Sample records for diel activity patterns
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Patterns of Diel Variation in Nitrate Concentrations in the Potomac River
Burns, D. A.; Miller, M. P.; Pellerin, B. A.; Capel, P. D.
2015-12-01
The Potomac River is the second largest source of nitrogen to Chesapeake Bay, where reducing nutrient loads has been a focus of efforts to improve estuarine trophic status. Two years of high frequency sensor measurements of nitrate (NO3-) concentrations in the Upper Potomac River at the Little Falls gage were analyzed to quantify seasonal variation in the magnitude and timing of the apparent loss of NO3- from the water column that results from diel-driven processes. In addition to broad seasonal and flow-driven variation in NO3- concentrations, clear diel patterns were evident in the river, especially during low flow conditions that follow stormflow by several days. Diel variation was about 0.01 mg N/L in winter and 0.02 to 0.03 mg N/L in summer with intermediate values during spring and fall. This variation was equivalent to 10% occurred during some summer days. Maximum diel concentrations occurred during mid- to late-morning in most seasons, with the most repeatable patterns in summer and wider variation in timing during fall and winter. Diel NO3- loss diminished loads by about 0.6% in winter and 1.3% in summer, and diel-driven processes were minor compared to estimates of total in-stream NO3- loss that averaged about one-third of the inferred groundwater NO3- contribution to the river network. The magnitude of diel NO3- variation was more strongly related to metrics based on water temperature and discharge than to metrics based on photosynthetically active radiation. Despite the fairly low diminishment of NO3- loads attributable to diel variation, estimates of diel NO3- uptake were fairly high compared to published values from smaller streams and rivers. The diel NO3- patterns observed in the Potomac River are consistent with photosynthesis of periphyton as a principal driver which may be linked to denitrification through the release of labile carbon. The extent to which these diel patterns are related to measures of aquatic metabolism are unknown as is the role
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Directory of Open Access Journals (Sweden)
Takashi Ikeda
Full Text Available The activity patterns of mammals are generally categorized as nocturnal, diurnal, crepuscular (active at twilight, and cathemeral (active throughout the day. These patterns are highly variable across regions and seasons even within the same species. However, quantitative data is still lacking, particularly for sympatric species. We monitored the seasonal and diel activity patterns of terrestrial mammals in Hokkaido, Japan. Through an intensive camera-trap survey a total of 13,279 capture events were recorded from eight mammals over 20,344 camera-trap days, i.e., two years. Diel activity patterns were clearly divided into four categories: diurnal (Eurasian red squirrels, nocturnal (raccoon dogs and raccoons, crepuscular (sika deer and mountain hares, and cathemeral (Japanese martens, red foxes, and brown bears. Some crepuscular and cathemeral mammals shifted activity peaks across seasons. Particularly, sika deer changed peaks from twilight during spring-autumn to day-time in winter, possibly because of thermal constraints. Japanese martens were cathemeral during winter-summer, but nocturnal in autumn. We found no clear indication of predator-prey and competitive interactions, suggesting that animal densities are not very high or temporal niche partitioning is absent among the target species. This long-term camera-trap survey was highly cost-effective and provided one of the most detailed seasonal and diel activity patterns in multiple sympatric mammals under natural conditions.
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Kadye, Wilbert T; Booth, Anthony J
2014-01-01
Animals exhibit diel periodicity in their activity in part to meet energy requirements whilst evading predation. A competing hypothesis suggests that partitioning of diel activities is less important because animals capitalise on opportunity. To test these hypotheses we examined the diel activity patterns for two cyprinid minnows, chubbyhead barb Barbus anoplus and the Eastern Cape redfin minnow Pseudobarbus afer that both occur within headwater streams in the Eastern Cape, South Africa. Chubbyhead barbs exhibited consistent nocturnal activity based on both field and laboratory observations. Due to the absence of fish predators within its habitat, its nocturnal behaviour suggests a response to the cost associated with diurnal activity, such as predation risk by diving and wading birds. In contrast, redfin minnows showed high diurnal activity and a shoaling behaviour in the wild, whereas, in the laboratory, they showed high refuge use during the diel cycle. Despite their preference for refuge in the laboratory, they were diurnally active, a behaviour that was consistent with observations in the wild. The diurnal activity of this species suggests a response to the cost associated with nocturnal activity. Such a cost could be inferred from the presence of the longfin eel, a native predator that was active at night, whereas the daytime shoaling behaviour suggests an anti-predator mechanism to diurnal visual predators. The implications of these findings relate to the impacts associated with the potential invasions by non-native piscivores that occur in the mainstem sections. Diurnal activity patterns for redfin minnows, that are IUCN-listed as endangered, may, in part, explain their susceptibility to high predation by visual non-native piscivores, such as bass and trout. In contrast, the nocturnal habits of chubbyhead barbs suggest a probable pre-adaptation to visual predation. The likelihood of invasion by nocturnally-active sharptooth catfish Clarias gariepinus
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Wilbert T Kadye
Full Text Available Animals exhibit diel periodicity in their activity in part to meet energy requirements whilst evading predation. A competing hypothesis suggests that partitioning of diel activities is less important because animals capitalise on opportunity. To test these hypotheses we examined the diel activity patterns for two cyprinid minnows, chubbyhead barb Barbus anoplus and the Eastern Cape redfin minnow Pseudobarbus afer that both occur within headwater streams in the Eastern Cape, South Africa. Chubbyhead barbs exhibited consistent nocturnal activity based on both field and laboratory observations. Due to the absence of fish predators within its habitat, its nocturnal behaviour suggests a response to the cost associated with diurnal activity, such as predation risk by diving and wading birds. In contrast, redfin minnows showed high diurnal activity and a shoaling behaviour in the wild, whereas, in the laboratory, they showed high refuge use during the diel cycle. Despite their preference for refuge in the laboratory, they were diurnally active, a behaviour that was consistent with observations in the wild. The diurnal activity of this species suggests a response to the cost associated with nocturnal activity. Such a cost could be inferred from the presence of the longfin eel, a native predator that was active at night, whereas the daytime shoaling behaviour suggests an anti-predator mechanism to diurnal visual predators. The implications of these findings relate to the impacts associated with the potential invasions by non-native piscivores that occur in the mainstem sections. Diurnal activity patterns for redfin minnows, that are IUCN-listed as endangered, may, in part, explain their susceptibility to high predation by visual non-native piscivores, such as bass and trout. In contrast, the nocturnal habits of chubbyhead barbs suggest a probable pre-adaptation to visual predation. The likelihood of invasion by nocturnally-active sharptooth catfish
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Anderson, Samantha R; Wiens, John J
2017-08-01
Many animals are active only during a particular time (e.g., day vs. night), a partitioning that may have important consequences for species coexistence. An open question is the extent to which this diel activity niche is evolutionarily conserved or labile. Here, we analyze diel activity data across a phylogeny of 1914 tetrapod species. We find strong phylogenetic signal, showing that closely related species tend to share similar activity patterns. Ancestral reconstructions show that nocturnality was the most likely ancestral diel activity pattern for tetrapods and many major clades within it (e.g., amphibians, mammals). Remarkably, nocturnal activity appears to have been maintained continuously in some lineages for ∼350 million years. Thus, we show that traits involved in local-scale resource partitioning can be conserved over strikingly deep evolutionary time scales. We also demonstrate a potentially important (but often overlooked) metric of niche conservatism. Finally, we show that diurnal lineages appear to have faster speciation and diversification rates than nocturnal lineages, which may explain why there are presently more diurnal tetrapod species even though diurnality appears to have evolved more recently. Overall, our results may have implications for studies of community ecology, species richness, and the evolution of diet and communication systems. © 2017 The Author(s). Evolution © 2017 The Society for the Study of Evolution.
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Area-use patterns and diel movements of white steenbras ...
African Journals Online (AJOL)
The mean length of estuary used by the 15 individuals was 1 888 m (SD 666). There was a distinct diel activity pattern, with certain individuals utilising deeper parts of the estuary during the day and shallow regions at night. The results indicate that the shallow littoral zone is a critical habitat for juvenile white steenbras.
