water so that the relative amount of available habitat was not reduced to the extent habitat models predicted. Overall, our results indicate that the prevalence and reproductive and demographic consequences of floating can change under extreme climatic events like severe drought.

Chapter 1: Introduction of the conservation assessment concept

Treesearch

Deborah M. Finch

2000-01-01

The goal of this document is to describe the current status, ecology, habitat, and threats of the southwestern willow flycatcher (Empidonax traillii extimus); to offer guidance for managing and protecting this Neotropical migrant and its habitats; and to identify gaps in our knowledge of the bird and its requirements. Goals, processes, and target...

Implications of climate change for bird conservation in the southwestern U.S

Treesearch

Megan M. Friggens; Deborah M. Finch

2015-01-01

Future expected changes in climate and human activity threaten many riparian habitats, particularly in the southwestern U.S. Using Maximum Entropy (MaxEnt3.3.3) modeling, we characterized habitat relationships and generated spatial predictions of habitat suitability for the Lucy’s warbler (Oreothlypis luciae), the Southwestern willow flycatcher (Empidonax...

Species and temporal factors affect predator-specific rates of nest predation for forest songbirds in the midwest

Treesearch

W. Andrew Cox; Frank R. III Thompson; John Faaborg

2012-01-01

Knowledge of the relative contributions of predator species to overall rates of nest predation can improve our understanding of why predation risk varies, but the identity of predators is seldom known. We used video technology to identify nest predators of the tree-nesting Acadian Flycatcher (Empidonax virescens) and the shrub-nesting Indigo Bunting...

Demographic Divergence History of Pied Flycatcher and Collared Flycatcher Inferred from Whole-Genome Re-sequencing Data

PubMed Central

Nadachowska-Brzyska, Krystyna; Burri, Reto; Olason, Pall I.; Kawakami, Takeshi; Smeds, Linnéa; Ellegren, Hans

2013-01-01

Profound knowledge of demographic history is a prerequisite for the understanding and inference of processes involved in the evolution of population differentiation and speciation. Together with new coalescent-based methods, the recent availability of genome-wide data enables investigation of differentiation and divergence processes at unprecedented depth. We combined two powerful approaches, full Approximate Bayesian Computation analysis (ABC) and pairwise sequentially Markovian coalescent modeling (PSMC), to reconstruct the demographic history of the split between two avian speciation model species, the pied flycatcher and collared flycatcher. Using whole-genome re-sequencing data from 20 individuals, we investigated 15 demographic models including different levels and patterns of gene flow, and changes in effective population size over time. ABC provided high support for recent (mode 0.3 my, range <0.7 my) species divergence, declines in effective population size of both species since their initial divergence, and unidirectional recent gene flow from pied flycatcher into collared flycatcher. The estimated divergence time and population size changes, supported by PSMC results, suggest that the ancestral species persisted through one of the glacial periods of middle Pleistocene and then split into two large populations that first increased in size before going through severe bottlenecks and expanding into their current ranges. Secondary contact appears to have been established after the last glacial maximum. The severity of the bottlenecks at the last glacial maximum is indicated by the discrepancy between current effective population sizes (20,000–80,000) and census sizes (5–50 million birds) of the two species. The recent divergence time challenges the supposition that avian speciation is a relatively slow process with extended times for intrinsic postzygotic reproductive barriers to evolve. Our study emphasizes the importance of using genome-wide data to

Demographic divergence history of pied flycatcher and collared flycatcher inferred from whole-genome re-sequencing data.

PubMed

Nadachowska-Brzyska, Krystyna; Burri, Reto; Olason, Pall I; Kawakami, Takeshi; Smeds, Linnéa; Ellegren, Hans

2013-11-01

Profound knowledge of demographic history is a prerequisite for the understanding and inference of processes involved in the evolution of population differentiation and speciation. Together with new coalescent-based methods, the recent availability of genome-wide data enables investigation of differentiation and divergence processes at unprecedented depth. We combined two powerful approaches, full Approximate Bayesian Computation analysis (ABC) and pairwise sequentially Markovian coalescent modeling (PSMC), to reconstruct the demographic history of the split between two avian speciation model species, the pied flycatcher and collared flycatcher. Using whole-genome re-sequencing data from 20 individuals, we investigated 15 demographic models including different levels and patterns of gene flow, and changes in effective population size over time. ABC provided high support for recent (mode 0.3 my, range <0.7 my) species divergence, declines in effective population size of both species since their initial divergence, and unidirectional recent gene flow from pied flycatcher into collared flycatcher. The estimated divergence time and population size changes, supported by PSMC results, suggest that the ancestral species persisted through one of the glacial periods of middle Pleistocene and then split into two large populations that first increased in size before going through severe bottlenecks and expanding into their current ranges. Secondary contact appears to have been established after the last glacial maximum. The severity of the bottlenecks at the last glacial maximum is indicated by the discrepancy between current effective population sizes (20,000-80,000) and census sizes (5-50 million birds) of the two species. The recent divergence time challenges the supposition that avian speciation is a relatively slow process with extended times for intrinsic postzygotic reproductive barriers to evolve. Our study emphasizes the importance of using genome-wide data to

Environmental Assessment for Leasing Nellis Air Force Base Land for Construction and Operation of a Solar Photovoltaic System, Clark County, Nevada

DTIC Science & Technology

2006-08-01

oxides OSHA Occupational Safety and Health Administration PL Public Law PM10 Particulate matter ≤ 10 microns in diameter POL Petroleum, oils , and...several years, costs and demand for energy produced through non- renewable resources, such as crude oil , have increased dramatically. In response to...flycatcher Empidonax difficilus Rough-winged swallow Stelgidopteryx serripennis Ruby-crowned kinglet Regulus calendula Northern mockingbird Mimus

Russian Olive Biology, Invasion, and Ecological Impacts in Western North America

DTIC Science & Technology

2016-07-01

habitat for bird species , but is not functionally equivalent to native vegetation. Leatherman (2011) lists a variety of birds that consume fruits, sap...abundance, but intermediate avian species richness and diversity, in Russian olive stands. Russian olive bird communities were somewhat similar to...provided distinctive habitat for some bird species (e.g., least flycatchers [Empidonax minimus], red-eyed vireos [Vireo olivaceous]), while providing

Red alder potential in Alaska

Treesearch

Allen Brackley; David Nicholls; Mike Hannan

2010-01-01

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

Red alder stand development and dynamics.

Treesearch

R.L. Deal

2006-01-01

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

Site curves for red alder.

Treesearch

Daniel M. Bishop; Floyd A. Johnson

1958-01-01

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

Southwestern willow flycatchers recaptured at wintering sites in Costa Rica

USGS Publications Warehouse

Koronkiewicz, Thomas J.; Sogge, Mark K.

2001-01-01

An adult Southwestern Willow Flycatcher banded in summer 1998 at Ash Meadows National Wildlife Refuge, Nevada, was recaptured the following winter in Santa Cruz, Costa Rica, then relocated at Ash Meadows during the 1999 breeding season. Another Southwestern Willow Flycatcher banded in 1999 as a nestling at Roosevelt Lake, Arizona, was recaptured in January 2000 on its wintering grounds in Bolsen, Costa Rica. The bird was recaptured at Roosevelt Lake in summer 2000, returned to the same wintering site in Bolsen the following winter, and was relocated at Roosevelt Lake in summer 2001.

Using a remote sensing/GIS model to predict southwestern Willow Flycatcher breeding habitat along the Rio Grande, New Mexico

USGS Publications Warehouse

Hatten, James R.; Sogge, Mark K.

2007-01-01

Introduction The Southwestern Willow Flycatcher (Empidonax traillii extimus; hereafter SWFL) is a federally endangered bird (USFWS 1995) that breeds in riparian areas in portions of New Mexico, Arizona, southwestern Colorado, extreme southern Utah and Nevada, and southern California (USFWS 2002). Across this range, it uses a variety of plant species as nesting/breeding habitat, but in all cases prefers sites with dense vegetation, high canopy, and proximity to surface water or saturated soils (Sogge and Marshall 2000). As of 2005, the known rangewide breeding population of SWFLs was roughly 1,214 territories, with approximately 393 territories distributed among 36 sites in New Mexico (Durst et al. 2006), primarily along the Rio Grande. One of the key challenges facing the management and conservation of the Southwestern Willow Flycatcher is that riparian areas are dynamic, with individual habitat patches subject to cycles of creation, growth, and loss due to drought, flooding, fire, and other disturbances. Former breeding patches can lose suitability, and new habitat can develop within a matter of only a few years, especially in reservoir drawdown zones. Therefore, measuring and predicting flycatcher habitat - either to discover areas that might support SWFLs, or to identify areas that may develop into appropriate habitat - requires knowledge of recent/current habitat conditions and an understanding of the factors that determine flycatcher use of riparian breeding sites. In the past, much of the determination of whether a riparian site is likely to support breeding flycatchers has been based on qualitative criteria (for example, 'dense vegetation' or 'large patches'). These determinations often require on-the-ground field evaluations by local or regional SWFL experts. While this has proven valuable in locating many of the currently known breeding sites, it is difficult or impossible to apply this approach effectively over large geographic areas (for example, the

Utilization and management of alder.

Treesearch

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

1978-01-01

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

Red alder: a state of knowledge.

Treesearch

Robert L. Deal; Constance A. Harrington

2006-01-01

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

Microwave-based reaction screening: tandem retro-Diels-Alder/Diels-Alder cycloadditions of o-quinol dimers.

PubMed

Dong, Suwei; Cahill, Katharine J; Kang, Moon-Il; Colburn, Nancy H; Henrich, Curtis J; Wilson, Jennifer A; Beutler, John A; Johnson, Richard P; Porco, John A

2011-11-04

We have accomplished a parallel screen of cycloaddition partners for o-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of o-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of o-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor.

Microwave-Based Reaction Screening: Tandem Retro-Diels-Alder/Diels-Alder Cycloadditions of ortho-Quinol Dimers

PubMed Central

Dong, Suwei; Cahill, Kath arine J.; Kang, Moon -Il; Colburn, Nancy H.; Henrich, Curtis J.; Wilson, Jennifer A.; Beutler, John A.; Johnson, Richard P.; Porco, John A.

2011-01-01

We have accomplished a parallel screen of cycloaddition partners for ortho-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of ortho-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of ortho-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor. PMID:21942286

Vortex wake, downwash distribution, aerodynamic performance and wingbeat kinematics in slow-flying pied flycatchers.

PubMed

Muijres, Florian T; Bowlin, Melissa S; Johansson, L Christoffer; Hedenström, Anders

2012-02-07

Many small passerines regularly fly slowly when catching prey, flying in cluttered environments or landing on a perch or nest. While flying slowly, passerines generate most of the flight forces during the downstroke, and have a 'feathered upstroke' during which they make their wing inactive by retracting it close to the body and by spreading the primary wing feathers. How this flight mode relates aerodynamically to the cruising flight and so-called 'normal hovering' as used in hummingbirds is not yet known. Here, we present time-resolved fluid dynamics data in combination with wingbeat kinematics data for three pied flycatchers flying across a range of speeds from near hovering to their calculated minimum power speed. Flycatchers are adapted to low speed flight, which they habitually use when catching insects on the wing. From the wake dynamics data, we constructed average wingbeat wakes and determined the time-resolved flight forces, the time-resolved downwash distributions and the resulting lift-to-drag ratios, span efficiencies and flap efficiencies. During the downstroke, slow-flying flycatchers generate a single-vortex loop wake, which is much more similar to that generated by birds at cruising flight speeds than it is to the double loop vortex wake in hovering hummingbirds. This wake structure results in a relatively high downwash behind the body, which can be explained by the relatively active tail in flycatchers. As a result of this, slow-flying flycatchers have a span efficiency which is similar to that of the birds in cruising flight and which can be assumed to be higher than in hovering hummingbirds. During the upstroke, the wings of slowly flying flycatchers generated no significant forces, but the body-tail configuration added 23 per cent to weight support. This is strikingly similar to the 25 per cent weight support generated by the wing upstroke in hovering hummingbirds. Thus, for slow-flying passerines, the upstroke cannot be regarded as inactive

Control of red alder by cutting.

Treesearch

Dean S. DeBell; Thomas C. Turpin

1989-01-01

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

A technique to produce aluminum color bands for avian research

USGS Publications Warehouse

Koronkiewicz, T.J.; Paxton, E.H.; Sogge, M.K.

2005-01-01

We developed a technique to produce metal (aluminum) color bands, in response to concerns about leg injuries caused by celluloid-plastic color bands applied to Willow Flycatchers (Empidonax traillii). The technique involves color-anodized aluminum bands (unnumbered blanks and federal numbered bands), with auto pin-striping tape and flexible epoxy sealant, to create a variety of solid, half- and triple-split colors. This allows for hundreds of unique, high-contrast color combinations. During six consecutive years of application, these colored metal bands have resisted color fade compared to conventional celluloid-plastic bands, and have reduced leg injuries in the flycatcher. Although not necessarily warranted for all color-banding studies, these metal bands may provide a lower-impact option for studies of species known to be impacted by plastic color bands.

Origins of Stereoselectivity in the trans-Diels-Alder Paradigm

PubMed Central

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

2010-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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).

Volume tables for red alder.

Treesearch

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

1949-01-01

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

Estimation of linkage disequilibrium and interspecific gene flow in Ficedula flycatchers by a newly developed 50k single-nucleotide polymorphism array

PubMed Central

Kawakami, Takeshi; Backström, Niclas; Burri, Reto; Husby, Arild; Olason, Pall; Rice, Amber M; Ålund, Murielle; Qvarnström, Anna; Ellegren, Hans

2014-01-01

With the access to draft genome sequence assemblies and whole-genome resequencing data from population samples, molecular ecology studies will be able to take truly genome-wide approaches. This now applies to an avian model system in ecological and evolutionary research: Old World flycatchers of the genus Ficedula, for which we recently obtained a 1.1 Gb collared flycatcher genome assembly and identified 13 million single-nucleotide polymorphism (SNP)s in population resequencing of this species and its sister species, pied flycatcher. Here, we developed a custom 50K Illumina iSelect flycatcher SNP array with markers covering 30 autosomes and the Z chromosome. Using a number of selection criteria for inclusion in the array, both genotyping success rate and polymorphism information content (mean marker heterozygosity = 0.41) were high. We used the array to assess linkage disequilibrium (LD) and hybridization in flycatchers. Linkage disequilibrium declined quickly to the background level at an average distance of 17 kb, but the extent of LD varied markedly within the genome and was more than 10-fold higher in ‘genomic islands’ of differentiation than in the rest of the genome. Genetic ancestry analysis identified 33 F1 hybrids but no later-generation hybrids from sympatric populations of collared flycatchers and pied flycatchers, contradicting earlier reports of backcrosses identified from much fewer number of markers. With an estimated divergence time as recently as <1 Ma, this suggests strong selection against F1 hybrids and unusually rapid evolution of reproductive incompatibility in an avian system. PMID:24784959

Status and breeding ecology of the southwestern willow flycatcher in the Grand Canyon

USGS Publications Warehouse

Sogge, M.K.; Tibbitts, T.J.; Petterson, J.R.

1997-01-01

Ernpidonax trailIll extirnus is one of several recognized subspecies of the Willow Flycatcher (Unitt 1987, Browning 1993), a neotropical migrant that breeds across much of North America. This southwestern race is a riparian obligate, nesting in dense patches of willow (Salix sp.), willow-cottonwood (Populus sp.), or other similarly structured habitats. In some areas of the Southwest, it nests in dense stands of tamarisk (Tamarix sp.). Willow Flycatchers were once widespread and locally common in the Southwest (Unitt 1987) but have declined to the point that E. t. extirnus was listed as an endangered subspecies in 1995 (USFWS 1995).

Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds

DOE PAGES

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

2017-05-17

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

Normal yield tables for red alder.

Treesearch

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

1960-01-01

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

Early reproductive success of western bluebirds and ash-throated flycatchers: a landscape-contaminant perspective.

PubMed

Fair, Jeanne M; Myers, Orrin B

2002-01-01

Eggshell quality, clutch size, sex ratio, and hatching success of western bluebirds (Sialia mexicana) and ash-throated flycatchers (Myiarchus cinerascens) were studied on a landscape-soil contaminant gradient at Los Alamos National Laboratory (LANL) in New Mexico from 1997 to 1999. A variety of contaminants (heavy metals, chemicals, insecticides, polychlorinated biphenyls (PCBs), organochlorines, and radioactive isotopes) range across different spatial scales and concentrations on LANL land. This study is an example of a monitoring program over a large area with varying degree of contamination that is used to highlight locations of concern for future research. There were two locations where the flycatcher had a lower hatching success. The bluebirds at Sandia wetland, a location of concern for PCBs. had a thinner eggshell thickness index (RATCLIFFE) and the eggs were smaller than at other locations. The flycatcher had thinner eggshells than bluebirds, which could add to sensitivity to exposure to contaminants. There was no variation in clutch size or sex ratio between locations or areas closer to contaminant release sites for both species. Percent females in the clutch ranged from 0 to 100% in the WEBL and from 33 to 67% for ATFL.

78 FR 343 - Endangered and Threatened Wildlife and Plants; Designation of Critical Habitat for Southwestern...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-01-03

...We, the U.S. Fish and Wildlife Service (Service), designate revised critical habitat for the southwestern willow flycatcher (Empidonax traillii extimus) (flycatcher) under the Endangered Species Act. In total, approximately 1,975 stream kilometers (1,227 stream miles) are being designated as critical habitat. These areas are designated as stream segments, with the lateral extent including the riparian areas and streams that occur within the 100-year floodplain or flood-prone areas encompassing a total area of approximately 84,569 hectares (208,973 acres). The critical habitat is located on a combination of Federal, State, tribal, and private lands in Inyo, Kern, Los Angeles, Riverside, Santa Barbara, San Bernardino, San Diego, and Ventura Counties in California; Clark, Lincoln, and Nye Counties in southern Nevada; Kane, San Juan, and Washington Counties in southern Utah; Alamosa, Conejos, Costilla, and La Plata Counties in southern Colorado; Apache, Cochise, Gila, Graham, Greenlee, La Paz, Maricopa, Mohave, Pima, Pinal, Santa Cruz, and Yavapai Counties in Arizona; and Catron, Grant, Hidalgo, Mora, Rio Arriba, Socorro, Taos, and Valencia Counties in New Mexico. The effect of this regulation is to conserve the flycatcher's habitat under the Endangered Species Act.

A new species of Muscicapa flycatcher from Sulawesi, Indonesia.

PubMed

Harris, J Berton C; Rasmussen, Pamela C; Yong, Ding Li; Prawiradilaga, Dewi M; Putra, Dadang Dwi; Round, Philip D; Rheindt, Frank E

2014-01-01

The Indonesian island of Sulawesi, a globally important hotspot of avian endemism, has been relatively poorly studied ornithologically, to the extent that several new bird species from the region have been described to science only recently, and others have been observed and photographed, but never before collected or named to science. One of these is a new species of Muscicapa flycatcher that has been observed on several occasions since 1997. We collected two specimens in Central Sulawesi in 2012, and based on a combination of morphological, vocal and genetic characters, we describe the new species herein, more than 15 years after the first observations. The new species is superficially similar to the highly migratory, boreal-breeding Gray-streaked Flycatcher Muscicapa griseisticta, which winters in Sulawesi; however, the new species differs strongly from M. griseisticta in several morphological characters, song, and mtDNA. Based on mtDNA, the new species is only distantly related to M. griseisticta, instead being a member of the M. dauurica clade. The new species is evidently widely distributed in lowland and submontane forest throughout Sulawesi. This wide distribution coupled with the species' apparent tolerance of disturbed habitats suggests it is not currently threatened with extinction.

Status and migration of the Southwestern willow flycatcher in New Mexico

Treesearch

Deborah M. Finch; Jeffrey F. Kelly

1999-01-01

In the Southwestern United States, recent degradation of riparian habitats has been linked to decline of the Southwestern subspecies of the Willow Flycatcher. During a 2-year banding effort, migration patterns and bird fat content were analyzed. Recommendations for managers, and outlines for conservation plans, are included.

Volume and taper tables for red alder.

Treesearch

Robert O. Curtis; David Bruce; Caryanne VanCoevering

1968-01-01

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

A facile microwave-assisted Diels-Alder reaction of vinylboronates.

PubMed

Sarotti, Ariel M; Pisano, Pablo L; Pellegrinet, Silvina C

2010-11-21

The Diels-Alder reaction of vinylboronates can be easily performed using microwave irradiation giving excellent yields of the cycloadducts. Pinacol vinylboronate was the reagent of choice due to its stability towards hydrolysis, operational simplicity and yields of Diels-Alder products. To the best of our knowledge, this is the first example of microwave-assisted Diels-Alder reaction of boron-substituted dienophiles. Subsequent in situ oxidation of the cycloadducts with alkaline hydrogen peroxide afforded the alcohols efficiently.

Ecological genomics predicts climate vulnerability in an endangered southwestern songbird.

PubMed

Ruegg, Kristen; Bay, Rachael A; Anderson, Eric C; Saracco, James F; Harrigan, Ryan J; Whitfield, Mary; Paxton, Eben H; Smith, Thomas B

2018-05-09

Few regions have been more severely impacted by climate change in the USA than the Desert Southwest. Here, we use ecological genomics to assess the potential for adaptation to rising global temperatures in a widespread songbird, the willow flycatcher (Empidonax traillii), and find the endangered desert southwestern subspecies (E. t. extimus) most vulnerable to future climate change. Highly significant correlations between present abundance and estimates of genomic vulnerability - the mismatch between current and predicted future genotype-environment relationships - indicate small, fragmented populations of the southwestern willow flycatcher will have to adapt most to keep pace with climate change. Links between climate-associated genotypes and genes important to thermal tolerance in birds provide a potential mechanism for adaptation to temperature extremes. Our results demonstrate that the incorporation of genotype-environment relationships into landscape-scale models of climate vulnerability can facilitate more precise predictions of climate impacts and help guide conservation in threatened and endangered groups. © 2018 John Wiley & Sons Ltd/CNRS.

A New Species of Muscicapa Flycatcher from Sulawesi, Indonesia

PubMed Central

Yong, Ding Li; Prawiradilaga, Dewi M.; Putra, Dadang Dwi; Round, Philip D.; Rheindt, Frank E.

2014-01-01

The Indonesian island of Sulawesi, a globally important hotspot of avian endemism, has been relatively poorly studied ornithologically, to the extent that several new bird species from the region have been described to science only recently, and others have been observed and photographed, but never before collected or named to science. One of these is a new species of Muscicapa flycatcher that has been observed on several occasions since 1997. We collected two specimens in Central Sulawesi in 2012, and based on a combination of morphological, vocal and genetic characters, we describe the new species herein, more than 15 years after the first observations. The new species is superficially similar to the highly migratory, boreal-breeding Gray-streaked Flycatcher Muscicapa griseisticta, which winters in Sulawesi; however, the new species differs strongly from M. griseisticta in several morphological characters, song, and mtDNA. Based on mtDNA, the new species is only distantly related to M. griseisticta, instead being a member of the M. dauurica clade. The new species is evidently widely distributed in lowland and submontane forest throughout Sulawesi. This wide distribution coupled with the species' apparent tolerance of disturbed habitats suggests it is not currently threatened with extinction. PMID:25419968

Production and assessment of red alder planting stock.

Treesearch

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

1992-01-01

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

African departure rather than migration speed determines variation in spring arrival in pied flycatchers.

PubMed

Ouwehand, Janne; Both, Christiaan

2017-01-01

Properly timed spring migration enhances reproduction and survival. Climate change requires organisms to respond to changes such as advanced spring phenology. Pied flycatchers Ficedula hypoleuca have become a model species to study such phenological adaptations of long-distance migratory songbirds to climate change, but data on individuals' time schedules outside the breeding season are still lacking. Using light-level geolocators, we studied variation in migration schedules across the year in a pied flycatcher population in the Netherlands, which sheds light on the ability for individual adjustments in spring arrival timing to track environmental changes at their breeding grounds. We show that variation in arrival dates to breeding sites in 2014 was caused by variation in departure date from sub-Saharan Africa and not by environmental conditions encountered en route. Spring migration duration was short for all individuals, on average 2 weeks. Males migrated ahead of females in spring, while migration schedules in autumn were flexibly adjusted according to breeding duties. Individuals were therefore not consistently early or late throughout the year. In fast migrants like our Dutch pied flycatchers, advancement of arrival to climate change likely requires changes in spring departure dates. Adaptation for earlier arrival may be slowed down by harsh circumstances in winter, or years with high costs associated with early migration. © 2016 The Authors. Journal of Animal Ecology published by John Wiley & Sons Ltd on behalf of British Ecological Society.

Niltavinae, a new taxon of Old World flycatchers (Aves: Muscicapidae).

PubMed

Sangster, George; Alström, Per; Forsmark, Emma; Olsson, Urban

2016-11-23

The relationships among Old World chats and flycatchers (Muscicapidae) have recently been clarified in two independent molecular phylogenetic studies (Sangster et al. 2010, Zuccon & Ericson 2010). Both studies recovered a well-supported clade of predominantly blue flycatchers of the genera Niltava, Cyornis, Eumyias and Cyanoptila, some species traditionally included in the genus Rhinomyias and one species traditionally included in Ficedula (F. monileger). The family-group name Niltavinae Sangster, Alström, Forsmark & Olsson, 2010, was introduced for this clade (Sangster et al. 2010). Unfortunately, our description of the new taxon Niltavinae did not include a diagnosis (sensu ICZN article 13.1.1) and thus inadvertently made this name unavailable for nomenclatural purposes (Zuccon 2011). The supplementary data associated with our original paper included evidence by which the taxon Niltavinae can be diagnosed: a 1 base pair (bp) deletion in the ornithine decarboxylase gene, as shown in Figure S1 in the online version (doi:10.1016/j.ympev.2010.07.008), but this was not mentioned in the printed version of our paper. Given that Niltavinae Sangster, Alström, Forsmark & Olsson, 2010 represents a nomen nudum, and the clade for which this name was intended thus remains unnamed, we here provide the following description.

Diels-Alder Cycloadditions of Masked o-Benzoquinones with Alkenes.

PubMed

Georgopanou, Effie; Martini, Katerina-Irene; Pantazis, Panagiotis; Pelagias, Paulos; Voulgari, Penelope; Hadjiarapoglou, Lazaros P

2015-10-02

Diels-Alder cycloadditions of 3-oxobut-1-enyl substituted orthoquinone monoketals with olefinic dienophiles furnished functionalized ortho-endo bicyclo[2.2.2]octenone derivatives with high regio- and stereoselectivities. The competition between self-dimerization and Diels-Alder cycloaddition with an external dienophile usually exists, except in the case of 5-substituted orthoquinone monoketal.

Climate, canker, and alder mortality in the Southern Rockies

Treesearch

James J. Worrall

2012-01-01

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

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

USGS Publications Warehouse

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

2004-01-01

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

Avian use of forest habitats in the Pembina Hills of northeastern North Dakota

USGS Publications Warehouse

Faanes, Craig A.; Andrew, Jonathan M.

1983-01-01

North Dakota has the least extensive total area of forested habitats of any of the 50 United States. Although occurring in limited area, forest communities add considerably to the total ecological diversity of the State. The forests of the Pembina Hills region in northeastern North Dakota are one of only three areas large enough to be considered of commercial value. During 1981 we studied the avifauna of the upper valley of the Pembina River in the Pembina Hills. Field work extended from 20 April to 23 July; breeding bird censuses were conducted 7 June to 2 July. Of the 120 bird species recorded during the study period, 79 species were recorded during the breeding season. The total breeding population was estimated at nearly 76,000 breeding pairs. The wood warblers (Parulidae) were the most numerous family, accounting for about 28,000 breeding pairs. The yellow warbler (Dendroica petechia) was the most abundant breeding species, making up 19.4% of the population. American redstart (Setophaga ruticilla) was second in abundance, accounting for 10.5% of the breeding population. Largest breeding densities occurred in the willow (Salix sp.) shrub community. Although supporting the lowest mean breeding density, quaking aspen (Populus tremuloides) forests supported the highest species diversity. First State breeding records were recorded for alder flycatcher (Empidonax alnorum) and golden-winged warbler (Vermivora chrysoptera). Records were obtained for 12 species considered rare or unusual in North Dakota during the breeding season. The status of all species known to have occurred in the study area is described in an annotated species list.

Myiarchus flycatchers are the primary seed dispersers of Bursera longipes in a Mexican dry forest

PubMed Central

Almazán-Núñez, R. Carlos; Eguiarte, Luis E.; Arizmendi, María del Coro

2016-01-01

We evaluated the seed dispersal of Bursera longipes by birds along a successional gradient of tropical dry forest (TDF) in southwestern Mexico. B. longipes is an endemic tree to the TDF in the Balsas basin. The relative abundance of frugivorous birds, their frequency of visits to B. longipes and the number of removed fruits were recorded at three study sites with different stages of forest succession (early, intermediate and mature) characterized by distinct floristic and structural elements. Flycatchers of the Myiarchus and Tyrannus genera removed the majority of fruits at each site. Overall, visits to B. longipes were less frequent at the early successional site. Birds that function as legitimate dispersers by consuming whole seeds and regurgitating or defecating intact seeds in the process also remove the pseudoaril from seeds, thereby facilitating the germination process. The highest germination percentages were recorded for seeds that passed through the digestive system of two migratory flycatchers: M. cinerascens and M. nutingii. Perch plants, mainly composed of legumes (e.g., Eysenhardtia polystachya, Acacia cochliacantha, Calliandra eryophylla, Mimosa polyantha), serve also as nurse plants since the number of young individuals recruited from B. longipes was higher under these than expected by chance. This study shows that Myiarchus flycatchers are the most efficient seed dispersers of B. longipes across all successional stages. This suggests a close mutualistic relationship derived from adaptive processes and local specializations throughout the distribution of both taxa, as supported by the geographic mosaic theory of coevolution. PMID:27326382

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

Treesearch

Robert L. Deal

1997-01-01

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

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

USGS Publications Warehouse

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

2001-01-01

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

CADMIUM EFFECTS ON THE NITROGEN FIXATION SYSTEM OF RED ALDER

EPA Science Inventory

Red alder (Alnus rubra) was grown in sand culture in the greenhouse to obtain data on the effects of cadmium (Cd) on a symbiotic nitrogen (N) fixation system which contributes to the fertility of forest soils. Treatment of red alder seedlings for 11 weeks with 0.545 to 136 microm...

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

PubMed

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

2015-11-01

Alders have already demonstrated their potential for the revegetation of both mining and industrial sites. These actinorhizal trees and shrubs and the actinobacteria Frankia associate in a nitrogen-fixing symbiosis which could however be negatively affected by the presence of heavy metals, and accumulate them. In our hydroponic assay with black alders, quantification of the roots and shoots metal concentrations showed that, in the absence of stress, symbiosis increases Mo and Ni root content and simultaneously decreases Mo shoot content. Interestingly, the Mo shoot content also decreases in the presence of Ni, Cu, Pb, Zn and Cd for symbiotic alders. In symbiotic alders, Pb shoot translocation was promoted in presence of Pb. On the other hand, Cd exclusion in symbiotic root tissues was observed with Pb and Cd. In the presence of symbiosis, only Cd and Pb showed translocation into aerial tissues when present in the nutrient solution. Moreover, the translocation of Ni to shoot was prevented by symbiosis in the presence of Cd, Ni and Pb. The hydroponic experiment demonstrated that alders benefit from the symbiosis, producing more biomass (total, root and shoot) than non nodulated alders in control condition, and in the presence of metals (Cu, Ni, Zn, Pb and Cd). Heavy metals did not reduce the nodule numbers (SNN), but the presence of Zn or Cd did reduce nodule allocation. Our study suggests that the Frankia-alder symbiosis is a promising (and a compatible) plant-microorganism association for the revegetation of contaminated sites, with minimal risk of metal dispersion. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enzymatic catalysis of the Diels-Alder reaction in the biosynthesis of natural products.

PubMed

Oikawa, Hideaki; Tokiwano, Tetsuo

2004-06-01

Recent studies on enzymes catalyzing the Diels- Alder reaction. often named "Diels-Alderases", clearlydemonstrated the involvement of this synthetically useful reaction in the biosynthesis of natural products.This review covers natural Diels-Alder type cycloadducts. synthetic efforts on the chemical feasibility ofthe biosynthctic Diels - Alder reaction and a brief history of studies on Diels-Alderases. In addition,reaction mechanisms of artificial and natural Diels--Alderases are discussed.

The hexadehydro-Diels-Alder reaction.

PubMed

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.

Bayesian Inference of Allele-Specific Gene Expression Indicates Abundant Cis-Regulatory Variation in Natural Flycatcher Populations

PubMed Central

Wang, Mi

2017-01-01

Abstract Polymorphism in cis-regulatory sequences can lead to different levels of expression for the two alleles of a gene, providing a starting point for the evolution of gene expression. Little is known about the genome-wide abundance of genetic variation in gene regulation in natural populations but analysis of allele-specific expression (ASE) provides a means for investigating such variation. We performed RNA-seq of multiple tissues from population samples of two closely related flycatcher species and developed a Bayesian algorithm that maximizes data usage by borrowing information from the whole data set and combines several SNPs per transcript to detect ASE. Of 2,576 transcripts analyzed in collared flycatcher, ASE was detected in 185 (7.2%) and a similar frequency was seen in the pied flycatcher. Transcripts with statistically significant ASE commonly showed the major allele in >90% of the reads, reflecting that power was highest when expression was heavily biased toward one of the alleles. This would suggest that the observed frequencies of ASE likely are underestimates. The proportion of ASE transcripts varied among tissues, being lowest in testis and highest in muscle. Individuals often showed ASE of particular transcripts in more than one tissue (73.4%), consistent with a genetic basis for regulation of gene expression. The results suggest that genetic variation in regulatory sequences commonly affects gene expression in natural populations and that it provides a seedbed for phenotypic evolution via divergence in gene expression. PMID:28453623

Climate sensitivity of thinleaf alder growth on an interior Alaska floodplain

Treesearch

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

2010-01-01

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

What Do Owls, Salamanders, Flycatchers and Cuckoos Have In Common?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Musgrave, Maria A.

This is an article from the Los Alamos Living magazine. Los Alamos National Laboratory sits on a beautiful and unique landscape that provides important protected habitat to many species, including a few that are federally-listed as threatened or endangered. These species are the Jemez Mountains Salamander, the Mexican Spotted Owl, the Southwestern Willow Flycatcher, the Yellow-billed Cuckoo, and the New Mexico Meadow Jumping Mouse. Part of the job of the Laboratory's wildlife biologists is to survey for these species each year and determine what actions need to be taken if they are found.

Water Relations of White Alder

Treesearch

Virginia I. Dains

1989-01-01

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

Climate adaptation and speciation: particular focus on reproductive barriers in Ficedula flycatchers.

PubMed

Qvarnström, Anna; Ålund, Murielle; McFarlane, S Eryn; Sirkiä, Päivi M

2016-01-01

Climate adaptation is surprisingly rarely reported as a cause for the build-up of reproductive isolation between diverging populations. In this review, we summarize evidence for effects of climate adaptation on pre- and postzygotic isolation between emerging species with a particular focus on pied (Ficedula hypoleuca) and collared (Ficedula albicollis) flycatchers as a model for research on speciation. Effects of climate adaptation on prezygotic isolation or extrinsic selection against hybrids have been documented in several taxa, but the combined action of climate adaptation and sexual selection is particularly well explored in Ficedula flycatchers. There is a general lack of evidence for divergent climate adaptation causing intrinsic postzygotic isolation. However, we argue that the profound effects of divergence in climate adaptation on the whole biochemical machinery of organisms and hence many underlying genes should increase the likelihood of genetic incompatibilities arising as side effects. Fast temperature-dependent co-evolution between mitochondrial and nuclear genomes may be particularly likely to lead to hybrid sterility. Thus, how climate adaptation relates to reproductive isolation is best explored in relation to fast-evolving barriers to gene flow, while more research on later stages of divergence is needed to achieve a complete understanding of climate-driven speciation.

Growth response of speckled alder and willow to depth of flooding

Treesearch

M. Dean Knighton

1981-01-01

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

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

Treesearch

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

2004-01-01

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

An Appreciation: Berni Julian Alder

NASA Astrophysics Data System (ADS)

Graham Hoover, William

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

Red alder harvesting opportunities in western Oregon.

Treesearch

Donald R. Gedney

1990-01-01

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

Growth and Survival of Hardwoods and Pine Interplanted with European Alder

Treesearch

William T. Plass

1977-01-01

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

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

Treesearch

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

1999-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, Sara K.; Patet, Ryan E.; Nikbin, Nima

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 themore » 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.« less

Arthropods of native and exotic vegetation and their association with willow flycatchers and Wilson's warblers

Treesearch

Linda S. DeLay; Deborah M. Finch; Sandra Brantley; Richard Fagerlund; Michael D. Means; Jeffrey F. Kelly

1999-01-01

We compared abundance of migrating Willow Flycatchers and Wilson's Warblers to the abundance of arthropods in exotic and native vegetation at Bosque del Apache National Wildlife Refuge. We trapped arthropods using glue-boards in 1996 and 1997 in the same cottonwood, saltcedar, and willow habitats where we mist-netted birds during spring and fall migration. There...

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

PubMed

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

2010-07-16

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

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

USGS Publications Warehouse

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

2012-01-01

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

Multi-locus phylogenetic analysis of Old World chats and flycatchers reveals extensive paraphyly at family, subfamily and genus level (Aves: Muscicapidae).