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Pérez-Sayas, Consuelo; Aguilar-Fenollosa, Ernestina; Hurtado, Mónica A; Jaques, Josep A; Pina, Tatiana
2017-06-16
Predatory mites of the Phytoseiidae family are considered one of the most important groups of natural enemies used in biological control. The behavioral patterns of arthropods can differ greatly daily and seasonally; however, there is a lack of literature related to Phytoseiidae diel and seasonal predation patterns. The predatory activity of three phytoseiid species (two Tetranychidae-specialists, Phytoseiulus persimilis and Neoseiulus californicus, and one omnivore, Euseius stipulatus) that occur naturally in Spanish citrus orchards was observed under laboratory conditions in winter and summer. The temperature and photoperiod of the climatic chamber where the mites were reared did not change during the experiment. Our study demonstrates that phytoseiids can exhibit diel and seasonal predatory patterns when feeding on Tetranychus urticae (Acari: Tetranychidae). Neoseiulus californicus was revealed to be a nocturnal predator in summer but diurnal in winter. In contrast, P. persimilis activity was maximal during the daytime, and E. stipulatus showed no clear daily predation patterns. The predatory patterns described in this study should be taken into account when designing laboratory studies and also in field samplings, especially when applying molecular techniques to unveil trophic relationships. © 2017 Institute of Zoology, Chinese Academy of Sciences.
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Diel dualism in the energy consumption of the European catfish Silurus glanis.
Slavík, O; Horký, P
2012-12-01
Twenty individuals of the largest European freshwater predator, the European catfish Silurus glanis, were tagged with electromyogram (EMG) physiological telemetry sensors. The fish were observed during diel cycles during the spring and summer in the Elbe and Berounka Rivers, Czech Republic. The purpose of this study was to determine whether diel dualism in the activity of S. glanis occurs naturally or is induced by the laboratory environment and by the conditions occurring in aquaculture. The results obtained from the riverine environment tended to show dualism in the use of the light and dark phases of the day because 35% of the individuals varied from a site-specific common diel activity pattern. The EMG values increased in accordance with the mass (M) of the fish. To eliminate the influence of M on individual energy consumption, the EMG records were analysed in terms of the EMG:M ratios. High individual variability was found in these ratios. The diel activity pattern of the individuals with relatively high energy consumption differed from the common diel activity pattern. In contrast, the fish that adopted the common diel activity pattern displayed relatively low energy consumption. The results of this study indicated that dualism and energy consumption are related. The EMG values also varied with the values of the environmental variables. Increasing temperature was associated with high EMG values, whereas the EMG values decreased with increasing flow. © 2012 The Authors. Journal of Fish Biology © 2012 The Fisheries Society of the British Isles.
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Rhythmic diel pattern of gene expression in juvenile maize leaf.
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Maciej Jończyk
Full Text Available BACKGROUND: Numerous biochemical and physiological parameters of living organisms follow a circadian rhythm. Although such rhythmic behavior is particularly pronounced in plants, which are strictly dependent on the daily photoperiod, data on the molecular aspects of the diurnal cycle in plants is scarce and mostly concerns the model species Arabidopsis thaliana. Here we studied the leaf transcriptome in seedlings of maize, an important C4 crop only distantly related to A. thaliana, throughout a cycle of 10 h darkness and 14 h light to look for rhythmic patterns of gene expression. RESULTS: Using DNA microarrays comprising ca. 43,000 maize-specific probes we found that ca. 12% of all genes showed clear-cut diel rhythms of expression. Cluster analysis identified 35 groups containing from four to ca. 1,000 genes, each comprising genes of similar expression patterns. Perhaps unexpectedly, the most pronounced and most common (concerning the highest number of genes expression maxima were observed towards and during the dark phase. Using Gene Ontology classification several meaningful functional associations were found among genes showing similar diel expression patterns, including massive induction of expression of genes related to gene expression, translation, protein modification and folding at dusk and night. Additionally, we found a clear-cut tendency among genes belonging to individual clusters to share defined transcription factor-binding sequences. CONCLUSIONS: Co-expressed genes belonging to individual clusters are likely to be regulated by common mechanisms. The nocturnal phase of the diurnal cycle involves gross induction of fundamental biochemical processes and should be studied more thoroughly than was appreciated in most earlier physiological studies. Although some general mechanisms responsible for the diel regulation of gene expression might be shared among plants, details of the diurnal regulation of gene expression seem to differ
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Diel Behavioral Activity Patterns in Adult Solitarious Desert Locust, Schistocerca gregaria (Forskål
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Sidi Ould Ely
2011-01-01
Full Text Available The responses of adult solitarious desert locust to odors from a host plant were evaluated in a two-choice wind tunnel. Solitarious desert locusts collected from the field (Red Sea Coast were more attracted to volatiles from potted Heliotropium ovalifolium in scotophase than in photophase. The attraction towards the host plant odors rather than to clean air, in both photophase and scotophase, concurs with previous observations on oviposition preferences near these plants. Diel behavioral activity patterns of adult solitarious desert locusts Schistocerca gregaria (Forskål that were collected from the field in Port Sudan were investigated by monitoring, scanning, resting, taking off, and walking/running in a wind tunnel. Solitarious locusts that had been propagated in the laboratory for 20 generations were also observed for comparison. In both groups of locusts, insects were significantly more active after sunset and this activity attained peak level at 1-2 hours after dusk. Of the two groups, solitarious locusts collected from the field were significantly more active. In the scotophase, the former traversed distances that were about seven times those covered by laboratory-reared locusts. Overall, the results show that the repertoire of behavioral activities of solitarious locusts is maintained in laboratory-reared insects, albeit at a lower level. The implications of these observations in the behavioral ecology of the desert locust are discussed.
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Assessing diel variation of CH4 flux from rice paddies through temperature patterns
Centeno, Caesar Arloo R.; Alberto, Ma Carmelita R.; Wassmann, Reiner; Sander, Bjoern Ole
2017-10-01
The diel variation in methane (CH4) flux from irrigated rice was characterized during the dry and wet cropping seasons in 2013 and 2014 using the eddy covariance (EC) technique. The EC technique has the advantage of obtaining measurements of fluxes at an extremely high temporal resolution (10Hz), meaning it records 36,000 measurements per hour. The EC measurements can very well capture the temporal variations of the diel (both diurnal and nocturnal) fluxes of CH4 and the environmental factors (temperature, surface energy flux, and gross ecosystem photosynthesis) at 30-min intervals. The information generated by this technique is important to enhance our mechanistic understanding of the different factors affecting the landscape scale diel CH4 flux. Distinct diel patterns of CH4 flux were observed when the data were partitioned into different cropping periods (pre-planting, growth, and fallow). The temporal variations of the diel CH4 flux during the dry seasons were more pronounced than during the wet seasons because the latter had so much climatic disturbance from heavy monsoon rains and occasional typhoons. Pearson correlation analysis and Granger causality test were used to confirm if the environmental factors evaluated were not only correlated with but also Granger-causing the diel CH4 flux. Soil temperature at 2.5 cm depth (Ts 2.5 cm) can be used as simple proxy for predicting diel variations of CH4 fluxes in rice paddies using simple linear regression during both the dry and wet seasons. This simple site-specific temperature response function can be used for gap-filling CH4 flux data for improving the estimates of CH4 source strength from irrigated rice production.
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Primo, Ana Lígia; Azeiteiro, Ulisses M.; Marques, Sónia C.; Ré, Pedro; Pardal, Miguel A.
2012-07-01
Vertical distribution and migration pattern of ichthyoplankton assemblage in the Mondego estuary were investigated in relation to diel and tidal cycle. Summer and winter communities were sampled, at surface and bottom, over a diel cycle during spring and neap tides at a fixed station at the mouth of the estuary. Summer presented higher larvae density mainly of Pomatoschistus spp., Gobius niger and Parablennius pilicornis. Main species in winter assemblages were Pomatoschistus spp. and Sardina pilchardus. There were no differences between depth stratums across diel or tide cycle. Nevertheless, main species larval densities showed significant periodic variation associated with tide (M2) and diel (K1) cycles presenting generally, higher density at night and around low tide. Conversely, vertical patterns observed could not be related with diel or tidal cycle. Tough, main species presented some extent of vertical migration. Vertical patterns observed appear to be related to seasonal stratification and river flow, increasing amplitude during periods of less stratification and lower water currents. Present study provides a better understanding of ichthyoplankton vertical movement patterns and of small scale dynamics at the interface of two coastal European systems.