PubMed

Sangster, George; Alström, Per; Forsmark, Emma; Olsson, Urban

2010-10-01

The chats and flycatchers (Muscicapidae) represent an assemblage of 275 species in 48 genera. Defining natural groups within this assemblage has been challenging because of its high diversity and a paucity of phylogenetically informative morphological characters. We assessed the phylogenetic relationships of 124 species and 34 genera of Muscicapidae, and 20 species of Turdidae, using molecular sequence data from one mitochondrial gene and three nuclear loci, in total 3240bp. Bayesian and maximum likelihood analyses yielded a well-resolved tree in which nearly all basal nodes were strongly supported. The traditionally defined Muscicapidae, Muscicapinae and Saxicolinae were paraphyletic. Four major clades are recognized in Muscicapidae: Muscicapinae, Niltavinae (new family-group name), Erithacinae and Saxicolinae. Interesting relationships recovered by this analysis include: (i) a clade comprising the 'blue' flycatcher genera Niltava, Cyornis, Cyanoptila and Eumyias and some species of Rhinomyias; (ii) the position of Erithacus rubecula in a clade of otherwise exclusively African species; (iii) a close relationship between the shortwing Heinrichia calligyna and the flycatcher Rhinomyias insignis; (iv) a sister-relationship between forktails Enicurus and whistling thrushes Myophonus; and (v) a sister relationship of Ficedula and the 'chats'Monticola, Phoenicurus, Saxicola and Oenanthe. A high number of traditionally defined genera was found to be paraphyletic or polyphyletic. Copyright 2010 Elsevier Inc. All rights reserved.

Variation in the foraging behaviors of two flycatchers: associations with stage of the breeding cycle

Treesearch

H.F. Sakai; B.R. Noon

1990-01-01

The foraging characteristics of Hammond’s and Western flycatchers in northwestern California varied with different stages of the breeding cycle during the breeding seasons (early April-mid August) in 1984 and 1985. The species’ behaviors did not always vary in parallel nor were all foraging behaviors distributed equally during the breeding cycle. For example, the...

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

PubMed Central

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

2011-01-01

The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond forming reactions should be broadly useful in synthetic chemistry. PMID:20647463

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

NASA Astrophysics Data System (ADS)

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

2013-06-01

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

Welcome and Reflections on Berni Alder

NASA Astrophysics Data System (ADS)

Tarter, C. Bruce

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

Red alder: A bibliography with abstracts

Treesearch

Charles F. Heebner; Mary Jane Bergener

1983-01-01

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

N2-fixing red alder indirectly accelerates ecosystem nitrogen cycling

USGS Publications Warehouse

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

2012-01-01

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

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

Treesearch

David Nicholls; Joseph Roos

2007-01-01

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

The Diels-Alder cyclization of ketenimines.

PubMed

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

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

Treesearch

Tricia L. Wurtz

2000-01-01

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

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

PubMed Central

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

2017-01-01

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

Biology and ecology of red alder.

Treesearch

Constance A. Harrington

2006-01-01

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

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

Treesearch

Carl M. Berntsen

1961-01-01

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

An evaluation of the grades and value of red alder lumber in southeast Alaska

Treesearch

Allen M. Brackley; David Nicholls; Michael Hannan

2009-01-01

Many stands in southeast Alaska harvested since 1950, especially where there has been a high degree of disturbance of mineral soil, have regenerated to red alder (Alnus rubra Bong.) and are now approaching maturity. The availability of red alder raises questions addressed in this study about the recovery of lumber from this resource. Information in...

A Diels-Alder Route to Angularly Functionalized Bicyclic Structures

PubMed Central

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

2010-01-01

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

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

PubMed

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.

PSMC analysis of effective population sizes in molecular ecology and its application to black-and-white Ficedula flycatchers.

PubMed

Nadachowska-Brzyska, Krystyna; Burri, Reto; Smeds, Linnéa; Ellegren, Hans

2016-03-01

Climatic fluctuations during the Quaternary period governed the demography of species and contributed to population differentiation and ultimately speciation. Studies of these past processes have previously been hindered by a lack of means and genetic data to model changes in effective population size (Ne ) through time. However, based on diploid genome sequences of high quality, the recently developed pairwise sequentially Markovian coalescent (PSMC) can estimate trajectories of changes in Ne over considerable time periods. We applied this approach to resequencing data from nearly 200 genomes of four species and several populations of the Ficedula species complex of black-and-white flycatchers. Ne curves of Atlas, collared, pied and semicollared flycatcher converged 1-2 million years ago (Ma) at an Ne of ≈ 200 000, likely reflecting the time when all four species last shared a common ancestor. Subsequent separate Ne trajectories are consistent with lineage splitting and speciation. All species showed evidence of population growth up until 100-200 thousand years ago (kya), followed by decline and then start of a new phase of population expansion. However, timing and amplitude of changes in Ne differed among species, and for pied flycatcher, the temporal dynamics of Ne differed between Spanish birds and central/northern European populations. This cautions against extrapolation of demographic inference between lineages and calls for adequate sampling to provide representative pictures of the coalescence process in different species or populations. We also empirically evaluate criteria for proper inference of demographic histories using PSMC and arrive at recommendations of using sequencing data with a mean genome coverage of ≥18X, a per-site filter of ≥10 reads and no more than 25% of missing data. © 2016 The Authors. Molecular Ecology Published by John Wiley & Sons Ltd.

Fourfold Diels-Alder reaction of tetraethynylsilane.

PubMed

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.

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

PubMed

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

2015-01-01

Phytophthora species were systematically sampled, isolated, identified and compared for presence in streams, soil and roots of alder (Alnus species) dominated riparian ecosystems in western Oregon. We describe the species assemblage and evaluate Phytophthora diversity associated with alder. We recovered 1250 isolates of 20 Phytophthora species. Only three species were recovered from all substrates (streams, soil, alder roots): P. gonapodyides, the informally described "P. taxon Pgchlamydo", and P. siskiyouensis. P. alni ssp. uniformis along with five other species not previously recovered in Oregon forests are included in the assemblage: P.citricola s.l., P. gregata, P. gallica, P. nicotianae and P. parsiana. Phytophthora species diversity was greatest in downstream riparian locations. There was no significant difference in species diversity comparing soil and unwashed roots (the rhizosphere) to stream water. There was a difference between the predominating species from the rhizosphere compared to stream water. The most numerous species was the informally described "P. taxon Oaksoil", which was mainly recovered from, and most predominant in, stream water. The most common species from riparian forest soils and alder root systems was P. gonapodyides. © 2015 by The Mycological Society of America.

A recyclable fluorous organocatalyst for Diels-Alder reactions

PubMed Central

Chu, Qianli; Zhang, Wei; Curran, Dennis P.

2007-01-01

Chiral fluorous imidazolidinone catalyst 2 provides consistently high enantioselectivities in Diels-Alder reactions of dienes and α, β-unsaturated aldehydes. The catalyst can be readily separated from the reaction products by fluorous solid-phase extraction, and recovered in excellent purity for direct reuse. PMID:17710220

Female ornamentation and territorial conflicts in collared flycatchers ( Ficedula albicollis)

NASA Astrophysics Data System (ADS)

Hegyi, Gergely; Garamszegi, László Zsolt; Eens, Marcel; Török, János

2008-10-01

Female ornaments in species with conventional sex roles often indicate individual quality, but the evolutionary forces maintaining them are less clear. Sexual competition for breeding opportunities may represent an important role for female signals, especially in polygynous species, but there is little experimental evidence for this. The wing patch size (WPS) of female collared flycatchers indicates age and body condition and predicts social mating patterns. We challenged nest-building females with decoy females of varying WPS and found that the aggressive response of residents increased with decoy WPS, suggesting a role for this female ornament in territorial competition. Our results explain why female WPS predicts territorial distances when mated to a polygynous male and indicate that the role of WPS in female competitive interactions is similar to that in males of the same population.

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

USGS Publications Warehouse

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

2005-01-01

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

Nature's Strategy for Catalyzing Diels-Alder Reaction.

PubMed

Oikawa, Hideaki

2016-04-21

The enzymes catalyzing a Diels-Alder-type reaction have been attractive targets for organic chemists for years. Recently, Zheng et al. (2016) reported the structure of a formal monofunctional Diels-Alderase PyrI4 complexed with the product and unveiled a detailed catalytic mechanism of a highly important enzyme. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemical basal treatment to control red alder.

Treesearch

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...

Covalently crosslinked diels-alder polymer networks.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2011-09-01

This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis ofmore » 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.« less

Berni Alder and Phase Transitions in Two Dimensions

NASA Astrophysics Data System (ADS)

Kosterlitz, J. Michael

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

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

Treesearch

Marshall D. Murray; Richard E. Miller

1986-01-01

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

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

Treesearch

Ernest. Wright

1954-01-01

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

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

PubMed

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

2016-08-25

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

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Ecology payoffs from red alder in southeast Alaska.

Treesearch

Sally Duncan

2004-01-01

Clearcutting has been the primary timber management practice in southeast Alaska forests since large-scale commercial forestry began in the 1950s. The dense, even-aged conifer stands that subsequently develop, however, may have undesirable consequences for some nontimber resources, most notably fish and wildlife.Red alder is frequently established in these...

Using Molecular Genetic Markers to Resolve a Subspecies Boundary: The Northern Boundary of the Southwestern Willow Flycatcher in the Four-Corner States

USGS Publications Warehouse

Paxton, Eben H.; Sogge, Mark K.; Theimer, Tad C.; Girard, Jessica; Keim, Paul

2008-01-01

*Executive Summary* The northern boundary of the endangered Southwestern Willow Flycatcher (Empidonax traillii extimus) is currently approximated as running through southern Colorado and Utah, but the exact placement is uncertain because this subspecies shares a border with the more northern and non-endangered E. t. adastus. To help resolve this issue, we evaluated the geographic distribution of mitochondrial and nuclear DNA by sampling breeding sites across the four-corner states (Arizona, Colorado, New Mexico, and Utah). We found that breeding sites clustered into two major groups generally consistent with the currently designated boundary, with the exception of three sites situated along the current boundary. However, delineating a precise boundary that would separate the two subspecies is made difficult because (1) we found evidence for a region of intergradation along the boundary area, suggesting the boundary is not discreet, and (2) the boundary region is sparsely populated, with too few extant breeding populations to precisely locate a boundary. The boundary region encompasses an area where elevation changes markedly over relatively short distances, with low elevation deserts to the south and more mesic, higher elevation habitats to the north. We hypothesized that latitudinal and elevational differences and their concomitant ecological effects could form an ecological barrier that inhibited gene flow between the subspecies, forming the basis for the subspecies boundary. We modeled changes in geographic patterns of genetic markers as a function of latitude and elevation finding significant support for this relationship. The model was brought into a GIS environment to create multiple subspecies boundaries, with the strength of each predicted boundary evaluated on the basis of how much genetic variation it explained. The candidate boundary that accounted for the most genetic variation was situated generally near the currently recognized subspecies boundary

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

Treesearch

Matthew Bumgardner; Nicholls David; Valerie Barber

2009-01-01

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

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

Treesearch

Matthew Bumgardner; David Nicholls; Valerie Barber

2009-01-01

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

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

PubMed

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

2004-03-19

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

Diels–Alder Exo-Selectivity in Terminal-Substituted Dienes and Dienophiles: Experimental Discoveries and Computational Explanations

PubMed Central

Lam, Yu-hong; Cheong, Paul Ha-Yeon; Mata, José M. Blasco; Stanway, Steven J.; Gouverneur, Véronique; Houk, K. N.

2009-01-01

The Diels–Alder reactions of a series of silyloxydienes and silylated dienes with acyclic α,β-unsaturated ketones and N-acyloxazolidinones have been investigated. The endo/exo stereochemical outcome is strongly influenced by the substitution pattern of the reactants. High exo selectivity was observed when the termini of the diene and the dienophile involved in the shorter forming bond are both substituted, while the normal endo preference was found otherwise. The exo-selective asymmetric Diels–Alder reactions using Evans’ oxazolidinone chiral auxiliary furnished a high level of π-facial selectivity in the same sense as their well-documented endo-selective counterparts. Computational results of these Diels–Alder reactions were consistent with the experimental endo/exo selectivity in most cases. A twist-asynchronous model accounts for the geometries and energies of the computed transition structures. PMID:19154113

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

EPA Science Inventory

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

Gene flow during glacial habitat shifts facilitates character displacement in a Neotropical flycatcher radiation.

PubMed

Chattopadhyay, Balaji; Garg, Kritika M; Gwee, Chyi Yin; Edwards, Scott V; Rheindt, Frank E

2017-09-01

Pleistocene climatic fluctuations are known to be an engine of biotic diversification at higher latitudes, but their impact on highly diverse tropical areas such as the Andes remains less well-documented. Specifically, while periods of global cooling may have led to fragmentation and differentiation at colder latitudes, they may - at the same time - have led to connectivity among insular patches of montane tropical habitat with unknown consequences on diversification. In the present study we utilized ~5.5 kb of DNA sequence data from eight nuclear loci and one mitochondrial gene alongside diagnostic morphological and bioacoustic markers to test the effects of Pleistocene climatic fluctuations on diversification in a complex of Andean tyrant-flycatchers of the genus Elaenia. Population genetic and phylogenetic approaches coupled with coalescent simulations demonstrated disparate levels of gene flow between the taxon chilensis and two parapatric Elaenia taxa predominantly during the last glacial period but not thereafter, possibly on account of downward shifts of montane forest habitat linking the populations of adjacent ridges. Additionally, morphological and bioacoustic analyses revealed a distinct pattern of character displacement in coloration and vocal traits between the two sympatric taxa albiceps and pallatangae, which were characterized by a lack of gene flow. Our study demonstrates that global periods of cooling are likely to have facilitated gene flow among Andean montane Elaenia flycatchers that are more isolated from one another during warm interglacial periods such as the present era. We also identify a hitherto overlooked case of plumage and vocal character displacement, underpinning the complexities of gene flow patterns caused by Pleistocene climate change across the Andes.

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

PubMed

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

2015-05-11

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

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.

PubMed

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.

Species-specific variation in nesting and postfledging resource selection for two forest breeding migrant songbirds.

PubMed

Jenkins, Julianna M A; Thompson, Frank R; Faaborg, John

2017-01-01

Habitat selection is a fundamental component of community ecology, population ecology, and evolutionary biology and can be especially important to species with complex annual habitat requirements, such as migratory birds. Resource preferences on the breeding grounds may change during the postfledging period for migrant songbirds, however, the degree to which selection changes, timing of change, and whether all or only a few species alter their resource use is unclear. We compared resource selection for nest sites and resource selection by postfledging juvenile ovenbirds (Seiurus aurocapilla) and Acadian flycatchers (Empidonax virescens) followed with radio telemetry in Missouri mature forest fragments from 2012-2015. We used Bayesian discrete choice modeling to evaluate support for local vegetation characteristics on the probability of selection for nest sites and locations utilized by different ages of postfledging juveniles. Patterns of resource selection variation were species-specific. Resource selection models indicated that Acadian flycatcher habitat selection criteria were similar for nesting and dependent postfledging juveniles and selection criteria diverged when juveniles became independent from adults. After independence, flycatcher resource selection was more associated with understory foliage density. Ovenbirds differed in selection criteria between the nesting and postfledging periods. Fledgling ovenbirds selected areas with higher densities of understory structure compared to nest sites, and the effect of foliage density on selection increased as juveniles aged and gained independence. The differences observed between two sympatric forest nesting species, in both the timing and degree of change in resource selection criteria over the course of the breeding season, illustrates the importance of considering species-specific traits and postfledging requirements when developing conservation efforts, especially when foraging guilds or prey bases differ

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

PubMed

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

2009-01-01

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

Chemical composition and deer browsing of red alder foliage

Treesearch

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

1978-01-01

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

Retro iminonitroso Diels-Alder reactions: interconversion of nitroso cycloadducts

PubMed Central

Yang, Baiyuan; Lin, Weimin; Krchnak, Viktor; Miller, Marvin J.

2009-01-01

Retro iminonitroso Diels-Alder reactions were investigated in both solution and solid phase. In thermal or Cu(I)-mediated reactions, interconversion of various nitroso cycloadducts occurred in the presence of separate dienes. Up to 99% of conversion was observed. Use of chiral ligands in the Cu(I)-medicated reactions gave new cycloadducts enantioselectively. PMID:20161032

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weinstein, R.D.; Renslo, A.R.; Danheiser, R.L.

1999-04-15

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

SHALTOUT,RAAFAT M.; LOY,DOUGLAS A.; MCCLAIN,MARK D.

1999-12-08

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

A method of site quality evaluation for red alder.

Treesearch

Constance A. Harrington

1986-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

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

PubMed Central

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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.

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

Treesearch

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

2007-01-01

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

Changing climate and the phenological response of great tit and collared flycatcher populations in floodplain forest ecosystems in Central Europe.

PubMed

Bauer, Zdenek; Trnka, Miroslav; Bauerová, Jana; Mozný, Martin; Stepánek, Petr; Bartosová, Lenka; Zalud, Zdenek

2010-01-01

This study is based on 47 years of observations (1961-2007) on two common bird species, the Great Tit (Parus major) and the Collared Flycatcher (Ficedula albicollis), and a dominant tree species in their habitat, the English Oak (Quercus robur). The study took place at four research sites in the Czech Republic located in full-grown, multi-aged floodplain forests with no forestry management. An increase in air temperature over the evaluated period clearly influenced the length of phenological phases. The full foliage date of English Oak has advanced by 8.7 days during the past 47 years. Great Tit and Collared Flycatcher populations have reacted to the changing climate in the same way, with first laying date and mean laying date advancing by between 6.0 and 9.0 days. In all cases, the trends are highly significant and consistent over all sites. Despite the ongoing shift in phenological stages toward the beginning of the year, the change does not appear to have led to mistiming in the trophic food chain. Overall, this study shows almost identical rates of change in egg laying dates for both bird species in all the floodplain forests studied, and these trends are coherent with those of English Oak and peak herbivorous caterpillar activity.

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

PubMed

Nandi, Sisir; Monesi, Alessandro; Drgan, Viktor; Merzel, Franci; Novič, Marjana

2013-10-30

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

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

Treesearch

Carl M. Berntsen

1962-01-01

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

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

PubMed

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

2004-01-21

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heilman, P.; Stettler, R.F.

1985-01-01

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

Enhancing the Scope of the Diels-Alder Reaction through Isonitrile Chemistry: Emergence of a New Class of Acyl-Activated Dienophiles

PubMed Central

Townsend, Steven D.; Wu, Xiangyang; Danishefsky, Samuel J.

2012-01-01

α,β-Unsaturated imides, formylated at the nitrogen atom, comprise a new and valuable family of dienophiles for servicing Diels-Alder reactions. These systems are assembled through extension of recently discovered isonitrile chemistry to the domain of α,β-unsaturated acids. Cycloadditions are facilitated by Et2AlCl, presumably via chelation between the two carbonyl groups of the N-formyl amide. Applications of the isonitrile/Diels-Alder logic to the IMDA reaction, as well as methodologies to modify the N-formyl amide of the resultant cycloaddition product, are described. It is expected that this easily executed chemistry will provide a significant enhancement for application of Diels-Alder reactions to many synthetic targets. PMID:22708980

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

PubMed Central

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

2015-01-01

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

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

Treesearch

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

1990-01-01

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

Enantioselective Diels-Alder reactions of unsaturated beta-ketoesters catalyzed by chiral ruthenium PNNP complexes.

PubMed

Schotes, Christoph; Mezzetti, Antonio

2011-01-01

We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt2)2(PNNP)](PF6)2, formed in situ from [RuCl2,(PNNP)] and (Et3O)PF6 (2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

A microwave assisted intramolecular-furan-Diels-Alder approach to 4-substituted indoles.

PubMed

Petronijevic, Filip; Timmons, Cody; Cuzzupe, Anthony; Wipf, Peter

2009-01-07

The key steps of a versatile new protocol for the convergent synthesis of 3,4-disubstituted indoles are the addition of an alpha-lithiated alkylaminofuran to a carbonyl compound, a microwave-accelerated intramolecular Diels-Alder cycloaddition and an in situ double aromatization reaction.

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

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

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

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

Treesearch

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

2006-01-01

Factors (riparian stand condition, management regimes, and channel properties) affecting distributions of wood, detritus (leaves and branches), and sediment were examined in headwater streams draining young-growth red alder (Alnus rubra Bong.)-conifer riparian forests (40 years old) in southeast Alaska. More riparian red alder were found along...

A microwave assisted intramolecular-furan-Diels–Alder approach to 4-substituted indoles†

PubMed Central

Petronijevic, Filip; Timmons, Cody; Cuzzupe, Anthony; Wipf, Peter

2009-01-01

The key steps of a versatile new protocol for the convergent synthesis of 3,4-disubstituted indoles are the addition of an α-lithiated alkylaminofuran to a carbonyl compound, a microwave-accelerated intramolecular Diels–Alder cycloaddition and an in situ double aromatization reaction. PMID:19082013

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

Treesearch

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

2005-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kraus, G.A.; Li, J.; Gordon, M.S.

1993-06-30

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

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

Treesearch

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

2006-01-01

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

Greenhouse germination trials of pelletized western redcedar and red alder seeds

Treesearch

Nabil Khadduri

2007-01-01

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

The reliability of determining age of red alder by ring counts

Treesearch

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

1978-01-01

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

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

NASA Astrophysics Data System (ADS)

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.

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

Treesearch

Mark E. Schultz; Toni L. De Santo

2008-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

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

PubMed Central

Gordillo, Ruth; Houk, K. N.

2011-01-01

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

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

Treesearch

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

2005-01-01

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

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

NASA Astrophysics Data System (ADS)

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

Enzymatic activity and partial purification of solanapyrone synthase: first enzyme catalyzing Diels-Alder reaction.

PubMed

Katayama, K; Kobayashi, T; Oikawa, H; Honma, M; Ichihara, A

1998-05-19

In cell-free extracts of Alternaria solani, an enzymatic activity converting prosolanapyrone II to solanapyrones A and D via oxidation and subsequent Diels-Alder reaction has been found. Chromatography with DEAE-Sepharose provided two active fractions, pools 1 and 2. The former fraction converted prosolanapyrone II to solanapyrones A and D in a ratio of 2.2:1 with optical purities of 99% and 45% ee, respectively. The latter fraction did so in a ratio of 7.6:1 with 99% and nearly 0% ee, respectively. The enzyme partially purified from pool 2 native molecular weight of 40-62 kD and a pl of 4.25. The high reactivity of prosolanapyrone III in aqueous solution and the chromatographic behavior of the enzyme in pool 2 suggest that a single enzyme catalyzes both the oxidation and Diels-Alder reaction.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Diels-Alder reactions onto fluorinated and hydrogenated graphene

NASA Astrophysics Data System (ADS)

Denis, Pablo A.

2017-09-01

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

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

PubMed Central

Flores, Beatris; Molinski, Tadeusz F.

2011-01-01

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

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

PubMed

Lee, Jihoon; Panek, James S

2014-06-20

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Z.; Espenson, J.H.

1997-04-16

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

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

NASA Astrophysics Data System (ADS)

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.

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

EPA Science Inventory

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

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

Treesearch

Krishna Poudel; Hailemariam Temesgen

2016-01-01

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

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

USGS Publications Warehouse

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

2006-01-01

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

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

PubMed

Xu, Jie; Wipf, Peter

2017-08-30

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

Ring-rearrangement metathesis of nitroso Diels-Alder cycloadducts.

PubMed

Vincent, Guillaume; Kouklovsky, Cyrille

2011-03-01

Strained nitroso Diels-Alder bicyclo[2.2.1] or [2.2.2] adducts functionalized with alkene side chains of diverse length undergo a ring-rearrangement metathesis process with external alkenes and Grubbs II or Hoveyda-Grubbs II ruthenium catalysts, under microwave irradiation or classical heating, to deliver cis-fused bicycles of various ring sizes, which contain a N-O bond. These scaffolds are of synthetic relevance for the generation of molecular diversity and to the total synthesis of alkaloids. The observation of unexpected reactions, such as epimerization or one-carbon homologation of the alkene side chain, is also reported. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

Fadel, Salah; Hajbi, Youssef; Khouili, Mostafa; Lazar, Said; Suzenet, Franck; Guillaumet, Gérald

2014-01-01

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

The Mouse-colored Tyrannulet (Phaeomyias murina) is a species complex that includes the Cocos Flycatcher (Nesotriccus ridgwayi), an island form that underwent a population bottleneck.

PubMed

Zucker, Marc R; Harvey, Michael G; Oswald, Jessica A; Cuervo, Andrés; Derryberry, Elizabeth; Brumfield, Robb T

2016-08-01

Simultaneous examination of evolutionary history in island forms and closely related mainland relatives can provide reciprocal insight into the evolution of island and mainland faunas. The Cocos Flycatcher (Nesotriccus ridgwayi) is a small tyrant flycatcher (Tyrannidae) endemic to Cocos Island, an oceanic island in the eastern Pacific Ocean. We first established its close relationship to the mainland species Mouse-colored Tyrannulet (Phaeomyias murina) using a phylogeny from genome-wide ultraconserved elements and exons. We then used mitochondrial DNA to explore the relationships between Nesotriccus and Phaeomyias populations from across its distribution in Central and South America. We found that Nesotriccus is nested within the Phaeomyias evolutionary tree, and that Phaeomyias represents a complex of at least four evolutionarily distinct species that differ in plumage, voice, and habitat association. Nesotriccus underwent a population bottleneck subsequent to its divergence from Central American and northern South American Phaeomyias populations in the middle Pleistocene. The 46 UCE loci containing alleles that are fixed between the two species are widely distributed across the genome, which suggests that selective or neutral processes responsible for divergence have occurred genome-wide. Overall, our simultaneous examination of Phaeomyias and Nesotriccus revealed divergent levels of genetic diversity and evolutionary histories between island and mainland forms. Copyright © 2016 Elsevier Inc. All rights reserved.

The influence of reaction conditions on the Diels-Alder cycloadditions of 2-thio-3-chloroacrylamides; investigation of thermal, catalytic and microwave conditions.

PubMed

Kissane, Marie; Lynch, Denis; Chopra, Jay; Lawrence, Simon E; Maguire, Anita R

2010-12-21

The Diels-Alder cycloadditions of cyclopentadiene and 2,3-dimethyl-1,3-butadiene to a range of 2-thio-3-chloroacrylamides under thermal, catalytic and microwave conditions is described. The influence of reaction conditions on the outcome of the cycloadditions, in particular the stereoselectivity and reaction efficiency, is discussed. While the cycloadditions have been attempted at the sulfide, sulfoxide and sulfone levels of oxidation, use of the sulfoxide derivatives is clearly beneficial for stereoselective construction of Diels-Alder cycloadducts.

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

Treesearch

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

2004-01-01

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

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

PubMed Central

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

2014-01-01

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

Dual function catalysts. Dehydrogenation and asymmetric intramolecular Diels-Alder cycloaddition of N-hydroxy formate esters and hydroxamic acids: evidence for a ruthenium-acylnitroso intermediate.

PubMed

Chow, Chun P; Shea, Kenneth J

2005-03-23

The chiral ruthenium salen complex, 13b, functions as an efficient catalyst for the sequential oxidation and asymmetric Diels-Alder cycloaddition of hydroxamic acids and N-hydroxy formate esters. This result provides evidence for the formation of a ruthenium-nitroso formate (acyl nitroso) intermediate. The Diels-Alder precursors are prepared from simple building blocks, and the cycloadducts, bridged oxazinolactams, can serve as useful intermediates in organic synthesis.

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

Treesearch

C. C. Gerhards

1964-01-01

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

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

ERIC Educational Resources Information Center

Rowley, Christopher N.; Woo, Tom K.

2009-01-01

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

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

EPA Science Inventory

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

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

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

PubMed Central

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

2015-01-01

Diels-Alder reactions of five-membered heterocycles containing one heteroatom with an N-arylmaleimide were studied. Cycloaddition of 2,5-dimethylfuran (4) with 2-(4-methylphenyl)maleimide (3) in toluene at 60 °C gave bicyclic adduct 5. Cycloadditions of 3 with 2,5-dimethylthiophene (11) and 1,2,5-trimethylpyrrole (14) were also studied. Interestingly, the bicyclic compound 5 cleanly rearranged, with loss of water, when treated with p-toluenesulfonic acid in toluene at 80 °C to give 4,7-dimethyl-2-p-tolylisoindoline-1,3-dione (6). PMID:25838605

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

Treesearch

M.A. Radwan

1987-01-01

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

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

Treesearch

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

2006-01-01

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

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

Treesearch

Kevin C. Peeler; Dean S. DeBell

1987-01-01

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

Multicatalytic asymmetric synthesis of complex tetrahydrocarbazoles via a Diels-Alder/benzoin reaction sequence.

PubMed

Liu, Yankai; Nappi, Manuel; Escudero-Adán, Eduardo C; Melchiorre, Paolo

2012-03-02

Expanding upon the recently developed aminocatalytic asymmetric indole-2,3-quinodimethane strategy, a straightforward synthesis of structurally and stereochemically complex tetrahydrocarbazoles has been devised. The chemistry's complexity-generating power was further harnessed by designing a multicatalytic, one-pot Diels-Alder/benzoin reaction sequence to stereoselectively access trans-fused tetracyclic indole-based compounds having four stereogenic centers with very high fidelity. © 2012 American Chemical Society

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

Treesearch

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

2005-01-01

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

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

PubMed

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

2013-08-14

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

Seasonal variation in concentrations of fiber, crude protein, and phenolic compounds in leaves of red alder (Alnus rubra): Nutritional implications for cervids

USGS Publications Warehouse

Gonzalez-Hernandez, M. P.; Starkey, Edward E.; Karchesy, J.

2000-01-01

We sought to determine whether changes in chemical composition could be a factor in increased utilization of red alder (Alnus rubra) by the two cervids, the Columbian black-tailed deer (Odocoileus hemionus columbianus) and Roosevelt elk (Cervus elaphus roosevelti), during the fall in parts of the Douglas fir region of the Pacific Northwest. We found that concentrations and astringency of phenolic compounds decreased from spring through fall, while crude protein content remained high. We conclude that red alder leaves provide a significant source of digestible protein for cervids during fall, when availability of nutrients in most forage species is generally declining.

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

Treesearch

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

2006-01-01

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

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

USDA-ARS?s Scientific Manuscript database

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

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

PubMed

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

2009-01-01

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

Enhancing Zeolite Performance by Catalyst Shaping in a Mesoscale Continuous-Flow Diels-Alder Process.

PubMed

Seghers, Sofie; Lefevere, Jasper; Mullens, Steven; De Vylder, Anton; Thybaut, Joris W; Stevens, Christian V

2018-03-26

In contrast to most lab-scale batch procedures, a continuous-flow implementation requires a thorough consideration of the solid catalyst design. In a previous study, irregular zeolite pellets were applied in a miniaturized continuous-flow reactor for the Diels-Alder reaction in the construction of norbornene scaffolds. After having faced the challenges of continuous operation, the aim of this study is to exploit catalyst structuring. To this end, microspheres with high uniformity and various sphere diameters were synthesized according to the vibrational droplet coagulation method. The influence of the use of these novel zeolite shapes in a mesoscale continuous-flow Diels-Alder process of cyclopentadiene and methyl acrylate is discussed. An impressive enhancement of catalyst lifetime is demonstrated, as even after a doubled process time of 14 h, the microspheres still exceeded the conversion after 7 h when using zeolite pellets by 30 %. A dual reason is found for this beneficial impact of catalyst shaping. The significant improvement in catalyst longevity can be attributed to the interplay of the chemical composition and the porosity structure of the microspheres. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

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

2013-01-01

Using femtosecond time resolved degenerate pump-probe mass spectrometry coupled with simple linearly chirped frequency modulated pulse, we elucidate that the dynamics of retro-Diels-Alder-like reaction of diclopentadiene (DCPD) to cyclopentadiene (CPD) in supersonic molecular beam occurs in ultrafast time scale. Negatively chirped pulse enhances the ion yield of CPD, as compared to positively chirped pulse. This indicates that by changing the frequency (chirp) of the laser pulse we can control the ion yield of a chemical reaction. PMID:23814449

Effects of reintroduced beaver (Castor canadensis) on riparian bird community structure along the upper San Pedro River, southeastern Arizona and northern Sonora, Mexico

USGS Publications Warehouse

Johnson, Glenn E.; van Riper, Charles

2014-01-01

Chapter 1.—We measured bird abundance and richness along the upper San Pedro River in 2005 and 2006, in order to document how beavers (Castor canadensis) may act as ecosystem engineers after their reintroduction to a desert riparian area in the Southwestern United States. In areas where beavers colonized, we found higher bird abundance and richness of bird groups, such as all breeding birds, insectivorous birds, and riparian specialists, and higher relative abundance of many individual species—including several avian species of conservation concern. Chapter 2.—We conducted bird surveys in riparian areas along the upper San Pedro River in southeastern Arizona (United States) and northern Sonora (Mexico) in order to describe factors influencing bird community dynamics and the distribution and abundance of species, particularly those of conservation concern. These surveys were also used to document the effects of the ecosystem-altering activities of a recently reintroduced beavers (Castor canadensis). Chapter 3.—We reviewed Southwestern Willow Flycatcher (Empidonax traillii extimus) nest records and investigated the potential for future breeding along the upper San Pedro River in southeastern Arizona, where in July 2005 we encountered the southernmost verifiable nest attempt for the species. Continued conservation and management of the area’s riparian vegetation and surface water has potential to contribute additional breeding sites for this endangered Willow Flycatcher subspecies. Given the nest record along the upper San Pedro River and the presence of high-density breeding sites to the north, the native cottonwood-willow forests of the upper San Pedro River could become increasingly important to E. t. extimus recovery, especially considering the anticipated effect of the tamarisk leaf beetle (Diorhabda carinulata) on riparian habitat north of the region.

Heavy metals and metalloids in egg contents and eggshells of passerine birds from Arizona

USGS Publications Warehouse

Mora, Miguel A.

2003-01-01

Concentrations of inorganic elements were determined in eggs of passerine birds including the endangered southwestern willow flycatcher (Empidonax traillii extimus) from four regions in Arizona. The main aim of the study was to determine the distribution of metals in egg contents and eggshells, with emphasis on the deposition of Sr in eggshells. Seventy eggs of 11 passerine species were collected at four nesting locations during 2000. Aluminum, Ba, Cr, Cu, Mn, Se, Sr, and Zn, were detected primarily in egg contents of all bird species. Arsenic, Ni, Pb, and V were detected primarily in eggshells. A proportion of most inorganic elements accumulated in the eggshell. Concentrations of Ba, Cu, Mn, Se, Sr, and Zn in egg contents and As, Ba, Cu, and V in eggshells of yellow-breasted chats (Icteria virens) were similar among locations. However, concentrations of Mn, Ni, Sr, and Zn in eggshells were significant different among locations. Except for Cu, Mn, Se, and Zn, concentrations of inorganic elements were 2–35 times greater in eggshells than in eggs. Most concentrations of metals and metalloids in eggs and eggshells of all the bird species were below levels known to affect reproduction or that have other deleterious effects. However, I found somewhat elevated concentrations of Sr in eggshells (highest mean=1505 μg/g dw, n=3) of yellow-breasted chats and willow flycatchers, and in egg contents of yellow warblers (Dendroica petechia) and song sparrows (Melospiza melodia). Whether current observed concentrations of Sr in eggshells are affecting nesting birds in Arizona remains to be determined. Strontium and other metals could be associated with lower hatching success in some areas. This study shows that a proportion of many inorganic elements accumulates in the eggshell and that the potential effects on the proper structure and functioning of the eggshell should not be ignored.

Polygyny and its fitness consequences for primary and secondary female pied flycatchers

PubMed Central

Huk, Thomas; Winkel, Wolfgang

2006-01-01

In polygynous species with biparental care, the amount of paternal support often varies considerably. In the pied flycatcher (Ficedula hypoleuca), females mated with monogamous males receive more male assistance during the nestling phase than females mated with bigynous males, as the latter have to share their mates with another female. Bigynous males, however, give more support to their primary broods than to their secondary broods. Using a long-term dataset (31 years), the present study revealed that direct reproductive success, i.e. number of fledglings, was lower in females that mated with bigynous males, especially in secondary broods without male assistance, than in females that mated with monogamous males. Secondary broods with male assistance were more affected than primary broods. Female survival was independent of mating status. In primary broods, a delayed compensation for inferior direct reproductive success was found in terms of the number of grandoffspring, a phenomenon that did not occur in secondary broods. Delayed compensation in primary broods refers to indirect effects, i.e. good genes. According to the sexy son hypothesis, genetically superior (i.e. sexy) males may have sons with a higher number of broods belonging to a polygynous breeding status than do sons from broods with a monogamous father. This was indeed the case for sons descending from primary broods, but not for sons descending from secondary broods. PMID:16769641

Trade-offs between sexual advertisement and immune function in the pied flycatcher (Ficedula hypoleuca).

PubMed

Kilpimaa, Janne; Alatalo, Rauno V; Siitari, Heli

2004-02-07

Good genes models of sexual selection assume that sexual advertisement is costly and thus the level of advertisement honestly reveals heritable viability. Recently it has been suggested that an important cost of sexual advertisement might be impairment of the functioning of the immune system. In this field experiment we investigated the possible trade-offs between immune function and sexual advertisement by manipulating both mating effort and activity of immune defence in male pied flycatchers. Mating effort was increased in a non-arbitrary manner by removing females from mated males during nest building. Widowed males sustained higher haematocrit levels than control males and showed higher expression of forehead patch height, suggesting that manipulation succeeded in increasing mating effort. Males that were experimentally forced to increase mating effort had reduced humoral immune responsiveness compared with control males. In addition, experimental activation of immune defence by vaccination with novel antigens reduced the expression of male ornament dimensions. To conclude, our results indicate that causality behind the trade-off between immune function and sexual advertisement may work in both directions: sexual activity suppresses immune function but immune challenge also reduces sexual advertisement.

Trade-offs between sexual advertisement and immune function in the pied flycatcher (Ficedula hypoleuca).

PubMed Central

Kilpimaa, Janne; Alatalo, Rauno V.; Siitari, Heli

2004-01-01

Good genes models of sexual selection assume that sexual advertisement is costly and thus the level of advertisement honestly reveals heritable viability. Recently it has been suggested that an important cost of sexual advertisement might be impairment of the functioning of the immune system. In this field experiment we investigated the possible trade-offs between immune function and sexual advertisement by manipulating both mating effort and activity of immune defence in male pied flycatchers. Mating effort was increased in a non-arbitrary manner by removing females from mated males during nest building. Widowed males sustained higher haematocrit levels than control males and showed higher expression of forehead patch height, suggesting that manipulation succeeded in increasing mating effort. Males that were experimentally forced to increase mating effort had reduced humoral immune responsiveness compared with control males. In addition, experimental activation of immune defence by vaccination with novel antigens reduced the expression of male ornament dimensions. To conclude, our results indicate that causality behind the trade-off between immune function and sexual advertisement may work in both directions: sexual activity suppresses immune function but immune challenge also reduces sexual advertisement. PMID:15058434

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

EPA Science Inventory

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

Low genetic variance in the duration of the incubation period in a collared flycatcher (Ficedula albicollis) population.

PubMed

Husby, Arild; Gustafsson, Lars; Qvarnström, Anna

2012-01-01

The avian incubation period is associated with high energetic costs and mortality risks suggesting that there should be strong selection to reduce the duration to the minimum required for normal offspring development. Although there is much variation in the duration of the incubation period across species, there is also variation within species. It is necessary to estimate to what extent this variation is genetically determined if we want to predict the evolutionary potential of this trait. Here we use a long-term study of collared flycatchers to examine the genetic basis of variation in incubation duration. We demonstrate limited genetic variance as reflected in the low and nonsignificant additive genetic variance, with a corresponding heritability of 0.04 and coefficient of additive genetic variance of 2.16. Any selection acting on incubation duration will therefore be inefficient. To our knowledge, this is the first time heritability of incubation duration has been estimated in a natural bird population. © 2011 by The University of Chicago.

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

Treesearch

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

ERIC Educational Resources Information Center

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

2010-01-01

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

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

PubMed Central

Kramer, Carsten S

2013-01-01

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

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

PubMed Central

Kocsis, Laura S.; Benedetti, Erica

2012-01-01

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

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

PubMed

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.

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

Treesearch

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

1983-01-01

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

A test of the "sexy son" hypothesis: sons of polygynous collared flycatchers do not inherit their fathers' mating status.

PubMed

Gustafsson, Lars; Qvarnström, Anna

2006-02-01

According to the original "sexy son" hypothesis, a female may benefit from pairing with an already-mated male despite a reduction in fecundity because her sons inherit their father's attractiveness. We used data from a long-term study of collared flycatchers (Ficedula albicollis) collected during 24 years to test this prediction. Our results show that the sons of polygynously mated females fledged in poor condition and therefore did not inherit their father's large forehead patch (a condition-dependent display trait) or mating status. From the female's perspective, polygynous pairing resulted in fewer recruited grandchildren than did a monogamous pairing. The reproductive value of sons did not outweigh the fecundity costs of polygyny because the low paternal care reduced the attractiveness of sons. When there are long-lasting parental effects on offspring attractiveness, costs of polygyny may include the production of nonsexy sons.

On the theory of Brownian motion with the Alder-Wainwright effect

NASA Astrophysics Data System (ADS)

Okabe, Yasunori

1986-12-01

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, we 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. We are interested in whether or not it can be measured experimentally.

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

Treesearch

T.A. Hanley; J.C. Barnard

1998-01-01

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

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

ERIC Educational Resources Information Center

Baar, Marsha R.; Wustholz, Kristin

2005-01-01

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

Detection of transient radical cations in electron transfer-initiated Diels-Alder reactions by electrospray ionization mass spectrometry.

PubMed

Fürmeier, Sven; Metzger, Jürgen O

2004-11-10

The coupling of a simple microreactor to an atmospheric pressure ion source, such as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI), allows the investigation of reactions in solution by mass spectrometry. The tris(p-bromophenyl)aminium hexachloroantimonate (1(*)(+)SbCl(6)(-))-initiated reactions of phenylvinylsulfide (2) and cyclopentadiene (3) and of trans-anethole (5) and isoprene (6) and the dimerization of 1,3-cyclohexadiene (8) to give the respective Diels-Alder products were studied. These preparatively interesting reactions proceed as radical cation chain reactions via the transient radical cations of the respective dienophiles and of the respective Diels-Alder addition products. These radical cations could be detected directly and characterized unambiguously in the reacting solution by ESI-MS-MS. The identity was confirmed by comparison with MS-MS spectra of the authentic radical cations obtained by APCI-MS and by CID experiments of the corresponding molecular ions generated by EI-MS. In addition, substrates and products could be monitored easily in the reacting solution by APCI-MS.

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

PubMed

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.

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

PubMed

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

2015-11-15

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

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

PubMed Central

Bodnar, Brian S.

2014-01-01

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

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

Treesearch

Dean S. DeBell; Constance A. Harrington

2002-01-01

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

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

PubMed Central

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

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. PMID:29507637

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

Treesearch

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.

PubMed

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

2010-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-05-01

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

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

ERIC Educational Resources Information Center

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

2015-01-01

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

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

PubMed Central

Callender, Katrina L.; Roy, Sébastien; Khasa, Damase P.; Whyte, Lyle G.; Greer, Charles W.

2016-01-01

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

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

PubMed

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

2015-11-01

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

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

Treesearch

Bernard T. Bormann

1985-01-01

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

L-Pyroglutamic Sulphonamide as Hydrogen-Bonding Organocatalyst: Enantioselective Diels-Alder Cyclization to Construct Carbazolespirooxindoles.

PubMed

Ren, Ji-Wei; Wang, Jing; Xiao, Jun-An; Li, Jun; Xiang, Hao-Yue; Chen, Xiao-Qing; Yang, Hua

2017-06-16

Hydrogen-bonding organocatalysts L-pyroglutamic sulphonamides were readily synthesized for the first time by fully exploiting the potentials of L-pyroglutamic acid. The newly designed catalyst was successfully applied in catalyzing asymmetric Diels-Alder cyclization of methyleneindolinones with 2-vinyl-1H-indoles to efficiently assemble carbazolespirooxindoles in excellent stereoselectivity (up to 99% ee, >20:1 dr) and yields (up to 99%). Mechanistic studies disclosed that the well-designed hydrogen-bonding modes between L-pyroglutamic sulphonamide and substrates were crucial for stereocontrol in the cyclization.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, R.L.; Glaeser, R.; Bush, D.

1999-11-01

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

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

PubMed

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

2015-01-01

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 nitrosocarbonyl hetero-Diels-Alder reaction as a useful tool for organic syntheses.

PubMed

Bodnar, Brian S; Miller, Marvin J

2011-06-14

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. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring the influence of Diels-Alder linker length on photothermal molecule release from gold nanorods.

PubMed

Vetterlein, Claudia; Vásquez, Rodrigo; Bolaños, Karen; Acosta, Gerardo A; Guzman, Fanny; Albericio, Fernando; Celis, Freddy; Campos, Marcelo; Kogan, Marcelo J; Araya, Eyleen

2018-06-01

We studied the photothermal release of carboxyfluorescein (CF) linked to the gold surface of gold nanorods (GNRs) by two Diels-Alder adducts of different lengths (n = 4 and n = 9). The functionalized GNRs were irradiated with infrared light to produce photothermal release of CF by a retro-Diels-Alder reaction. The adducts were chemisorbed on the GNRs and the functionalized nanoparticles were characterized by UV-vis, DLS, zeta potential and Raman and surface-enhanced Raman spectroscopy (SERS). On the basis of the degree of nanoparticle functionalization and the SERS results, we inferred the orientation of CF on the surface of the gold nanoparticle. Moreover, we determined the photothermal release profiles of CF from the gold surface by laser irradiation. The release was faster for the longer linker (n = 9). SERS revealed that, for the shorter linker (n = 4), molecules are oriented perpendicularly with respect to the gold surface, thereby maintaining the CF far from the surface. In contrast, the longer linker was observed to be tilted, thus maintaining CF close to the gold surface and therefore potentially favoring the photothermal transfer of energy. These results are relevant for the future development of the spatial and temporal controlled release of drugs by means of gold nanoparticles. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed

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.

PubMed

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.

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

Treesearch

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

2012-01-01

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

Avian habitat relationships in pinyon-juniper woodland

USGS Publications Warehouse

Sedgwick, James A.

1987-01-01

Habitat relationships of breeding birds were examined in northwestern Colorado in pinyon-juniper (Pinus edulis-Juniperus osteosperma) woodland and in openings where most overstory trees had been knocked down by anchor chaining. Vegetation characteristics and physical habitat features were measured in 233 0.04-ha circular plots around singing males of 13 species of birds from 15 May to 15 July 1980. Thirteen-group discriminant function analysis ordinated bird species along three habitat dimensions described by (1) canopy height; (2) slope, shrub size, and shrub species diversity; and (3) percentage canopy cover, large tree density, distance from a habitat edge, litter cover, and green cover. Woodland, open-area, and intermediate edge species were clearly segregated along the first discriminant axis, and species' associations with shrubs, inclination, ground cover, and edges were revealed by the ordinations along the second and third discriminant axes. Two-group discriminant analyses comparing occupied and available plots identified additional and more specific habitat associations. For example, Hermit Thrushes (Catharus guttatus) were associated with mature forested habitats and forest interiors, Virginia's Warblers (Vermivora virginiae) favored steep, oak-covered draws, Rock Wrens (Salpinctes obsoletus) selected areas where percentage log cover and small tree density were high, and Dusky Flycatchers (Empidonax oberholseri) preferred shrubby slopes with scattered large trees near woodland edges.

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

DOE PAGES

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

2015-11-28

Sulfonated diels alder poly(phenylene) (SDAPP), alternative aromatic hydrocarbon membranes for vanadium redox flow batteries (VRFBs) are characterized using electron paramagnetic resonance (EPR). Membranes soaked in sulfuric acid and vanadyl sulfate are analyzed to determine the membrane environment in which the vanadyl ion (VO 2+) diffuses in the membranes. These results are compared to Nafion 117 membranes. In contrast to Nafion, the VO 2+ in SDAPP membranes exists in two different environments. The results of analysis of rotational diffusion determined from fits the EPR spectral lineshapes in comparison with previously reported permeation studies and measurements of partitioning functions reported here suggestmore » that the diffusion pathways in SDAPP are very different than in Nafion.« less

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

ERIC Educational Resources Information Center

Celius, Tevye C.

2010-01-01

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

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

PubMed

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.

Diels-Alder cycloadditions by microwave-assisted, continuous flow organic synthesis (MACOS): the role of metal films in the flow tube.

PubMed

Shore, Gjergji; Organ, Michael G

2008-02-21

Thin Pd films have been deposited on the inside of capillary-sized tubes through which compounds undergoing Diels-Alder reactions have been flowed while being heated with microwave irradiation; dramatic rate accelerations are observed in the presence of the film, which has been shown to play both a heating and catalytic role.

78 FR 65843 - General Provisions; Revised List of Migratory Birds

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-01

..., 2008, 2009, and 2010), on matters of taxonomy, nomenclature, and the sequence of species and other... Flycatcher, Ficedula albicilla (AOU 1982, 1983, 1998, 2006); Dark-sided Flycatcher, Muscicapa sibirica (AOU...). Mugimaki Flycatcher, Ficedula mugimaki (1). Taiga Flycatcher, Ficedula albicilla (1). Dark-sided Flycatcher...

Foveolar Müller Cells of the Pied Flycatcher: Morphology and Distribution of Intermediate Filaments Regarding Cell Transparency.

PubMed

Zueva, Lidia; Golubeva, Tatiana; Korneeva, Elena; Makarov, Vladimir; Khmelinskii, Igor; Inyushin, Mikhail

2016-04-01

Specialized intermediate filaments (IFs) have critical importance for the clearness and uncommon transparency of vertebrate lens fiber cells, although the physical mechanisms involved are poorly understood. Recently, an unusual low-scattering light transport was also described in retinal Müller cells. Exploring the function of IFs in Müller cells, we have studied the morphology and distribution pattern of IFs and other cytoskeletal filaments inside the Müller cell main processes in the foveolar part of the avian (pied flycatcher) retina. We found that some IFs surrounded by globular nanoparticles (that we suggest are crystallines) are present in almost every part of the Müller cells that span the retina, including the microvilli. Unlike IFs implicated in the mechanical architecture of the cell, these IFs are not connected to any specific cellular membranes. Instead, they are organized into bundles, passing inside the cell from the endfeet to the photoreceptor, following the geometry of the processes, and repeatedly circumventing numerous obstacles. We believe that the presently reported data effectively confirm that the model of nanooptical channels built of the IFs may provide a viable explanation of Müller cell transparency.

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

Treesearch

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

2000-01-01

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

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

PubMed

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

2012-12-01

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

Divergent patterns of age-dependence in ornamental and reproductive traits in the collared flycatcher.

PubMed

Evans, Simon R; Gustafsson, Lars; Sheldon, Ben C

2011-06-01

Sexual ornaments are predicted to honestly signal individual condition. We might therefore expect ornament expression to show a senescent decline, in parallel with late-life deterioration of other characters. Conversely, life-history theory predicts the reduced residual reproductive value of older individuals will favor increased investment in sexually attractive traits. Using a 25-year dataset of more than 5000 records of breeding collared flycatchers (Ficedula albicollis) of known age, we quantify cross-sectional patterns of age-dependence in ornamental plumage traits and report long-term declines in expression that mask highly significant positive age-dependency. We partition this population-level age-dependency into its between- and within-individual components and show expression of ornamental white plumage patches exhibits within-individual increases with age in both sexes, consistent with life-history theory. For males, ornament expression also covaries with life span, such that, within a cohort, ornamentation indicates survival. Finally, we compared longitudinal age-dependency of reproductive traits and ornamental traits in both sexes, to assess whether these two trait types exhibit similar age-dependency. These analyses revealed contrasting patterns: reproductive traits showed within-individual declines in late-life females consistent with senescence; ornamental traits showed the opposite pattern in both males and females. Hence, our results for both sexes suggest that age-dependent ornament expression is consistent with life-history models of optimal signaling and, unlike reproductive traits, proof against senescence. © 2011 The Author(s). Evolution© 2011 The Society for the Study of Evolution.

Nutritional correlates and mate acquisition role of multiple sexual traits in male collared flycatchers

NASA Astrophysics Data System (ADS)

Hegyi, Gergely; Szöllősi, Eszter; Jenni-Eiermann, Susanne; Török, János; Eens, Marcel; Garamszegi, László Zsolt

2010-06-01

The information content of a sexual signal may predict its importance in a multiple signal system. Many studies have correlated sexual signal expression with the absolute levels of nutrient reserves. In contrast, the changes of nutrient reserves associated with signal expression are largely unknown in the wild due to technical limitations although they are important determinants of signal information content. We compared two visual and eight acoustic sexual traits in male collared flycatchers to see whether the nutritional correlates of expression predict the role of the signal in sexual selection. We used single point assays of plasma lipid metabolites to estimate short-term changes in nutritional state in relation to sexual trait expression during courtship. As a measure of sexual selection, we estimated the relationship with pairing latency after arrival in a 4-year dataset. Males which found a mate rapidly were characterized by large wing and forehead patches, but small song strophe complexity and small figure repertoire size. Traits more strongly related to pairing latency were also more closely related to changes in nutrient reserves. This indicates a link between signal role and information content. Small wing patches and, surprisingly, complex songs seemed to indicate poor phenotypic quality and were apparently disfavoured at mate acquisition in our population. Future studies of the information content of sexual traits, especially dynamic traits such as song, may benefit from the use of plasma metabolite profiles as non-invasive indicators of short-term changes in body condition.

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

ERIC Educational Resources Information Center

Sauvage, Xavier; Delaude, Lionel

2008-01-01

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

High-speed microwave-promoted hetero-Diels-Alder reactions of 2(1H)-pyrazinones in ionic liquid doped solvents.

PubMed

Van Der Eycken, Erik; Appukkuttan, Prasad; De Borggraeve, Wim; Dehaen, Wim; Dallinger, Doris; Kappe, C Oliver

2002-11-01

Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed.

Diels-Alder Cycloadditions: A MORE Experiment in the Organic Laboratory Including a Diene Identification Exercise Involving NMR Spectroscopy and Molecular Modeling

ERIC Educational Resources Information Center

Shaw, Roosevelt; Severin, Ashika; Balfour, Miguel; Nettles, Columbus

2005-01-01

Two Diels-Alder reactions are described that are suitable for a MORE (microwave-induced organic reaction enhanced) experiment in the organic chemistry laboratory course. A second experiment in which the splitting patterns of the vinyl protons in the nuclear magnetic resonance (NMR) spectra of two MORE adducts are used in conjunction with molecular…

Domino Acylation/Diels-Alder Synthesis of N-Alkyl-octahydroisoquinolin-1-one-8-carboxylic Acids under Low-Solvent Conditions.

PubMed

Slauson, Stephen R; Pemberton, Ryan; Ghosh, Partha; Tantillo, Dean J; Aubé, Jeffrey

2015-05-15

The development of the domino reaction between an aminoethyl-substituted diene and maleic anhydride to afford an N-substituted octahydroisoquinolin-1-one is described. A typical procedure involves the treatment of a 1-aminoethyl-substituted butadiene with maleic anhydride at 0 °C to room temperature for 20 min under low-solvent conditions, which affords a series of isoquinolinone carboxylic acids in moderate to excellent yields. NMR monitoring suggested that the reaction proceeded via an initial acylation step followed by an intramolecular Diels-Alder reaction. For the latter step, a significant rate difference was observed depending on whether the amino group was substituted by a phenyl or an alkyl (usually benzyl) substituent, with the former noted by NMR to be substantially slower. The Diels-Alder step was studied by density functional theory (DFT) methods, leading to the conclusion that the degree of preorganization in the starting acylated intermediate had the largest effect on the reaction barriers. In addition, the effect of electronics on the aromatic ring in N-phenyl substrates was studied computationally and experimentally. Overall, this protocol proved considerably more amenable to scale up compared to earlier methods by eliminating the requirement of microwave batch chemistry for this reaction as well as significantly reducing the quantity of solvent.

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

PubMed

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

2010-12-15

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

Tyrosine-Lipid Peroxide Adducts from Radical Termination: Para-Coupling and Intramolecular Diels-Alder Cyclization

PubMed Central

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

2013-01-01

Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogs 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 as well as by mass spectrometry. 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 13C 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 13C chemical shifts at ~198 ppm. All NMR HMBC and HSQC correlations support the structure assignment of the primary and Diels-Alder adducts, as does MS collision induced dissociation. Kinetic rate constants and activation parameters for the IMDA reaction were determined and the primary adducts were reduced with cuprous ion giving a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found either in the primary or the 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 crosslinks via interprotein Michael adducts. PMID:21090613

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

PubMed

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

2015-02-01

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

Selection of ribozymes that catalyse multiple-turnover Diels–Alder cycloadditions by using in vitro compartmentalization

PubMed Central

Agresti, Jeremy J.; Kelly, Bernard T.; Jäschke, Andres; Griffiths, Andrew D.

2005-01-01

In vitro compartmentalization (IVC) has previously been used to evolve protein enzymes. Here, we demonstrate how IVC can be applied to select RNA enzymes (ribozymes) for a property that has previously been unselectable: true intermolecular catalysis. Libraries containing 1011 ribozyme genes are compartmentalized in the aqueous droplets of a water-in-oil emulsion, such that most droplets contain no more than one gene, and transcribed in situ. By coencapsulating the gene, RNA, and the substrates/products of the catalyzed reaction, ribozymes can be selected for all enzymatic properties: substrate recognition, product formation, rate acceleration, and turnover. Here we exploit the complementarity of IVC with systematic evolution of ligands by exponential enrichment (SELEX), which allows selection of larger libraries (≥1015) and for very small rate accelerations (kcat/kuncat) but only selects for intramolecular single-turnover reactions. We selected ≈1014 random RNAs for Diels–Alderase activity with five rounds of SELEX, then six to nine rounds with IVC. All selected ribozymes catalyzed the Diels–Alder reaction in a truly bimolecular fashion and with multiple turnover. Nearly all ribozymes selected by using eleven rounds of SELEX alone contain a common catalytic motif. Selecting with SELEX then IVC gave ribozymes with significant sequence variations in this catalytic motif and ribozymes with completely novel motifs. Interestingly, the catalytic properties of all of the selected ribozymes were quite similar. The ribozymes are strongly product inhibited, consistent with the Diels–Alder transition state closely resembling the product. More efficient Diels–Alderases may need to catalyze a second reaction that transforms the product and prevents product inhibition. PMID:16260754

Microwave-Assisted Organocatalytic Intramolecular Knoevenagel/Hetero Diels-Alder Reaction with O-(Arylpropynyloxy)-Salicylaldehydes: Synthesis of Polycyclic Embelin Derivatives.

PubMed

Martín-Acosta, Pedro; Feresin, Gabriela; Tapia, Alejandro; Estévez-Braun, Ana

2016-10-21

A highly efficient and regioselective approach to new polycyclic embelin derivatives through a domino Knoevenagel condensation/intramolecular hetero Diels-Alder reaction using O-(arylpropynyloxy)-salicylaldehydes in the presence of ethylenediamine diacetate (EDDA) is reported. This organocatalyzed protocol is compatible toward a wide range of aryl-substituted alkynyl ethers with electron-donating and electron-withdrawing groups. When other active methylene compounds were subjected to this domino reaction the corresponding adducts were obtained in high yield.

Microcontact Printing Patterning of an HOPG Surface by an Inverse Electron Demand Diels-Alder Reaction.

PubMed

Zhu, Jun; Hiltz, Jonathan; Tefashe, Ushula M; Mauzeroll, Janine; Lennox, R Bruce

2018-06-21

The chemical modification of an sp 2 hybridized carbon surface in a controllable manner is very challenging but also crucial for many applications. An inverse electron demand Diels-Alder (IEDDA) reaction using microcontact printing technique is introduced to spatially control the modification of a highly ordered pyrolytic graphite (HOPG) surface under ambient conditions. The covalent modification was characterized by Raman spectroscopy, XPS, and SECM. Tetrazine derivatives can effectively react with an HOPG surface and with microcontact printing methods resulting in spatially patterned surfaces being produced with micrometer-scale resolution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

2015-01-01

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

Geographical trends in the yolk carotenoid composition of the pied flycatcher (Ficedula hypoleuca).

PubMed

Eeva, Tapio; Ruuskanen, Suvi; Salminen, Juha-Pekka; Belskii, Eugen; Järvinen, Antero; Kerimov, Anvar; Korpimäki, Erkki; Krams, Indrikis; Moreno, Juan; Morosinotto, Chiara; Mänd, Raivo; Orell, Markku; Qvarnström, Anna; Siitari, Heli; Slater, Fred M; Tilgar, Vallo; Visser, Marcel E; Winkel, Wolfgang; Zang, Herwig; Laaksonen, Toni

2011-02-01

Carotenoids in the egg yolks of birds are considered to be important antioxidants and immune stimulants during the rapid growth of embryos. Yolk carotenoid composition is strongly affected by the carotenoid composition of the female's diet at the time of egg formation. Spatial and temporal differences in carotenoid availability may thus be reflected in yolk concentrations. To assess whether yolk carotenoid concentrations or carotenoid profiles show any large-scale geographical trends or differences among habitats, we collected yolk samples from 16 European populations of the pied flycatcher, Ficedula hypoleuca. We found that the concentrations and proportions of lutein and some other xanthophylls in the egg yolks decreased from Central Europe northwards. The most southern population (which is also the one found at the highest altitude) also showed relatively low carotenoid levels. Concentrations of β-carotene and zeaxanthin did not show any obvious geographical gradients. Egg yolks also contained proportionally more lutein and other xanthophylls in deciduous than in mixed or coniferous habitats. We suggest that latitudinal gradients in lutein and xanthophylls reflect the lower availability of lutein-rich food items in the northern F. hypoleuca populations and in montane southern populations, which start egg-laying earlier relative to tree phenology than the Central European populations. Similarly, among-habitat variation is likely to reflect the better availability of lutein-rich food in deciduous forests. Our study is the first to indicate that the concentration and profile of yolk carotenoids may show large-scale spatial variation among populations in different parts of the species' geographical range. Further studies are needed to test the fitness effects of this geographical variation.

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

NASA Astrophysics Data System (ADS)

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.

Diels-Alder addition to H2O@C60 an electronic and structural study

NASA Astrophysics Data System (ADS)

Reveles, J. Ulises; Govinda, K. C.; Baruah, Tunna; Zope, Rajendra R.

2017-10-01

Exohedral reactivity of endohedral fullerenes has aroused a significant interest because of its potential applications. The present letter examines the effect of an entrapped single water molecule on the reactivity of C60. We study the thermodynamics and kinetics of a Diels-Alder reaction occurring at all non-identical bonds of free C60 and H2O@C60. Our calculations show that encapsulation of water does not have a significant effect on H2O@C60 reactivity compared to C60, as attested by the investigation of the reaction under several orientations of H2O inside C60. Reaction and activation energies indicate that [6,6] bonds are the most reactive sites.

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

PubMed

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.

PubMed

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.

PubMed

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.

Tamarix and Diorhabda leaf beetle interactions: implications for Tamarix water use and riparian habitat

USGS Publications Warehouse

Nagler, Pamela; Glenn, Edward P.

2013-01-01

Tamarix leaf beetles (Diorhabda carinulata) have been widely released on western United States rivers to control introduced shrubs in the genus Tamarix, with the goals of saving water through removal of an assumed high water-use plant, and of improving habitat value by removing a competitor of native riparian trees. We review recent studies addressing three questions: (1) to what extent are Tamarix weakened or killed by recurrent cycles of defoliation; (2) can significant water salvage be expected from defoliation; and (3) what are the effects of defoliation on riparian ecology, particularly on avian habit? Defoliation has been patchy at many sites, and shrubs at some sites recover each year even after multiple years of defoliation. Tamarix evapotranspiration (ET) is much lower than originally assumed in estimates of potential water savings, and are the same or lower than possible replacement plants. There is concern that the endangered southwestern willow flycatcher (Empidonax trailli extimus) will be negatively affected by defoliation because the birds build nests early in the season when Tamarix is still green, but are still on their nests during the period of summer defoliation. Affected river systems will require continued monitoring and development of adaptive management practices to maintain or enhance riparian habitat values. Multiplatform remote sensing methods are playing an essential role in monitoring defoliation and rates of ET on affected river systems.

Isoprene/methyl acrylate Diels-Alder reaction in supercritical carbon dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, B.; Akgerman, A.

1999-12-01

The Diels-Alder reaction between isoprene and methyl acrylate was carried out in supercritical carbon dioxide in the temperature range 110--140 C and the pressure range 95.2--176.9 atm in a 300 cm{sup 3} autoclave. The high-pressure phase behavior of the reaction mixture in the vicinity of its critical region was determined in a mixed vessel with a sight window to ensure that all the experiments were performed in the supercritical single-phase region. Kinetic data were obtained at different temperatures, pressures, and reaction times. It was observed that in the vicinity of the critical point the reaction rate constant decreases with increasingmore » pressure. It was also determined that the reaction selectivity does not change with operating conditions. Transition-state theory was used to explain the effect of pressure on reaction rate and product selectivity. Additional experiments were conducted at constant temperature but different phase behaviors (two-phase region, liquid phase, supercritical phase) by adjusting the initial composition and pressure. It was shown that the highest reaction rate is in the supercritical region.« less

Fluorogenic Behaviour of the Hetero-Diels-Alder Ligation of 5-Alkoxyoxazoles with Maleimides and their Applications.

PubMed

Renault, Kévin; Jouanno, Laurie-Anne; Lizzul-Jurse, Antoine; Renard, Pierre-Yves; Sabot, Cyrille

2016-12-19

Fluorogenic reactions are largely underrepresented in the toolbox of chemoselective ligations despite their tremendous potential, particularly in chemical biology and biochemistry. In this respect, we have investigated in full detail the fluorescence behaviour of the azaphthalamide, a scaffold which is generated through a hetero-Diels-Alder reaction of 5-alkoxyoxazole and maleimide derivatives under mild conditions that are compatible with, among others, peptide chemistry. The scope and limitations of such a fluorogenic labelling strategy were examined through four distinct applications, which target enzymatic activities or bioorthogonal reactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessing the superelectrophilic dimension through sigma-complexation, SNAr and Diels-Alder reactivity.

PubMed

Buncel, Erwin; Terrier, François

2010-05-21

In the domain of organic chemistry, S(N)Ar substitutions represent a class of reactions of overwhelming importance, both in synthesis and in the understanding of structure-reactivity relationships, especially the role of sigma-complex intermediates. The primary factor necessary for achievement of S(N)Ar reactions is the presence of a good leaving group, which allows facile rearomatization of the ring undergoing nucleophilic attack. Consistent is the finding that the superelectrophilic chloronitrobenzofuroxans--or furazans--exhibit a very high S(N)Ar reactivity, allowing a number of C-C, C-N, C-O couplings to be achieved that are not accessible with the classical series of nitro-substituted aromatics. Of particular interest is the synthesis of a number of indoles, indolizines, pyrroles and extended pi-excessive aromatic structures like azulene substituted by superelectrophilic moieties. The remarkable driving force for the facile completion of these reactions is the 10 orders of magnitude greater reactivity of 10pi-electron-deficient heteroaromatics such as 4,6-dinitrobenzofuroxan (DNBF) than of the most reactive trinitrobenzene derivatives in sigma-adduct complexation. Among the factors that have been recognized as governing superelectrophilicity, there is the poor aromaticity of 6-membered 10pi-electron structures investigated, with a common origin for sigma-complexation and pericyclic processes. A remarkable capacity of these structures is actually to contribute to a variety of Diels-Alder reactions. As an example, the DNBF molecule formally behaves as a nitroalkene, being susceptible to act as a dienophile as well as a heterodiene. Another remarkable Diels-Alder pathway is the capacity of the 6-membered carbocyclic ring of DNBF to act as a carbodiene. Also noteworthy is the successful Diels-Alder trapping of the dinitroso intermediate associated with 1-oxide/3-oxide tautomerism of the furoxan moiety of 4-aza-6-nitrobenzofuroxan. A point of fundamental importance

Mechanical power curve measured in the wake of pied flycatchers indicates modulation of parasite power across flight speeds.

PubMed

Johansson, L Christoffer; Maeda, Masateru; Henningsson, Per; Hedenström, Anders

2018-01-01

How aerodynamic power required for animal flight varies with flight speed determines optimal speeds during foraging and migratory flight. Despite its relevance, aerodynamic power provides an elusive quantity to measure directly in animal flight. Here, we determine the aerodynamic power from wake velocity fields, measured using tomographical particle image velocimetry, of pied flycatchers flying freely in a wind tunnel. We find a shallow U-shaped power curve, which is flatter than expected by theory. Based on how the birds vary body angle with speed, we speculate that the shallow curve results from increased body drag coefficient and body frontal area at lower flight speeds. Including modulation of body drag in the model results in a more reasonable fit with data than the traditional model. From the wake structure, we also find a single starting vortex generated from the two wings during the downstroke across flight speeds (1-9 m s -1 ). This is accomplished by the arm wings interacting at the beginning of the downstroke, generating a unified starting vortex above the body of the bird. We interpret this as a mechanism resulting in a rather uniform downwash and low induced power, which can help explain the higher aerodynamic performance in birds compared with bats. © 2018 The Author(s).

Out of Amazonia again and again: episodic crossing of the Andes promotes diversification in a lowland forest flycatcher

PubMed Central

Miller, Matthew J; Bermingham, Eldredge; Klicka, John; Escalante, Patricia; do Amaral, Fabio S. Raposo; Weir, Jason T; Winker, Kevin

2008-01-01

Most Neotropical lowland forest taxa occur exclusively on one side of the Andes despite the availability of appropriate habitat on both sides. Almost all molecular phylogenies and phylogenetic analyses of species assemblages (i.e. area cladograms) have supported the hypothesis that Andean uplift during the Late Pliocene created a vicariant barrier affecting lowland lineages in the region. However, a few widespread plant and animal species occurring in lowland forests on both sides of the Andes challenge the generality of this hypothesis. To understand the role of the Andes in the history of such organisms, we reconstructed the phylogeographic history of a widespread Neotropical flycatcher (Mionectes oleagineus) in the context of the other four species in the genus. A molecular phylogeny based on nuclear and mitochondrial sequences unambiguously showed an early basal split between montane and lowland Mionectes. The phylogeographic reconstruction of lowland taxa revealed a complex history, with multiple cases in which geographically proximate populations do not represent sister lineages. Specifically, three populations of M. oleagineus west of the Andes do not comprise a monophyletic clade; instead, each represents an independent lineage with origins east of the Andes. Divergence time estimates suggest that at least two cross-Andean dispersal events post-date Andean uplift. PMID:18285279

Solid-supported nitroso hetero Diels-Alder reactions. 1. Acylnitroso dienophiles: scope and limitations.

PubMed

Krchnák, Viktor; Moellmann, Ute; Dahse, Hans-Martin; Miller, Marvin J

2008-01-01

Polymer-supported acylnitroso dienophiles were prepared and used in hetero Diels-Alder (HDA) reactions with a variety of dienes. The transient acylnitroso dienophiles were prepared in situ from immobilized hydroxamates, which were attached to solid supports via several linkers each cleavable by different cleavage reagents, and served for the synthesis of both N-unsubstituted and N-derivatized HDA adducts. Model compounds were used to (i) optimize reaction conditions for solid-supported HDA reactions, (ii) evaluate the outcome of the reactions with various dienes, (iii) compare relative reactivities of dienes, and (iv) assess the stability of HDA adducts toward cleavage conditions typically used in solid-phase syntheses. Cleaved products were submitted to biological assays, and the results are reported. The accompanying paper, focused on complementary arylnitroso HDA reactions, includes a comparison of both HDA reactions.

Stereoselective protecting group free synthesis of D,L-gulose ethyl glycoside via multicomponent enyne cross metathesis--hetero Diels-Alder reaction.

PubMed

Castagnolo, Daniele; Botta, Lorenzo; Botta, Maurizio

2009-07-27

An efficient and stereoselective synthesis of D,L-gulose was described. The key step of the synthetic route is represented by a multicomponent enyne cross metathesis-hetero Diels-Alder reaction which allows the formation of the pyran ring from cheap and commercially available substrates in a single synthetic step. The synthesis of D,L-gulose was accomplished without the use of protecting groups making this approach highly desirable also in terms of atom economy.

Oxidative Processing Lowers the Ice Nucleation Activity of Birch and Alder Pollen

NASA Astrophysics Data System (ADS)

Gute, Ellen; Abbatt, Jonathan P. D.

2018-02-01

Pollen carry water extractable compounds with ice nucleating (IN) activity. This study investigates whether the hydroxyl radical, as the major atmospheric oxidant, can affect the IN activity of silver birch and grey alder subpollen particles under in-cloud conditions for deposition freezing mode conditions at 234 K. It is found that oxidation increases the supersaturation ratio with respect to ice necessary for the onset of ice nucleation and decreases the fraction of particles which initiate ice nucleation. This reduction of IN activity under equivalent oxidation conditions does not occur with a mineral dust sample (Arizona Test Dust). Chemical analysis of fresh and oxidized pollen material indicates a change of molecular structure with a loss of conjugation and an increase in oxidized functional groups, such as carbonyls. This is the first demonstration that in-cloud oxidation may lower the IN abilities of biological particles such as pollen.

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

PubMed Central

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

Diastereoselective Diels-Alder reactions of alpha-fluorinated alpha,beta-unsaturated carbonyl compounds: chemical consequences of fluorine substitution. 2.

PubMed

Essers, Michael; Mück-Lichtenfeld, Christian; Haufe, Günter

2002-07-12

Two alpha-fluoro alpha,beta-unsaturated carbonyl compounds, i.e., benzyl 2-fluoroacrylate (3) and 2-fluorooct-1-en-3-one (4), as well as the corresponding nonfluorinated parent compounds, were synthesized and subjected to Diels-Alder reactions with cyclopentadiene. The cycloadditions were conducted thermally, microwave-assisted, and Lewis acid-mediated (TiCl(4)). The fluorinated dienophiles exhibited a lower reactivity and exo diastereoselectivity, while the corresponding nonfluorinated parent compounds reacted endo selectively. DFT calculations suggest that kinetic effects of fluorine determine the stereoselectivity rather than higher thermodynamic stability of the exo products.

Chlorotheolides A and B, Spiroketals Generated via Diels-Alder Reactions in the Endophytic Fungus Pestalotiopsis theae.

PubMed

Liu, Ling; Han, Yu; Xiao, Junhai; Li, Li; Guo, Liangdong; Jiang, Xuejun; Kong, Lingyi; Che, Yongsheng

2016-10-28

Chlorotheolides A (1) and B (2), two new spiroketals possessing the unique [4,7]methanochromene and dispiro-trione skeletons, respectively, and their putative biosynthetic precursors, 1-undecen-2,3-dicarboxylic acid (3) and maldoxin (4), were isolated from the solid substrate fermentation of the plant endophytic fungus Pestalotiopsis theae (N635). Their structures were elucidated based on NMR spectroscopic data and electronic circular dichroism calculations. Biogenetically, compounds 1 and 2 could be generated from the co-isolated 3 and 4 via Diels-Alder reactions. Chlorotheolide (2) showed an antiproliferative effect against the human tumor cell line HeLa and induced an autophagic process in the cells.