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Application of activity sensors for estimating behavioral patterns
Roberts, Caleb P.; Cain, James W.; Cox, Robert D.
2016-01-01
The increasing use of Global Positioning System (GPS) collars in habitat selection studies provides large numbers of precise location data points with reduced field effort. However, inclusion of activity sensors in many GPS collars also grants the potential to remotely estimate behavioral state. Thus, only using GPS collars to collect location data belies their full capabilities. Coupling behavioral state with location data would allow researchers and managers to refine habitat selection models by using diel behavioral state changes to partition fine-scale temporal shifts in habitat selection. We tested the capability of relatively unsophisticated GPS-collar activity sensors to estimate behavior throughout diel periods using free-ranging female elk (Cervus canadensis) in the Jemez Mountains of north-central New Mexico, USA, 2013–2014. Collars recorded cumulative number of movements (hits) per 15-min recording period immediately preceding GPS fixes at 0000, 0600, 1200, and 1800 hr. We measured diel behavioral patterns of focal elk, categorizing active (i.e., foraging, traveling, vigilant, grooming) and inactive (i.e., resting) states. Active behaviors (foraging, traveling) produced more average hits (0.87 ± 0.69 hits/min, 4.0 ± 2.2 hits/min, respectively; 95% CI) and inactive (resting) behavior fewer hits (−1.1 ± 0.61 95% CI). We differentiated active and inactive behavioral states with a bootstrapped threshold of 5.9 ± 3.9 hits/15-min recording period. Mean cumulative activity-sensor hits corresponded with observed diel behavioral patterns: hits increased during crepuscular (0600, 1800 hr) observations when elk were most active (0000–0600 hr: d = 0.19; 1200–1800 hr: d = 0.64) and decreased during midday and night (0000 hr, 1200 hr) when elk were least active (1800–0000 hr: d = −0.39; 0600–1200 hr: d = −0.43). Even using relatively unsophisticated GPS-collar activity sensors, managers can
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Estimating dew formation in rice, using seasonally averaged diel patterns of weather variables
Luo, W.; Goudriaan, J.
2004-01-01
If dew formation cannot be measured it has to be estimated. Available simulation models for estimating dew formation require hourly weather data as input. However, such data are not available for places without an automatic weather station. In such cases the diel pattern of weather variables might
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Digital Repository Service at National Institute of Oceanography (India)
Vineetha, G.; Jyothibabu, R.; Madhu, N.V.; Kusum, K.K.; Sooria, P.M.; Shivaprasad, A.; Reny, P.D.; Deepak, M.P.
habitats is often determined by their dominant behavioral patterns: diel vertical migration (DVM) and tidal vertical migration (TVM). The modes of these endogenous rhythms often vary among estuaries based on the river runoff and tidal characteristics...
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Arumugam, Selvanathan; Orski, Sara V; Locklin, Jason; Popik, Vladimir V
2012-01-11
Reactive polymer brushes grown on silicon oxide surfaces were derivatized with photoreactive 3-(hydroxymethyl)naphthalene-2-ol (NQMP) moieties. Upon 300 or 350 nm irradiation, NQMP efficiently produces o-naphthoquinone methide (oNQM), which in turn undergoes very rapid Diels-Alder addition to vinyl ether groups attached to a substrate, resulting in the covalent immobilization of the latter. Any unreacted oNQM groups rapidly add water to regenerate NQMP. High-resolution surface patterning is achieved by irradiating NQMP-derivatized surfaces using photolithographic methods. The Diels-Alder photoclick reaction is orthogonal to azide-alkyne click chemistry, enabling sequential photoclick/azide-click derivatizations to generate complex surface functionalities. © 2011 American Chemical Society
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Niobium Pentachloride Activation of Enone Derivatives: Diels-Alder and Conjugate Addition Products
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Gil Valdo José da Silva
2002-05-01
Full Text Available Niobium pentachloride has proven to be a powerful activating agent for Diels-Alder or conjugate addition reactions of cycloenones. The Diels-Alder product was obtained only with an unsubstituted enone (cyclohexenone and the highly reactive diene cyclopentadiene; substituents in the b-position of enones seem to prevent Diels-Alder reaction: oxygenated substituents favor the formation of vinyl chlorides (ethyl ether or dichloromethane as solvents or enol ethers (ethyl acetate as solvent, while a methyl substituent prevents any kind of transformation with NbCl5. Less reactive dienes, furan and 2-methylfuran gave the conjugate addition products of the furan ring to the enone system.
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Diel predator activity drives a dynamic landscape of fear
Kohl, Michel T.; Stahler, Daniel R.; Metz, Matthew C.; Forester, James D.; Kauffman, Matthew J.; Varley, Nathan; White, P.J.; Smith, Douglas W.; MacNulty, Daniel R.
2017-01-01
A "landscape of fear" (LOF) is a map that describes continuous spatial variation in an animal's perception of predation risk. The relief on this map reflects, for example, places that an animal avoids to minimize risk. Although the LOF concept is a potential unifying theme in ecology that is often invoked to explain the ecological and conservation significance of fear, quantified examples of a LOF over large spatial scales are lacking as is knowledge about the daily dynamics of a LOF. Despite theory and data to the contrary, investigators often assume, implicitly or explicitly, that a LOF is a static consequence of a predator's mere presence. We tested the prediction that a LOF in a large-scale, free-living system is a highly-dynamic map with "peaks" and "valleys" that alternate across the diel (24-hour) cycle in response to daily lulls in predator activity. We did so with extensive data from the case study of Yellowstone elk (Cervus elaphus) and wolves (Canis lupus) that was the original basis for the LOF concept. We quantified the elk LOF, defined here as spatial allocation of time away from risky places and times, across nearly 1000-km2 of northern Yellowstone National Park and found that it fluctuated with the crepuscular activity pattern of wolves, enabling elk to use risky places during wolf downtimes. This may help explain evidence that wolf predation risk has no effect on elk stress levels, body condition, pregnancy, or herbivory. The ability of free-living animals to adaptively allocate habitat use across periods of high and low predator activity within the diel cycle is an underappreciated aspect of animal behavior that helps explain why strong antipredator responses may trigger weak ecological effects, and why a LOF may have less conceptual and practical importance than direct killing.
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Castellanos-Galindo, G. A.; Krumme, U.
2014-08-01
Intertidal fish assemblages are thought to respond to tidal and diel rhythms although the assumption that these patterns are stable over long time scales (>1 year) is largely untested. Testing the validity of this assumption is necessary to assess whether short-term temporal patterns, once established, can be extrapolated over time and give a better understanding of the temporal dynamics of fish assemblages in coastal habitats. Here, we compare the fish assemblage structure from two intertidal mangrove creeks in North Brazil (Bragança Peninsula, Caeté estuary) sampled with the same sampling methodology (block nets), effort (two lunar cycles) and design (accounting for the combination of tidal and diel cycle) in the rainy seasons of 1999 and 2012 to evaluate the persistence, stability and recurrence of short-term patterns in the fish community organization. The interaction of tidal and diel cycles (inundations at spring tide-night, spring tide-day, neap tide-night, neap tide-day), found to be stable after 13 years, resulted in recurrent and stable intertidal mangrove fish assemblage compositions. The intertidal mangrove creek fish assemblage consisted of a persistent number of dominant species (seven). However, there were notable changes in fish catch mass, abundance and species dominance between 1999 and 2012. The most severe drought in North Brazil in 30 years, linked to lower precipitation and river runoff in the rainy season of 2012, may have resulted in (1) lower abundance of small juveniles of several dominant species in this assemblage (especially Ariidae - Cathorops agassizii and Sciades herzbergii) and (2) increased dominance of large-sized specimens of the tetraodontid Colomesus psittacus. Our findings highlight: (1) the overriding importance and stability of the interactive pulse of the tidal and diel cycles in determining short-term temporal patterns in intertidal mangrove fish assemblages in neotropical macrotidal estuaries despite the occurrence of
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Seasonal and diel patterns in cetacean use and foraging at a potential marine renewable energy site.