Recyclable thermosetting thermal pad using silicone-based polyurethane crosslinked by Diels-Alder adduct

NASA Astrophysics Data System (ADS)

Kim, Jong-Woong; Lee, Da Hee; Jeon, Hee-Jeong; Jang, Sung Il; Cho, Hyun Min; Kim, Youngmin

2018-01-01

The recyclable silicone-based thermoset was successfully synthesized by making use of a Diels-Alder (DA) adduct as a cross-linker. The incorporation of the furan-tethered diol 1 into the polymer backbones realized the crosslinking of polymers via the DA reaction. The thermosetting polymer was dissolved in DMF after the retro DA reaction which was monitored by 1H NMR spectroscopy. Due to the retro DA reaction, polymer showed the mendable behavior when it was scratched followed by being heated. This polymer was mixed with alumina powders to fabricate the thermal pad. The thermal resistance of this pad was measured to be 0.48 K/W by a thermal transient test. The thermosetting composite was recycled via the retro DA reaction. The thermal resistance of the recycled one was similar to that of the original one.

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

PubMed

Kozma, Eszter; Demeter, Orsolya; Kele, Péter

2017-03-16

Bio-orthogonal labelling schemes based on inverse-electron-demand Diels-Alder (IEDDA) cycloaddition have attracted much attention in chemical biology recently. The appealing features of this reaction, such as the fast reaction kinetics, fully bio-orthogonal nature and high selectivity, have helped chemical biologists gain deeper understanding of biochemical processes at the molecular level. Listing the components and discussing the possibilities and limitations of these reagents, we provide a recent snapshot of the field of IEDDA-based biomolecular manipulation with special focus on fluorescent modulation approaches through the use of bio-orthogonalized building blocks. At the end, we discuss challenges that need to be addressed for further developments in order to overcome recent limitations and to enable researchers to answer biomolecular questions in more detail. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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

ERIC Educational Resources Information Center

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

2011-01-01

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

Excellent acceleration of the Diels-Alder reaction by microwave irradiation for the synthesis of new fluorine-substituted ligands of NMDA receptor.

PubMed

Sasaki, S; Ishibashi, N; Kuwamura, T; Sano, H; Matoba, M; Nisikawa, T; Maeda, M

1998-11-03

A series of 6,11-ethanobenzo[b]quinolizinium derivatives was synthesized through the Diels-Alder reaction between azoniaanthracne and the corresponding 1,1-disubstituted olefin. After a systematic investigation for achieving rapid synthesis, it was found that the reaction is accelerated in polar media such as H2O and trifluoroethanol. In particular, excellent acceleration was effected by microwave irradiation. The new fluorine-substituted ligands thus obtained exhibited potential affinity toward NMDA receptors.

Possible roles for corticosterone and critical size in the fledging of nestling pied flycatchers.

PubMed

Kern, M; Bacon, W; Long, D; Cowie, R J

2001-01-01

Our study was designed to see whether corticosterone (B) rises abruptly in the blood of nestling pied flycatchers (Ficedula hypoleuca) at the time they fledge, as reported recently for kestrels, and if so, why. We measured the growth and blood levels of B and selected nutrients of nestlings in broods of five, seven, and nine chicks during 1998 and 1999. In half of the broods, we clipped selected wing and tail feathers of both parents with the intention of making it more difficult for them to provide their chicks with food. We collected blood samples when the chicks were six to 10 d old (period of rapid growth) and 15 d of age or older (0-5 d before fledging). B increased substantially several days before the chicks left the nest and then declined somewhat. We found no differences in rates of growth or blood levels of B, nutrients, and hematocrit as a function of either brood size or parental handicapping. Nestlings within a day of fledging appear to have been food deprived in 1998; their glucose was significantly reduced, and B, free fatty acids, and glycerol were significantly elevated compared to levels in chicks 1-4 d younger. Such changes did not occur in 1999. Blood levels of B were significantly correlated with brood size near the day of fledging, but not earlier, in both years of the study. It was possible to predict the day on which chicks would leave the nest, using their wing length when 12 d old. These results suggest that high blood levels of B associated with food restriction and sibling competition induce chicks to fledge, provided they have reached a critical size, and that the importance of fasting, sibling competition, and B may vary from year to year.

Theoretical study of Diels-Alder cycloadditions of butadiene to C{sub 70}. An insight into the chemical reactivity of C{sub 70} as compared to C{sub 60}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mestres, J.; Duran, M.; Sola, M.

1996-05-02

The eight unique Diels-Alder cycloadditions of butadiene to C{sub 70} are analyzed theoretically and compared with the well-established, two possible Diels-Alder cycloadditions of butadiene to C{sub 60}. Full geometry optimizations of reactants, adducts, and transition states are performed using the AMI semiempirical method followed by single-point ab initio energy calculations. The results show that the cycloaddition of butadiene to the C{sub 70} fullerene in the gas phase is slightly more reactive than that to C{sub 60}. However, in toluene solution calculations yield that the different solvent effects on C{sub 60} and C{sub 70} cause a significant decrease of the energymore » barrier in the C{sub 60} cycloaddition, thus predicting a larger reactivity for C{sub 60} as compared to the C{sub 70} fullerene. 36 refs., 2 figs., 3 tabs.« less

Net degradation of methyl mercury in alder swamps.

PubMed

Kronberg, Rose-Marie; Tjerngren, Ida; Drott, Andreas; Björn, Erik; Skyllberg, Ulf

2012-12-18

Wetlands are generally considered to be sources of methyl mercury (MeHg) in northern temperate landscapes. However, a recent input-output mass balance study during 2007-2010 revealed a black alder (Alnus glutinosa) swamp in southern Sweden to be a consistent and significant MeHg sink, with a 30-60% loss of MeHg. The soil pool of MeHg varied substantially between years, but it always decreased with distance from the stream inlet to the swamp. The soil MeHg pool was significantly lower in the downstream as compared to the upstream half of the swamp (0.66 and 1.34 ng MeHg g⁻¹ SOC⁻¹ annual average⁻¹, respectively, one-way ANOVA, p = 0.0006). In 2008 a significant decrease of %MeHg in soil was paralleled by a significant increase in potential demethylation rate constant (k(d), p < 0.02 and p < 0.004, respectively). In contrast, the potential methylation rate constant (k(m)) was unrelated to distance (p = 0.3). Our results suggest that MeHg was net degraded in the Alnus swamp, and that it had a rapid and dynamic internal turnover of MeHg. Snapshot stream input-output measurements at eight additional Alnus glutinosa swamps in southern Sweden indicate that Alnus swamps in general are sinks for MeHg. Our findings have implications for forestry practices and landscape planning, and suggest that restored or preserved Alnus swamps may be used to mitigate MeHg produced in northern temperate landscapes.

Integrated plumage colour variation in relation to body condition, reproductive investment and laying date in the collared flycatcher

NASA Astrophysics Data System (ADS)

Laczi, Miklós; Hegyi, Gergely; Herényi, Márton; Kiss, Dorottya; Markó, Gábor; Nagy, Gergely; Rosivall, Balázs; Szöllősi, Eszter; Török, János

2013-10-01

The possible integration of different sexual ornaments into a composite system, and especially the information content of such ornament complexes, is poorly investigated. Many bird species display complex plumage coloration, but whether this represents one integrated or several independent sexual traits can be unclear. Collared flycatchers ( Ficedula albicollis) display melanised and depigmented plumage areas, and the spectral features (brightness and UV chroma) of these are correlated with each other across the plumage. In a 5-year dataset of male and female plumage reflectance, we examined some of the potential information content of integrated, plumage-level colour attributes by estimating their relationships to previous and current year body condition, laying date and clutch size. Females were in better condition the year before they became darker pigmented, and males in better current year condition were also darker pigmented. Female pigment-based brightness was positively, while male structurally based brightness was negatively related to current laying date. Finally, the overall UV chroma of white plumage areas in males was positively associated with current clutch size. Our results show that higher degree of pigmentation is related to better condition, while the structural colour component is associated with some aspects of reproductive investment. These results highlight the possibility that correlated aspects of a multiple plumage ornamentation system may reflect together some aspects of individual quality, thereby functioning as a composite signal.

[Visual input affects the expression of the early genes c-Fos and ZENK in auditory telencephalic centers of pied flycatcher nestlings during the acoustically-guided freezing].

PubMed

Korneeva, E V; Tiunova, A A; Aleksandrov, L I; Golubeva, T B; Anokhin, K V

2014-01-01

The present study analyzed expression of transcriptional factors c-Fos and ZENK in 9-day-old pied flycatcher nestlings' (Ficedula hypoleuca) telencephalic auditory centers (field L, caudomedial nidopallium and caudomedial mesopallium) involved in the acoustically-guided defense behavior. Species-typical alarm call was presented to the young in three groups: 1--intact group (sighted control), 2--nestlings visually deprived just before the experiment for a short time (unsighted control) 3--nestlings visually deprived right after hatching (experimental deprivation). Induction of c-Fos as well as ZENK in nestlings from the experimental deprivation group was decreased in both hemispheres as compared with intact group. In the group of unsighted control, only the decrease of c-Fos induction was observed exclusively in the right hemisphere. These findings suggest that limitation of visual input changes the population of neurons involved into the acoustically-guided behavior, the effect being dependant from the duration of deprivation.

Effects of pollution on land snail abundance, size and diversity as resources for pied flycatcher, Ficedula hypoleuca.

PubMed

Eeva, Tapio; Rainio, Kalle; Suominen, Otso

2010-09-01

Passerine birds need extra calcium during their breeding for developing egg shells and proper growth of nestling skeleton. Land snails are an important calcium source for many passerines and human-induced changes in snail populations may pose a severe problem for breeding birds. We studied from the bird's viewpoint how air pollution affects the shell mass, abundance and diversity of land snail communities along a pollution gradient of a copper smelter. We sampled remnant snail shells from the nests of an insectivorous passerine, the pied flycatcher, Ficedula hypoleuca, to find out how the availability of land snails varies along the pollution gradient. The total snail shell mass increased towards the pollution source but declined abruptly in the vicinity of the smelter. This spatial variation in shell mass was evident also within a single snail species and could not be wholly explained by spatially varying snail numbers or species composition. Instead, the total shell mass was related to their shell size, individuals being largest at the moderately polluted areas. Smaller shell size suggests inferior growth of snails in the most heavily polluted area. Our study shows that pollution affects the diversity, abundance (available shell mass) and individual quality of land snails, posing reproductive problems for birds that rely on snails as calcium sources during breeding. There are probably both direct pollution-related (heavy metal and calcium levels) and indirect (habitat change) effects behind the observed changes in snail populations. Copyright 2010 Elsevier B.V. All rights reserved.

Diels-Alder active-template synthesis of rotaxanes and metal-ion-switchable molecular shuttles.

PubMed

Crowley, James D; Hänni, Kevin D; Leigh, David A; Slawin, Alexandra M Z

2010-04-14

A synthesis of [2]rotaxanes in which Zn(II) or Cu(II) Lewis acids catalyze a Diels-Alder cycloaddition to form the axle while simultaneously acting as the template for the assembly of the interlocked molecules is described. Coordination of the Lewis acid to a multidentate endotopic 2,6-di(methyleneoxymethyl)pyridyl- or bipyridine-containing macrocycle orients a chelated dienophile through the macrocycle cavity. Lewis acid activation of the double bond causes it to react with an incoming "stoppered" diene, affording the [2]rotaxane in up to 91% yield. Unusually for an active-template synthesis, the metal binding site "lives on" in these rotaxanes. This was exploited in the synthesis of a molecular shuttle containing two different ligating sites in which the position of the macrocycle could be switched by complexation with metal ions [Zn(II) and Pd(II)] with different preferred coordination geometries.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 selectivemore » reaction conditions.« less

Inverse electron demand Diels-Alder reactions in chemical biology.

PubMed

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

2017-08-14

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

Nest site preference depends on the relative density of conspecifics and heterospecifics in wild birds.

PubMed

Samplonius, Jelmer M; Kromhout Van Der Meer, Iris M; Both, Christiaan

2017-01-01

Social learning allows animals to eavesdrop on ecologically relevant knowledge of competitors in their environment. This is especially important when selecting a habitat if individuals have relatively little personal information on habitat quality. It is known that birds can use both conspecific and heterospecific information for social learning, but little is known about the relative importance of each information type. If provided with the choice between them, we expected that animals should copy the behaviour of conspecifics, as these confer the best information for that species. We tested this hypothesis in the field for Pied Flycatchers Ficedula hypoleuca arriving at their breeding grounds to select a nest box for breeding. We assigned arbitrary symbols to nest boxes of breeding pied flycatchers (conspecifics) and blue and great tits, Cyanistes caeruleus and Parus major (heterospecifics), in 2014 and 2016 in two areas with different densities of tits and flycatchers. After ca 50% of flycatchers had returned and a flycatcher symbol was assigned to their nest box, we gave the later arriving flycatchers the choice between empty nest boxes with either a conspecific (flycatcher) or a heterospecific (tit) symbol. As expected, Pied Flycatchers copied the perceived nest box choice of conspecifics, but only in areas that were dominated by flycatchers. Against our initial expectation, flycatchers copied the perceived choice of heterospecifics in the area heavily dominated by tits, even though conspecific minority information was present. Our results confirm that the relative density of conspecifics and heterospecifics modulates the propensity to copy or reject novel behavioural traits. By contrasting conspecific and heterospecific ecology in the same study design we were able to draw more general conclusions about the role of fluctuating densities on social information use.

Effect of Rubber Polarity on Cluster Formation in Rubbers Cross-Linked with Diels–Alder Chemistry

PubMed Central

2017-01-01

Diels–Alder chemistry has been used for the thermoreversible cross-linking of furan-functionalized ethylene/propylene (EPM) and ethylene/vinyl acetate (EVM) rubbers. Both furan-functionalized elastomers were successfully cross-linked with bismaleimide to yield products with a similar cross-link density. NMR relaxometry and SAXS measurements both show that the apolar EPM-g-furan precursor contains phase-separated polar clusters and that cross-linking with polar bismaleimide occurs in these clusters. The heterogeneously cross-linked network of EPM-g-furan contrasts with the homogeneous network in the polar EVM-g-furan. The heterogeneous character of the cross-links in EPM-g-furan results in a relatively high Young’s modulus, whereas the more uniform cross-linking in EVM-g-furan results in a higher tensile strength and elongation at break. PMID:29213149

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

PubMed

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.

Nesting success of grassland and savanna birds on reclaimed surface coal mines of the midwestern United States

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galligan, E.W.; DeVault, T.L.; Lima, S.L.

2006-12-15

Reclaimed surface coal mines in southwestern Indiana support many grassland and shrub/savanna bird species of conservation concern. We examined the nesting success of birds on these reclaimed mines to assess whether such 'unnatural' places represent productive breeding habitats for such species. We established eight study sites on two large, grassland-dominated mines in southwestern Indiana and classified them into three categories (open grassland, shrub/savanna, and a mixture of grassland and shrub/savanna) based on broad vegetation and landscape characteristics. During the 1999 and 2000 breeding seasons, we found and monitored 911 nests of 31 species. Daily nest survival for the most commonlymore » monitored grassland species ranged from 0.903 (Dickcissel, Spiza americana) to 0.961 (Grasshopper Sparrow, Ammodramus savannarum). Daily survival estimates for the dominant shrub/savanna nesting species ranged from 0.932 (Brown Thrasher, Toxostoma rufum) to 0.982 (Willow Flycatcher, Empidonax traillii). Vegetation and landscape effects on nesting success were minimal, and only Eastern Meadowlarks (Sturnella magna) showed a clear time-of-season effect, with greater nesting success in the first half of the breeding season. Rates of Brown-headed Cowbird (Molothrus ater) parasitism were only 2.1% for grassland species and 12.0% for shrub/savanna species. The nesting success of birds on reclaimed mine sites was comparable to that in other habitats, indicating that reclaimed habitats on surface mines do not necessarily represent reproductive traps for birds.« less

Mesohabitat use of threatened hemlock forests by breeding birds of the Delaware River basin in northeastern United States

USGS Publications Warehouse

Ross, R.M.; Redell, L.A.; Bennett, R.M.; Young, J.A.

2004-01-01

Avian biodiversity may be at risk in eastern parks and forests due to continued expansion of the hemlock woolly adelgid (Adelges tsugae), an exotic homopteran insect native to East Asia. To assess avian biodiversity, mesohabitat relations, and the risk of species loss with declining hemlock forests in Appalachian park lands, 80 randomly distributed fixed-radius plots were established in which territories of breeding birds were estimated on four forest-terrain types (hemlock and hardwood benches and ravines) in the Delaware Water Gap National Recreation Area. Both species richness and number of territories were higher in hardwood than hemlock forest types and in bench than ravine terrain types. Four insectivorous species, Acadian flycatcher (Empidonax virescens), blue-headed vireo (Vireo solitarius), black-throated green warbler (Dendroica virens), and Blackburnian warbler (Dendroica fusca), showed high affinity for hemlock forest type and exhibited significantly greater numbers of territories in hemlock than hardwood sites. These species are hemlock-associated species at risk from continued hemlock decline in the Delaware River valley and similar forests of the mid-Atlantic east slope. Two of these species, the blue-headed vireo and Blackburnian warbler, appeared to specialize on ravine mesohabitats of hemlock stands, the vireo a low-to-mid canopy species, the warbler a mid-to-upper canopy forager. Unchecked expansion of the exotic adelgid and subsequent hemlock decline could negatively impact 3,600 pairs from the park and several million pairs from northeastern United States hemlock forests due to elimination of preferred habitat.

Birds of a high-altitude cloud forest in Alta Verapaz, Guatemala.

PubMed

Eisermann, Knut; Schulz, Ulrich

2005-01-01

The Northern Central American Highlands have been recognized as endemic bird area, but little is known about bird communities in Guatemalan cloud forests. From 1997 to 2001 a total of 142 bird species were recorded between 2000 and 2400 masl in cloud forest and agricultural clearings on Montaña Caquipec (Alta Verapaz, Guatemala). The bird community is described based on line transect counts within the forest. Pooling census data from undisturbed and disturbed forest, the Gray-breasted Wood-Wren (Henicorhina leucophrys) was found to be the most abundant species, followed in descending order by the Common Bush-Tanager (Chlorospingus ophthalmicus), the Paltry Tyrannulet (Zimmerius vilissimus), the Yellowish Flycatcher (Empidonax flavescens), the Ruddy-capped Nightingale-Thrush (Catharus frantzi), and the Amethyst-throated Hummingbird (Lampornis amethystinus). Bird communities in undisturbed and disturbed forest were found to be similar (Serensen similarity index 0.85), indicating low human impact. Of all recorded species, approximately 27% were Nearctic-Neotropical migratory birds. The most abundant one was the Wilson's Warbler (Wilsonia pusilla). The Montaña Caquipec is an important area for bird conservation, which is indicated by the presence of four species listed in the IUCN Red List (Highland Guan Penelopina nigra, Resplendent Quetzal Pharomachrus mocinno, Pink-headed Warbler Ergaticus versicolor, Golden-cheeked Warbler Dendroica chrysoparia), and 42 Mesoamerican endemics, of which 14 species are endemic to the Central American Highlands. The results presented here will be useful as baseline data for a long-term monitoring.

Building hierarchical models of avian distributions for the State of Georgia

USGS Publications Warehouse

Howell, J.E.; Peterson, J.T.; Conroy, M.J.

2008-01-01

To predict the distributions of breeding birds in the state of Georgia, USA, we built hierarchical models consisting of 4 levels of nested mapping units of decreasing area: 90,000 ha, 3,600 ha, 144 ha, and 5.76 ha. We used the Partners in Flight database of point counts to generate presence and absence data at locations across the state of Georgia for 9 avian species: Acadian flycatcher (Empidonax virescens), brownheaded nuthatch (Sitta pusilla), Carolina wren (Thryothorus ludovicianus), indigo bunting (Passerina cyanea), northern cardinal (Cardinalis cardinalis), prairie warbler (Dendroica discolor), yellow-billed cuckoo (Coccyxus americanus), white-eyed vireo (Vireo griseus), and wood thrush (Hylocichla mustelina). At each location, we estimated hierarchical-level-specific habitat measurements using the Georgia GAP Analysis18 class land cover and other Geographic Information System sources. We created candidate, species-specific occupancy models based on previously reported relationships, and fit these using Markov chain Monte Carlo procedures implemented in OpenBugs. We then created a confidence model set for each species based on Akaike's Information Criterion. We found hierarchical habitat relationships for all species. Three-fold cross-validation estimates of model accuracy indicated an average overall correct classification rate of 60.5%. Comparisons with existing Georgia GAP Analysis models indicated that our models were more accurate overall. Our results provide guidance to wildlife scientists and managers seeking predict avian occurrence as a function of local and landscape-level habitat attributes.

Tamarisk biocontrol using tamarisk beetles: Potential consequences for riparian birds in the southwestern United States

USGS Publications Warehouse

Paxton, Eben H.; Theimer, Tad C.; Sogge, Mark K.

2011-01-01

The tamarisk beetle (Diorhabda spp.), a non-native biocontrol agent, has been introduced to eradicate tamarisk (Tamarix spp.), a genus of non-native tree that has become a dominant component of riparian woodlands in the southwestern United States. Tamarisk beetles have the potential to spread widely and defoliate large expanses of tamarisk habitat, but the effects of such a widespread loss of riparian vegetation on birds remains unknown. We reviewed literature on the effects of other defoliating insects on birds to investigate the potential for tamarisk beetles to affect birds positively or negatively by changing food abundance and vegetation structure. We then combined data on the temporal patterns of tamarisk defoliation by beetles with nest productivity of a well-studied riparian obligate, the Southwestern Willow Flycatcher (Empidonax traillii extimus), to simulate the potential demographic consequences of beetle defoliation on breeding riparian birds in both the short and long term. Our results highlight that the effects of tamarisk biocontrol on birds will likely vary by species and population, depending upon its sensitivity to seasonal defoliation by beetles and net loss of riparian habitat due to tamarisk mortality. Species with restricted distributions that include areas dominated by tamarisk may be negatively affected both in the short and long term. The rate of regeneration and/or restoration of native cottonwoods (Populus spp.) and willows (Salix spp.) relative to the rate of tamarisk loss will be critical in determining the long-term effect of this large-scale ecological experiment.

Breeding phenology of birds: mechanisms underlying seasonal declines in the risk of nest predation.

PubMed

Borgmann, Kathi L; Conway, Courtney J; Morrison, Michael L

2013-01-01

Seasonal declines in avian clutch size are well documented, but seasonal variation in other reproductive parameters has received less attention. For example, the probability of complete brood mortality typically explains much of the variation in reproductive success and often varies seasonally, but we know little about the underlying cause of that variation. This oversight is surprising given that nest predation influences many other life-history traits and varies throughout the breeding season in many songbirds. To determine the underlying causes of observed seasonal decreases in risk of nest predation, we modeled nest predation of Dusky Flycatchers (Empidonax oberholseri) in northern California as a function of foliage phenology, energetic demand, developmental stage, conspecific nest density, food availability for nest predators, and nest predator abundance. Seasonal variation in the risk of nest predation was not associated with seasonal changes in energetic demand, conspecific nest density, or predator abundance. Instead, seasonal variation in the risk of nest predation was associated with foliage density (early, but not late, in the breeding season) and seasonal changes in food available to nest predators. Supplemental food provided to nest predators resulted in a numerical response by nest predators, increasing the risk of nest predation at nests that were near supplemental feeders. Our results suggest that seasonal changes in foliage density and factors associated with changes in food availability for nest predators are important drivers of temporal patterns in risk of avian nest predation.

Breeding Phenology of Birds: Mechanisms Underlying Seasonal Declines in the Risk of Nest Predation

PubMed Central

Borgmann, Kathi L.; Conway, Courtney J.; Morrison, Michael L.

2013-01-01

Seasonal declines in avian clutch size are well documented, but seasonal variation in other reproductive parameters has received less attention. For example, the probability of complete brood mortality typically explains much of the variation in reproductive success and often varies seasonally, but we know little about the underlying cause of that variation. This oversight is surprising given that nest predation influences many other life-history traits and varies throughout the breeding season in many songbirds. To determine the underlying causes of observed seasonal decreases in risk of nest predation, we modeled nest predation of Dusky Flycatchers (Empidonax oberholseri) in northern California as a function of foliage phenology, energetic demand, developmental stage, conspecific nest density, food availability for nest predators, and nest predator abundance. Seasonal variation in the risk of nest predation was not associated with seasonal changes in energetic demand, conspecific nest density, or predator abundance. Instead, seasonal variation in the risk of nest predation was associated with foliage density (early, but not late, in the breeding season) and seasonal changes in food available to nest predators. Supplemental food provided to nest predators resulted in a numerical response by nest predators, increasing the risk of nest predation at nests that were near supplemental feeders. Our results suggest that seasonal changes in foliage density and factors associated with changes in food availability for nest predators are important drivers of temporal patterns in risk of avian nest predation. PMID:23776566

76 FR 50541 - Endangered and Threatened Wildlife and Plants; Designation of Revised Critical Habitat for...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-15

... centimeters (5.8 inches) in length. The flycatcher is one of four subspecies of the willow flycatcher... clustering into two groups separated approximately along the currently recognized boundary; however, they... central Arizona. Flycatchers are believed to exist and interact as groups of metapopulations (Service 2002...

Microwave-promoted catalyst- and solvent-free aza-Diels-Alder reaction of aldimines with 6-[2-(dimethylamino)vinyl]-1,3-dimethyluracil.

PubMed

Sarma, Rupam; Sarmah, Manas M; Prajapati, Dipak

2012-02-17

A microwave-promoted aza-Diels-Alder reaction between 6-[2-(dimethylamino)vinyl]-1,3-dimethyluracil and aldimines has been developed for the construction of dihydropyrido[4,3-d]pyrimidines. Urea is effectively employed as an environmentally benign source of ammonia in the absence of any catalyst or solvent. The key step in the reaction is in situ generation and trapping of the reactive aldimine formed from urea and aldehyde by the diene system of the uracil. The reaction is clean, and excellent yields are obtained in a matter of a few minutes.

Solvent effects in acid-catalyzed dehydration of the Diels-Alder cycloadduct between 2,5-dimethylfuran and maleic anhydride

NASA Astrophysics Data System (ADS)

Salavati-fard, Taha; Caratzoulas, Stavros; Doren, Douglas J.

2017-03-01

Dehydration of the cycloadduct produced from the Diels-Alder reaction between 2,5-dimethylfuran and maleic anhydride to 3,6-dimethylphthalic anhydride exemplifies an important step in producing platform chemicals from biomass. The mechanisms of dehydration and catalytic effects of Lewis and Brønsted acids are investigated with density functional theory. The uncatalyzed reaction has a very high activation barrier (68.7 kcal/mol) in the gas phase and it is not significantly affected by solvation. With a Lewis acid catalyst, modeled as an alkali ion, the activation barriers are reduced, but intermediates are also stabilized. The net effect in vacuum is that the energetic span, or apparent activation energy of the catalytic cycle, is 77.9 kcal/mol, even higher than the barrier in the uncatalyzed case. In solution, however, the energetic span is reduced by as much as 20 kcal/mol, due to differences in the solvation energy of the transition states and intermediates. In the case of a Brønsted acid catalyst, modeled as a proton, the gas phase transition state energies are reduced even more than in the Lewis acid case, and there is no strong stabilization of the intermediates. The energetic span in vacuum is only 13.8 kcal/mol and is reduced even further in solution. Brønsted acid catalysis appears to be the preferred mechanism for dehydration of this cycloadduct. Since the Diels-Alder reaction that produced the molecule has previously been shown to be catalyzed by Brønsted acids, this suggests that a single catalyst could be used to accelerate both steps.

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

PubMed

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

2015-09-01

A triol-functional crosslinker combining the thermoreversible properties of Diels-Alder (DA) adducts in one molecule is designed, synthesized, and used as an ideal substitute of a traditional crosslinker to prepare thermal recyclable cross-linked polyurethanes with excellent mechanical properties and recyclability in a very simple and efficient way. The recycle property of these materials achieved by the DA/retro-DA reaction at a suitable temperature is verified by differential scanning calorimetry and in situ variable temperature solid-state NMR experiments during the cyclic heating and cooling processes. The thermal recyclability and remending ability of the bulk polyurethanes is demonstrated by three polymer processing methods, including hot-press molding, injection molding, and solution casting. It is notable that all the recycled cross-linked polymers display nearly invariable elongation/stress at break compared to the as-synthesized samples. Further end-group functionalization of this single molecular DA crosslinker provides the potential in preparing a wide range of recyclable cross-linked polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactions of hexadehydro-Diels-Alder benzynes with structurally complex multifunctional natural products

NASA Astrophysics Data System (ADS)

Ross, Sean P.; Hoye, Thomas R.

2017-06-01

An important question in organic chemistry concerns the extent to which benzynes—one of the classical reactive intermediates in organic chemistry—can react in discriminating fashion with trapping reagents. In particular, whether these species can react selectively with substrates containing multiple functional groups and possible sites of reactivity has remained unanswered. Natural products comprise a palette of multifunctional compounds with which to address this question. Here, we show that benzynes produced by the hexadehydro-Diels-Alder (HDDA) reaction react with many secondary metabolites with a preference for one among several pathways. Examples demonstrating such selectivity include reactions with: phenolics, through dearomatizing ortho-substitution; alkaloids, through Hofmann-type elimination; tropolone and furan, through cycloaddition; and alkaloids, through three-component fragmentation-coupling reactions. We also demonstrate that the cinchona alkaloids quinidine and quinine give rise to products (some in as few as three steps) that enable subsequent and rapid access to structurally diverse polyheterocyclic compounds. The results show that benzynes are quite discriminating in their reactivity—a trait perhaps not broadly enough appreciated.

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

PubMed

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.

Diels-Alder reactions of 12-hydroxy-9(10®20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione.

PubMed

Majetich, George; Zhang, Yong; Tian, Xinrong; Zou, Ge; Li, Yang; Wang, Yangyang; Hu, Shougang; Huddleston, Eric

2013-06-14

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.

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

PubMed Central

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

One-pot Diels–Alder cycloaddition/gold(I)-catalyzed 6-endo-dig cyclization for the synthesis of the complex bicyclo[3.3.1]alkenone framework

PubMed Central

Sow, Boubacar; Bellavance, Gabriel; Barabé, Francis

2011-01-01

Summary The rapid synthesis of bicyclo[m.n.1]alkanone cores possessing quaternary carbon centers adjacent to a bridged ketone represents a significant synthetic challenge. This type of architectural feature is embedded in various complex biologically active compounds such as hyperforin and garsubellin A. Herein, we report a highly diastereoselective one-pot Diels–Alder reaction/Au(I)-catalyzed carbocyclization to generate bicyclo[3.3.1]alkanones in yields ranging from 48–93%. PMID:21915201

Heteropoly acid-catalyzed microwave-assisted three-component aza-Diels-Alder cyclizations: diastereoselective synthesis of potential drug candidates for Alzheimer's disease.

PubMed

Borkin, Dmitry; Morzhina, Elena; Datta, Silpi; Rudnitskaya, Aleksandra; Sood, Abha; Török, Marianna; Török, Béla

2011-03-07

A highly diastereoselective microwave-assisted three component synthesis of azabicyclo[2.2.2]octan-5-ones by a silicotungstic acid-catalyzed aza-Diels-Alder cyclization is described. The one-pot process involves the formation of the in situ generated Schiff base and its immediate cyclization with cyclohex-2-enone. The short reaction times, good yields and excellent diastereoselectivity make this annulation a practical and environmentally attractive method for the synthesis of the target compounds. Preliminary assays were carried out to determine the activity of the products in AChE as well as in amyloid β fibrillogenesis inhibition.

Cross-Diels-Alder reactions of 6-oxo-1-sulfonyl-1,6-dihydropyridine-3-carboxylates.

PubMed

Teyssot, Marie-Laure; Lormier, Anh-Tuan; Chataigner, Isabelle; Piettre, Serge R

2007-03-30

Electron-poor 6-oxo-1-sulfonyl-1,6-dihydropyridine-3-carboxylates 1b-d undergo cross-Diels-Alder reactions with electron-rich dienes 4a-f under hyperbaric conditions, reacting either as dienophiles to yield normal-electron-demand (NED) cycloadducts 10 and/or 11 or as dienes to give inverse-electron-demand (IED) cycloadducts 12 and/or 13. The latter are converted into 14 and/or 15 through an NED cycloaddition with a second equivalent of electron-rich diene. Acyclic dienes display a propensity to yield NED products, whereas cyclic dienes tend to favor IED cycloadducts. High-pressure activation compares favorably with thermal or microwave activation in terms of both yields and suppression of the transformation of 1 into unreactive pyridines 3. Whereas the Cope rearrangement from IED to NED occurs under thermal conditions, no evidence of its involvement under high pressure could be detected. These and other data point to similar activation energies for the NED and IED processes under these conditions.

Three-Dimensional Graphene Structure for Healable Flexible Electronics Based on Diels-Alder Chemistry.

PubMed

Li, Jinhui; Liu, Qiang; Ho, Derek; Zhao, Songfang; Wu, Shuwen; Ling, Lei; Han, Fei; Wu, Xinxiu; Zhang, Guoping; Sun, Rong; Wong, Ching-Ping

2018-03-21

Wearable electronics with excellent stretchability and sensitivity have emerged as a very promising field with wide applications such as e-skin and human motion detection. Although three-dimensional (3D) graphene structures (GS) have been reported for high-performance strain sensors, challenges still remain such as the high cost of GS preparation, low stretchability, and the lack of ability to heal itself. In this paper, we reported a novel self-healing flexible electronics with 3D GS based on Diels-Alder (DA) chemistry. Furfurylamine (FA) was employed as a reducing as well as a modifying agent, forming GS by FA (FAGS)/DA bonds contained polyurethane with the "infiltrate-gel-dry" process. The as-prepared composite exhibited excellent stretchability (200%) and intrinsic conductivity with low incorporation of graphene (about 2 wt %), which could be directly employed for flexible electronics to detect human motions. Besides, the FAGS/DAPU composite exhibited lower temperature retro-DA response for the continuous graphene networks. Highly effective healing of the composites by heat and microwave has been demonstrated successfully.

A diels-alder modulated approach to control and sustain the release of dexamethasone and induce osteogenic differentiation of human mesenchymal stem cells

PubMed Central

Koehler, Kenneth C.; Alge, Daniel L.; Anseth, Kristi S.; Bowman, Christopher N.

2013-01-01

We report a new approach to controlled drug release based upon exploiting the dynamic equilibrium that exists between Diels-Alder reactants and products, demonstrating the release of a furan containing dexamethasone peptide (dex-KGPQG-furan) from a maleimide containing hydrogel. Using a reaction-diffusion model, the release kinetics were tuned to achieve sustained concentrations conducive to osteogenic differentiation of human mesenchymal stem cells (hMSCs). Efficacy was first demonstrated in a 2D culture model, in which dexamethasone release induced significant increases in alkaline phosphatase (ALP) activity and mineral deposition in hMSCs compared to a dexamethasone-free treatment. The results were similar to that observed with a soluble dexamethasone treatment. More dramatic differences were observed in 3D culture, where co-encapsulation of a dexamethasone releasing hydrogel depot within an hMSC-laden extracellular matrix mimetic poly(ethylene glycol) hydrogel resulted in a local and robust osteogenic differentiation. ALP activity reached levels that were up to six times higher than the dexamethasone free treatment. Interestingly, at 5 and 10 day time points, the ALP activity exceeded the dexamethasone positive control, suggesting a potential benefit of sustained release in 3D culture. After 21 days, substantial mineralization comparable to the positive control was also observed in the hydrogels. Collectively, these results demonstrate Diels-Alder modulated release as an effective and versatile new platform for controlled drug delivery that may prove especially beneficial for sustaining the release of low molecular weight molecules in hydrogel systems. PMID:23465826

Monitoring breeding and migration of neotropical migratory birds at Point Loma, San Diego County, California, 5-year summary, 2011–15

USGS Publications Warehouse

Lynn, Suellen; Madden, Melanie C.; Kus, Barbara E.

2017-04-27

Executive SummaryWe operated a bird banding station on the Point Loma peninsula in western San Diego County, California, during spring and summer from 2011 to 2015. The station was established in 2010 as part of a long-term monitoring program for neotropical migratory birds during spring migration and for breeding birds as part of the Monitoring Avian Productivity and Survivorship (MAPS) program.During spring migration (April and May), 2011–15, we captured 1,760 individual birds of 54 species, 91 percent (1,595) of which were newly banded, fewer than 1 percent (3) of which were recaptures that were banded in previous years, and 9 percent (143 hummingbirds, 2 hawks, and 17 other birds) of which we released unbanded. We observed an additional 22 species that were not captured. Thirty-four individuals were captured more than once. Bird capture rate averaged 0.49 ± 0.07 captures per net-hour (range 0.41–0.56). Species richness per day averaged 6.87 ± 0.33. Cardellina pusilla (Wilson’s warbler) was the most abundant spring migrant captured, followed by Empidonax difficilis (Pacific-slope flycatcher), Vireo gilvus (warbling vireo), Zonotrichia leucophrys (white-crowned sparrow), and Selasphorus rufus (rufous hummingbird). Captures of white-crowned sparrow decreased, and captures of Pacific-slope flycatcher increased, over the 5 years of our study. Fifty-six percent of known-sex individuals were male and 44 percent were female. The peak number of new species arriving per day ranged from April 1 (2013-six species) to April 16 (2012-five species). A significant correlation was determined between the number of migrants captured each day per net-hour and the density of echoes on the Next-Generation Radar (NEXRAD) images across all 5 years, and in each year except 2014. NEXRAD radar imagery appears to be a useful tool for detecting pulses in migration.Our results indicate that Point Loma provides stopover habitat during migration for 76 migratory species, including 20

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

PubMed Central

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

2014-01-01

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

Intramolecular Aza-Diels-Alder Reactions of ortho-Quinone Methide Imines: Rapid, Catalytic, and Enantioselective Assembly of Benzannulated Quinolizidines.

PubMed

Kretzschmar, Martin; Hofmann, Fabian; Moock, Daniel; Schneider, Christoph

2018-04-16

Aza-Diels-Alder reactions (ADARs) are powerful processes that furnish N-heterocycles in a straightforward fashion. Intramolecular variants offer the additional possibility of generating bi- and polycyclic systems with high stereoselectivity. We report herein a novel Brønsted acid catalyzed process in which ortho-quinone methide imines tethered to the dienophile via the N substituent react in an intramolecular ADAR to form complex quinolizidines and oxazinoquinolines in a one-step process. The reactions proceed under very mild conditions, with very good yields and good to very good diastereo- and enantioselectivities. Furthermore, the process was extended to a domino reaction that efficiently combines substrate synthesis, ortho-quinone methide imine formation, and ADAR. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2015-04-13

The [4+2] cycloaddition of 3-alkoxyfurans with N-substituted maleimides provides the first general route for preparing endo-cantharimides. Unlike the corresponding reaction with 3H furans, the reaction can tolerate a broad range of 2-substitued furans including alkyl, aromatic, and heteroaromatic groups. The cycloaddition products were converted into a range of cantharimide products with promising lead-like properties for medicinal chemistry programs. Furthermore, the electron-rich furans are shown to react with a variety of alternative dienophiles to generate 7-oxabicyclo[2.2.1]heptane derivatives under mild conditions. DFT calculations have been performed to rationalize the activation effect of the 3-alkoxy group on a furan Diels-Alder reaction. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Natural selection and inheritance of breeding time and clutch size in the collared flycatcher.

PubMed

Sheldon, B C; Kruuk, L E B; Merilä, J

2003-02-01

Many characteristics of organisms in free-living populations appear to be under directional selection, possess additive genetic variance, and yet show no evolutionary response to selection. Avian breeding time and clutch size are often-cited examples of such characters. We report analyses of inheritance of, and selection on, these traits in a long-term study of a wild population of the collared flycatcher Ficedula albicollis. We used mixed model analysis with REML estimation ("animal models") to make full use of the information in complex multigenerational pedigrees. Heritability of laying date, but not clutch size, was lower than that estimated previously using parent-offspring regressions, although for both traits there was evidence of substantial additive genetic variance (h2 = 0.19 and 0.29, respectively). Laying date and clutch size were negatively genetically correlated (rA = -0.41 +/- 0.09), implying that selection on one of the traits would cause a correlated response in the other, but there was little evidence to suggest that evolution of either trait would be constrained by correlations with other phenotypic characters. Analysis of selection on these traits in females revealed consistent strong directional fecundity selection for earlier breeding at the level of the phenotype (beta = -0.28 +/- 0.03), but little evidence for stabilising selection on breeding time. We found no evidence that clutch size was independently under selection. Analysis of fecundity selection on breeding values for laying date, estimated from an animal model, indicated that selection acts directly on additive genetic variance underlying breeding time (beta = -0.20 +/- 0.04), but not on clutch size (beta = 0.03 +/- 0.05). In contrast, selection on laying date via adult female survival fluctuated in sign between years, and was opposite in sign for selection on phenotypes (negative) and breeding values (positive). Our data thus suggest that any evolutionary response to selection on

Male-male competition and parental care in collared flycatchers (Ficedula albicollis): an experiment controlling for differences in territory quality.

PubMed

Qvarnström, A; Grifffith, S C; Gustafsson, L

2000-12-22

Females are known to benefit from mate choice in several different ways but the relationship between these benefits has received little attention. The quality of resources provided by males, such as nest sites, and paternal care are often assumed to covary positively However, because the location of the nest affects the cost of parental care, these two benefits from mate choice can easily be confounded. To investigate the provisioning ability of successful competitors while controlling for differences in territory quality we removed early-settled pairs of collared flycatchers (Ficedula albicollis) and allowed replacement by later-arriving males or floaters (i.e.'poor competitors'). A control group of early-settled males (i.e. 'good competitors') had their females removed. Females paired to good competitors enjoyed a significantly higher reproductive success and tended to receive more parental assistance from their mates compared with females mated to poor competitors. Thus, some males seem able not only to compete successfully over resources but also to feed their offspring at a relatively higher rate. An alternative explanation, that poor competitors invested less in offspring quality in response to a lower share of paternity, could be rejected. The rate of extra-pair paternity did not differ between the two treatment groups. Our results suggest that male- male competition can sometimes facilitate female choice of superior care-givers. Thus, a female's benefit from choosing a competitive male may not be restricted to the quality of the resource he defends but can also include superior paternal care.

Tamarisk biocontrol using tamarisk beetles: Potential consequences for riparian birds in the southwestern United States

USGS Publications Warehouse

Paxton, E.H.; Theimer, T.C.; Sogge, M.K.

2011-01-01

The tamarisk beetle (Diorhabda spp.), a non-native biocontrol agent, has been introduced to eradicate tamarisk (Tamarix spp.), a genus of non-native tree that has become a dominant component of riparian woodlands in the southwestern United States. Tamarisk beetles have the potential to spread widely and defoliate large expanses of tamarisk habitat, but the effects of such a widespread loss of riparian vegetation on birds remains unknown. We reviewed literature on the effects of other defoliating insects on birds to investigate the potential for tamarisk beetles to affect birds positively or negatively by changing food abundance and vegetation structure. We then combined data on the temporal patterns of tamarisk defoliation by beetles with nest productivity of a wellstudied riparian obligate, the Southwestern Willow Flycatcher (Empidonax traillii extimus), to simulate the potential demographic consequences of beetle defoliation on breeding riparian birds in both the short and long term. Our results highlight that the effects of tamarisk biocontrol on birds will likely vary by species and population, depending upon its sensitivity to seasonal defoliation by beetles and net loss of riparian habitat due to tamarisk mortality. Species with restricted distributions that include areas dominated by tamarisk may be negatively affected both in the short and long term. The rate of regeneration and/or restoration of native cottonwoods (Populus spp.) and willows (Salix spp.) relative to the rate of tamarisk loss will be critical in determining the long-term effect of this large-scale ecological experiment. ?? The Cooper Ornithological Society 2011.

Planned flooding and Colorado River riparian trade-offs downstream from Glen Canyon Dam, Arizona

USGS Publications Warehouse

Stevens, Lawrence E.; Ayers, T.J.; Bennett, J.B.; Christensen, K.; Kearsley, M.J.C.; Meretsky, V.J.; Phillips, A. M.; Parnell, R.A.; Spence, J.; Sogge, M.K.; Springer, A.E.; Wegner, D.L.

2001-01-01

Regulated river restoration through planned flooding involves trade-offs between aquatic and terrestrial components, between relict pre-dam and novel post-dam resources and processes, and between management of individual resources and ecosystem characteristics. We review the terrestrial (wetland and riparian) impacts of a 1274 m3/s test flood conducted by the U.S. Bureau of Reclamation in March/April 1996, which was designed to improve understanding of sediment transport and management downstream from Glen Canyon Dam in the Colorado River ecosystem. The test flood successfully restored sandbars throughout the river corridor and was timed to prevent direct impacts to species of concern. A total of 1275 endangered Kanab ambersnail (Oxyloma haydeni kanabensis) were translocated above the flood zone at Vaseys Paradise spring, and an estimated 10.7% of the total snail habitat and 7.7% of the total snail population were lost to the flood. The test flood scoured channel margin wetlands, including potential foraging habitats of endangered Southwestern Willow Flycatcher (Empidonax traillii extimus). It also buried ground-covering riparian vegetation under >1 m of fine sand but only slightly altered woody sandbar vegetation and some return-current channel marshes. Pre-flood control efforts and appropriate flood timing limited recruitment of four common nonnative perennial plant species. Slight impacts on ethnobotanical resources were detected >430 km downstream, but those plant assemblages recovered rapidly. Careful design of planned flood hydrograph shape and seasonal timing is required to mitigate terrestrial impacts during efforts to restore essential fluvial geomorphic and aquatic habitats in regulated river ecosystems.

Subtle but ubiquitous selection on body size in a natural population of collared flycatchers over 33 years.

PubMed

Björklund, M; Gustafsson, L

2017-07-01

Understanding the magnitude and long-term patterns of selection in natural populations is of importance, for example, when analysing the evolutionary impact of climate change. We estimated univariate and multivariate directional, quadratic and correlational selection on four morphological traits (adult wing, tarsus and tail length, body mass) over a time period of 33 years (≈ 19 000 observations) in a nest-box breeding population of collared flycatchers (Ficedula albicollis). In general, selection was weak in both males and females over the years regardless of fitness measure (fledged young, recruits and survival) with only few cases with statistically significant selection. When data were analysed in a multivariate context and as time series, a number of patterns emerged; there was a consistent, but weak, selection for longer wings in both sexes, selection was stronger on females when the number of fledged young was used as a fitness measure, there were no indications of sexually antagonistic selection, and we found a negative correlation between selection on tarsus and wing length in both sexes but using different fitness measures. Uni- and multivariate selection gradients were correlated only for wing length and mass. Multivariate selection gradient vectors were longer than corresponding vector of univariate gradients and had more constrained direction. Correlational selection had little importance. Overall, the fitness surface was more or less flat with few cases of significant curvature, indicating that the adaptive peak with regard to body size in this species is broader than the phenotypic distribution, which has resulted in weak estimates of selection. © 2017 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2017 European Society For Evolutionary Biology.

Genomic distribution and estimation of nucleotide diversity in natural populations: perspectives from the collared flycatcher (Ficedula albicollis) genome.

PubMed

Dutoit, Ludovic; Burri, Reto; Nater, Alexander; Mugal, Carina F; Ellegren, Hans

2017-07-01

Properly estimating genetic diversity in populations of nonmodel species requires a basic understanding of how diversity is distributed across the genome and among individuals. To this end, we analysed whole-genome resequencing data from 20 collared flycatchers (genome size ≈1.1 Gb; 10.13 million single nucleotide polymorphisms detected). Genomewide nucleotide diversity was almost identical among individuals (mean = 0.00394, range = 0.00384-0.00401), but diversity levels varied extensively across the genome (95% confidence interval for 200-kb windows = 0.0013-0.0053). Diversity was related to selective constraint such that in comparison with intergenic DNA, diversity at fourfold degenerate sites was reduced to 85%, 3' UTRs to 82%, 5' UTRs to 70% and nondegenerate sites to 12%. There was a strong positive correlation between diversity and chromosome size, probably driven by a higher density of targets for selection on smaller chromosomes increasing the diversity-reducing effect of linked selection. Simulations exploring the ability of sequence data from a small number of genetic markers to capture the observed diversity clearly demonstrated that diversity estimation from finite sampling of such data is bound to be associated with large confidence intervals. Nevertheless, we show that precision in diversity estimation in large outbred population benefits from increasing the number of loci rather than the number of individuals. Simulations mimicking RAD sequencing showed that this approach gives accurate estimates of genomewide diversity. Based on the patterns of observed diversity and the performed simulations, we provide broad recommendations for how genetic diversity should be estimated in natural populations. © 2016 The Authors. Molecular Ecology Resources Published by John Wiley & Sons Ltd.

Random quaternary ammonium Diels-Alder poly(phenylene) copolymers for improved vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

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.

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

PubMed Central

Chen, Wei; Sun, Lipeng; Tang, Zhiye; Ali, Zulfikhar A.; Wong, Bryan M.; Chang, Chia-en A.

2018-01-01

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. PMID:29938117

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

PubMed Central

Acero, Nuria

2012-01-01

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

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

NASA Astrophysics Data System (ADS)

Aydin, Ismail; Colakoglu, Gursel

2005-10-01

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

Synthesis of Polyheterocyclic Pyrrolo[3,4-b]pyridin-5-ones via a One-Pot (Ugi-3CR/aza Diels-Alder/N-acylation/aromatization/SN2) Process. A Suitable Alternative towards Novel Aza-Analogues of Falipamil.

PubMed

Zamudio-Medina, Angel; García-González, Ailyn N; Herrera-Carrillo, Genesis K; Zárate-Zárate, Daniel; Benavides-Macías, Adriana; Tamariz, Joaquín; Ibarra, Ilich A; Islas-Jácome, Alejandro; González-Zamora, Eduardo

2018-03-27

We describe the one-pot synthesis of twenty polyheterocyclic pyrrolo[3,4- b ]pyridin-5-ones via a cascade process (Ugi-3CR/aza Diels-Alder/ N -acylation/aromatization) in 20 to 95% overall yields, as well as four pharmacologically promising analogues via an improved cascade process (Ugi-3CR/aza Diels-Alder/ N -acylation/aromatization/S N 2): two piperazine-linked pyrrolo[3,4- b ]pyridin-5-ones in 33 and 34%, and a couple of Falipamil aza-analogues in 30 and 35% overall yields. It is worth highlighting the good substrate scope found, because final products are furnished with alkyl, aryl, and heterocyclic substituents. The use of chain-ring tautomerizable isocyanides (as key reagents for the Ugi-type three component reaction) allowed for a rapid and efficient assembly of the polysubstituted oxindoles, which were used in situ toward the complex products, conferring features like robustness, sustainability, and the one-pot approach to this synthetic methodology.

Novel Diels-Alder based self-healing epoxies for aerospace composites

NASA Astrophysics Data System (ADS)

Coope, T. S.; Turkenburg, D. H.; Fischer, H. R.; Luterbacher, R.; van Bracht, H.; Bond, I. P.

2016-08-01

Epoxy resins containing Diels-Alder (DA) furan and maleimide moieties are presented with the capability to self-heal after exposure to an external heat source. A conventional epoxy amine system has been combined with furfuryl and maleimide functional groups in a two-step process, to avoid major side-reactions, and the concentration of a thermo-reversibly binding cross-linker was considered to balance thermoset and thermoplastic behaviours, and the subsequent self-healing performance. In the context of self-repair technologies an inbuilt ‘intrinsic’ self-healing system is deemed favourable as the healing agent can be placed in known ‘hot spot’ regions (i.e. skin-stringer run outs, ply drops and around drilled holes) where operational damage predominately occurs in load bearing aerospace structures. In this study, the mechanical and self-healing performance of furan functionalised epoxy resins containing varying amounts (10, 20, 30 or 40 pph) of bismaleimide were investigated using a bulk epoxy polymer tapered double cantilever beam test specimen geometry. Two forms, a thin film and a bulk material, were evaluated to account for future integration methods into fibre reinforced polymer (FRP) composites. The highest healing efficiency, with respect to the obtained initial load value, was observed from the 20 pph bulk material derivative. The polymers were successful in achieving consistent multiple (three) healing cycles when heated at 150 °C for 5 min. This novel investigated DA material exhibits favourable processing characteristics for FRP composites as preliminary studies have shown successful coextrution with reinforcing fibres to form free standing films and dry fibre impregnation.

Habitat shifts in the evolutionary history of a Neotropical flycatcher lineage from forest and open landscapes

PubMed Central

2008-01-01

Background Little is known about the role ecological shifts play in the evolution of Neotropical radiations that have colonized a variety of environments. We here examine habitat shifts in the evolutionary history of Elaenia flycatchers, a Neotropical bird lineage that lives in a range of forest and open habitats. We evaluate phylogenetic relationships within the genus based on mitochondrial and nuclear DNA sequence data, and then employ parsimony-based and Bayesian methods to reconstruct preferences for a number of habitat types and migratory behaviour throughout the evolutionary history of the genus. Using a molecular clock approach, we date the most important habitat shifts. Results Our analyses resolve phylogenetic relationships among Elaenia species and confirm several species associations predicted by morphology while furnishing support for other taxon placements that are in conflict with traditional classification, such as the elevation of various Elaenia taxa to species level. While savannah specialism is restricted to one basal clade within the genus, montane forest was invaded from open habitat only on a limited number of occasions. Riparian growth may have been favoured early on in the evolution of the main Elaenia clade and subsequently been deserted on several occasions. Austral long-distance migratory behaviour evolved on several occasions. Conclusion Ancestral reconstructions of habitat preferences reveal pronounced differences not only in the timing of the emergence of certain habitat preferences, but also in the frequency of habitat shifts. The early origin of savannah specialism in Elaenia highlights the importance of this habitat in Neotropical Pliocene and late Miocene biogeography. While forest in old mountain ranges such as the Tepuis and the Brazilian Shield was colonized early on, the most important colonization event of montane forest was in conjunction with Pliocene Andean uplift. Riparian habitats may have played an important role in

Diels Alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

DOE PAGES

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

2015-10-23

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

Temperature-controlled cross-linking of silver nanoparticles with diels-alder reaction and its application on antibacterial property

NASA Astrophysics Data System (ADS)

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.

A role for hydrophobicity in a Diels–Alder reaction catalyzed by pyridyl-modified RNA

PubMed Central

Gagnon, Keith T.; Ju, Show-Yi; Goshe, Michael B.; Maxwell, E. Stuart; Franzen, Stefan

2009-01-01

New classes of RNA enzymes or ribozymes have been obtained by in vitro evolution and selection of RNA molecules. Incorporation of modified nucleotides into the RNA sequence has been proposed to enhance function. DA22 is a modified RNA containing 5-(4-pyridylmethyl) carboxamide uridines, which has been selected for its ability to promote a Diels–Alder cycloaddition reaction. Here, we show that DA_TR96, the most active member of the DA22 RNA sequence family, which was selected with pyridyl-modified nucleotides, accelerates a cycloaddition reaction between anthracene and maleimide derivatives with high turnover. These widely used reactants were not used in the original selection for DA22 and yet here they provide the first demonstration of DA_TR96 as a true multiple-turnover catalyst. In addition, the absence of a structural or essential kinetic role for Cu2+, as initially postulated, and nonsequence-specific hydrophobic interactions with the anthracene substrate have led to a reevaluation of the pyridine modification's role. These findings broaden the catalytic repertoire of the DA22 family of pyridyl-modified RNAs and suggest a key role for the hydrophobic effect in the catalytic mechanism. PMID:19304744

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

NASA Technical Reports Server (NTRS)

Tyson, Daniel S.; Ilhan, Faysal; Meador, Mary Ann B.; Smith, Dee Dee; Scheiman, Daniel A.; Meador, Michael A.

2004-01-01

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

Prediction of the chemo- and regioselectivity of Diels-Alder reactions of o-benzoquinone derivatives with thiophenes by means of DFT-based reactivity indices

NASA Astrophysics Data System (ADS)

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.

Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

DOE PAGES

Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; ...

2015-11-14

In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm 2.« less

Diels-Alder and Stille Coupling Approach for the Short Protecting-Group-Free Synthesis of Mycophenolic Acid, Its Phenylsulfenyl and Phenylselenyl Analogues, and Reactive Oxygen Species (ROS) Probing Capacity in Water.

PubMed

Halle, Mahesh B; Yudhistira, Tesla; Lee, Woo-Hyun; Mulay, Sandip V; Churchill, David G

2018-06-15

A short, protecting-group-free synthesis is achieved. The synthesis is step-efficient and general. A Diels-Alder and Stille cross-coupling approach includes key transformations, allowing for a competitive synthesis which involves a rare halophenol Stille cross-coupling study. The phenylselenyl and phenylsulfenyl analogues were prepared as novel compounds in good overall yield. The applicability of one of the intermediates as a potential probe for reactive oxygen species (ROS) in water is investigated.

Monitoring avian productivity and survivorship (MAPS) 5-year summary, Naval Outlying Landing Field, Imperial Beach, southwestern San Diego County, California, 2009-13

USGS Publications Warehouse

Lynn, Suellen; Madden, Melanie C.; Houston, Alexandra; Kus, Barbara E.

2015-01-01

During 2009–13, a Monitoring Avian Productivity and Survivorship (MAPS) banding station was operated at the Naval Outlying Landing Field (NOLF), Imperial Beach, in southwestern San Diego County, California. The station was established as part of a long-term monitoring program of Neotropical migratory bird populations on NOLF and helps Naval Base Coronado (NOLF is a component) meet the goals and objectives of Department of Defense Partners in Flight program and the Birds and Migratory Birds Management Strategies of the Naval Base Coronado Integrated Natural Resources Management Plan. During 2009–13, captures averaged 644 ±155 per year. Fifty-seven species were captured, of which 44 are Neotropical migratory species and 33 breed at the MAPS station. Twenty-two sensitive species were detected, including Least Bell’s Vireo (Vireo bellii pusillus), Willow Flycatcher (Empidonax traillii), Yellow-breasted Chat (Icteria virens) and Yellow Warbler (Setophaga petechia). Local population trends varied among species and years, as did annual productivity (number of young per adult). We found no significant relationship between productivity and the observed population size in the subsequent year for any species, nor did we find an association between productivity and precipitation for the current bio-year. Similarly, survivorship varied across species and years, and there was no obvious relationship between adult survivorship and observed population size for any species except Wrentit (Chamaea fasciata), for which the relationship was positive. Adult survivorship was unrelated to precipitation at the MAPS station. Additional years of data will be required to generate sample sizes adequate for more rigorous analyses of survivorship and productivity as predictors of population growth.

77 FR 41147 - Endangered and Threatened Wildlife and Plants; Designation of Revised Critical Habitat for the...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-07-12

... segments and associated flycatcher habitat are anticipated to support the strategy, rationale, and science... strategy, rationale, and science of flycatcher conservation in order to meet territory and habitat-related... costs associated with monitoring and education activities, fencing, habitat restoration and creation...

Mild and modular surface modification of cellulose via hetero Diels-Alder (HDA) cycloaddition.

PubMed

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.

Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes.

PubMed

Cao, Yang; Liang, Yong; Zhang, Lei; Osuna, Sílvia; Hoyt, Andra-Lisa M; Briseno, Alejandro L; Houk, K N

2014-07-30

The Diels-Alder (DA) reactions of pentacene (PT), 6,13-bis(2-trimethylsilylethynyl)pentacene (TMS-PT), bistetracene (BT), and 8,17-bis(2-trimethylsilylethynyl)bistetracene (TMS-BT) with the [6,6] double bond of [60]fullerene have been investigated by density functional theory calculations. Reaction barriers and free energies have been obtained to assess the effects of frameworks and substituent groups on the DA reactivity and product stability. Calculations indicate that TMS-BT is about 5 orders of magnitude less reactive than TMS-PT in the reactions with [60]fullerene. This accounts for the observed much higher stability of TIPS-BT than TIPS-PT when mixed with PCBM. Surprisingly, calculations predict that the bulky silylethynyl substituents of TMS-PT and TMS-BT have only a small influence on reaction barriers. However, the silylethynyl substituents significantly destabilize the corresponding products due to steric repulsions in the adducts. This is confirmed by experimental results here. Architectures of the polycyclic aromatic hydrocarbons (PAHs) play a crucial role in determining both the DA barrier and the adduct stability. The reactivities of different sites in various PAHs are related to the loss of aromaticity, which can be predicted using the simple Hückel molecular orbital localization energy calculations.

Whole-genome patterns of linkage disequilibrium across flycatcher populations clarify the causes and consequences of fine-scale recombination rate variation in birds.

PubMed

Kawakami, Takeshi; Mugal, Carina F; Suh, Alexander; Nater, Alexander; Burri, Reto; Smeds, Linnéa; Ellegren, Hans

2017-08-01

Recombination rate is heterogeneous across the genome of various species and so are genetic diversity and differentiation as a consequence of linked selection. However, we still lack a clear picture of the underlying mechanisms for regulating recombination. Here we estimated fine-scale population recombination rate based on the patterns of linkage disequilibrium across the genomes of multiple populations of two closely related flycatcher species (Ficedula albicollis and F. hypoleuca). This revealed an overall conservation of the recombination landscape between these species at the scale of 200 kb, but we also identified differences in the local rate of recombination despite their recent divergence (<1 million years). Genetic diversity and differentiation were associated with recombination rate in a lineage-specific manner, indicating differences in the extent of linked selection between species. We detected 400-3,085 recombination hotspots per population. Location of hotspots was conserved between species, but the intensity of hotspot activity varied between species. Recombination hotspots were primarily associated with CpG islands (CGIs), regardless of whether CGIs were at promoter regions or away from genes. Recombination hotspots were also associated with specific transposable elements (TEs), but this association appears indirect due to shared preferences of the transposition machinery and the recombination machinery for accessible open chromatin regions. Our results suggest that CGIs are a major determinant of the localization of recombination hotspots, and we propose that both the distribution of TEs and fine-scale variation in recombination rate may be associated with the evolution of the epigenetic landscape. © 2017 The Authors. Molecular Ecology Published by John Wiley & Sons Ltd.

Catalysis in the Diels-Alder Cycloaddition of Biomass-Derived Furan and Methyl Acrylate by Transition Metal Oxide Surfaces.

NASA Astrophysics Data System (ADS)

Salavati-Fard, Taha; Jenness, Glen; Caratzoulas, Stavros; Doren, Douglas

Using computational methods, the catalytic effects of oxide surfaces on the Diels-Alder reaction between biomass-derived furan and methyl acrylate are investigated. The cycloadduct can be dehydrated later to produce methyl benzoic which is an important step toward benzoic acid production. Different systems such as clean, partially hydroxylated and fully hydroxylated ZrO2 are considered. The Langmuir and Eley-Rideal mechanisms are studied, as well. Our calculations show that the oxide surfaces catalyze the reaction significantly through the interaction of metal sites with the electron-poor reactant. The calculations are interpreted by making use of the total and projected electronic density of states and band structure of the catalyst. This material is based on work supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001004.

(125)I-Tetrazines and Inverse-Electron-Demand Diels-Alder Chemistry: A Convenient Radioiodination Strategy for Biomolecule Labeling, Screening, and Biodistribution Studies.

PubMed

Albu, Silvia A; Al-Karmi, Salma A; Vito, Alyssa; Dzandzi, James P K; Zlitni, Aimen; Beckford-Vera, Denis; Blacker, Megan; Janzen, Nancy; Patel, Ramesh M; Capretta, Alfredo; Valliant, John F

2016-01-20

A convenient method to prepare radioiodinated tetrazines was developed, such that a bioorthogonal inverse electron demand Diels-Alder reaction can be used to label biomolecules with iodine-125 for in vitro screening and in vivo biodistribution studies. The tetrazine was prepared by employing a high-yielding oxidative halo destannylation reaction that concomitantly oxidized the dihydrotetrazine precursor. The product reacts quickly and efficiently with trans-cyclooctene derivatives. Utility was demonstrated through antibody and hormone labeling experiments and by evaluating products using standard analytical methods, in vitro assays, and quantitative biodistribution studies where the latter was performed in direct comparison to Bolton-Hunter and direct iodination methods. The approach described provides a convenient and advantageous alternative to conventional protein iodination methods that can expedite preclinical development and evaluation of biotherapeutics.

Solution-phase parallel synthesis of hexahydro-1H-isoindolone libraries via tactical combination of Cu-catalyzed three-component coupling and Diels-Alder reactions.

PubMed

Zhang, Lei; Lushington, Gerald H; Neuenswander, Benjamin; Hershberger, John C; Malinakova, Helena C

2008-01-01

Parallel solution-phase synthesis of combinatorial libraries of hexahydro-1 H-isoindolones exploiting a novel "tactical combination" of Cu-catalyzed three-component coupling and Diels-Alder reactions was accomplished. Three distinct libraries consisting of 24 members (library I), 60 members (library II), and 32 members (library III) were constructed. Variation of three substituents on the isoindolone scaffold in library I was exclusively achieved by the choice of the building blocks. In the syntheses of libraries II and III, sublibraries of isoindolone scaffolds were prepared initially in a one-pot/two-step process and were further diversified via Pd-catalyzed Suzuki cross-coupling reaction with boronic acids at two different diversification points. The Lipinski profiles and calculated ADME properties of the compounds are also reported.

Self-healable interfaces based on thermo-reversible Diels-Alder reactions in carbon fiber reinforced composites.

PubMed

Zhang, W; Duchet, J; Gérard, J F

2014-09-15

Thermo-reversible Diels-Alder (DA) bonds formed between maleimide and furan groups have been used to generate an interphase between carbon fiber surface and an epoxy matrix leading to the ability of interfacial self-healing in carbon:epoxy composite materials. The maleimide groups were grafted on an untreated T700 carbon fiber from a three step surface treatment: (i) nitric acid oxidization, (ii) tetraethylenepentamine amination, and (iii) bismaleimide grafting. The furan groups were introduced in the reactive epoxy system from furfuryl glycidyl ether. The interface between untreated carbon fiber and epoxy matrix was considered as a reference. The interfacial shear strength (IFSS) was evaluated by single fiber micro-debonding test. The debonding force was shown to have a linear dependence with embedded length. The highest healing efficiency calculated from the debonding force was found to be about 82% more compared to the value for the reference interface. All the interphases designed with reversible DA bonds have a repeatable self-healing ability. As after the fourth healing, they can recover a relatively high healing efficiency (58% for the interphase formed by T700-BMI which is oxidized for 60 min during the first treatment step). Copyright © 2014 Elsevier Inc. All rights reserved.

Breeding birds in managed forests on public conservation lands in the Mississippi Alluvial Valley

USGS Publications Warehouse

Twedt, Daniel J.; Wilson, R. Randy

2017-01-01

Managers of public conservation lands in the Mississippi Alluvial Valley have implemented forest management strategies to improve bottomland hardwood habitat for target wildlife species. Through implementation of various silvicultural practices, forest managers have sought to attain forest structural conditions (e.g., canopy cover, basal area, etc.) within values postulated to benefit wildlife. We evaluated data from point count surveys of breeding birds on 180 silviculturally treated stands (1049 counts) that ranged from 1 to 20 years post-treatment and 134 control stands (676 counts) that had not been harvested for >20 years. Birds detected during 10-min counts were recorded within four distance classes and three time intervals. Avian diversity was greater on treated stands than on unharvested stands. Of 42 commonly detected species, six species including Prothonotary Warbler (Prothonotaria citrea) and Acadian Flycatcher (Empidonax virescens) were indicative of control stands. Similarly, six species including Indigo Bunting (Passerina cyanea) and Yellow-breasted Chat (Icteria virens) were indicative of treated stands. Using a removal model to assess probability of detection, we evaluated occupancy of bottomland forests at two spatial scales (stands and points within occupied stands). Wildlife-forestry treatment improved predictive models of species occupancy for 18 species. We found years post treatment (range = 1–20), total basal area, and overstory canopy were important species-specific predictors of occupancy, whereas variability in basal area was not. In addition, we used a removal model to estimate species-specific probability of availability for detection, and a distance model to estimate effective detection radius. We used these two estimated parameters to derive species densities and 95% confidence intervals for treated and unharvested stands. Avian densities differed between treated and control stands for 16 species, but only Common Yellowthroat

Implications of Climate Change for Bird Conservation in the Southwestern U.S. under Three Alternative Futures

PubMed Central

Friggens, Megan M.; Finch, Deborah M.

2015-01-01

Future expected changes in climate and human activity threaten many riparian habitats, particularly in the southwestern U.S. Using Maximum Entropy (MaxEnt3.3.3) modeling, we characterized habitat relationships and generated spatial predictions of habitat suitability for the Lucy’s warbler (Oreothlypis luciae), the Southwestern willow flycatcher (Empidonax traillii extimus) and the Western yellow-billed cuckoo (Coccyzus americanus). Our goal was to provide site- and species-specific information that can be used by managers to identify areas for habitat conservation and/or restoration along the Rio Grande in New Mexico. We created models of suitable habitat for each species based on collection and survey samples and climate, biophysical, and vegetation data. We projected habitat suitability under future climates by applying these models to conditions generated from three climate models for 2030, 2060 and 2090. By comparing current and future distributions, we identified how habitats are likely to change as a result of changing climate and the consequences of those changes for these bird species. We also examined whether land ownership of high value sites shifts under changing climate conditions. Habitat suitability models performed well. Biophysical characteristics were more important that climate conditions for predicting habitat suitability with distance to water being the single most important predictor. Climate, though less important, was still influential and led to declines of suitable habitat of more than 60% by 2090. For all species, suitable habitat tended to shrink over time within the study area leaving a few core areas of high importance. Overall, climate changes will increase habitat fragmentation and reduce breeding habitat patch size. The best strategy for conserving bird species within the Rio Grande will include measures to maintain and restore critical habitat refugia. This study provides an example of a presence-only habitat model that can be

Implications of Climate Change for Bird Conservation in the Southwestern U.S. under Three Alternative Futures.

PubMed

Friggens, Megan M; Finch, Deborah M

2015-01-01

Future expected changes in climate and human activity threaten many riparian habitats, particularly in the southwestern U.S. Using Maximum Entropy (MaxEnt3.3.3) modeling, we characterized habitat relationships and generated spatial predictions of habitat suitability for the Lucy's warbler (Oreothlypis luciae), the Southwestern willow flycatcher (Empidonax traillii extimus) and the Western yellow-billed cuckoo (Coccyzus americanus). Our goal was to provide site- and species-specific information that can be used by managers to identify areas for habitat conservation and/or restoration along the Rio Grande in New Mexico. We created models of suitable habitat for each species based on collection and survey samples and climate, biophysical, and vegetation data. We projected habitat suitability under future climates by applying these models to conditions generated from three climate models for 2030, 2060 and 2090. By comparing current and future distributions, we identified how habitats are likely to change as a result of changing climate and the consequences of those changes for these bird species. We also examined whether land ownership of high value sites shifts under changing climate conditions. Habitat suitability models performed well. Biophysical characteristics were more important that climate conditions for predicting habitat suitability with distance to water being the single most important predictor. Climate, though less important, was still influential and led to declines of suitable habitat of more than 60% by 2090. For all species, suitable habitat tended to shrink over time within the study area leaving a few core areas of high importance. Overall, climate changes will increase habitat fragmentation and reduce breeding habitat patch size. The best strategy for conserving bird species within the Rio Grande will include measures to maintain and restore critical habitat refugia. This study provides an example of a presence-only habitat model that can be used

Songbird response to increased willow (Salix spp.) growth in Yellowstone's northern range.

PubMed

Baril, Lisa M; Hansen, Andrew J; Renkin, Roy; Lawrence, Rick

2011-09-01

After nearly a century of height suppression, willows (Salix spp.) in the northern range of Yellowstone National Park, U.S.A., are increasing in height growth as a possible consequence of wolf (Canis lupus) restoration, climate change, or other factors. Regardless of the drivers, the recent release of this rare but important habitat type could have significant implications for associated songbirds that are exhibiting declines in the region. Our objective was to evaluate bird response to releasing willows by comparing willow structure and bird community composition across three willow growth conditions: height suppressed, recently released, and previously tall (i.e., tall prior to the height increase of released willows). Released and previously tall willows exhibited high and similar vertical structure, but released willows were significantly lower in horizontal structure. Suppressed willows were significantly shorter and lower in horizontal cover than released or previously tall willows. Bird richness increased along a gradient from lowest in suppressed to highest in previously tall willows, but abundance and diversity were similar between released and previously tall willows, despite lower horizontal cover in the released condition. Common Yellowthroat (Geothlypis trichas) and Lincoln's Sparrow (Melospiza lincolnii) were found in all three growth conditions; however, Yellow Warbler (Dendroica petechia), Warbling Vireo (Vireo gilvus), Willow Flycatcher (Empidonax traillii), and Song Sparrow (Melospiza melodii) were present in released and previously tall willows only. Wilson's Warbler (Wilsonia pusilla) was found in previously tall willows only, appearing to specialize on tall, dense willows. The results of our a priori habitat models indicated that foliage height diversity was the primary driver of bird richness, abundance, and diversity. These results indicate that vertical structure was a more important driver of bird community variables than horizontal

A removal model for estimating detection probabilities from point-count surveys

USGS Publications Warehouse

Farnsworth, G.L.; Pollock, K.H.; Nichols, J.D.; Simons, T.R.; Hines, J.E.; Sauer, J.R.

2002-01-01

Use of point-count surveys is a popular method for collecting data on abundance and distribution of birds. However, analyses of such data often ignore potential differences in detection probability. We adapted a removal model to directly estimate detection probability during point-count surveys. The model assumes that singing frequency is a major factor influencing probability of detection when birds are surveyed using point counts. This may be appropriate for surveys in which most detections are by sound. The model requires counts to be divided into several time intervals. Point counts are often conducted for 10 min, where the number of birds recorded is divided into those first observed in the first 3 min, the subsequent 2 min, and the last 5 min. We developed a maximum-likelihood estimator for the detectability of birds recorded during counts divided into those intervals. This technique can easily be adapted to point counts divided into intervals of any length. We applied this method to unlimited-radius counts conducted in Great Smoky Mountains National Park. We used model selection criteria to identify whether detection probabilities varied among species, throughout the morning, throughout the season, and among different observers. We found differences in detection probability among species. Species that sing frequently such as Winter Wren (Troglodytes troglodytes) and Acadian Flycatcher (Empidonax virescens) had high detection probabilities (∼90%) and species that call infrequently such as Pileated Woodpecker (Dryocopus pileatus) had low detection probability (36%). We also found detection probabilities varied with the time of day for some species (e.g. thrushes) and between observers for other species. We used the same approach to estimate detection probability and density for a subset of the observations with limited-radius point counts.

Supramolecular hydrogel formation between chitosan and hydroxypropyl β-cyclodextrin via Diels-Alder reaction and its drug delivery.

PubMed

Zhang, Mengke; Wang, Jinpeng; Jin, Zhengyu

2018-07-15

Chitosan-cyclodextrin hydrogel (CFCD) was prepared via Diels-Alder reaction between furfural functionalized chitosan (CF) and N-maleoyl alanine functionalized hydroxypropyl β-cyclodextrin (HPCD-AMI) in aqueous media without any catalyst or initiator. The CF and HPCD-AMI were confirmed by Fourier transform infrared spectroscopy and 1 H nuclear magnetic resonance spectroscopy. The resultant CFCD hydrogel was characterized in terms of thermal peripteries, microstructure, rheology behavior, and swelling capacity. The rheology analysis found that the storage modulus G' ranged from 1pa to 1200pa as the degree of furfural substitute on chitosan increased from 2.6% to 28.3%, indicating the hydrogel strength can be tuned readily by reaction stoichiometry. The swelling behaviors proved that CFCD hydrogel was pH-responsive with low swelling capacity, which would be preferable for drug delivery. Drug adsorption analysis showed the introduction of cyclodextrin into CFCD hydrogels promoted drug adsorption capacity. In addition, methyl orange cumulative release in PBS buffer was only 48.85% after 24h, suggesting CFCD hydrogel had good sustained release capacity on the loaded drug. Copyright © 2018 Elsevier B.V. All rights reserved.