Nuuttila, Hanna K; Bertelli, Chiara M; Mendzil, Anouska; Dearle, Nessa
2018-04-01
Marine renewable energy (MRE) developments often coincide with sites frequented by small cetaceans. To understand habitat use and assess potential impact from development, echolocation clicks were recorded with acoustic click loggers (C-PODs) in Swansea Bay, Wales (UK). General Additive Models (GAMs) were applied to assess the effects of covariates including month, hour, tidal range and temperature. Analysis of inter-click intervals allowed the identification of potential foraging events as well as patterns of presence and absence. Data revealed year-round presence of porpoise, with distinct seasonal and diel patterns. Occasional acoustic encounters of dolphins were also recorded. This study provides further evidence of the need for assessing temporal trends in cetacean presence and habitat use in areas considered for development. These findings could assist MRE companies to monitor and mitigate against disturbance from construction, operation and decommissioning activities by avoiding times when porpoise presence and foraging activity is highest in the area. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Rosati, F.; Roelfes, J.G.
A structure-activity relationship study of the first generation ligands for the DNA-based asymmetric hydration of enones and Diels-Alder reaction in water is reported. The design of the ligand was optimized resulting in a maximum ee of 83% in the hydration reaction and 75% in the Diels-Alder
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Diel variation in the catch of fishes and penaeid shrimps in a tropical estuary
Stoner, Allan W.
1991-07-01
In Laguna Joyuda, Puerto Rico, 24-h trawl surveys were conducted to test the hypothesis that there is no diel variation in the catch rate of fishes and penaeid shrimps in a turbid, microtidal estuary relatively free of visual predation. The null hypothesis was not rejected for the two most abundant fishes in the lagoon, Eucinostomus gula (Gerreidae) and Achirus lineatus (Bothidae). Conversely, the total number of fishes, Diapterus rhombeus (Gerreidae), and the engraulids Anchoa cubana and A. hepsetus were collected in significantly higher numbers during hours of darkness. Total penaeid catch was significantly higher in night than in day collections. The most abundant species were Penaeus notialis and P. subtilis, both of which appeared to be strong daytime burrowers. Small penaeids demonstrated greater diel variation in trawl capture rate than larger (subadult) shrimps. Diel variation in capture rate was related to habitat associations of individual species. Fauna resident in the very turbid lagoon demonstrated no diel variation in activity patterns and trawl susceptibility. Those species which spend only the early part of their lives in the lagoon, or live in both turbid and clear water, had significant diel variation in activity and trawl catchability.
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Cicolani Bruno
2011-04-01
Full Text Available Abstract Background Although most freshwater planarias are well known photonegative organisms, their diel rhythms have never been quantified. Differences in daily activity rhythms may be particularly important for temperate-climate, freshwater planarias, which tend to overlap considerably in spatial distribution and trophic requirements. Methods Activity of stress-free, individually tested young adults of three common planarian species was recorded at 3-h intervals in a 10-d experiment under natural sunlight and photoperiod during autumnal equinox (D:L ~12:12. Individual activity status was averaged over the 10-d experiment, each tested individual thus serving as a true replicate. Twelve individuals per species were tested. Food was provided every 36 h, resulting in alternating day- and nighttime feeding events. Activity during the first post-feeding h was recorded and analyzed separately. Statistical procedures included ANOVAs, correlations, and second-order analyses of angles. Results Dugesia (= Girardia tigrina Girard 1850 exhibited clear nocturnal behavior, Dugesia (= Schmidtea polychroa Schmidt 1861 was predominantly but not exclusively nocturnal, and Polycelis tenuis Ijima 1884 was relatively more active from midnight through noon. Species-specific activity peaks were statistically similar, with peaks at dawn for P. tenuis and just before midnight for the two dugesiids; however, D. tigrina was comparatively more active in the early night hours, while D. polychroa was more active than D. tigrina during daytime. D. tigrina also responded less readily to daytime food addition. P. tenuis remained poorly active and unresponsive throughout the experiment. Individual variability in diel behavior was highest for D. polychroa and lowest for D. tigrina. P. tenuis's general low degree of activity and late activity peak in the experiment may be related to a strong reliance on external stimuli. Conclusions The tested species are mainly nocturnal
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Diel biogeochemical processes in terrestrial waters
Nimick, David A.; Gammons, Christopher H.
2011-01-01
Many biogeochemical processes in rivers and lakes respond to the solar photocycle and produce persistent patterns of measureable phenomena that exhibit a day–night, or 24-h, cycle. Despite a large body of recent literature, the mechanisms responsible for these diel fluctuations are widely debated, with a growing consensus that combinations of physical, chemical, and biological processes are involved. These processes include streamflow variation, photosynthesis and respiration, plant assimilation, and reactions involving photochemistry, adsorption and desorption, and mineral precipitation and dissolution. Diel changes in streamflow and water properties such as temperature, pH, and dissolved oxygen concentration have been widely recognized, and recently, diel studies have focused more widely by considering other constituents such as dissolved and particulate trace metals, metalloids, rare earth elements, mercury, organic matter, dissolved inorganic carbon (DIC), and nutrients. The details of many diel processes are being studied using stable isotopes, which also can exhibit diel cycles in response to microbial metabolism, photosynthesis and respiration, or changes in phase, speciation, or redox state. In addition, secondary effects that diel cycles might have, for example, on biota or in the hyporheic zone are beginning to be considered.This special issue is composed primarily of papers presented at the topical session “Diurnal Biogeochemical Processes in Rivers, Lakes, and Shallow Groundwater” held at the annual meeting of the Geological Society of America in October 2009 in Portland, Oregon. This session was organized because many of the growing number of diel studies have addressed just a small part of the full range of diel cycling phenomena found in rivers and lakes. This limited focus is understandable because (1) fundamental aspects of many diel processes are poorly understood and require detailed study, (2) the interests and expertise of individual
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Nandi, Sisir; Monesi, Alessandro; Drgan, Viktor; Merzel, Franci; Novič, Marjana
2013-10-30
In the present study, we show the correlation of quantum chemical structural descriptors with the activation barriers of the Diels-Alder ligations. A set of 72 non-catalysed Diels-Alder reactions were subjected to quantitative structure-activation barrier relationship (QSABR) under the framework of theoretical quantum chemical descriptors calculated solely from the structures of diene and dienophile reactants. Experimental activation barrier data were obtained from literature. Descriptors were computed using Hartree-Fock theory using 6-31G(d) basis set as implemented in Gaussian 09 software. Variable selection and model development were carried out by stepwise multiple linear regression methodology. Predictive performance of the quantitative structure-activation barrier relationship (QSABR) model was assessed by training and test set concept and by calculating leave-one-out cross-validated Q2 and predictive R2 values. The QSABR model can explain and predict 86.5% and 80% of the variances, respectively, in the activation energy barrier training data. Alternatively, a neural network model based on back propagation of errors was developed to assess the nonlinearity of the sought correlations between theoretical descriptors and experimental reaction barriers. A reasonable predictability for the activation barrier of the test set reactions was obtained, which enabled an exploration and interpretation of the significant variables responsible for Diels-Alder interaction between dienes and dienophiles. Thus, studies in the direction of QSABR modelling that provide efficient and fast prediction of activation barriers of the Diels-Alder reactions turn out to be a meaningful alternative to transition state theory based computation.
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International Nuclear Information System (INIS)
Paul, J.H.; Deflaun, M.F.; Jeffrey, W.H.; David, A.W.
1988-01-01
Dissolved DNA and microbial biomass and activity parameters were measured over a 15-month period at three stations along a salinity gradient in Tampa Bay, Fla. Dissolved DNA showed seasonal variation, with minimal values in December and January and maximal values in summer months (July and August). This pattern of seasonal variation followed that of particulate DNA and water temperature and did not correlate with bacterioplankton (direct counts and [ 3 H] thymidine incorporation) or phytoplankton (chlorophyll α and 14 CO 2 fixation) biomass and activity. Microautotrophic populations showed maxima in the spring and fall, whereas microheterotrophic activity was greatest in late summer (September). Both autotrophic and heterotrophic microbial activity was greatest at the high estuarine (low salinity) station and lowest at the mouth of the bay (high salinity station), irrespective of season. Dissolved DNA carbon and phosphorus constituted 0.11 +/- 0.05% of the dissolved organic carbon and 6.6 +/- 6.5% of the dissolved organic phosphorus, respectively. Strong diel periodicity was noted in dissolved DNA and in microbial activity in Bayboro Harbor during the dry season. A noon maximum in primary productivity was followed by an 8 p.m. maximum in heterotrophic activity and a midnight maximum in dissolved DNA. This diel periodicity was less pronounced in the wet season, when microbial parameters were strongly influenced by episodic inputs of freshwater
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Vineetha, G.
2015-04-03
Monsoonal estuaries, located along the coastline of the Indian subcontinent, differ from other estuaries by their time dependence on the salinity characteristics. Effective sustenance and retention of the mesozooplankton community in the estuarine habitats is often determined by their dominant behavioral patterns: diel vertical migration (DVM) and tidal vertical migration (TVM). The modes of these endogenous rhythms often vary among estuaries based on the river runoff and tidal characteristics. The present study is a pioneering attempt to depict the vertical migration pattern of zooplankton along a diel and tidal scale in a tropical, microtidal, monsoonal estuary. We observed that in spite of the prominent asymmetry in the magnitude of the river runoff between the seasons, most of the zooplankton groups exhibited strong DVM, with a clear increase in biomass and abundance in surface waters during night. The peak increase in biomass and abundance at night always synchronized with the slack periods in the tidal cycles, which differed from the general concepts of downward migration during ebb tide and upward migration during flood tide in estuarine systems. The weak currents during the slack period might have favored the effective vertical migration of the mesozooplankton community in this monsoonal estuarine system. © 2015 Society of Wetland Scientists
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Willand, J.E.; McCravy, K.W.
2006-01-01
Diel activities of carabids (Coleoptera: Carabidae) associated with a coal mine remnant and surrounding soybean field were studied in west-central Illinois from June through October 2002. A total of 1,402 carabids, representing 29 species and 17 genera, were collected using pitfall traps. Poecilus chalcites (Say) demonstrated roughly equal diurnal and nocturnal activity in June, but greater diurnal activity thereafter. Pterostichus permundus (Say), Cyclotrachelus seximpressus (LeConte), Amara obesa (Say), and Scarites quadriceps Chaudoir showed significant nocturnal activity. Associations between habitat and diel activity were found for three species: P. chalcites associated with the remnant and edge habitats showed greater diurnal activity than those associated with the soybean field; C. seximpressus was most active diurnally in the remnant, and Harpalus pensylvanicus (DeGeer) showed the greatest nocturnal activity in the remnant and edge habitats. We found significant temporal and habitat-related variation in diel activity among carabid species inhabiting agricultural areas in west-central Illinois.
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Levi-Zada, Anat; Fefer, Daniela; David, Maayan; Eliyahu, Miriam; Franco, José Carlos; Protasov, Alex; Dunkelblum, Ezra; Mendel, Zvi
2014-08-01
The diel periodicity of sex pheromone release was monitored in two mealybug species, Planococcus citri and Planococcus ficus (Hemiptera; Pseudococcidae), using sequential SPME/GCMS analysis. A maximal release of 2 ng/h pheromone by 9-12-day-old P. citri females occurred 1-2 h before the beginning of photophase. The highest release of pheromone by P. ficus females was 1-2 ng/2 h of 10-20-day-old females, approximately 2 h after the beginning of photophase. Mating resulted in termination of the pheromone release in both mealybug species. The temporal flight activity of the males was monitored in rearing chambers using pheromone baited delta traps. Males of both P. citri and P. ficus displayed the same flight pattern and began flying at 06:00 hours when the light was turned on, reaching a peak during the first and second hour of the photophase. Our results suggest that other biparental mealybug species display also diel periodicities of maximal pheromone release and response. Direct evaluation of the diel periodicity of the pheromone release by the automatic sequential analysis is convenient and will be very helpful in optimizing the airborne collection and identification of other unknown mealybug pheromones and to study the calling behavior of females. Considering this behavior pattern may help to develop more effective pheromone-based management strategies against mealybugs.
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Reinthaler, David; Roy, Jacques; Landais, Damien; Piel, Clement; Resco de Dios, Victor; Bahn, Michael
2015-04-01
Soil respiration (Rs) is the biggest source of CO2 emitted from terrestrial ecosystems to the atmosphere. Therefore the understanding of its drivers is of major importance for models of carbon cycling. Next to temperature as a major abiotic factor, photosynthesis has been suggested as an important driver influencing diel patterns in Rs. Under natural conditions it is difficult to disentangle abiotic and biotic effects on soil CO2 production, as fluctuating light intensity affects both photosynthetic activity and soil temperature. To analyse individual and combined effects of soil temperature and light on the dynamics of soil CO2 production and efflux, we performed a controlled environment study at the ECOTRON facility in Montpellier. The study manipulated temperature and photosynthetically active radiation independently and was carried out in large macrocosms, hosting canopies of either a woody (cotton) or a herbaceous (bean) crop. In each macrocosm membrane tubes had been installed across the soil profile for continuous measurement of soil CO2 concentrations. In addition, an automated soil respiration system was installed in each macrocosm, whose data were also used for validating a model of soil CO2 production and transport based on the concentration profiles. Both for cotton and for bean canopies, under conditions of naturally fluctuating temperature and light conditions, soil CO2 production and efflux followed a clear diel pattern. Under constantly dark conditions (excluding immediate effects of photosynthesis) and constant temperature, no significant diel changes in Rs could be observed. Furthermore, soil CO2 production and efflux did not increase significantly upon exposure of previously darkened macrocosms to light. Under constant temperature and fluctuating light conditions, we observed a dampened diel pattern of Rs, which did not match diurnal solar cycles. A detailed residual analysis accounting for temporal trends in soil moisture suggested a significant
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Wang, Zhi-Tao; Nachtigall, Paul E; Akamatsu, Tomonari; Wang, Ke-Xiong; Wu, Yu-Ping; Liu, Jian-Chang; Duan, Guo-Qin; Cao, Han-Jiang; Wang, Ding
2015-01-01
A growing demand for sustainable energy has led to an increase in construction of offshore windfarms. Guishan windmill farm will be constructed in the Pearl River Estuary, China, which sustains the world's largest known population of Indo-Pacific humpback dolphins (Sousa chinensis). Dolphin conservation is an urgent issue in this region. By using passive acoustic monitoring, a baseline distribution of data on this species in the Pearl River Estuary during pre-construction period had been collected. Dolphin biosonar detection and its diel, lunar, seasonal and tidal patterns were examined using a Generalized Linear Model. Significant higher echolocation detections at night than during the day, in winter-spring than in summer-autumn, at high tide than at flood tide were recognized. Significant higher echolocation detections during the new moon were recognized at night time. The diel, lunar and seasonal patterns for the echolocation encounter duration also significantly varied. These patterns could be due to the spatial-temporal variability of dolphin prey and illumination conditions. The baseline information will be useful for driving further effective action on the conservation of this species and in facilitating later assessments of the effects of the offshore windfarm on the dolphins by comparing the baseline to post construction and post mitigation efforts.
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Directory of Open Access Journals (Sweden)
Zhi-Tao Wang
Full Text Available A growing demand for sustainable energy has led to an increase in construction of offshore windfarms. Guishan windmill farm will be constructed in the Pearl River Estuary, China, which sustains the world's largest known population of Indo-Pacific humpback dolphins (Sousa chinensis. Dolphin conservation is an urgent issue in this region. By using passive acoustic monitoring, a baseline distribution of data on this species in the Pearl River Estuary during pre-construction period had been collected. Dolphin biosonar detection and its diel, lunar, seasonal and tidal patterns were examined using a Generalized Linear Model. Significant higher echolocation detections at night than during the day, in winter-spring than in summer-autumn, at high tide than at flood tide were recognized. Significant higher echolocation detections during the new moon were recognized at night time. The diel, lunar and seasonal patterns for the echolocation encounter duration also significantly varied. These patterns could be due to the spatial-temporal variability of dolphin prey and illumination conditions. The baseline information will be useful for driving further effective action on the conservation of this species and in facilitating later assessments of the effects of the offshore windfarm on the dolphins by comparing the baseline to post construction and post mitigation efforts.