N-(furfural) chitosan hydrogels based on Diels-Alder cycloadditions and application as microspheres for controlled drug release.

PubMed

Montiel-Herrera, Marcelino; Gandini, Alessandro; Goycoolea, Francisco M; Jacobsen, Neil E; Lizardi-Mendoza, Jaime; Recillas-Mota, Maricarmen; Argüelles-Monal, Waldo M

2015-09-05

In this study, chitosan was chemically modified by reductive amination in a two-step process. The synthesis of N-(furfural) chitosan (FC) was confirmed by FT-IR and (1)H NMR analysis, and the degrees of substitution were estimated as 8.3 and 23.8%. The cross-linkable system of bismaleimide (BM) and FC shows that FC shared properties of furan-maleimide chemistry. This system produced non-reversible hydrogel networks by Diels-Alder cycloadditions at 85 °C. The system composed of BM and FC (23.8% substitution) generated stronger hydrogel networks than those of FC with an 8.3% degree of substitution. Moreover, the FC-BM system was able to produce hydrogel microspheres. Environmental scanning electron microscopy revealed the surface of the microspheres to be non-porous with small protuberances. In water, the microspheres swelled, increasing their volume by 30%. Finally, microspheres loaded with methylene blue were able to release the dye gradually, obeying second-order kinetics for times less than 600 min. This behavior suggests that diffusion is governed by the relaxation of polymer chains in the swelled state, thus facilitating drug release outside the microspheres. Copyright © 2015 Elsevier Ltd. All rights reserved.

The [2 + 2] Cycloaddition-Retroelectrocyclization and [4 + 2] Hetero-Diels-Alder Reactions of 2-(Dicyanomethylene)indan-1,3-dione with Electron-Rich Alkynes: Influence of Lewis Acids on Reactivity.

PubMed

Donckele, Etienne J; Finke, Aaron D; Ruhlmann, Laurent; Boudon, Corinne; Trapp, Nils; Diederich, François

2015-07-17

The reaction of electrophilic 2-(dicyanomethylene)indan-1,3-dione (DCID) with substituted, electron-rich alkynes provides two classes of push-pull chromophores with interesting optoelectronic properties. The formal [2 + 2] cycloaddition-retroelectrocyclization reaction at the exocyclic double bond of DCID gives cyanobuta-1,3-dienes, and the formal [4 + 2] hetero-Diels-Alder (HDA) reaction at an enone moiety of DCID generates fused 4H-pyran heterocycles. Both products can be obtained in good yield and excellent selectivity by carefully tuning the reaction conditions; in particular, the use of Lewis acids dramatically enhances formation of the HDA adduct.

Spiroketals of Pestalotiopsis fici provide evidence for a biosynthetic hypothesis involving diversified Diels-Alder reaction cascades.

PubMed

Liu, Ling; Li, Yan; Li, Li; Cao, Ya; Guo, Liangdong; Liu, Gang; Che, Yongsheng

2013-04-05

Chloropestolides B-G (1-6), six new metabolites featuring the chlorinated spiro[benzo[d][1,3]dioxine-2,7'-bicyclo[2.2.2]octane]-4,8'-dione (1-3) and spiro[benzo[d][1,3]dioxine-2,1'-naphthalene]-2',4-dione (4-6) skeletons, and their putative biosynthetic precursor dechloromaldoxin (7) were isolated from the scale-up fermentation cultures of the plant endophytic fungus Pestalotiopsis fici . The structures of 1-7 were determined mainly by NMR experiments. The absolute configurations of 1-3 were deduced by analogy to the previously isolated metabolites from the same fungus (9 and 13-18), whereas those of 4, 5, and 7 were assigned by electronic circular dichroism (ECD) calculations. Structurally, the spiroketal skeletons found in 1-3 and 4-6 could be derived from 2,6-dihydroxy-4-methylbenzoic acid with chlorinated bicyclo[2.2.2]oct-2-en-5-one and 4a,5,8,8a-tetrahydronaphthalen-2(1H)-one, respectively. Biogenetically, compounds 1-6 were derived from the same Diels-Alder precursors as the previously isolated 9 and 12-18. In addition, compounds 2 and 3 were proposed as the biosynthetic intermediates of 17 and 16, respectively. Compound 1 was cytotoxic to three human tumor cell lines.

Microwave-assisted intramolecular dehydrogenative Diels-Alder reactions for the synthesis of functionalized naphthalenes/solvatochromic dyes.

PubMed

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

2013-04-01

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to the preparation of new organic dyes. Although numerous strategies have been reported to access naphthalene scaffolds, many procedures still present limitations in terms of incorporating functionality, which in turn narrows the range of available substrates. The development of versatile methods for direct access to substituted naphthalenes is therefore highly desirable. The Diels-Alder (DA) cycloaddition reaction is a powerful and attractive method for the formation of saturated and unsaturated ring systems from readily available starting materials. A new microwave-assisted intramolecular dehydrogenative DA reaction of styrenyl derivatives described herein generates a variety of functionalized cyclopenta[b]naphthalenes that could not be prepared using existing synthetic methods. When compared to conventional heating, microwave irradiation accelerates reaction rates, enhances yields, and limits the formation of undesired byproducts. The utility of this protocol is further demonstrated by the conversion of a DA cycloadduct into a novel solvatochromic fluorescent dye via a Buchwald-Hartwig palladium-catalyzed cross-coupling reaction. Fluorescence spectroscopy, as an informative and sensitive analytical technique, plays a key role in research fields including environmental science, medicine, pharmacology, and cellular biology. Access to a variety of new organic fluorophores provided by the microwave-assisted dehydrogenative DA reaction allows for further advancement in these fields.

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

PubMed Central

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

2013-01-01

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to the preparation of new organic dyes. Although numerous strategies have been reported to access naphthalene scaffolds, many procedures still present limitations in terms of incorporating functionality, which in turn narrows the range of available substrates. The development of versatile methods for direct access to substituted naphthalenes is therefore highly desirable. The Diels-Alder (DA) cycloaddition reaction is a powerful and attractive method for the formation of saturated and unsaturated ring systems from readily available starting materials. A new microwave-assisted intramolecular dehydrogenative DA reaction of styrenyl derivatives described herein generates a variety of functionalized cyclopenta[b]naphthalenes that could not be prepared using existing synthetic methods. When compared to conventional heating, microwave irradiation accelerates reaction rates, enhances yields, and limits the formation of undesired byproducts. The utility of this protocol is further demonstrated by the conversion of a DA cycloadduct into a novel solvatochromic fluorescent dye via a Buchwald-Hartwig palladium-catalyzed cross-coupling reaction. Fluorescence spectroscopy, as an informative and sensitive analytical technique, plays a key role in research fields including environmental science, medicine, pharmacology, and cellular biology. Access to a variety of new organic fluorophores provided by the microwave-assisted dehydrogenative DA reaction allows for further advancement in these fields. PMID:23609566

Novel N-allyl/propargyl tetrahydroquinolines: Synthesis via Three-component Cationic Imino Diels-Alder Reaction, Binding Prediction, and Evaluation as Cholinesterase Inhibitors.

PubMed

Rodríguez, Yeray A; Gutiérrez, Margarita; Ramírez, David; Alzate-Morales, Jans; Bernal, Cristian C; Güiza, Fausto M; Romero Bohórquez, Arnold R

2016-10-01

New N-allyl/propargyl 4-substituted 1,2,3,4-tetrahydroquinolines derivatives were efficiently synthesized using acid-catalyzed three components cationic imino Diels-Alder reaction (70-95%). All compounds were tested in vitro as dual acetylcholinesterase and butyryl-cholinesterase inhibitors and their potential binding modes, and affinity, were predicted by molecular docking and binding free energy calculations (∆G) respectively. The compound 4af (IC50 = 72 μm) presented the most effective inhibition against acetylcholinesterase despite its poor selectivity (SI = 2), while the best inhibitory activity on butyryl-cholinesterase was exhibited by compound 4ae (IC50 = 25.58 μm) with considerable selectivity (SI = 0.15). Molecular docking studies indicated that the most active compounds fit in the reported acetylcholinesterase and butyryl-cholinesterase active sites. Moreover, our computational data indicated a high correlation between the calculated ∆G and the experimental activity values in both targets. © 2016 The Authors Chemical Biology & Drug Design Published by John Wiley & Sons Ltd.

Intramolecular inverse-electron-demand Diels-Alder reactions of imidazoles with 1,2,4-triazines: a new route to 1,2,3,4-tetrahydro-1,5-naphthyridines and related heterocycles.

PubMed

Lahue, Brian R; Lo, Sie-Mun; Wan, Zhao-Kui; Woo, Grace H C; Snyder, John K

2004-10-15

The intramolecular inverse-electron-demand Diels-Alder reaction between imidazoles and 1,2,4-triazines linked by a trimethylene tether from the imidazole N1 position to the triazine C3 proceed in excellent yields to produce 1,2,3,4-tetrahydro-1,5-naphthyridines. The reaction proceeds by a cycloaddition with subsequent loss of nitrogen, followed by a presumed stepwise loss of a nitrile. The analogous intramolecular cycloadditions employing a tetramethylene tether also proceeded to give 2,3,4,5-tetrahydro-1H-pyrido[3,2-b]azepines in acceptable yields. The reaction to produce the tetrahydro-1,5-naphthyridines can also be promoted with microwave irradiation.

Retrospective multicenter evaluation of the "fly-catching syndrome" in 24 dogs: EEG, BAER, MRI, CSF findings and response to antiepileptic and antidepressant treatment.

PubMed

Wrzosek, Marcin; Płonek, Marta; Nicpoń, Józef; Cizinauskas, Sigitas; Pakozdy, Akos

2015-12-01

The fly-catching syndrome (FCS) is a rare canine condition of sudden, occasional, or constant episodes of biting the air. It may be accompanied by jumping, licking, and swallowing. The etiology of FCS is unknown and controversial. Various explanations for its occurrence have included epileptoid disorders such as visual cortex epileptiform disturbances and simple and complex partial seizures as well as compulsive disorders, hallucinatory behavior, and stereotypy. A retrospective multicenter analysis of 24 dogs with clinical symptoms of FCS is presented. Clinical signs at the time of presentation, the mean age at onset of the disease, the response to treatment, and the clinical outcome were recorded and analyzed in all patients. All dogs underwent clinical, neurological, and otoscopic examinations. Complete blood cell counts (CBCs) and serum chemistry panels were obtained from each dog. Diagnostic testing included MRI and EEG examinations in 21 cases, BAER in 19 cases, and CSF analysis in 20 cases. The EEG revealed spike activity in 8 (38%) of the 21 cases, 7 of which had activity in the occipital lobes. The brainstem auditory evoked response (BAER) revealed three cases of bilateral deafness. The MRI revealed six cases of Chiari malformation (CM), one case of syringohydromyelia (SM), and one case of a falx cerebri meningioma. The dogs were divided into groups according to their treatment protocol. Group A included dogs treated with phenobarbital (PB), and group B consisted of dogs treated with fluoxetine (FLX). Thirty-six percent of the dogs in group A responded to PB, while 100% of the dogs in group B responded to FLX. The results suggest that FCS is more responsive to FLX than PB. However, the etiology of this behavior remains unclear in most cases. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Molecular Engineering of Perylene Imides for High-Performance Lithium Batteries: Diels-Alder Extension and Chiral Dimerization.

PubMed

Li, Lei; Hong, Yu-Jian; Chen, Dong-Yang; Lin, Mei-Jin

2017-11-21

The search for high-performance electrode materials in organic rechargeable batteries remains a key challenge. Reported herein is a molecular structural modification of perylene imides, a promising class of redox-active electrode materials, for improved battery performance. The Diels-Alder extension of perylene imides at the lateral position led to the simultaneous incorporation of two electron-withdrawing carbonyl groups and extension of the π system, which is supposed to favor high specific capacity, operating voltage, and electronic conductivity. After the chiral dimerization of the extended species with 1,2-diaminocyclohexane, it was anticipated that the porosity and coulombic interactions with lithium ions would be promoted, which would be beneficial for fast reaction kinetics and long cycling life. As expected, in lithium batteries, the obtained chiral and π-extended tweezer, which features six imide groups and a porous solid-state network of 42.2 % accessible cell volume, was found to deliver a reversible capacity of 92.1 mA h g -1 at a charge/discharge rate of 1 C within an operating voltage window of 1.60-2.80 V versus Li + /Li, around 75 and 50 % of which was maintained after 100 and 300 galvanostatic cycles, respectively, much better than those of unmodified species. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

Schweiger, Peter F

2016-10-20

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

Rapid synthesis of carbohydrate derivatives, including mimetics of C-linked disaccharides and C-linked aza disaccharides, using the hetero-Diels-Alder reaction.

PubMed

Burland, Peter A; Coisson, David; Osborn, Helen M I

2010-11-05

In this work we demonstrate the value of performing a hetero-Diels-Alder reaction (HDAR) between Danishefsky's diene and a range of aldehydes or imines, under microwave irradiation. By using a range of aldehydes and imines, including those derived from carbohydrates, access to functionalized 2,3-dihydro-4H-pyran-4-ones or 2,3-dihydro-4-pyridinones in good to excellent synthetic yields is possible. A particular strength of the methodology is its ability to access mimetics of C-linked disaccharides and C-linked aza disaccharides, targets of current therapeutic interest, in a rapid, convenient, and diastereoselective manner. The effect of high pressure on the HDARs involving carbohydrate-derived aldehydes and imines is also explored, with enhancement in yields occurring for the aldehyde substrates. Finally, HDARs using carbohydrate derived ketones, enones, and enals are described under a range of conditions. Optimum results were obtained under high-pressure conditions, with highly functionalized carbohydrate derivatives being afforded, in good yields, in this way.

Hetero-Diels-Alder reactions of novel 3-triazolyl-nitrosoalkenes as an approach to functionalized 1,2,3-triazoles with antibacterial profile.

PubMed

Lopes, Susana M M; Novais, Juliana S; Costa, Dora C S; Castro, Helena C; Figueiredo, Agnes Marie S; Ferreira, Vitor F; Pinho E Melo, Teresa M V D; da Silva, Fernando de Carvalho

2018-01-01

The generation and reactivity of 3-triazolyl-nitrosoalkenes are reported for the first time. The study showed that hetero-Diels-Alder reaction of these heterodienes is an interesting synthetic strategy to functionalized 1,2,3-triazoles, including 1,2,3-triazolyl-pyrroles, 1,2,3-triazolyl-dipyrromethanes and 1,2,3-triazolyl-indoles. The evaluation of the antibacterial profile against Gram-positive and Gram-negative strains revealed the new 5,5'-diethyldipyrromethane bearing a side chain incorporating a triazole and oxime moieties. The antibacterial profile detected was within the Clinical and Laboratory Standard Institute (CLSI) range and against important Staphylococcus species including Methicillin-resistant strain (S. aureus ATCC 25923, S. epidermidis ATCC 12228 and S. simulans ATCC 27851 and MRSA). Interestingly, this new 1,2,3-triazole presented hemocompatibility and low in silico toxicity profile similar to antibiotics current in use. It also has an usual antibiofilm activity against MRSA, which reinforced its potential as a new antibacterial prototype. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Design of New Bridge-Ring Energetic Compounds Obtained by Diels-Alder Reactions of Tetranitroethylene Dienophile.

PubMed

He, Piao; Mei, Hao-Zheng; Wu, Le; Yang, Jun-Qing; Zhang, Jian-Guo; Cohen, Adva; Gozin, Michael

2018-03-29

The density functional theory method was employed to calculate three-dimensional structures for a series of novel explosophores. The design of new molecules (DA1-DA12) was based on the bridge-ring structures that could be formed via Diels-Alder (DA) reaction of selected nitrogen-rich dienes and tetranitroethylene dienophile. The feasibility of the proposed DA reactions was predicted on the basis of the molecular orbital theory. The strong interactions between the HOMO of dienes, with electron-donating groups (Diene2, Diene6, and Diene8), and the LUMO of tetranitroethylene dienophile suggested thermodynamically favorable formation of the desired DA reaction products. In addition to molecular structures of the explored DA compounds, their physicochemical and energetic properties were also calculated in detail. Due to compact bridge-ring structures, new energetic molecules have highly positive heats of formation (up to 1124.90 kJ·mol -1 ) and high densities (up to 2.04 g·cm -3 ). Also, as a result of all-right ratios of nitrogen and oxygen, most of the new compounds possess high detonation velocities (8.28-10.02 km·s -1 ) and high detonation pressures (30.87-47.83 GPa). Energetic compounds DA1, DA4, and DA12 exhibit a superior detonation performance over widely used HMX explosive, and DA5, DA7, and DA10 could be comparable to the state-of-the-art CL-20 and ONC explosives. Our proposed designs and synthetic methodology should provide a platform for the development of novel energetic materials with superior performance.

Characterization of Sulfonated Diels-Alder Poly(phenylene) Membranes for Electrolyte Separators in Vanadium Redox Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Zhijiang; Lawton, Jamie S.; Sun, Che-Nan

2014-09-03

Here, sulfonated Diels-Alder poly(phenylene) (SDAPP) membranes were synthesized and characterized as potential electrolyte separators for vanadium redox flow batteries. The SDAPP membranes studied had ion exchange capacities of 1.4, 1.8 and 2.3 meq/g. Transmission electron microscopy imaging shows that the ionic domains in SDAPP are roughly 0.5 nm in dimension, while Nafion has a hydrophilic phase width of around 5 nm. The sulfuric acid uptake by SDAPP was higher than that for Nafion, but the materials had similar water uptake from solutions of various sulfuric acid concentrations. In equilibration with sulfuric acid concentrations ranging from 0–17.4 mol·kg -1, SDAPP withmore » a IEC of 2.3 meq/g had the highest conductivity, ranging from 0.21 to 0.05 S·cm -1, while SDAPP with a IEC of 1.8 had conductivity close to Nafion 117, ranging from 0.11 to 0.02 S·cm -1. With varying sulfuric acid concentration and temperature, vanadium permeability in SDAPP is positively correlated to the membrane's IEC. The vanadium permeability of SDAPP 2.3 is similar to that of Nafion, but permeability values for SDAPP 1.8 and SDAPP 1.4 are substantially lower. The vanadium permeation decreases with increasing electrolyte sulfuric acid concentration. Lastly, vanadium diffusion activation energy is about 20 kJ·mol -1 in both SDAPP and Nafion.« less

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

PubMed

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

2015-06-15

A synthetic method to prepare 3a,6-methanoisoindole esters efficiently by gold(I)-catalyzed tandem 1,2-acyloxy migration/Nazarov cyclization followed by Diels-Alder reaction of 1,4,9-dienyne esters is described. We also report the ability of one example to inhibit binding of tumor necrosis factor-α (TNF-α) to the tumor necrosis factor receptor 1 (TNFR1) site and TNF-α-induced nuclear factor κ-light-chain-enhancer of activated B cells (NF-κB) activation in cell at a half-maximal inhibitory concentration (IC50 ) value of 6.6 μM. Along with this is a study showing the isoindolyl derivative to exhibit low toxicity toward human hepatocellular liver carcinoma (HepG2) cells and its possible mode of activity based on molecular modeling analysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nasal mites from birds of a Guatemalan cloud forest (Acarina: rhinonyssidae)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spicer, G.S.

1984-01-01

A survey of the nasal mites from Guatemalan cloud forest birds is reported. Seventy-eight birds, representing 10 families and 18 species, were examined. Prevalence of infection was 24%. Two new species are described: Sternostoma darlingi from Mitrephanes phaeocercus (Tyrannidae) and S. pencei from Empidonax flavescens (Tyrannidae). New host records are reported for S. priangae from Chlorospingus opthalmicus (Thraupidae), S. hutsoni from Catharus dryas (Turdidae), Ptilonyssus sairae from Chlorospingus opthalmicus (Thraupidae), and Myioborus miniatus (Parulidae), P. euroturdi from Catharus dryas (Turdidae), P. tyrannus from Empidonax flavescens and Mitrephanes phaeocercus (both Tyannidae), and Tinaminyssus ixoreus from Catharus dryas (Turdidae). The subspecies Ptilonyssusmore » euroturdi mimicola Fain and Hyland is synonymized with the nominate subspecies. Data are presented to suggest that the Rhinonyssidae may be a polyphyletic assemblage. 35 references, 12 figures, 1 table.« less

Females discriminate against heterospecific sperm in a natural hybrid zone.

PubMed

Cramer, Emily R A; Ålund, Murielle; McFarlane, S Eryn; Johnsen, Arild; Qvarnström, Anna

2016-08-01

When hybridization is maladaptive, species-specific mate preferences are selectively favored, but low mate availability may constrain species-assortative pairing. Females paired to heterospecifics may then benefit by copulating with multiple males and subsequently favoring sperm of conspecifics. Whether such mechanisms for biasing paternity toward conspecifics act as important reproductive barriers in socially monogamous vertebrate species remains to be determined. We use a combination of long-term breeding records from a natural hybrid zone between collared and pied flycatchers (Ficedula albicollis and F. hypoleuca), and an in vitro experiment comparing conspecific and heterospecific sperm performance in female reproductive tract fluid, to evaluate the potential significance of female cryptic choice. We show that the females most at risk of hybridizing (pied flycatchers) frequently copulate with multiple males and are able to inhibit heterospecific sperm performance. The negative effect on heterospecific sperm performance was strongest in pied flycatcher females that were most likely to have been previously exposed to collared flycatcher sperm. We thus demonstrate that a reproductive barrier acts after copulation but before fertilization in a socially monogamous vertebrate. While the evolutionary history of this barrier is unknown, our results imply that there is opportunity for it to be accentuated via a reinforcement-like process. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

High performance addition-type thermoplastics (ATTs) - Evidence for the formation of a Diels-Alder adduct in the reaction of an acetylene-terminated material and a bismaleimide

NASA Technical Reports Server (NTRS)

Pater, R. H.; Soucek, M. D.; Chang, A. C.; Partos, R. D.

1991-01-01

Recently, the concept and demonstration of a new versatile synthetic reaction for making a large number of high-performance addition-type thermoplastics (ATTs) were reported. The synthesis shows promise for providing polymers having an attractive combination of easy processability, good toughness, respectable high temperature mechanical performance, and excellent thermo-oxidative stability. The new chemistry involves the reaction of an acetylene-terminated material with a bismaleimide or benzoquinone. In order to clarify the reaction mechanism, model compound studies were undertaken in solutions as well as in the solid state. The reaction products were purified by flash chromatography and characterized by conventional analytical techniques including NMR, FT-IR, UV-visible, mass spectroscopy, and high pressure liquid chromatography. The results are presented of the model compound studies which strongly support the formation of a Diels-Alder adduct in the reaction of an acetylene-terminated compound and a bismaleimide or benzoquinone.

Thermal phenomena under microwave field in the organic synthesis processes: Application to the Diels Alder reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saillard, R.; Poux, M.; Audhuy-Peaudecerf, M.

1996-12-31

The influence of the microwave heating on chemical reactions were investigated. The kinetic of the Diels Alder reaction were studied under microwave irradiation at a frequency of 2.45 GHz in a single mode cavity and were compared to the kinetic obtained by a conventional heating. Experiments were carried out in a liquid solvent in order to have a better control of the medium temperature measurement. In a second part, the presence of a catalytic solid phase was introduced. Some thermal fluctuations which are due to an heterogeneity of the electric field were detected in the medium. They reduce the precisionmore » of the results and cause problems of experimental reproducibility. A thermoluminescent material allow a good visualization of these phenomena. In addition, the profiles of the electric field intensity were modelled by a 2D finite elements method in the reactor in the presence of a solvent. Despite the small size of the sample and the use of a monomode cavity which both limited the heterogeneities of the medium temperature, the authors showed a great heterogeneity of the electric field intensity and as a result the heterogeneity of the temperature in their sample. In order to avoid these phenomena which induce a lack of reproducibility, a stirring device was developed. The values of the kinetics obtained under the 2 heating modes with the introduction of the stirring device. So, it induces a good control of the medium temperature. All those investigations prompted the authors to the conclusion that there is no difference between microwave heating and a classical heating in the studied reaction.« less

76 FR 26313 - Endangered and Threatened Species Permit Applications

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-06

..., during normal business hours at the U.S. Fish and Wildlife Service, 500 Gold Ave., SW., Room 6034...: Rhea Environmental Consulting, Mancos, Colorado. Applicant requests a renewal to a current permit for... (Empidonax traillii extimus) within Arizona, New Mexico, Colorado, and Utah. Permit TE-150490 Applicant: John...

Vitamin profiles in two free-living passerine birds under a metal pollution gradient - A calcium supplementation experiment.

PubMed

Ruiz, Sandra R; Espín, Silvia; Sánchez-Virosta, Pablo; Salminen, Juha-Pekka; Lilley, Thomas M; Eeva, Tapio

2017-04-01

Vitamin and carotenoid deficiency may impair development in free-living vertebrates, because of the importance of these micronutrients to growth, antioxidant defense and calcium regulation. Micronutrient and calcium insufficiency can be intensified by metal pollution which can interfere with nutrient homeostasis or indirectly reduce food availability. Furthermore, absorption of dietary heavy metals is dependent on food calcium and vitamin levels. We investigated the effect of calcium on plasma vitamin and carotenoid profiles and how these affected growth and survival in two passerine birds with different calcium turnover living along a metal pollution gradient. Vitamins (A, D 3 and E) and carotenoids were quantified from blood plasma of great tit (Parus major) and pied flycatcher (Ficedula hypoleuca) nestlings. Metal concentrations in soil and in feces from the same nestlings were used to assess the exposure to air pollution. Additionally, we examined the vitamin level variation between developmental stages (eggs and nestlings within the same brood). Our results showed that generally higher concentrations of vitamins and carotenoids circulate in blood of great tits than in pied flycatchers. In general, birds inhabiting the polluted zone presented lower concentrations of the studied micronutrients. Calcium supplementation and metal pollution decreased vitamin A concentration in pied flycatcher, but not in great tit, while vitamin A affected growth and survival in great tit and pied flycatcher respectively. Our results suggest that populations under exposure to metal pollution may experience increased vitamin A deficiency, and that the two passerine species, while obtaining similar micronutrients in food, respond differently to environmental disturbance of nutrients. Copyright © 2017 Elsevier Inc. All rights reserved.

Insights into the genetic architecture of morphological traits in two passerine bird species.

PubMed

Silva, C N S; McFarlane, S E; Hagen, I J; Rönnegård, L; Billing, A M; Kvalnes, T; Kemppainen, P; Rønning, B; Ringsby, T H; Sæther, B-E; Qvarnström, A; Ellegren, H; Jensen, H; Husby, A

2017-09-01

Knowledge about the underlying genetic architecture of phenotypic traits is needed to understand and predict evolutionary dynamics. The number of causal loci, magnitude of the effects and location in the genome are, however, still largely unknown. Here, we use genome-wide single-nucleotide polymorphism (SNP) data from two large-scale data sets on house sparrows and collared flycatchers to examine the genetic architecture of different morphological traits (tarsus length, wing length, body mass, bill depth, bill length, total and visible badge size and white wing patches). Genomic heritabilities were estimated using relatedness calculated from SNPs. The proportion of variance captured by the SNPs (SNP-based heritability) was lower in house sparrows compared with collared flycatchers, as expected given marker density (6348 SNPs in house sparrows versus 38 689 SNPs in collared flycatchers). Indeed, after downsampling to similar SNP density and sample size, this estimate was no longer markedly different between species. Chromosome-partitioning analyses demonstrated that the proportion of variance explained by each chromosome was significantly positively related to the chromosome size for some traits and, generally, that larger chromosomes tended to explain proportionally more variation than smaller chromosomes. Finally, we found two genome-wide significant associations with very small-effect sizes. One SNP on chromosome 20 was associated with bill length in house sparrows and explained 1.2% of phenotypic variation (V P ), and one SNP on chromosome 4 was associated with tarsus length in collared flycatchers (3% of V P ). Although we cannot exclude the possibility of undetected large-effect loci, our results indicate a polygenic basis for morphological traits.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Synthesis and Antifungal in Vitro Evaluation of Pyrazolo[3,4-b]pyridines Derivatives Obtained by Aza-Diels-Alder Reaction and Microwave Irradiation.

PubMed

Quiroga, Jairo; Villarreal, Yazmín; Gálvez, Jaime; Ortíz, Alejandro; Insuasty, Braulio; Abonia, Rodrigo; Raimondi, Marcela; Zacchino, Susana

2017-02-01

A series of pyrazolo[3,4-b]pyridines were prepared by a microwave-assisted aza-Diels-Alder reaction between pyrazolylformimidamides 1 and β-nitrostyrenes 2 in toluene as the solvent. This procedure provides a simple one-step and environmentally friendly methodology with good yields for the synthesis of these compounds. All compounds were tested for antifungal activity against two clinically important fungi Candida albicans and Cryptococcus neoformans. Within the compounds of the series bearing a -CH 3 group on the carbon C-3 of the azole ring (3a-e), the compound without a substituent on the p'-phenyl ring (3a), showed the best activity against both fungi, followed by the p'-Br-phenyl (3c). Within the compounds of the series bearing a tert-butyl group in the carbon C-3 of the azole ring (3f-j), the non-substituted p'-compound (3f) was the most active one, followed by (3h) (p'-Br substituted) that showed the best activity against both fungi. The remaining compounds of this sub-series (3g, i, j) showed similar moderate activities. The antifungal activity of the compounds of the series was found to be correlated with a higher log P and a lower dipole moment in the more active compounds.

Intramolecular Diels-Alder Reaction of N-Alkyl-2-cyano-1-azadienes: A Study of the Eschenmoser Cycloreversion of Dihydrooxazines as a Route to N-Alkyl-2-cyano-1-azadienes.

PubMed

Motorina, Irina A.; Fowler, Frank W.; Grierson, David S.

1997-04-04

In connection with the development of the intramolecular Diels-Alder reaction (IMDA) of 1-azadienes, the 5,6-dihydro-4H-1,2-oxazine 12has been evaluated as a synthon equivalent of the 2-cyano-1-azadiene system. It was found that the dihydrooxazonium salt 27, generated in situ from the cyclic hydroxamic acid derivative 26, is converted directly to azadiene 4a via tautomerization to the corresponding enamine and a particularly facile Eschenmoser type cycloreversion process. Conditions were subsequently found for the preparation of synthon 12. N-Alkylation of this intermediate with alkyl bromides in the presence of Ag(+) ion also resulted in direct formation of the 2-cyano-1-azadiene products 38a-dand 4a. Microwave irradiation of a benzene solution of azadiene 4a proved to be a convenient means to effect its IMDA conversion to indolizidine 5a. To avoid decomposition of azadiene 38c, its intramolecular cycloaddition giving 40 (60%) was achieved by flash vacuum thermolysis.

Comparison of Five Woody Species for Reclamation of an Upper Coastal Plain Spoil Bank

Treesearch

J.W. McMinn; R.R. Roth; C.R. Berry; W.H. McNab

1980-01-01

Third-year survival and height are compared for autumn olive. European black alder, flowering crab apple, sawtooth oak, and Virginia pine on a sandy clay loam spoil bank in South Carolina. Flowering crab apple and sawtooth oak exhibited the best survival, while autumn olive and European black alder had greater height growth. Only European black alder failed to become...

Interspecific Plant Interactions Reflected in Soil Bacterial Community Structure and Nitrogen Cycling in Primary Succession

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knelman, Joseph E.; Graham, Emily B.; Prevéy, Janet S.

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 successional trajectories in 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 sinuata (alder) to late successional Picea sitchensis (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 tomore » 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 drives shifts in the relative abundance of major taxa of bacteria in alder-influenced soils, including declines in those that are enriched by alder. 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. Our results show that spruce leachate addition more strongly structures bacterial communities than alders (less dispersion in bacterial community beta diversity). Such insights bolster theory relating the importance of plant-microbe interactions with late-successional plants and interspecific plant interactions more generally.« less

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

PubMed

Puc, Małgorzata; Kasprzyk, Idalia

2013-01-01

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

Mechanisms of the Knoevenagel hetero Diels-Alder sequence in multicomponent reactions to dihydropyrans: experimental and theoretical investigations into the role of water.

PubMed

Frapper, Gilles; Bachmann, Christian; Gu, Yanlong; Coval De Sousa, Rodolphe; Jérôme, François

2011-01-14

The role of water in a multicomponent domino reaction (MCR) involving styrene, 2,4-pentanedione, and formaldehyde was studied. Whereas anhydrous conditions produced no reaction, the MCR successfully proceeded in the presence of water, affording the targeted dihydropyran derivatives with good yield. The mechanism of this MCR (Knoevenagel hetero Diels-Alder sequence) was studied with and without explicit water molecules using the SMD continuum solvation model in combination with the B3LYP density functional and the 6-311++G** basis set to compute the water and acetone (aprotic organic solvent) solution Gibbs free energies. In the Knoevenagel step, we found that water acted as a proton relay to favor the formation of more flexible six-membered ring transition state structures both in concerted (direct H(2)O elimination) and stepwise (keto-enol tautomerization and dehydration) pathways. The inclusion of a water molecule in our model resulted in a significant decrease (-8.5 kcal mol(-1)ΔG(water)(‡)) of the direct water elimination activation barrier. Owing to the presence of water, all chemical steps involved in the MCR mechanism had activation free energies barriers lower than 39 kcal mol(-1) at 25 °C in aqueous solvent (<21 kcal mol(-1) ZPE corrected electronic energies barriers). Consequently, the MCR proceeded without the assistance of any catalyst.

Determination of ergocalciferol in human plasma after Diels-Alder derivatization by LC-MS/MS and its application to a bioequivalence study.

PubMed

Contractor, Pritesh; Gandhi, Abhishek; Solanki, Gajendra; Shah, Priyanka A; Shrivastav, Pranav S

2017-12-01

An accurate, sensitive and selective method is developed for determination of ergocalciferol (vitamin D 2 ) in human plasma using LC-MS/MS. After liquid-liquid extraction with n- hexane, ergocalciferol was derivatized by reacting with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), a strong dienophile based on Diels-Alder reaction. Ergocalciferol and its deuterated internal standard, ergocalciferol-d6, were analyzed on X Select CSH C 18 (100 mm×4.6 mm, 2.5 µm) column using acetonitrile and 0.1% (v/v) formic acid in water containing 0.14% methylamine within 6.0 min under gradient elution mode. Tandem mass spectrometry in positive ionization mode was used to quantify ergocalciferol by multiple reaction monitoring (MRM). Entire data processing was done using Watson LIMS™ software which provided excellent data integrity and high throughput with improved operational efficiency. The major advantage of this method includes higher sensitivity (0.10 ng/mL), superior extraction efficiency (≥83%) and small sample volume (100 µL) for processing. The method was linear in the concentration range of 0.10-100 ng/mL for ergocalciferol. The intra-batch and inter-batch accuracy and precision (% CV) values varied from 97.3% to 109.0% and 1.01% to 5.16%, respectively. The method was successfully applied to support a bioequivalence study of 1.25 mg ergocalciferol capsules in 12 healthy subjects.

Genetic Selection for Improved Abzymes in E. Coli

DTIC Science & Technology

1994-08-03

immunoassay to scemen antibody phage libraries directly for catalysis of a bimolecular Diels - Alder reaction and have identified several active clones...sensitive growth selection assay in F coli for catalysts with chorismate mutase activity; and (3) we identified new abzymes for a Diels - Alder ...generated combinatorial antibody libraries from mRNA isolated from the spleens of mice hyperimmunized with transition state analogs for Diels - Alder and

N-O chemistry for antibiotics: discovery of N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds as selective antibacterial agents using nitroso Diels-Alder and ene chemistry.

PubMed

Wencewicz, Timothy A; Yang, Baiyuan; Rudloff, James R; Oliver, Allen G; Miller, Marvin J

2011-10-13

The discovery, syntheses, and structure-activity relationships (SAR) of a new family of heterocyclic antibacterial compounds based on N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds are described. A structurally diverse library of ∼100 heterocyclic molecules generated from Lewis acid-mediated nucleophilic ring-opening reactions with nitroso Diels-Alder cycloadducts and nitroso ene reactions with substituted alkenes was evaluated in whole cell antibacterial assays. Compounds containing the N-alkyl-N-(pyridin-2-yl)hydroxylamine structure demonstrated selective and potent antibacterial activity against the Gram-positive bacterium Micrococcus luteus ATCC 10240 (MIC(90) = 2.0 μM or 0.41 μg/mL) and moderate activity against other Gram-positive strains including antibiotic resistant strains of Staphylococcus aureus (MRSA) and Enterococcus faecalis (VRE). A new synthetic route to the active core was developed using palladium-catalyzed Buchwald-Hartwig amination reactions of N-alkyl-O-(4-methoxybenzyl)hydroxylamines with 2-halo-pyridines that facilitated SAR studies and revealed the simplest active structural fragment. This work shows the value of using a combination of diversity-oriented synthesis (DOS) and parallel synthesis for identifying new antibacterial scaffolds.

N-O Chemistry for Antibiotics: Discovery of N-Alkyl-N-(pyridin-2-yl)hydroxylamine Scaffolds as Selective Antibacterial Agents Using Nitroso Diels-Alder and Ene Chemistry

PubMed Central

Wencewicz, Timothy A.; Yang, Baiyuan; Rudloff, James R.; Oliver, Allen G.; Miller, Marvin J.