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Wang, Zhi-Tao; Nachtigall, Paul E.; Akamatsu, Tomonari; Wang, Ke-Xiong; Wu, Yu-Ping; Liu, Jian-Chang; Duan, Guo-Qin; Cao, Han-Jiang; Wang, Ding
2015-01-01
A growing demand for sustainable energy has led to an increase in construction of offshore windfarms. Guishan windmill farm will be constructed in the Pearl River Estuary, China, which sustains the world’s largest known population of Indo-Pacific humpback dolphins (Sousa chinensis). Dolphin conservation is an urgent issue in this region. By using passive acoustic monitoring, a baseline distribution of data on this species in the Pearl River Estuary during pre-construction period had been collected. Dolphin biosonar detection and its diel, lunar, seasonal and tidal patterns were examined using a Generalized Linear Model. Significant higher echolocation detections at night than during the day, in winter-spring than in summer-autumn, at high tide than at flood tide were recognized. Significant higher echolocation detections during the new moon were recognized at night time. The diel, lunar and seasonal patterns for the echolocation encounter duration also significantly varied. These patterns could be due to the spatial-temporal variability of dolphin prey and illumination conditions. The baseline information will be useful for driving further effective action on the conservation of this species and in facilitating later assessments of the effects of the offshore windfarm on the dolphins by comparing the baseline to post construction and post mitigation efforts. PMID:26580966
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Directory of Open Access Journals (Sweden)
Mark J Corcoran
Full Text Available Southern stingrays, Dasyatis americana, have been provided supplemental food in ecotourism operations at Stingray City Sandbar (SCS, Grand Cayman since 1986, with this site becoming one of the world's most famous and heavily visited marine wildlife interaction venues. Given expansion of marine wildlife interactive tourism worldwide, there are questions about the effects of such activities on the focal species and their ecosystems. We used a combination of acoustic telemetry and tag-recapture efforts to test the hypothesis that human-sourced supplemental feeding has altered stingray activity patterns and habitat use at SCS relative to wild animals at control sites. Secondarily, we also qualitatively estimated the population size of stingrays supporting this major ecotourism venue. Tag-recapture data indicated that a population of at least 164 stingrays, over 80% female, utilized the small area at SCS for prolonged periods of time. Examination of comparative movements of mature female stingrays at SCS and control sites revealed strong differences between the two groups: The fed animals demonstrated a notable inversion of diel activity, being constantly active during the day with little movement at night compared to the nocturnally active wild stingrays; The fed stingrays utilized significantly (p<0.05 smaller 24 hour activity spaces compared to wild conspecifics, staying in close proximity to the ecotourism site; Fed stingrays showed a high degree of overlap in their core activity spaces compared to wild stingrays which were largely solitary in the spaces utilized (72% vs. 3% overlap respectively. Supplemental feeding has strikingly altered movement behavior and spatial distribution of the stingrays, and generated an atypically high density of animals at SCS which could have downstream fitness costs for individuals and potentially broader ecosystem effects. These findings should help environmental managers plan mitigating measures for existing
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Directory of Open Access Journals (Sweden)
Emmanuelle C Leroy
Full Text Available Passive acoustic monitoring is an efficient way to provide insights on the ecology of large whales. This approach allows for long-term and species-specific monitoring over large areas. In this study, we examined six years (2010 to 2015 of continuous acoustic recordings at up to seven different locations in the Central and Southern Indian Basin to assess the peak periods of presence, seasonality and migration movements of Antarctic blue whales (Balaenoptera musculus intermedia. An automated method is used to detect the Antarctic blue whale stereotyped call, known as Z-call. Detection results are analyzed in terms of distribution, seasonal presence and diel pattern of emission at each site. Z-calls are detected year-round at each site, except for one located in the equatorial Indian Ocean, and display highly seasonal distribution. This seasonality is stable across years for every site, but varies between sites. Z-calls are mainly detected during autumn and spring at the subantarctic locations, suggesting that these sites are on the Antarctic blue whale migration routes, and mostly during winter at the subtropical sites. In addition to these seasonal trends, there is a significant diel pattern in Z-call emission, with more Z-calls in daytime than in nighttime. This diel pattern may be related to the blue whale feeding ecology.
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Corcoran, Mark J; Wetherbee, Bradley M; Shivji, Mahmood S; Potenski, Matthew D; Chapman, Demian D; Harvey, Guy M
2013-01-01
Southern stingrays, Dasyatis americana, have been provided supplemental food in ecotourism operations at Stingray City Sandbar (SCS), Grand Cayman since 1986, with this site becoming one of the world's most famous and heavily visited marine wildlife interaction venues. Given expansion of marine wildlife interactive tourism worldwide, there are questions about the effects of such activities on the focal species and their ecosystems. We used a combination of acoustic telemetry and tag-recapture efforts to test the hypothesis that human-sourced supplemental feeding has altered stingray activity patterns and habitat use at SCS relative to wild animals at control sites. Secondarily, we also qualitatively estimated the population size of stingrays supporting this major ecotourism venue. Tag-recapture data indicated that a population of at least 164 stingrays, over 80% female, utilized the small area at SCS for prolonged periods of time. Examination of comparative movements of mature female stingrays at SCS and control sites revealed strong differences between the two groups: The fed animals demonstrated a notable inversion of diel activity, being constantly active during the day with little movement at night compared to the nocturnally active wild stingrays; The fed stingrays utilized significantly (pecotourism site; Fed stingrays showed a high degree of overlap in their core activity spaces compared to wild stingrays which were largely solitary in the spaces utilized (72% vs. 3% overlap respectively). Supplemental feeding has strikingly altered movement behavior and spatial distribution of the stingrays, and generated an atypically high density of animals at SCS which could have downstream fitness costs for individuals and potentially broader ecosystem effects. These findings should help environmental managers plan mitigating measures for existing operations, and develop precautionary policies regarding proposed feeding sites.
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Seasonal and diel patterns in sedimentary flux of krill fecal pellets recorded by an echo sounder
Røstad, Anders
2013-11-01
We used a moored upward-facing 200 kHz echo sounder to address sedimentation of fecal pellets (FPs) from dielly migrating Meganyctiphanes norvegica. The echo sounder was located on the bottom at 150 m depth in the Oslofjord, Norway, and was cabled to shore for continuous measurements during winter and spring. Records of sinking pellets were for the first time observed with an echo sounder. Seasonal patterns of sedimentation of krill FPs were strongly correlated with data from continuous measurement of fluorescence, which illustrate the development of the spring bloom. Sedimenting particles were first observed as fluorescence values started to increase at the end of February and continued to increase until the bloom suddenly culminated at the end of March. This collapse of the bloom was detected on the echo sounder as a pulse of slowly sinking acoustic targets over a 2 d period. Prior to this event, there was a strong diel pattern in sedimentation, which correlated, with some time lag, with the diel migration of krill foraging at night near the surface. Pellet average sinking speeds ranged between 423 m d−1 and 804 m d−1, with a strong relation to pellet target strength, which is an acoustic proxy for size. This novel approach shows that echo sounders may be a valuable tool in studies of vertical pellet flux and, thereby, carbon flux, providing temporal resolution and direct observation of the sedimentation process, which are not obtained from standard methods.
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Rice, Stephen; Johnson, Matthew; Reeds, Jake; Longstaff, Holly; Extence, Chris
2013-04-01
The signal crayfish (Pacifasticus leniusculus) is a formidable invasive species that has had a deleterious impact on native freshwater fauna across Europe. We contend that the impact of this animal extends beyond ecology into geomorphology and hypothesise that crayfish are significant agents of fine sediment recruitment and mobilisation, with potentially profound impacts on water quality, substrate quality and fine sediment fluxes. Building on pioneering work by colleagues at Queen Mary University, London this poster considers the role of crayfish in fine sediment suspension in a lowland, gravel-bed river. The hypothesis that nocturnal increases in crayfish activity are associated with a greater frequency of sediment suspension events and increases in ambient turbidity, is tested. Strong diel fluctuations in water turbidity were recorded at several sites on the Brampton Arm of the River Nene in England, a river heavily populated by signal crayfish, during August and September 2012. With the exception of three summer flood events, stage measurements during the same period were essentially flat, ruling out a hydraulic cause for overnight rises in turbidity. Water samples collected at midnight and at midday at one site confirm this diel pattern for suspended sediment concentration. Higher mean turbidity values overnight are associated with an increase in the magnitude and frequency of isolated turbidity spikes or events and this is consistent with crayfish nocturnalism. In particular, we suspect that turbidity events are caused by the construction and maintenenance of burrows and by interactions between crayfish and the river bed while foraging, fighting and avoiding each other. Tying the diel SSC signal directly to crayfish activity proved difficult, but several lines of argument presented here suggest that crayfish are the most likely cause of the diel pattern. These results provide substantial support for the idea that signal crayfish are important zoogeomorphic
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Atmospheric turbulence triggers pronounced diel pattern in karst carbonate geochemistry
Roland, M.; Serrano-Ortiz, P.; Kowalski, A. S.; Goddéris, Y.; Sánchez-Cañete, E. P.; Ciais, P.; Domingo, F.; Cuezva, S.; Sanchez-Moral, S.; Longdoz, B.; Yakir, D.; Van Grieken, R.; Schott, J.; Cardell, C.; Janssens, I. A.
2013-07-01
CO2 exchange between terrestrial ecosystems and the atmosphere is key to understanding the feedbacks between climate change and the land surface. In regions with carbonaceous parent material, CO2 exchange patterns occur that cannot be explained by biological processes, such as disproportionate outgassing during the daytime or nighttime CO2 uptake during periods when all vegetation is senescent. Neither of these phenomena can be attributed to carbonate weathering reactions, since their CO2 exchange rates are too small. Soil ventilation induced by high atmospheric turbulence is found to explain atypical CO2 exchange between carbonaceous systems and the atmosphere. However, by strongly altering subsurface CO2 concentrations, ventilation can be expected to influence carbonate weathering rates. By imposing ventilation-driven CO2 outgassing in a carbonate weathering model, we show here that carbonate geochemistry is accelerated and does play a surprisingly large role in the observed CO2 exchange pattern of a semi-arid ecosystem. We found that by rapidly depleting soil CO2 during the daytime, ventilation disturbs soil carbonate equilibria and therefore strongly magnifies daytime carbonate precipitation and associated CO2 production. At night, ventilation ceases and the depleted CO2 concentrations increase steadily. Dissolution of carbonate is now enhanced, which consumes CO2 and largely compensates for the enhanced daytime carbonate precipitation. This is why only a relatively small effect on global carbonate weathering rates is to be expected. On the short term, however, ventilation has a drastic effect on synoptic carbonate weathering rates, resulting in a pronounced diel pattern that exacerbates the non-biological behavior of soil-atmosphere CO2 exchanges in dry regions with carbonate soils.
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Weiss, Julia; Terry, Marta I; Martos-Fuentes, Marina; Letourneux, Lisa; Ruiz-Hernández, Victoria; Fernández, Juan A; Egea-Cortines, Marcos
2018-02-14
Cowpea (Vigna unguiculata) is an important source of protein supply for animal and human nutrition. The major storage globulins VICILIN and LEGUMIN (LEG) are synthesized from several genes including LEGA, LEGB, LEGJ and CVC (CONVICILIN). The current hypothesis is that the plant circadian core clock genes are conserved in a wide array of species and that primary metabolism is to a large extent controlled by the plant circadian clock. Our aim was to investigate a possible link between gene expression of storage proteins and the circadian clock. We identified cowpea orthologues of the core clock genes VunLHY, VunTOC1, VunGI and VunELF3, the protein storage genes VunLEG, VunLEGJ, and VunCVC as well as nine candidate reference genes used in RT-PCR. ELONGATION FACTOR 1-A (ELF1A) resulted the most suitable reference gene. The clock genes VunELF3, VunGI, VunTOC1 and VunLHY showed a rhythmic expression profile in leaves with a typical evening/night and morning/midday phased expression. The diel patterns were not completely robust and only VungGI and VungELF3 retained a rhythmic pattern under free running conditions of darkness. Under field conditions, rhythmicity and phasing apparently faded during early pod and seed development and was regained in ripening pods for VunTOC1 and VunLHY. Mature seeds showed a rhythmic expression of VunGI resembling leaf tissue under controlled growth chamber conditions. Comparing time windows during developmental stages we found that VunCVC and VunLEG were significantly down regulated during the night in mature pods as compared to intermediate ripe pods, while changes in seeds were non-significant due to high variance. The rhythmic expression under field conditions was lost under growth chamber conditions. The core clock gene network is conserved in cowpea leaves showing a robust diel expression pattern except VunELF3 under growth chamber conditions. There appears to be a clock transcriptional reprogramming in pods and seeds compared to
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Moeckel, Claudia; Macleod, Matthew; Hungerbühler, Konrad; Jones, Kevin C
2008-05-01
Short-term variability of concentrations of polybrominated diphenyl ethers (PBDEs) and chlordanes in air at a semirural site in England over a 5 day period is reported. Four-hour air samples were collected during a period dominated by a high pressure system that produced stable diel (24-h) patterns of meteorological conditions such as temperature and atmospheric boundary layer height. PBDE and chlordane concentrations showed clear diel variability with concentrations in the afternoon and evening being 1.9 - 2.7 times higher than in the early morning. The measurements are interpreted using a multimedia mass balance model parametrized with forcing functions representing local temperature, atmospheric boundary layer height, wind speed and hydroxyl radical concentrations. Model results indicate that reversible, temperature-controlled air-surface exchange is the primary driver of the diel concentration pattern observed for chlordanes and PBDE 28. For higher brominated PBDE congeners (47, 99 and 100), the effect of variable atmospheric mixing height in combination with irreversible deposition on aerosol particles is dominant and explains the diel patterns almost entirely. Higher concentrations of chlordanes and PBDEs in air observed at the end of the study period could be related to likely source areas using back trajectory analysis. This is the first study to clearly document diel variability in concentrations of PBDEs in air over a period of several days. Our model analysis indicates that high daytime and low nighttime concentrations of semivolatile organic chemicals can arise from different underlying driving processes, and are not necessarily evidence of reversible air-surface exchange on a 24-h time scale.
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Di Lorenzo, Manfredi; Fernández, Tomás Vega; Badalamenti, Fabio; Guidetti, Paolo; Starr, Richard M; Giacalone, Vincenzo Maximiliano; Di Franco, Antonio; D'Anna, Giovanni
2016-05-01
Fish populations are often comprised of individuals that use habitats and associated resources in different ways. We placed sonic transmitters in, and tracked movements of, white sea bream (Diplodus sargus sargus) in the no-take zone of a Mediterranean marine protected area: the Torre Guaceto marine protected area, (Adriatic Sea, Italy). Tagged fish displayed three types of diel activity patterns in three different habitats: sand, rocky reefs and "matte" of the seagrass Posidonia oceanica. Individuals were more active during the day than at night. Overall, white sea bream displayed a remarkable behavioural plasticity in habitat use. Our results indicate that the observed behavioural plasticity in the marine protected area could be the result of multiple ecological and environmental drivers such as size, sex and increased intra-specific competition. Our findings support the view that habitat diversity helps support high densities of fishes. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Cantín, Ángel; Gomez, M Victoria; de la Hoz, Antonio
2016-01-01
Diels-Alder cycloaddition between cyclopentadiene and p -benzoquinone has been studied in the confined space of a pure silica zeolite Beta and the impact on reaction rate due to the concentration effect within the pore and diffusion limitations are discussed. Introduction of Lewis or Brønsted acid sites on the walls of the zeolite strongly increases the reaction rate. However, contrary to what occurs with mesoporous molecular sieves (MCM-41), Beta zeolite does not catalyse the retro-Diels-Alder reaction, resulting in a highly selective catalyst for the cycloaddition reaction.