2011-01-01

The discovery, syntheses, and structure-activity relationships (SAR) of a new family of heterocyclic antibacterial compounds based on N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds are described. A structurally diverse library of ~100 heterocyclic molecules generated from Lewis acid-mediated nucleophilic ring opening reactions with nitroso Diels-Alder cycloadducts and nitroso ene reactions with substituted alkenes was evaluated in whole cell antibacterial assays. Compounds containing the N-alkyl-N-(pyridin-2-yl)hydroxylamine structure demonstrated selective and potent antibacterial activity against the Gram-positive bacterium Micrococcus luteus ATCC 10240 (MIC90 = 2.0 μM or 0.41 μg/mL) and moderate activity against other Gram-positive strains including antibiotic resistant strains of Staphylococcus aureus (MRSA) and Enterococcus faecalis (VRE). A new synthetic route to the active core was developed using palladium-catalyzed Buchwald-Hartwig amination reactions of N-alkyl-O-(4-methoxybenzyl)hydroxylamines with 2-halo-pyridines that facilitated SAR studies and revealed the simplest active structural fragment. This work shows the value of using a combination of diversity-oriented synthesis (DOS) and parallel synthesis for identifying new antibacterial scaffolds. PMID:21859126

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wright, L.L.; Perlack, R.D.; Wenzel, C.R.

1985-08-01

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

A new class of dual responsive self-healable hydrogels based on a core crosslinked ionic block copolymer micelle prepared via RAFT polymerization and Diels-Alder "click" chemistry.

PubMed

Banerjee, Sovan Lal; Singha, Nikhil K

2017-12-06

Amphiphilic diblock copolymers of poly(furfuryl methacrylate) (PFMA) with cationic poly(2-(methacryloyloxy)ethyltrimethyl ammonium chloride) (PFMA-b-PMTAC) and anionic poly(sodium 4-vinylbenzenesulfonate) (PFMA-b-PSS) were prepared via reversible addition fragmentation chain-transfer (RAFT) polymerization by using PFMA as a macro-RAFT agent. The formation of the block copolymer was confirmed by FTIR and 1 H NMR analyses. In water, the amphiphilic diblock copolymers, (PFMA-b-PMTAC) and (PFMA-b-PSS), formed micelles with PFMA in the core and the rest of the hydrophilic polymers like PMTAC and PSS in the corona. The PFMA core was crosslinked by using Diels-Alder (DA) "Click" chemistry in water at 60 °C where bismaleimide acted as a crosslinker. Afterwards, both the core crosslinked micelles were mixed at an almost equal charge ratio which was determined by zeta potential analysis to prepare the self-assembled hydrogel. The de-crosslinking of the hydrophobic PFMA core in the self-assembled hydrogel via rDA reaction took place at 165 °C as determined from DSC analysis. This hydrogel showed self-healing behavior using ionic interaction (in the presence of water) and DA chemistry (in the presence of heat).

Final Supplemental Environmental Impact Statement for Airborne Laser Program at Kirtland Air Force Base (AFB) and White Sands Missile Range/Holloman AFB, NM, and Edwards AFB and Vandenberg AFB, CA

DTIC Science & Technology

2003-06-01

californicus- _" -~ T ~ - 1" T - E I T Coho salmon Unarmoured three- spined stickleback I Tidewater goby 1 Eucyclogobius n e w b e p i ,.I...ENDANGERED Black-footed ferret (Mustela nigripes)"" Northern aplomado falcon (Falcofemoralis septentrionalis) Kuenzler hedgehog cachls (Echi...Empidonax traillii ertimus) Kuenzler hedgehog cactus (Echinocer~.~rendleri var. kuenzleri) Todsen’s pennyroyal (Hedeoma fodsenii) Sacramento

Interspecific Plant Interactions Reflected in Soil Bacterial Community Structure and Nitrogen Cycling in Primary Succession.

PubMed

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.

Interspecific Plant Interactions Reflected in Soil Bacterial Community Structure and Nitrogen Cycling in Primary Succession

PubMed Central

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. PMID:29467741

On the effect of tether composition on cis/trans selectivity in intramolecular Diels-Alder reactions.

PubMed

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 <3 kJ mol(-1)), they follow a clear and systematic trend. Specifically, as the electronegativity of the tether group X is reduced (X=O --> 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

[Chemistry and biosynthesis of prenylflavonoids].

PubMed

Nomura, T

2001-07-01

Many isoprenylated flavonoids have been isolated from mulberry trees and related plants (Moraceae). Among them, kuwanons G (13) and H (14) were the first isolated active substances exhibiting a hypotensive effect from the Japanese Morus root bark. These compounds are considered to be formed through an enzymatic Diels-Alder reaction of a chalcone (15) and dehydro-kuwanon C (16) or its equivalent. Since that time, about forty kinds of Diels-Alder type adducts structurally similar to that of 13 have been isolated from the moraceous plants. Some strains of Morus alba as well as M. bombycis callus tissues have a high productivity of mulberry Diels-Alder type adducts, such as chalcomoracin (26) and kuwanon J (28). The biosynthesis of the mulberry Diels-Alder type adducts has been studied with the aid of the cell strain. Chalcomoracin (26) and kuwanon J (28) were proved to be enzymatic Diels-Alder type reaction products by the administration experiment with O-methylchalcone derivatives. Furthermore, for the isoprenoid biosynthesis of prenylflavonoids in Morus alba callus tissues, a novel way through the junction of glycolysis and pentose-phosphate cycle was proposed. The crude enzyme fraction catalyzing the Morus Diels-Alder type reaction could be isolated. Studies of phenolic constituents of licorice (Glycyrrhiza species) were carried out. On the course of the structure determination of the phenolic constituents of licorice, two new NMR structure determination methods for prenylflavonoids were found. Furthermore, the prenylphenols isolated from licorice were summarized according to the origin of the materials.

Chemistry and biosynthesis of isoprenylated flavonoids from Japanese mulberry tree

PubMed Central

Nomura, Taro; Hano, Yoshio; Fukai, Toshio

2009-01-01

Many isoprenylated flavonoids have been isolated from Japanese mulberry tree (Moraceae). Among them, kuwanons G (1) and H (2) were the first isolated active substances exhibiting a hypotensive effect. These compounds are considered to be formed through an enzymatic Diels-Alder type reaction between an isoprenyl portion of an isoprenylphenol as the diene and an α, β-double bond of chalcone as the dienophile. The absolute configurations of these Diels-Alder type adducts were confirmed by three different methods. The stereochemistries of the adducts were consistent with those of ones in the Diels-Alder reaction involving exo- and endo-addition. Some strains of Morus alba callus tissues have a high productivity of mulberry Diels-Alder type adducts, such as chalcomoracin (3) and kuwanon J (4). The biosynthetic studies of the mulberry Diels-Alder type adducts have been carried out with the aid of the cell strain. Chalcomoracin (3) and kuwanon J (4) were proved to be enzymatic Diels-Alder type reaction products by the administration experiments with O-methylchalcone derivatives. Furthermore, for the isoprenoid biosynthesis of prenylflavonoids in Morus alba callus tissues by administration of [1,3-13C2]- and [2-13C]-glycerol, a novel way through the junction of glycolysis and pentose-phosphate cycle was proved. Two independent isoprenoid biosynthetic pathways, that for sterols and that for isoprenoidphenols, operate in the Morus alba cell cultures. The former is susceptible to compactin (ML-236) and the latter resists to compactin in the cell cultures, respectively. PMID:19907125

Widespread Expansion of Boreal Shrublands in the Siberian Low Arctic Is Linked to Cryogenic Disturbance and Geomorphology

NASA Astrophysics Data System (ADS)

Frost, G. V.; Epstein, H. E.; Walker, D. A.

2012-12-01

Declassified imagery from the KH-4B "Corona" and KH-7 "Gambit" Cold War satellite surveillance systems (1963-1972) are a unique, high-resolution dataset that establishes a baseline for landcover-change studies in the Russian Arctic spanning 6 decades. We co-registered Corona/Gambit and modern high-resolution imagery for seven ~65 km2 Low Arctic sites in northwest Siberia and Chukotka and quantified changes in the extent of tall shrublands dominated by Siberian alder (Alnus fruticosa) using a point-intercept sampling approach. We made ground observations at two sites to identify important geomorphic processes and physiographic units associated with shrub expansion. Alder shrubland cover increased at all sites; relative to the 1960s extent, shrubland extent increased by 5-31% at the northwest Siberian sites and by 9% at both Chukotkan sites,. In northwest Siberia, alder expansion was closely linked to cryogenic disturbances related to patterned-ground and active-layer detachments. At the Chukotkan sites, most alder expansion occurred on hillslope colluvium and floodplains; we also observed modest increases in Siberian dwarf pine (Pinus pumila). The close correspondence between expanding shrub patches and disturbance processes indicates that sparsely-vegetated, mineral-rich seedbeds strongly facilitate alder recruitment, and that the spatio-temporal attributes of disturbance mechanisms are a key determinant of landscape susceptibility to shrub expansion. Shrub expansion, in turn, initiates a cascade of effects on permafrost thermal regime and disturbance, promoting the accumulation of biomass and potentially buffering permafrost from climate warming.; Recently-established alder shrubs growing on non-sorted circles in patterned ground near Obskaya, northwest Siberia.

Effects of invasive European bird cherry (Prunus padus) on leaf litter processing by aquatic invertebrate shredder communities in urban Alaskan streams

USGS Publications Warehouse

Roon, David A.; Wipfli, Mark S.; Wurtz, Tricia L.

2014-01-01

European bird cherry (Prunus padus) (EBC) is an invasive ornamental tree that is spreading rapidly in riparian forests of urban Alaska. To determine how the spread of EBC affects leaf litter processing by aquatic invertebrate shredders, we conducted complementary leaf pack experiments in two streams located in Anchorage, Alaska. The first experiment contrasted invasive EBC with three native tree species—thin-leaf alder (Alnus tenuifolia), paper birch (Betula neoalaskana), and black cottonwood (Populus trichocarpa)—in one reach of Chester Creek; finding that EBC leaf litter broke down significantly faster than birch and cottonwood, but at a similar rate to alder. The second experiment contrasted EBC with alder in four reaches of Campbell and Chester creeks; finding that while EBC leaf litter broke down significantly faster than alder in Chester Creek, EBC broke down at a similar rate to alder in Campbell Creek. Although EBC sometimes supported fewer shredders by both count and mass, shredder communities did not differ significantly between EBC and native plants. Collectively, these data suggest that invasive EBC is not currently exhibiting strong negative impacts on leaf litter processing in these streams, but could if it continues to spread and further displaces native species over time.

ELF Communications System Ecological Monitoring Program: A Summary Report for 1982-1992

DTIC Science & Technology

1993-10-01

autumn- abscised alder leaves were used in the packs; since 1990, only fresh alder leaves have been used. Leaf packs were periodically retrieved and...red pine planting survival. Northern Journal of Applied Forestry, 5:14; 1988. 56. Connaughton, P. The effects of acid precipitation on nutrient levels

Hardwood price reporting.

Treesearch

Brent L. Sohngen; Richard W. Haynes

1994-01-01

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

Edge-glued panels from Alaska hardwoods: retail manager perspectives

Treesearch

David Nicholls; Matthew Bumgardner; Valerie Barber

2010-01-01

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

75 FR 9281 - General Provisions; Revised List of Migratory Birds

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-01

... York (AOU 1982, 1983, 1998); Flycatcher, La Sagra's, Myiarchus sagrae--Alabama, Florida (AOU 1982, 1983..., Belcher's, Larus belcheri--Florida (AOU 1982, 1983, 1998, 2003); Hawk, Roadside, Buteo magnirostis--Texas..., Southern, Progne elegans--Florida (AOU 1982, 1983, 1998); Mockingbird, Bahama, Mimus gundlachii--Florida...

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

Treesearch

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

2002-01-01

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

Quantum mechanical/molecular mechanical modeling finds Diels-Alder reactions are accelerated less on the surface of water than in water.

PubMed

Thomas, Laura L; Tirado-Rives, Julian; Jorgensen, William L

2010-03-10

Quantum and molecular mechanics calculations for the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the vacuum-water interface and in the gas phase. In conjunction with previous studies of these cycloadditions in dilute solution, a more complete picture of aqueous environmental effects emerges with implications for the origin of observed rate accelerations using heterogeneous aqueous suspensions, "on water" conditions. The pure TIP4P water slab maintains the bulk density and hydrogen-bonding properties in central water layers. The bulk region merges to vacuum over a ca. 5 A band with progressive diminution of the density and hydrogen bonding. The relative free energies of activation and transition structures for the reactions at the interface are found to be intermediate between those calculated in the gas phase and in bulk water; i.e., for the reaction with 1,4-naphthoquinone, the DeltaDeltaG(++) values relative to the gas phase are -3.6 and -7.3 kcal/mol at the interface and in bulk water, respectively. Thus, the results do not support the notion that a water surface is more effective than bulk water for catalysis of such pericyclic reactions. The trend is in qualitative agreement with expectations based on density considerations and estimates of experimental rate constants for the gas phase, a heterogeneous aqueous suspension, and a dilute aqueous solution for the reaction of cyclopentadiene with methyl vinyl ketone. Computed energy pair distributions reveal a uniform loss of 0.5-1.0 hydrogen bond for the reactants and transition states in progressing from bulk water to the vacuum-water interface. Orientational effects are apparent at the surface; e.g., the carbonyl group in the methyl vinyl ketone transition structure is preferentially oriented into the surface. Also, the transition structure for the 1,4-naphthoquinone case is buried more in the surface, and the free energy of

Organic Chemical Concentrations in Eggs and Nestlings of Cavity Nesting Birds at and around Los Alamos National Laboratory

DOE PAGES

Gaukler, Shannon M.; Hathcock, Charles D.; Fair, Jeanne M.

2018-02-13

In 1943, Los Alamos National Laboratory (LANL) was established as part of the Manhattan project to design atomic weapons. LANL now operates as a multidisciplinary research institution. As part of an ongoing assessment of siterelated ecological risk, organochlorine pesticides, their metabolites, polycyclic aromatic hydrocarbons, polychlorinated biphenyls (PCBs), and 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) were evaluated in western bluebird (Sialia mexicana) and ash-throated flycatcher (Myiarchus cinerascens) eggs relative to a developed but non-industrial reference area; PCBs and TEQs were also evaluated in nestlings. Chemicals were below detection limits in the majority of samples. Western bluebird eggs collected from the study area hadmore » significantly lower concentrations of dieldrin, oxychlordane, and trans-nonachlor when compared with eggs from the reference area. No differences were observed in concentrations of dichlorodiphenyldichloroethylene (DDE), dichlorodiphenyltrichloroethane (DDT), and heptachlor epoxide. Ash-throated flycatcher eggs contained higher total TEQ concentrations when compared with western bluebird eggs; however, no differences in concentrations of DDE, DDT, dieldrin, or total PCBs were observed. No differences were observed in total PCBs or TEQs in nestlings between the two species. Western bluebird eggs contained higher levels of total PCBs and TEQs when compared with nestlings; no differences were observed in total PCBs or TEQs between ash-throated flycatcher eggs and nestlings. Chemical concentrations detected in eggs of both species were below levels that are associated with adverse effects reported in the scientific literature, suggesting that concentrations of organic chemicals observed here appear to be at levels causing negligible risks to local bird populations.« less

Organic Chemical Concentrations in Eggs and Nestlings of Cavity Nesting Birds at and around Los Alamos National Laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaukler, Shannon M.; Hathcock, Charles D.; Fair, Jeanne M.

In 1943, Los Alamos National Laboratory (LANL) was established as part of the Manhattan project to design atomic weapons. LANL now operates as a multidisciplinary research institution. As part of an ongoing assessment of siterelated ecological risk, organochlorine pesticides, their metabolites, polycyclic aromatic hydrocarbons, polychlorinated biphenyls (PCBs), and 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) were evaluated in western bluebird (Sialia mexicana) and ash-throated flycatcher (Myiarchus cinerascens) eggs relative to a developed but non-industrial reference area; PCBs and TEQs were also evaluated in nestlings. Chemicals were below detection limits in the majority of samples. Western bluebird eggs collected from the study area hadmore » significantly lower concentrations of dieldrin, oxychlordane, and trans-nonachlor when compared with eggs from the reference area. No differences were observed in concentrations of dichlorodiphenyldichloroethylene (DDE), dichlorodiphenyltrichloroethane (DDT), and heptachlor epoxide. Ash-throated flycatcher eggs contained higher total TEQ concentrations when compared with western bluebird eggs; however, no differences in concentrations of DDE, DDT, dieldrin, or total PCBs were observed. No differences were observed in total PCBs or TEQs in nestlings between the two species. Western bluebird eggs contained higher levels of total PCBs and TEQs when compared with nestlings; no differences were observed in total PCBs or TEQs between ash-throated flycatcher eggs and nestlings. Chemical concentrations detected in eggs of both species were below levels that are associated with adverse effects reported in the scientific literature, suggesting that concentrations of organic chemicals observed here appear to be at levels causing negligible risks to local bird populations.« less

Development of Alnus tenuifolia stands on an Alaskan floodplain: patterns of recruitment, disease, and succession

Treesearch

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

2011-01-01

We investigated the population dynamics of the keystone symbiotic N-fixing species Alnus tenuifolia (thinleaf alder) and the patterns of primary succession on the Tanana River floodplains of interior Alaska, USA. The goals of this study were to characterize (i) the variation in the population structure of thinleaf alder and its influence on...

Maintaining cultures of wood-rotting fungi.

Treesearch

E.E. Nelson; H.A. Fay

1985-01-01

Phellinus weirii cultures were stored successfully for 10 years in small alder (Alnus rubra Bong.) disks at 2 °C. The six isolates tested appeared morphologically identical and after 10 years varied little in growth rate from those stored on malt agar slants. Long-term storage on alder disks reduces the time required for...

The [C{sub 6}H{sub 10}]{sup {sm{underscore}bullet}+} hypersurface: The parent radical cation Diels-Alder reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, M.; Schaefer, H.F. III

1999-07-21

Various possible reaction pathways between ethene and butadiene radical cation (cis- and trans-), have been investigated at different levels of theory up to UCCSD(T)/DZP/UMP2(fc)/DZP and with density functional theory at B3LYP/DZP. A stepwise addition involving open chain intermediates and leading to the Diels-Alder product, the cyclohexene radical cation, was found to have a total activation barrier {Delta}G{sup 298{ne}} = 6.3 kcal mol{sup {minus}1} and a change in free Gibbs energy, {Delta}G{sup 298}, of {minus}33.5 kcal mol{sup {minus}1}. On the E{degree} potential energy surface, all transition states are lower in energy than separated ethene and butadiene, the exothermicity {Delta}E = -45.6more » kcal mol{sup {minus}1}. A more direct path could be characterized as stepwise with one intermediate only at the SCF level but not at electron-correlated levels and hence might actually be a concerted strongly asynchronous addition with a very small or no activation barrier (UCCSD(T)/DZP/UHF/6-31G* gives a {Delta}G{sup 298{ne}} of 0.8 kcal mol{sup {minus}1}). The critical step for another alternative, the cyclobutanation-vinylcyclobutane/cyclohexene rearrangement, is a 1,3-alkyl shift which involves a barrier ({Delta}G{sup 298{ne}}) only 1.7 kcal mol{sup {minus}1} higher than that of stop use addition for both cis-, and trans-butadiene radical cation. However, from the (ethene and trans-butadiene) reactions, ring expansion of the vinylcyclobutane radical cation intermediate, to a methylene cyclopentane radical cation, requires an activation only 1.3 kcal mol{sup {minus}1} larger than for (trans-butadiene radical). While cis/trans isomerization of free butadiene radical cation requires a high activation (24.9 kcal mol{sup {minus}1}), a reaction sequence involving addition of ethene (to stepwise give an open chain intermediate and vinyl cyclobutane radical cation) has a barrier of only 3.5 kcal mol{sup {minus}1} ({Delta}G{sup 298{ne}}). This sequence also makes ethene

Chip Debarking of Several Western Species

Treesearch

William A. Hillstrom

1974-01-01

Discusses processing and conditioning treatments before and aftger compression debarking of western hemlock, Douglas fir, red alder, and bigleaf maple. Bark removal and wood recovery from red alder far exceeded the other species tested. Approximately 90 percent of the wood fiber input was recovered at a residual bark content of less than 2 percent by weight.

Micro-flow photosynthesis of new dienophiles for inverse-electron-demand Diels–Alder reactions. Potential applications for pretargeted in vivo PET imaging† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc02933g Click here for additional data file.

PubMed Central

Billaud, Emilie M. F.; Shahbazali, Elnaz; Ahamed, Muneer; Cleeren, Frederik; Noël, Timothy; Koole, Michel; Verbruggen, Alfons; Hessel, Volker

2017-01-01

Pretargeted PET imaging has emerged as an effective two-step in vivo approach that combines the superior affinity and selectivity of antibodies with the rapid pharmacokinetics and favorable dosimetry of smaller molecules radiolabeled with short-lived radionuclides. This approach can be based on the bioorthogonal inverse-electron-demand Diels–Alder (IEDDA) reaction between tetrazines and trans-cyclooctene (TCO) derivatives. We aimed to develop new [18F]TCO–dienophiles with high reactivity for IEDDA reactions, and favorable in vivo stability and pharmacokinetics. New dienophiles were synthesized using an innovative micro-flow photochemistry process, and their reaction kinetics with a tetrazine were determined. In vivo stability and biodistribution of the most promising 18F-radiolabeled-TCO-derivative ([18F]3) was investigated, and its potential for in vivo pretargeted PET imaging was assessed in tumor-bearing mice. We demonstrated that [18F]3 is a suitable dienophile for IEDDA reactions and for pretargeting applications. PMID:28451267

Computational Insights into an Enzyme-Catalyzed [4+2] Cycloaddition

PubMed Central

2017-01-01

The enzyme SpnF, involved in the biosynthesis of spinosyn A, catalyzes a formal [4+2] cycloaddition of a 22-membered macrolactone, which may proceed as a concerted [4+2] Diels–Alder reaction or a stepwise [6+4] cycloaddition followed by a Cope rearrangement. Quantum mechanics/molecular mechanics (QM/MM) calculations combined with free energy simulations show that the Diels–Alder pathway is favored in the enzyme environment. OM2/CHARMM free energy simulations for the SpnF-catalyzed reaction predict a free energy barrier of 22 kcal/mol for the concerted Diels–Alder process and provide no evidence of a competitive stepwise pathway. Compared with the gas phase, the enzyme lowers the Diels–Alder barrier significantly, consistent with experimental observations. Inspection of the optimized geometries indicates that the enzyme may prearrange the substrate within the active site to accelerate the [4+2] cycloaddition and impede the [6+4] cycloaddition through interactions with active-site residues. Judging from partial charge analysis, we find that the hydrogen bond between the Thr196 residue of SpnF and the substrate C15 carbonyl group contributes to the enhancement of the rate of the Diels–Alder reaction. QM/MM simulations show that the substrate can easily adopt a reactive conformation in the active site of SpnF because interconversion between the C5–C6 s-trans and s-cis conformers is facile. Our QM/MM study suggests that the enzyme SpnF does behave as a Diels-Alderase. PMID:29131960

Watershed influences on the structure and function of riparian wetlands associated with headwater streams - Kenai Peninsula, Alaska.

PubMed

Whigham, D F; Walker, C M; Maurer, J; King, R S; Hauser, W; Baird, S; Keuskamp, J A; Neale, P J

2017-12-01

Riparian wetlands are dynamic components of landscapes. Located between uplands and aquatic environments, riparian habitats intercept sediments and nutrients before they enter aquatic environments. They are a source of organic matter and nutrients to aquatic systems, and they provide important habitat for animals, often serving as corridors for the movement of animals between habitats in fragmented landscapes. In this project, we focused on the structure and function of riparian wetlands associated with headwater streams in Alaska that serve as nursery habitats for juvenile salmonids. We asked whether or not the structure and function of headwater wetlands differed between watersheds with and without nitrogen-fixing Alder (Alnus spp.). We found that the aboveground biomass of riparian vegetation was higher in the watershed with Alder, but the largest differences were in the litter layer and belowground where vegetation in the watershed with no Alder had significantly higher root biomass. Interstitial water chemistry also differed between the study sites with significantly higher inorganic N and significantly different characteristics of colored dissolved organic matter at the site with Alder on the watershed. The biomass of litter that hung over the creek bank was less at the site with Alder on the watershed and an in situ decomposition experiment showed significant differences between the two systems. Results of the research demonstrates that watershed characteristics can impact the ecology of headwater streams in ways that had not been previously recognized. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Nitrous oxide fluxes from tree stems of temperate forests

NASA Astrophysics Data System (ADS)

Wen, Yuan; Corre, Marife D.; Rachow, Christine; Veldkamp, Edzo

2017-04-01

Although trees are recognized as conduits of soil-generated N2O, little is known about N2O fluxes from mature trees under field conditions and thier contributions to total forest N2O fluxes. Here, we quantified in situ stem N2O fluxes from mature alder trees on poorly-drained soil and mature beech and spruce trees on well-drained soils in Solling, Germany from March to October 2015. Soil N2O fluxes, soil N2O concentrations at 40-cm depth, and soil and climatic variables known to influence N2O fluxes were also measured concurrently with the stem N2O fluxes. Alder, beech and spruce consistently emitted N2O via stems and all displayed higher emission rates in summer than in spring and in autumn. Stem N2O fluxes from alder stand were higher than those from beech and spruce stands (P < 0.01), which was attributed to the presence of aerenchyma and lenticels as well as higher soil water content and soil C and N availability in the alder stand (P < 0.01-0.05). The correlations of stem N2O fluxes from alder with soil N2O fluxes, soil N2O concentrations, soil and air temperature and vapor pressure deficit (R = 0.60 - 0.90, P < 0.01-0.05) suggest that N2O transport in alder was facilitated by a combination of passive gas diffusion through aerenchyma and active transport of dissolved N2O through sap flow. In the beech and spruce stands, correlations of stem N2O fluxes with soil and air temperature and vapor pressure deficit (R = 0.57 - 0.78, P < 0.01-0.07) suggest that active transport of dissolved N2O via xylem sap was the major mechanism for stem N2O emissions in upland trees. Stem N2O fluxes represented 8-11% of the total (soil + stem) N2O fluxes in the spruce and beech stands whereas in the alder stand, with its large soil N2O emission, stem emission contributed only 1% of the total flux. Our results suggest that the relative contribution of tree-mediated N2O fluxes is more important in upland trees than in wetland trees.

Design and Synthesis of a Library of Tetracyclic Hydroazulenoisoindoles

PubMed Central

Brummond, Kay M.; Mao, Shuli; Shinde, Sunita N.; Johnston, Paul J.; Day, Billy W.

2009-01-01

Forty-four tetracyclic hydroazulenoisoindoles were synthesized via a tandem cyclopropanation/Cope rearrangement followed by a Diels-Alder sequence from easily available five-membered cyclic cross-conjugated trienones. These trienones were obtained from two different routes depending upon whether R1 and R2 are alkyl or amino acid derived functional groups, via a rhodium(I)-catalyzed cycloisomerization reaction. In order to increase diversity, four maleimides and two 1,2,4-triazoline-3,5-diones were used as dienophiles in the Diels-Alder step. Several Diels-Alder adducts were further reacted under palladium-catalyzed hydrogenation conditions, leading to a diastereoselective reduction of the trisubstituted double bond. This library has demonstrated rapid access to a variety of structurally complex natural product-like compounds via stereochemical diversity and building block diversity approaches. PMID:19366169

77 FR 75646 - Kenai National Wildlife Refuge, Soldotna, AK; Draft Environmental Impact Statement for the...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-21

..., and Cook Inlet Region, Inc. (CIRI), owns the subsurface estate of coal, oil, and gas in the project..., snowshoe hares, and numerous species of Neotropical birds, such as olive-sided flycatchers, myrtle warblers... received the subsurface oil, gas, and coal estate to nearly 200,000 acres within the Refuge as part of its...

A Field Guide to Common Educator Birds.

ERIC Educational Resources Information Center

Smock, Judith N.

1990-01-01

Teaching may be for the birds, but many educator birds have been abandoning the field of late for downier nests. Several species still remain, including the crown-tufted superintendent bird, the red-throated assistant superintendent bird, the crested fly-catcher principal bird, the exotic scenery bird, the roadrunner psychologist bird, and the…

Silence is not golden: the hissing calls of tits affect the behaviour of a nest predator.

PubMed

Zub, Karol; Czeszczewik, Dorota; Ruczyński, Ireneusz; Kapusta, Anna; Walankiewicz, Wiesław

2017-01-01

Nest predation is one of the most important mortality factors of birds. Field observations showed that tits (Paridae) produce hissing calls and, usually, have lower breeding losses than nesting Ficedula flycatchers, which do not make such calls. We hypothesise that differences in fledgling success can be directly attributed to the vocal reaction of tits. We tested experimentally whether the hissing calls can affect the behaviour of a potential predator, analysing the response of the Yellow-necked Mouse Apodemus flavicollis to playback of calls of three Parid species. The number of visits by mice to two types of cavities (with playback and control) was not significantly different, but the average time spent by mice in cavities with playback (3.9 s) was significantly shorter than in cavities without playback (26.3 s). This suggests that hissing behaviour of tits significantly changes the exploration activity of predators, which may ultimately increase the breeding success of this group of birds relative to the flycatchers. Nest predation is one of the most important mortality factors of small land birds, but some anti-predatory mechanisms are still poorly recognised. Numerous studies demonstrate that incubating tits make hissing sounds, when a predator is near, but despite almost a century of research, there is little evidence these calls indeed affect behaviour of predators. By using a simple laboratory experiment, we demonstrated that the hissing acoustic signals used by tits may change the behaviour of yellow-necked mice, which are an important predator of cavity-nesting birds in temperate forests. Intruding mice withdrew from cavities where hissing sounds were played back. Our results suggest that the hissing behaviour of tits can change the exploration activity of potential predators and may increase breeding success of this group of birds relative to the flycatchers, which stay silent when their nest is threatened.

Bird populations in logged and unlogged western larch/Douglas-fir forest in northwestern Montana

Treesearch

Bret W. Tobalske; Raymond C. Shearer; Richard L. Hutto

1991-01-01

Of 32 species of abundant breeding birds, populations of 10 species differed significantly between small cutting units and adjacent uncut forest. Foliage foragers and tree gleaners were less abundant in cutting units, while flycatching species and ground foragers were more common there. Of nesting guilds, conifer tree nesters were least abundant in cutting units, and...

Chapter 10: Management recommendations

Treesearch

Deborah M. Finch; Janie Agyagos; Tracy McCarthey; Robert M. Marshall; Scott H. Stoleson; Mary J. Whitfield

2000-01-01

This chapter was developed over a series of meetings using a group-consensus process. Our recommendations are based on published results, on information compiled in the previous chapters, on expert opinion, and on unpublished data of conservation team members. This chapter is available as temporary guidance until the Recovery Plan for the southwestern willow flycatcher...

Bacteria-killing ability of fresh blood plasma compared to frozen blood plasma

DOE PAGES

Jacobs, Anne C.; Fair, Jeanne Marie

2015-10-09

In recent years, the bacteria-killing assay (BKA) has become a popular technique among ecoimmunologists. New variations of that assay allow researchers to use smaller volumes of blood, an important consideration for those working on small-bodied animals. However, this version of the assay requires access to a lab with a nanodrop spectrophotometer, something that may not be available in the field. One possible solution is to freeze plasma for transport; however, this assumes that frozen plasma samples will give comparable results to fresh ones. Here, we tested this assumption using plasma samples from three species of birds: chickens (Gallus gallus), ash-throatedmore » flycatchers (Myiarchus cinerascens), and western bluebirds (Sialia mexicana). Chicken plasma samples lost most or all of their bacterial killing ability after freezing. This did not happen in flycatchers and bluebirds; however, frozen plasma did not produce results comparable to those obtained using fresh plasma. Finally, we caution researchers using the BKA to use fresh samples whenever possible, and to validate the use of frozen samples on a species-by-species basis.« less

Bacteria-killing ability of fresh blood plasma compared to frozen blood plasma.

PubMed

Jacobs, Anne C; Fair, Jeanne M

2016-01-01

In recent years, the bacteria-killing assay (BKA) has become a popular technique among ecoimmunologists. New variations of that assay allow researchers to use smaller volumes of blood, an important consideration for those working on small-bodied animals. However, this version of the assay requires access to a lab with a nanodrop spectrophotometer, something that may not be available in the field. One possible solution is to freeze plasma for transport; however, this assumes that frozen plasma samples will give comparable results to fresh ones. We tested this assumption using plasma samples from three species of birds: chickens (Gallus gallus), ash-throated flycatchers (Myiarchus cinerascens), and western bluebirds (Sialia mexicana). Chicken plasma samples lost most or all of their bacterial killing ability after freezing. This did not happen in flycatchers and bluebirds; however, frozen plasma did not produce results comparable to those obtained using fresh plasma. We caution researchers using the BKA to use fresh samples whenever possible, and to validate the use of frozen samples on a species-by-species basis. Copyright © 2015 Elsevier Inc. All rights reserved.

Bacteria-killing ability of fresh blood plasma compared to frozen blood plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, Anne C.; Fair, Jeanne Marie

In recent years, the bacteria-killing assay (BKA) has become a popular technique among ecoimmunologists. New variations of that assay allow researchers to use smaller volumes of blood, an important consideration for those working on small-bodied animals. However, this version of the assay requires access to a lab with a nanodrop spectrophotometer, something that may not be available in the field. One possible solution is to freeze plasma for transport; however, this assumes that frozen plasma samples will give comparable results to fresh ones. Here, we tested this assumption using plasma samples from three species of birds: chickens (Gallus gallus), ash-throatedmore » flycatchers (Myiarchus cinerascens), and western bluebirds (Sialia mexicana). Chicken plasma samples lost most or all of their bacterial killing ability after freezing. This did not happen in flycatchers and bluebirds; however, frozen plasma did not produce results comparable to those obtained using fresh plasma. Finally, we caution researchers using the BKA to use fresh samples whenever possible, and to validate the use of frozen samples on a species-by-species basis.« less

Exploiting the Electrophilic and Nucleophilic Dual Role of Nitrile Imines: One-Pot, Three-Component Synthesis of Furo[2,3-d]pyridazin-4(5H)-ones.

PubMed

Giustiniano, Mariateresa; Mercalli, Valentina; Amato, Jussara; Novellino, Ettore; Tron, Gian Cesare

2015-08-21

An expeditious multicomponent reaction to synthesize tetrasubstituted furo[2,3-d]pyridazin-4(5H)-ones is reported. In brief, hydrazonoyl chlorides react with isocyanoacetamides, in the presence of TEA, to give 1,3-oxazol-2-hydrazones which, without being isolated, can react with dimethylacetylene dicarboxylate to afford furo[2,3-d]pyridazin-4(5H)-ones with an unprecedented level of complexity in a triple domino Diels-Alder/retro-Diels-Alder/lactamization reaction sequence.

Processing Conjugated-Diene-Containing Polymers

NASA Technical Reports Server (NTRS)

Bell, Vernon L.; Havens, Stephen J.

1987-01-01

Diels-Alder reaction used to cross-linked thermoplastics. Process uses Diels-Alder reaction to cross-link and/or extend conjugated-diene-containing polymers by reacting them with bis-unsaturated dienophiles results in improved polymer properties. Quantities of diene groups required for cross-linking varies from very low to very high concentrations. Process also used to extend, or build up molecular weights of, low-molecular-weight linear polymers with terminal conjugated dienic groups.

Chapter 2: Population status on breeding grounds

Treesearch

Robert M. Marshall

2000-01-01

In his review of the overall population status of the southwestern willow flycatcher, Unitt (1987) concluded that "Even if a few hundred pairs persist in New Mexico, the total population of the subspecies is well under 1000 pairs; I suspect 500 is more likely." Since Unitt's review, a substantial amount of information has been collected rangewide on the...

The role of indicator species: Neotropical migratory song birds

Treesearch

Theodore R. Simons; Kerry N. Rabenold; David A. Buehler; Jaime A. Collazo; Kathleen E. Franzreb

1999-01-01

Southern Appalachian forests support some of the richest avian diversity in North America, including some 75 species of Neotropical migrants, birds that perform the remarkable feat of making much of the Western Hemisphere their home. This diverse group includes the swallows, kingbirds, and other flycatchers that feed in the air on flying insects. The Eastern kingbird...

The Role of MC1R in Speciation & Phylogeny

ERIC Educational Resources Information Center

Offner, Susan

2013-01-01

A point mutation in the MC1R gene, a G-protein-coupled receptor, has been found that could have led to the formation of two subspecies of Solomon Island flycatcher from a single ancestral population. I discuss the many roles that G-protein-coupled receptors play in vertebrate physiology and how one particular point mutation can have enormous…

Chapter 11: Research needs

Treesearch

Scott H. Stoleson; Janie Agyagos; Deborah M. Finch; Tracy McCarthey; Jamie Uyehara; Mary J. Whitfield

2000-01-01

Until the southwestern willow flycatcher was proposed for listing as an endangered species in 1993, it was subject to relatively little scientific scrutiny, in part because it is drab, prone to inhabiting dense, wet thickets, and difficult to identify and observe. Consequently, it remained one of the lesser-known of North American birds. Since that time, it has become...

National Research Council Resident Research Associateship (NRC-RRA) program

DTIC Science & Technology

1988-08-01

Davis, C. J. Dymek, J. J. P. Stewart, H. P. Clark, W. J. Lauderdale, J. Am. Chem. Soc., 107, 5041-5046 (1985). 7. "Mechanism of the Diels - Alder ...Package" Dewar Research Group and J. J. P. Stewart, Quantum Chemistry Program Exchange, no. 506, nn, nnn, (1986) 16. "Mechanism of the Diels - Alder ...Kvisle, 0. Nirisen, M. Ystenes, and H. A. Oye, Proceedings of 1986 International Symposium on Transition Metals Catalyzed Polymerizations, Institute of

Regiochemically controlled synthesis of a β-4-β' [70]fullerene bis-adduct

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cerón, Maira R.; Castro, Edison; Neti, Venkata S. Pavan K.

2016-12-22

A β-4-β' C 70 bis-adduct regioisomer and an uncommon mono-adduct β-malonate C 70 derivative were synthesized by using a Diels–Alder cycloaddition followed by an addition–elimination of bromo-ethylmalonate and a retro-Diels–Alder cycloaddition reaction. Here, we also report the regioselective synthesis and spectroscopic characterization of C s-symmetric tris- and C 2v-symmetric tetra-adducts of C 70, which are the precursors of the mono- and bis-adduct final products.

How Does Salinity Shape Bacterial and Fungal Microbiomes of Alnus glutinosa Roots?

PubMed Central

Thiem, Dominika; Gołębiewski, Marcin; Hulisz, Piotr; Piernik, Agnieszka; Hrynkiewicz, Katarzyna

2018-01-01

Black alder (Alnus glutinosa Gaertn.) belongs to dual mycorrhizal trees, forming ectomycorrhizal (EM) and arbuscular (AM) root structures, as well as represents actinorrhizal plants that associate with nitrogen-fixing actinomycete Frankia sp. We hypothesized that the unique ternary structure of symbionts can influence community structure of other plant-associated microorganisms (bacterial and fungal endophytes), particularly under seasonally changing salinity in A. glutinosa roots. In our study we analyzed black alder root bacterial and fungal microbiome present at two forest test sites (saline and non-saline) in two different seasons (spring and fall). The dominant type of root microsymbionts of alder were ectomycorrhizal fungi, whose distribution depended on site (salinity): Tomentella, Lactarius, and Phialocephala were more abundant at the saline site. Mortierella and Naucoria (representatives of saprotrophs or endophytes) displayed the opposite tendency. Arbuscular mycorrhizal fungi belonged to Glomeromycota (orders Paraglomales and Glomales), however, they represented less than 1% of all identified fungi. Bacterial community structure depended on test site but not on season. Sequences affiliated with Rhodanobacter, Granulicella, and Sphingomonas dominated at the saline site, while Bradyrhizobium and Rhizobium were more abundant at the non-saline site. Moreover, genus Frankia was observed only at the saline site. In conclusion, bacterial and fungal community structure of alder root microsymbionts and endophytes depends on five soil chemical parameters: salinity, phosphorus, pH, saturation percentage (SP) as well as total organic carbon (TOC), and seasonality does not appear to be an important factor shaping microbial communities. Ectomycorrhizal fungi are the most abundant symbionts of mature alders growing in saline soils. However, specific distribution of nitrogen-fixing Frankia (forming root nodules) and association of arbuscular fungi at early stages of

How Does Salinity Shape Bacterial and Fungal Microbiomes of Alnus glutinosa Roots?

PubMed

Thiem, Dominika; Gołębiewski, Marcin; Hulisz, Piotr; Piernik, Agnieszka; Hrynkiewicz, Katarzyna

2018-01-01

Black alder ( Alnus glutinosa Gaertn.) belongs to dual mycorrhizal trees, forming ectomycorrhizal (EM) and arbuscular (AM) root structures, as well as represents actinorrhizal plants that associate with nitrogen-fixing actinomycete Frankia sp. We hypothesized that the unique ternary structure of symbionts can influence community structure of other plant-associated microorganisms (bacterial and fungal endophytes), particularly under seasonally changing salinity in A. glutinosa roots. In our study we analyzed black alder root bacterial and fungal microbiome present at two forest test sites (saline and non-saline) in two different seasons (spring and fall). The dominant type of root microsymbionts of alder were ectomycorrhizal fungi, whose distribution depended on site (salinity): Tomentella , Lactarius , and Phialocephala were more abundant at the saline site. Mortierella and Naucoria (representatives of saprotrophs or endophytes) displayed the opposite tendency. Arbuscular mycorrhizal fungi belonged to Glomeromycota (orders Paraglomales and Glomales), however, they represented less than 1% of all identified fungi. Bacterial community structure depended on test site but not on season. Sequences affiliated with Rhodanobacter , Granulicella , and Sphingomonas dominated at the saline site, while Bradyrhizobium and Rhizobium were more abundant at the non-saline site. Moreover, genus Frankia was observed only at the saline site. In conclusion, bacterial and fungal community structure of alder root microsymbionts and endophytes depends on five soil chemical parameters: salinity, phosphorus, pH, saturation percentage (SP) as well as total organic carbon (TOC), and seasonality does not appear to be an important factor shaping microbial communities. Ectomycorrhizal fungi are the most abundant symbionts of mature alders growing in saline soils. However, specific distribution of nitrogen-fixing Frankia (forming root nodules) and association of arbuscular fungi at early stages

"Clickable" Polymeric Nanofibers through Hydrophilic-Hydrophobic Balance: Fabrication of Robust Biomolecular Immobilization Platforms.

PubMed

Kalaoglu-Altan, Ozlem I; Sanyal, Rana; Sanyal, Amitav

2015-05-11

Fabrication of hydrophilic polymeric nanofibers that undergo facile and selective functionalization through metal catalyst-free Diels-Alder "click" reaction in aqueous environment is outlined. Electrospinning of copolymers containing an electron-rich furan moiety, hydrophobic methyl methacrylate units and hydrophilic poly(ethylene glycol)s as side chains provide specifically functionalizable yet antibiofouling fibers that remain stable in aqueous media due to appropriate hydrophobic hydrophilic balance. Efficient functionalization of these nanofibers is accomplished through the Diels-Alder reaction by exposing them to maleimide-containing molecules and ligands. Diels-Alder conjugation based functionalization is demonstrated through attachment of fluorescein-maleimide and a maleimide tethered biotin ligand. Biotinylated nanofibers were utilized to mediate immobilization of the protein streptavidin, as well as streptavidin coated quantum dots. Facile fabrication from readily available polymers and their effective functionalization under mild and reagent-free conditions in aqueous media make these "clickable" nanofibers attractive candidates as functionalizable scaffolds for various biomedical applications.

Patterned-ground facilitates shrub expansion in Low Arctic tundra

NASA Astrophysics Data System (ADS)

Frost, Gerald V.; Epstein, Howard E.; Walker, Donald A.; Matyshak, Georgiy; Ermokhina, Ksenia

2013-03-01

Recent expansion of tall shrubs in Low Arctic tundra is widely seen as a response to climate warming, but shrubification is not occurring as a simple function of regional climate trends. We show that establishment of tall alder (Alnus) is strongly facilitated by small, widely distributed cryogenic disturbances associated with patterned-ground landscapes. We identified expanding and newly established shrub stands at two northwest Siberian sites and observed that virtually all new shrubs occurred on bare microsites (‘circles’) that were disturbed by frost-heave. Frost-heave associated with circles is a widespread, annual phenomenon that maintains mosaics of mineral seedbeds with warm soils and few competitors that are immediately available to shrubs during favorable climatic periods. Circle facilitation of alder recruitment also plausibly explains the development of shrublands in which alders are regularly spaced. We conclude that alder abundance and extent have increased rapidly in the northwest Siberian Low Arctic since at least the mid-20th century, despite a lack of summer warming in recent decades. Our results are consistent with findings in the North American Arctic which emphasize that the responsiveness of Low Arctic landscapes to climate change is largely determined by the frequency and extent of disturbance processes that create mineral-rich seedbeds favorable for tall shrub recruitment. Northwest Siberia has high potential for continued expansion of tall shrubs and concomitant changes to ecosystem function, due to the widespread distribution of patterned-ground landscapes.

Environmental Assessment for Demolition of Building 2148 and Construction of a New Facility

DTIC Science & Technology

2004-02-01

Athene cunicularia SP Caspian Tern Sterna caspia SP Ferruginous Hawk Buteo regalis T Grasshopper Sparrow Ammodramus savannarum SP/SD Lewis’ Woodpecker...northern latitudes winter along streams and lakes throughout Utah and have been observed at the Weber River just north of the Base. Willow Flycatchers...Pelecanus erythrorhynchos SD Black Tern Chlidonias niger SP Blue Grosbeak Guiraca caerulea SP/SD Bobolink Dolichonyx oryzivorus SP/SD Burrowing Owl

Legacy Bird Species at Risk Monitoring in and Around Camp Navajo and the Naval Observatory Flagstaff Station, AZ

DTIC Science & Technology

2010-04-16

19th century due to a convergence of complex stressors such as overgrazing, timber harvest, drought , and fire suppression (Allen et al. 2002, Moore... pinus 16 Olive Warbler Peucedramus taeniatus 5 Plumbeous Vireo Vireo solitarius 60 Pygmy Nuthatch Sitta pygmaea 177 Red Crossbill Loxia...Dove Zenaida macroura 14 Northern Flicker Colaptes auratus 50 Pine Siskin Carduelis pinus 58 Olive-sided Flycatcher Contopus cooperi 1

Natal habitat imprinting counteracts the diversifying effects of phenotype-dependent dispersal in a spatially structured population.

PubMed

Camacho, Carlos; Canal, David; Potti, Jaime

2016-08-08

Habitat selection may have profound evolutionary consequences, but they strongly depend on the underlying preference mechanism, including genetically-determined, natal habitat and phenotype-dependent preferences. It is known that different mechanisms may operate at the same time, yet their relative contribution to population differentiation remains largely unexplored empirically mainly because of the difficulty of finding suitable study systems. Here, we investigate the role of early experience and genetic background in determining the outcome of settlement by pied flycatchers (Ficedula hypoleuca) breeding in two habitat patches between which dispersal and subsequent reproductive performance is influenced by phenotype (body size). For this, we conducted a cross-fostering experiment in a two-patch system: an oakwood and a conifer plantation separated by only 1 km. Experimental birds mostly returned to breed in the forest patch where they were raised, whether it was that of their genetic or their foster parents, indicating that decisions on where to settle are determined by individuals' experience in their natal site, rather than by their genetic background. Nevertheless, nearly a third (27.6 %) moved away from the rearing habitat and, as previously observed in unmanipulated individuals, dispersal between habitats was phenotype-dependent. Pied flycatchers breeding in the oak and the pine forests are differentiated by body size, and analyses of genetic variation at microsatellite loci now provide evidence of subtle genetic differentiation between the two populations. This suggests that phenotype-dependent dispersal may contribute to population structure despite the short distance and widespread exchange of birds between the study plots. Taken together, the current and previous findings that pied flycatchers do not always settle in the habitat to which they are best suited suggest that their strong tendency to return to the natal patch regardless of their body size

Interspecific variation in the relationship between clutch size, laying date and intensity of urbanization in four species of hole-nesting birds.

PubMed

Vaugoyeau, Marie; Adriaensen, Frank; Artemyev, Alexandr; Bańbura, Jerzy; Barba, Emilio; Biard, Clotilde; Blondel, Jacques; Bouslama, Zihad; Bouvier, Jean-Charles; Camprodon, Jordi; Cecere, Francesco; Charmantier, Anne; Charter, Motti; Cichoń, Mariusz; Cusimano, Camillo; Czeszczewik, Dorota; Demeyrier, Virginie; Doligez, Blandine; Doutrelant, Claire; Dubiec, Anna; Eens, Marcel; Eeva, Tapio; Faivre, Bruno; Ferns, Peter N; Forsman, Jukka T; García-Del-Rey, Eduardo; Goldshtein, Aya; Goodenough, Anne E; Gosler, Andrew G; Grégoire, Arnaud; Gustafsson, Lars; Harnist, Iga; Hartley, Ian R; Heeb, Philipp; Hinsley, Shelley A; Isenmann, Paul; Jacob, Staffan; Juškaitis, Rimvydas; Korpimäki, Erkki; Krams, Indrikis; Laaksonen, Toni; Lambrechts, Marcel M; Leclercq, Bernard; Lehikoinen, Esa; Loukola, Olli; Lundberg, Arne; Mainwaring, Mark C; Mänd, Raivo; Massa, Bruno; Mazgajski, Tomasz D; Merino, Santiago; Mitrus, Cezary; Mönkkönen, Mikko; Morin, Xavier; Nager, Ruedi G; Nilsson, Jan-Åke; Nilsson, Sven G; Norte, Ana C; Orell, Markku; Perret, Philippe; Perrins, Christopher M; Pimentel, Carla S; Pinxten, Rianne; Richner, Heinz; Robles, Hugo; Rytkönen, Seppo; Senar, Juan Carlos; Seppänen, Janne T; Pascoal da Silva, Luis; Slagsvold, Tore; Solonen, Tapio; Sorace, Alberto; Stenning, Martyn J; Tryjanowski, Piotr; von Numers, Mikael; Walankiewicz, Wieslaw; Møller, Anders Pape

2016-08-01

The increase in size of human populations in urban and agricultural areas has resulted in considerable habitat conversion globally. Such anthropogenic areas have specific environmental characteristics, which influence the physiology, life history, and population dynamics of plants and animals. For example, the date of bud burst is advanced in urban compared to nearby natural areas. In some birds, breeding success is determined by synchrony between timing of breeding and peak food abundance. Pertinently, caterpillars are an important food source for the nestlings of many bird species, and their abundance is influenced by environmental factors such as temperature and date of bud burst. Higher temperatures and advanced date of bud burst in urban areas could advance peak caterpillar abundance and thus affect breeding phenology of birds. In order to test whether laying date advance and clutch sizes decrease with the intensity of urbanization, we analyzed the timing of breeding and clutch size in relation to intensity of urbanization as a measure of human impact in 199 nest box plots across Europe, North Africa, and the Middle East (i.e., the Western Palearctic) for four species of hole-nesters: blue tits (Cyanistes caeruleus), great tits (Parus major), collared flycatchers (Ficedula albicollis), and pied flycatchers (Ficedula hypoleuca). Meanwhile, we estimated the intensity of urbanization as the density of buildings surrounding study plots measured on orthophotographs. For the four study species, the intensity of urbanization was not correlated with laying date. Clutch size in blue and great tits does not seem affected by the intensity of urbanization, while in collared and pied flycatchers it decreased with increasing intensity of urbanization. This is the first large-scale study showing a species-specific major correlation between intensity of urbanization and the ecology of breeding. The underlying mechanisms for the relationships between life history and

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

PubMed Central

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

2016-01-01

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

Distinct temperature sensitivity among taiga and tundra shrubs in Alaska

NASA Astrophysics Data System (ADS)

Andreu-Hayles, L.; Anchukaitis, K. J.; D'Arrigo, R.

2014-12-01

Shrub expansion into Arctic and alpine tundra ecosystems is well documented, mostly over the last 50 years, based on remote sensing data, aerial photography, and in-situ observations. Warming temperatures are considered the main driver of the observed change in shrub vegetation patterns. Here, we assess the relationship between temperatures and shrub growth from five populations of Salix spp. (willow) and Alnus spp. (alder) in Alaska growing within the tundra and the boreal forest (~taiga) using dendrochronological techniques. The three tundra shrub sites are located on the Dalton Highway north from Toolik Lake (~69ºN 148ºW), whereas the two taiga shrub sites are located closer to Fairbanks at the Twelve Mile Summit site (~65ºN 146ºW). Because shrub ages vary among the studied populations lead to different time spans for the ring-width chronologies generated, a common period with available satellite data spanning from 1982 to 2010 was selected for this study. All tundra shrub chronologies shared a strong positive response to summer temperatures despite growing in heterogeneous site conditions and belonging to different species. In contrast, in the taiga, summer temperatures enhance willow growth, whereas alder growth appears almost insensitive to temperature over the interval studied. Extending the analyses back in time, a very strong positive relationship was found between alder ring-width and June temperatures prior to 1970. This phenomenon, a weakening of the previously existing relationship between growth and temperatures, was also detected in white spruce (Picea glauca) growing at the same site, and it is known in the literature as the 'divergence problem'. Thus, at this taiga location, alder shrubs and trees seem to have similar growth patterns. Summer temperatures no longer seem to enhance taiga alder growth. Shrubs of different species exposed to the same climatic conditions can exhibit varied growth responses. The distinct temperature sensitivities

Total synthesis of the thiopeptide antibiotic amythiamicin D.

PubMed

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

2005-11-09

The thiopeptide (or thiostrepton) antibiotics are a class of sulfur containing highly modified cyclic peptides with interesting biological properties, including reported activity against MRSA and malaria. Described herein is the total synthesis of the thiopeptide natural product amythiamicin D, which utilizes a biosynthesis-inspired hetero-Diels-Alder route to the pyridine core of the antibiotic as a key step. Preliminary studies using a range of serine-derived 1-ethoxy-2-azadienes established that hetero-Diels-Alder reaction with N-acetylenamines proceeded efficiently under microwave irradiation to give 2,3,6-trisubstituted pyridines. The thiazole building blocks of the antibiotic were obtained by either classical Hantzsch reactions or by dirhodium(II)-catalyzed chemoselective carbene N-H insertion followed by thionation, and were combined to give the bis-thiazole that forms the left-hand fragment of the antibiotic. The key Diels-Alder reaction of a tris-thiazolyl azadiene with benzyl 2-(1-acetylaminoethenyl)thiazole-4-carboxylate gave the core tetrathiazolyl pyridine, which was elaborated into the natural product by successive incorporation of glycine and bis-thiazole fragments followed by macrocyclization.

Synthesis of tripeptide derivatized cyclopentadienyl complexes of technetium and rhenium as radiopharmaceutical probes.

PubMed

Nadeem, Qaisar; Can, Daniel; Shen, Yunjun; Felber, Michael; Mahmood, Zaid; Alberto, Roger

2014-03-28

We describe the syntheses of half-sandwich complexes of the type [(η(5)-Cp(CONH-R))M(CO)3] with M = Re or (99m)Tc. The R group represents different tri-peptides (tpe) which display high binding affinities for oligopeptide transporters PEPT2. The (99m)Tc complexes were prepared directly from [(99m)Tc(OH2)3(CO)3](+) and Diels-Alder dimerized, cyclopentadienyl derivatized peptides in water. This approach corroborates the feasibility of metal-mediated retro Diels-Alder reactions for the preparation of not only small molecules but also peptides carrying a [(η(5)-Cp)(99m)Tc(CO)3] tag. We synthesized the Diels-Alder product [(HCpCONH-tpe)2] from Thiele's acid [(η(5)-HCpCOOH)2] via double peptide coupling. The Re-complexes [(η(5)-CpCONH-tpe)Re(CO)3] were obtained by attaching [(Cp-COOH)Re(CO)3] directly to the N-terminus of peptides as received from SPPS. The authenticity of the (99m)Tc-complexes is confirmed by chromatographic comparison with the corresponding rhenium complexes, fully characterized by spectroscopic techniques.

Stream restoration at Denali National Park and Preserve

USGS Publications Warehouse

Densmore, Roseann V.; Karle, Kenneth F.

1999-01-01

Placer mining for gold has severely disturbed many riparian ecosystems in northern regions. We are conducting a long-term project to test methods to promote restoration of a placer-mined watershed in Denali National Park and Preserve. The project included hydrological restoration of the unstable and excessively confined stream with heavy equipment. We stabilized the floodplain with bioengineering techniques, including alder and willow brush bars anchored laterally to the channel and willow cuttings along the channel. A moderate flood near the end of construction showed that the brush bars provided substantial protection, but some bank erosion and changes in slope and sinuosity occurred. Subsequent refinements included greater sinuosity and channel depth, pool/riffie construction with stone weirs, and buried alder and willow brush projecting from the bank. The reconstructed stream and floodplain have remained stable for five years, but have not been re-tested by a another large flood. The willow/alder riparian plant community is naturally revegetating on the new floodplains, but vigorous willows which sprouted from branches in brush bars and banks still provide the erosion protection.

Leaf litter dynamics and nitrous oxide emission in a Mediterranean riparian forest: implications for soil nitrogen dynamics.

PubMed

Bernal, S; Butturini, A; Nin, E; Sabater, F; Sabater, S

2003-01-01

Mediterranean riparian zones can experience severe drought periods that lead to low soil moisture content, which dramatically affects their performance as nitrate removal systems. In the Mediterranean riparian zone of this study, we determined that N2O emission was practically nil. To understand the role of forest floor processes in nitrogen retention of a Mediterranean riparian area, we studied leaf litter dynamics of two tree species, London planetree [Platanus x acerifolia (Aiton) Willd.] and alder [Alnus glutinosa (L.) Gaertn.], for two years, along with soil nitrogen mineralization rates. Annual leaf litter fall equaled 562.6 +/- 10.1 (standard error) g dry wt. m(-2), 68% of which was planetree and 32% of which was alder. The temporal distribution of litterfall showed a two-peak annual cycle, one occurring in midsummer, the other in autumn. Planetree provided the major input of organic nitrogen to the forest floor, and the amount of planetree leaves remaining on the forest floor was equivalent to approximately four years of stock. Leaf litter decomposition was three times higher for alder (decay coefficient [k] = 1.13 yr(-1)) than for planetree (k = 0.365 yr(-1)). Mineralization rates showed a seasonal pattern, with the maximum rate in summer (1.92 mg N kg(-1) d(-1)). Although the forest floor was an important sink for nitrogen due to planetree leaf accumulation, 7.5% of this leaf litter was scoured to the streambed by wind. This loss was irrelevant for alder leaves. Due to the litter quality, the forest floor of this Mediterranean riparian forest acts as a nitrogen sink.

Thermally cleavable surfactants

DOE Office of Scientific and Technical Information (OSTI.GOV)

McElhanon, James R; Simmons, Blake A; Zifer, Thomas

2009-11-24

Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments or the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

Thermally cleavable surfactants

DOE Office of Scientific and Technical Information (OSTI.GOV)

McElhanon, James R; Simmons, Blake A; Zifer, Thomas

2009-09-29

Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments or the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

Thermally cleavable surfactants

DOEpatents

McElhanon, James R [Manteca, CA; Simmons, Blake A [San Francisco, CA; Zifer, Thomas [Manteca, CA; Jamison, Gregory M [Albuquerque, NM; Loy, Douglas A [Albuquerque, NM; Rahimian, Kamyar [Albuquerque, NM; Long, Timothy M [Urbana, IL; Wheeler, David R [Albuquerque, NM; Staiger, Chad L [Albuquerque, NM

2006-04-04

Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments and the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

Sex chromosome linked genetic variance and the evolution of sexual dimorphism of quantitative traits.

PubMed

Husby, Arild; Schielzeth, Holger; Forstmeier, Wolfgang; Gustafsson, Lars; Qvarnström, Anna

2013-03-01

Theory predicts that sex chromsome linkage should reduce intersexual genetic correlations thereby allowing the evolution of sexual dimorphism. Empirical evidence for sex linkage has come largely from crosses and few studies have examined how sexual dimorphism and sex linkage are related within outbred populations. Here, we use data on an array of different traits measured on over 10,000 individuals from two pedigreed populations of birds (collared flycatcher and zebra finch) to estimate the amount of sex-linked genetic variance (h(2)z ). Of 17 traits examined, eight showed a nonzero h(2)Z estimate but only four were significantly different from zero (wing patch size and tarsus length in collared flycatchers, wing length and beak color in zebra finches). We further tested how sexual dimorphism and the mode of selection operating on the trait relate to the proportion of sex-linked genetic variance. Sexually selected traits did not show higher h(2)Z than morphological traits and there was only a weak positive relationship between h(2)Z and sexual dimorphism. However, given the relative scarcity of empirical studies, it is premature to make conclusions about the role of sex chromosome linkage in the evolution of sexual dimorphism. © 2012 The Author(s). Evolution© 2012 The Society for the Study of Evolution.

DNA-DNA hybridization-based phylogeny for "higher" nonpasserines: reevaluating a key portion of the avian family tree.

PubMed

Bleiweiss, R; Kirsch, J A; Lapointe, F J

1994-09-01

A matrix of delta T mode values for 10 birds, including 9 nonpasserines and a suboscine passerine flycatcher, was generated by DNA-DNA hybridization. Within the most derived lineages, all bootstrapped and jackknifed FITCH trees lend strong support to sister-groupings of the two swift families, of hummingbirds to swifts, and of these to a clade containing both owls and night-hawks. The outgroup duck roots the tree between the woodpecker (Piciformes) and the remaining taxa, indicating that Piciformes are among the earliest branches within nonpasserines. However, the succeeding branches to kingfisher, mousebird, and suboscine passerine flycatcher are based on short internodes that are poorly supported by bootstrapping and that give inconsistent results in jackknifing. Although these 3 orders may have arisen through rapid or near-simultaneous divergence, placement of the "advanced" Passeriformes deep within a more "primitive" radiation indicates that nonpasserines are paraphyletic, echoing the same distinction for reptiles with respect to their advanced descendants. Despite significant rate variation among different taxa, these results largely concur with those obtained with the same technique by Sibley and Ahlquist, who used the delta T50H measure and UPGMA analysis. This agreement lends credence to some of their more controversial claims.

Effects of nocturnal illumination on life-history decisions and fitness in two wild songbird species

PubMed Central

de Jong, Maaike; Ouyang, Jenny Q.; Da Silva, Arnaud; van Grunsven, Roy H. A.; Kempenaers, Bart; Visser, Marcel E.; Spoelstra, Kamiel

2015-01-01

The effects of artificial night lighting on animal behaviour and fitness are largely unknown. Most studies report short-term consequences in locations that are also exposed to other anthropogenic disturbance. We know little about how the effects of nocturnal illumination vary with different light colour compositions. This is increasingly relevant as the use of LED lights becomes more common, and LED light colour composition can be easily adjusted. We experimentally illuminated previously dark natural habitat with white, green and red light, and measured the effects on life-history decisions and fitness in two free-living songbird species, the great tit (Parus major) and pied flycatcher (Ficedula hypoleuca) in two consecutive years. In 2013, but not in 2014, we found an effect of light treatment on lay date, and of the interaction of treatment and distance to the nearest lamp post on chick mass in great tits but not in pied flycatchers. We did not find an effect in either species of light treatment on breeding densities, clutch size, probability of brood failure, number of fledglings and adult survival. The finding that light colour may have differential effects opens up the possibility to mitigate negative ecological effects of nocturnal illumination by using different light spectra. PMID:25780240

Effects of cadmium and resource quality on freshwater detritus processing chains: a microcosm approach with two insect species.

PubMed

Campos, Diana; Alves, Artur; Lemos, Marco F L; Correia, António; Soares, Amadeu M V M; Pestana, João L T

2014-07-01

Detritus processing is vital for freshwater ecosystems that depend on the leaf litter from riparian vegetation and is mediated by microorganisms and aquatic invertebrates. Shredder invertebrates transform coarse particulate organic matter into fine particulate organic matter used as food by collector species. Direct and indirect effects of contaminants can impair detritus processing and thus affect the functioning of these ecosystems. Here, we assessed the combined effects of a toxic metal (cadmium) and resource quality (leaf species) on detritus processing and shredder-collector interactions. We considered two types of leaves, alder and eucalyptus that were microbially conditioned under different Cd concentrations in the laboratory. The microbial communities present on leaves were analyzed by Denaturing Gradient Gel Electrophoresis (DGGE), and we also measured microbial respiration rates. Sericostoma vittatum (a caddisfly shredder) and Chironomus riparius (a midge collector) were also exposed to Cd and allowed to consume the corresponding alder or eucalyptus leaves. We evaluated C. riparius growth and leaf mass loss in multispecies microcosms. Cadmium exposure affected leaf conditioning and fungal diversity on both leaf species, as assessed by DGGE. Cadmium exposure also affected the mass loss of alder leaves by reductions in detritivore feeding, and impaired C. riparius growth. Chironomus riparius consumed alder leaf discs in the absence of shredders, but S. vittatum appear to promote C. riparius growth in treatments containing eucalyptus. These results show that indirect effects of contaminants along detritus-processing chains can occur through effects on shredder-collector interactions such as facilitation but they also depend on the nutritional quality of detritus and on sensitivity and feeding plasticity of detritivore species.

Why Non-Equilibrium is Different

NASA Astrophysics Data System (ADS)

Dorfman, J. Robert; Kirkpatrick, Theodore R.; Sengers, Jan V.

The 1970 paper, "Decay of the Velocity Correlation Function" [Phys. Rev. A1, 18 (1970), see also Phys. Rev. Lett. 18, 988, (1967)] by Berni Alder and Tom Wainwright, demonstrated, by means of computer simulations, that the velocity autocorrelation function for a particle moving diffusively in a gas of hard disks decays algebraically in time as t-1, and as t-3/2 for a gas of hard spheres. These decays appear in non-equilibrium fluids and have no counterpart in fluids in thermodynamic equilibrium. The work of Alder and Wainwright stimulated theorists to find explanations for these "long time tails" using kinetic theory or a mesoscopic mode-coupling theory. This paper has had a profound influence on our understanding of the non-equilibrium properties of fluid systems. Here we discuss the kinetic origins of the long time tails, the microscopic foundations of modecoupling theory, and the implications of these results for the physics of fluids. We also mention applications of the long time tails and mode-coupling theory to other, seemingly unrelated, fields of physics. We are honored to dedicate this short review to Berni Alder on the occasion of his 90th birthday!

Development of Remendable Polymer Composites using a Thermoreversible Reaction

NASA Astrophysics Data System (ADS)

Peterson, Amy Michelle

2011-12-01

Materials that can repair cracks and recover from mechanical failure are desirable. Because remendable materials both repair and prevent the propagation of cracks on the micro scale, they offer the potential for increased durability, safety, and cost efficiency for many applications. The focus of this work was to understand the kinetic and physical parameters that control thermoreversible Diels-Alder bond formation in different types of healable polymeric systems. Three healing systems were developed based on the thermoreversible Diets-Alder reaction of furan and maleimide. In one, crack healing of a thermoset was induced by thermally reversible cross-linking of a secondary phase. In another, a furan-functionalized epoxy-amine thermoset were healed with a bismaleimide solution at room temperature and minimal pressure, with significant load recovery possible multiple times. The third system allowed for interfacial healing of glass fiber-reinforced epoxy-amine composites via compatible functionalization of glass fibers and the polymer network. The Diels-Alder reaction was characterized in all systems as well as highly mobile small molecule solutions. It was found that mobility, coupled with kinetics, dictate the extent of reaction and consequent strength recovery.

Nest survival of forest birds in the Mississippi Alluvial Valley

USGS Publications Warehouse

Twedt, D.J.; Wilson, R.R.; Henne-Kerr, J.L.; Hamilton, R.B.

2001-01-01

vimns, 7%), eastern towhee (14%), indigo bunting (14%), and northern cardinal (17%) did not differ from nest success in cottonwood plantations that were coppiced from root sprouts following pulpwood harvest. Within bottomland hardwood forests, uneven-aged group-selection timber harvest reduced the combined daily nest survival of all species from 0.958 to 0.938, which reduced nest success by about 14%. Specifically, timber harvest reduced nest success of species that nest in the forest midstory and canopy, such as Acadian flycatcher (Empidonax virescens)--from 32% before harvest to 14% after harvest. Conversely, those species that nest primarily in the shrubby understory--such as northern cardinal--were not affected by timber harvest and maintained an overall nest success of about 33%. Thus, birds nesting in the understory of bottomland hardwood forests are not adversely impacted by selective timber harvest, but there is a short-term reduction in nest success for birds that nest in the canopy and midstory.

Photochemistry of tricyclo[5.2.2.0(2,6)]undeca-4,10-dien-8-ones: an efficient general route to substituted linear triquinanes from 2-methoxyphenols. Total synthesis of (+/-)-Delta(9(12))-capnellene.

PubMed

Hsu, Day-Shin; Chou, Yu-Yu; Tung, Yen-Shih; Liao, Chun-Chen

2010-03-08

An efficient and short entry to polyfunctionalized linear triquinanes from 2-methoxyphenols is described by utilizing the following chemistry. The Diels-Alder reactions of masked o-benzoquinones, derived from 2-methoxyphenols, with cyclopentadiene afford tricyclo[5.2.2.0(2,6)]undeca-4,10-dien-8-ones. Photochemical oxa-di-pi-methane (ODPM) rearrangements and 1,3-acyl shifts of the Diels-Alder adducts are investigated. The ODPM-rearranged products are further converted to linear triquinanes by using an O-stannyl ketyl fragmentation. Application of this efficient strategy to the total synthesis of (+/-)-Delta(9(12))-capnellene was accomplished from 2-methoxy-4-methylphenol in nine steps with 20 % overall yield.

Yeast and Macroinvertebrate Communities Associated with Leaf Litter Decomposition in a Second Order Stream

NASA Astrophysics Data System (ADS)

Sampaio, Ana; Cortes, Rui; Leão, Cecília

2004-11-01

The composition of yeast and macroinvertebrate communities was studied on black alder, blue gum eucalyptus and English oak leaves decaying in a stream during a six-month period. ANOVA analysis showed significantly different values (p < 0.0001) of yeast and macroinvertebrate densities among the three leaf litters. Some yeast species such as Cryptococcus albidus (Saito), C. laurentii (Kufferath), Rhodothorula glutinis (Fresenius), R. colostri (Castelli), and Debaryomyces hansenii (Lodder and Kreger-van Rij) were present in all litter types. Other yeasts were restricted to a specific type of litter. Macroinvertebrates were dominated by collectors-gatherers on oak and eucalyptus leaves. Shredders reached highest densities in alder leaves. (

The 2.5-diacyl-1,4-dimethylbenzenes: Examples of bisphotoenol equivalents

NASA Technical Reports Server (NTRS)

Meador, Michael A.

1987-01-01

The photochemistry of 2,5-dibenzoyl(DBX)-and 2,5-diacetyl-1,4-dimethylbenzene (DAX) has been investigated. Both compounds readily undergo photoenolization similar to 0-alkylphenyl ketones. However, unlike 0-alkylphenyl ketones DAX and DBX are each capable of undergoing two tandem photoenolizations. Photoenols derived from o-alkylphenyl ketones have been successfully trapped with Diels-Alder dienophiles to provide a convenient synthesis of substituted tetralins. Similarly, Diels-Alder trapping of DBX photoenils afforded substituted tetra- and octahydro anthracenes. Further mainpulation of these photadducts provided the corresponding anthracenes in good yield. The photochemistry of DAX and DBX will be discussed, in particular their use in the synthesis of substituted anthracenes.

Closure of George Air Force Base, San Bernardino County, California

DTIC Science & Technology

1990-05-01

and welfare , crops, livestock, and property. " Resource Conservation and Recovery Act (RCRA). Regulates the disposal of haza,’dous wastes. 1-4...Willow flycatcher X (ErnroidQon tail) Yellow breasted chat X (Icteria virens) Summer tanager X (EPcrag rubra) Bendire’s thrasher X (Toxostoma bendirei...Veteran’s Administration. An Ld. of 55 dB is recognized by HUD, DOT, and EPA as an outdoor goal for protecting public welfare in residential areas. This

Influences of Moisture Regimes and Functional Plant Types on Nutrient Cycling in Permafrost Regions

NASA Astrophysics Data System (ADS)

McCaully, R. E.; Arendt, C. A.; Newman, B. D.; Heikoop, J. M.; Wilson, C. J.; Sevanto, S.; Wales, N. A.; Wullschleger, S.

2017-12-01

In the permafrost-dominated Arctic, climatic feedbacks exist between permafrost, soil moisture, functional plant type and presence of nutrients. Functional plant types present within the Arctic regulate and respond to changes in hydrologic regimes and nutrient cycling. Specifically, alders are a member of the birch family that use root nodules to fix nitrogen, which is a limiting nutrient strongly linked to fertilizing Arctic ecosystems. Previous investigations in the Seward Peninsula, AK show elevated presence of nitrate within and downslope of alder patches in degraded permafrost systems, with concentrations an order of magnitude greater than that of nitrate measured above these patches. Further observations within these degraded permafrost systems are crucial to assess whether alders are drivers of, or merely respond to, nitrate fluxes. In addition to vegetative feedbacks with nitrate supply, previous studies have also linked low moisture content to high nitrate production. Within discontinuous permafrost regions, the absence of permafrost creates well-drained regions with unsaturated soils whereas the presence of permafrost limits vertical drainage of soil-pore water creating elevated soil moisture content, which likely corresponds to lower nitrate concentrations. We investigate these feedbacks further in the Seward Peninsula, AK, through research supported by the United States Department of Energy Next Generation Ecosystem Experiment (NGEE) - Arctic. Using soil moisture and thaw depth as proxies to determine the extent of permafrost degradation, we identify areas of discontinuous permafrost over a heterogeneous landscape and collect co-located soilwater chemistry samples to highlight the complex relationships that exist between alder patches, soil moisture regimes, the presence of permafrost and available nitrate supply. Understanding the role of nitrogen in degrading permafrost systems, in the context of both vegetation present and soil moisture, is crucial

Distribution of radionuclides between atmosphere and ash during combustion of contaminated vegetation.

PubMed

Zhou, Liufang Jenny; Rao, Raghu; Corcoran, Emily; Kelly, David

2016-12-01

A series of laboratory-scale combustion tests were conducted under well-controlled conditions to measure the release of 90 Sr and 137 Cs nuclides to the atmosphere (air) from combustion of vegetation and organic soil samples contaminated with radioactivity. These vegetation and soil samples were collected from a controlled contaminated forest area within the Canadian Nuclear Laboratories - Chalk River site. The combustion products including ash and smoke particulates, along with gaseous emissions, were collected and then analyzed for 137 Cs and 90 Sr concentrations by radiometric techniques. The experimental results reveal that the releases of 90 Sr to the atmosphere (air) from combustion of vegetation are very low with most of the 90 Sr activity remaining in ash residues, even at a temperature of 800 °C. The detailed combustion experiments with surface litter and twigs, alder twigs, alder leaves, and organic soil indicate that 0.5 ± 0.1%, 0.3 ± 0.1%, 0.9 ± 0.1%, and 0.3 ± 0.1% of 90 Sr is released to the atmosphere (air), respectively. On the other hand, the releases of 137 Cs are found to be highly dependent on the combustion temperature as well as the nature of vegetation. The releases of 137 Cs obtained at 800 °C are 45 ± 7%, 77 ± 9%, 92 ± 5%, and 2.4 ± 0.5% for surface litter and twigs, alder twigs, alder leaves, and organic soil, respectively. The mechanism associated with the high release of 137 Cs at a high temperature of 800 °C was explored. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.