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Directory of Open Access Journals (Sweden)
Han Zheng
Full Text Available Evapotranspiration (ET is an important component of the water cycle in terrestrial ecosystems. Understanding the ways in which ET changes with meteorological factors is central to a better understanding of ecological and hydrological processes. In this study, we used eddy covariance measurements of ET from a typical alpine shrubland meadow ecosystem in China to investigate the hysteresis response of ET to environmental variables including air temperature (Ta, vapor pressure deficit (VPD and net radiation (Rn at a diel timescale. Meanwhile, the simulated ET by Priestly-Taylor equation was used to interpret the measured ET under well-watered conditions. Pronounced hysteresis was observed in both Ta and VPD response curves of ET. At a similar Ta and VPD, ET was always significantly depressed in the afternoon compared with the morning. But the hysteresis response of ET to Rn was not evident. Similar hysteresis patterns were also observed in the Ta/VPD response curves of simulated ET. The magnitudes of the measured and simulated hysteresis loops showed similar seasonal variation, with relatively smaller values occurring from May to September, which agreed well with the lifetime of plants and the period of rainy season at this site. About 62% and 23% of changes in the strength of measured ET-Ta and ET-VPD loops could be explained by the changes in the strength of simulated loops, respectively. Thus, the time lag between Rn and Ta/VPD is the most important factor generating and modulating the ET-Ta/VPD hysteresis, but plants and water status also contribute to the hysteresis response of ET. Our research confirmed the different hysteresis in the responses of ET to meteorological factors and proved the vital role of Rn in driving the diel course of ET.
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BLOKZIJL, W; BLANDAMER, MJ; ENGBERTS, JBFN
1991-01-01
Second-order rate constants and isobaric activation parameters for the intermolecular Diels-Alder reactions of cyclopentadiene with alkyl vinyl ketones (2a,b) and 5-substituted-1,4-naphthoquinones (3a-c) as well as for the intramolecular Diels-Alder reaction of N-furfuryl-N-methylmaleamic acid (4)
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Poiré, Richard; Wiese-Klinkenberg, Anika; Parent, Boris; Mielewczik, Michael; Schurr, Ulrich; Tardieu, François; Walter, Achim
2010-06-01
Diel (24 h) leaf growth patterns were differently affected by temperature variations and the circadian clock in several plant species. In the monocotyledon Zea mays, leaf elongation rate closely followed changes in temperature. In the dicotyledons Nicotiana tabacum, Ricinus communis, and Flaveria bidentis, the effect of temperature regimes was less obvious and leaf growth exhibited a clear circadian oscillation. These differences were related neither to primary metabolism nor to altered carbohydrate availability for growth. The effect of endogenous rhythms on leaf growth was analysed under continuous light in Arabidopsis thaliana, Ricinus communis, Zea mays, and Oryza sativa. No rhythmic growth was observed under continuous light in the two monocotyledons, while growth rhythmicity persisted in the two dicotyledons. Based on model simulations it is concluded that diel leaf growth patterns in mono- and dicotyledons result from the additive effects of both circadian-clock-controlled processes and responses to environmental changes such as temperature and evaporative demand. Apparently very distinct diel leaf growth behaviour of monocotyledons and dicotyledons can thus be explained by the different degrees to which diel temperature variations affect leaf growth in the two groups of species which, in turn, depends on the extent of the leaf growth control by internal clocks.
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Diels-Alder reactions of inert aromatic compounds within a self-assembled coordination cage.
Horiuchi, Shinnosuke; Murase, Takashi; Fujita, Makoto
2011-07-04
A self-assembled coordination cage serves as a nanometer-sized molecular flask to promote the Diels-Alder reactions of aromatic hydrocarbons with N-cyclohexylmaleimide. The coordination cage accelerated the Diels-Alder reaction of anthracene at the electronically unfavorable, terminal benzene ring to give a compact, cavity-restrained syn-adduct. Activation-parameter measurements for the reactions revealed considerable reduction in the entropy cost, and preorganization of the substrates is a dominant factor in the enhanced reactivity. Owing to this entropy-cost reduction, otherwise-unreactive aromatic compounds, such as naphthalenes or triphenylene, also underwent Diels-Alder reactions in a regio- and stereocontrolled fashion. In the naphthalene Diels-Alder reaction, X-ray crystallographic analysis of the guest-inclusion complex clarified the reinforced orientation and proximity of the substrate pairs before the reaction. A perylene Diels-Alder adduct was stabilized inside the cage and protected from aerial oxidation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Fell, Jason S; Martin, Blanton N; Houk, K N
2017-02-17
The reactivities of butadiene, cyclopentadiene, furan, thiophene, pyrrole, and their 1-aza- and 2-aza-derivatives in Diels-Alder reactions with ethylene and fumaronitrile were investigated with density functional theory (M06-2X/6-311G(d,p)). The activation free energies for the Diels-Alder reactions of cyclic 1-azadienes are 10-14 kcal mol -1 higher than those of cyclic 2-azadienes, and the reaction free energies are 17-20 kcal mol -1 more endergonic. The distortion/interaction model shows that the increased activation energies of cyclic 1-azadienes originate from increased transition state distortion energies and unfavorable interaction energies, arising from addition to the nitrogen terminus of the C═N bond.
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Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio, Argentina
Parker, Stephen R.; Gammons, Christopher H.; Pedrozo, Fernando L.; Wood, Scott A.
2008-12-01
Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters. The results of this study of a naturally-acidic river are very similar to diel trends recently obtained from mining-impacted streams receiving acid rock drainage. The results are also used to explore the link between geochemistry and microbiology in acidic eco-systems. For example, Fe(III) photoreduction produces chemical potential energy (in the form of metastable Fe 2+) that helps support the bacterial community in this unique extreme environment.
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Covalently crosslinked diels-alder polymer networks.
Energy Technology Data Exchange (ETDEWEB)
Bowman, Christopher (University of Colorado, Boulder, CO); Adzima, Brian J. (University of Colorado, Boulder, CO); Anderson, Benjamin John
2011-09-01
This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis of the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.
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Deeper Insight into the Diels-Alder Reaction through the Activation Strain Model.
Fernández, Israel; Bickelhaupt, F Matthias
2016-12-06
In this Focus Review, we present the application of the so-called Activation Strain Model of chemical reactivity to the Diels-Alder cycloaddition reaction. To this end, representative recent examples have been selected to illustrate the power of this new computational approach to gain a deeper quantitative understanding of this fundamental process in chemistry. We cover a wide range of issues, such as, the "endo-rule", reactivity trends emerging from systematic variation in the reactants' strain, and cycloaddition reactions involving relevant species in material science, that is, fullerenes, polycyclic aromatic hydrocarbons and nanotubes. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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The pentadehydro-Diels-Alder reaction.
Wang, Teng; Naredla, Rajasekhar Reddy; Thompson, Severin K; Hoye, Thomas R
2016-04-28
In the classic Diels-Alder [4 + 2] cycloaddition reaction, the overall degree of unsaturation (or oxidation state) of the 4π (diene) and 2π (dienophile) pairs of reactants dictates the oxidation state of the newly formed six-membered carbocycle. For example, in the classic Diels-Alder reaction, butadiene and ethylene combine to produce cyclohexene. More recent developments include variants in which the number of hydrogen atoms in the reactant pair and in the resulting product is reduced by, for example, four in the tetradehydro-Diels-Alder (TDDA) and by six in the hexadehydro-Diels-Alder (HDDA) reactions. Any oxidation state higher than tetradehydro (that is, lacking more than four hydrogens) leads to the production of a reactive intermediate that is more highly oxidized than benzene. This increases the power of the overall process substantially, because trapping of the reactive intermediate can be used to increase the structural complexity of the final product in a controllable and versatile manner. Here we report an unprecedented overall 4π + 2π cycloaddition reaction that generates a different, highly reactive intermediate known as an α,3-dehydrotoluene. This species is in the same oxidation state as a benzyne. Like benzynes, α,3-dehydrotoluenes can be captured by various trapping agents to produce structurally diverse products that are complementary to those arising from the HDDA process. We call this new cycloisomerization process a pentadehydro-Diels-Alder (PDDA) reaction-a nomenclature chosen for chemical taxonomic reasons rather than mechanistic ones. In addition to alkynes, nitriles (RC≡N), although non-participants in aza-HDDA reactions, readily function as the 2π component in PDDA cyclizations to produce, via trapping of the α,3-(5-aza)dehydrotoluene intermediates, pyridine-containing products.
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Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.
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.
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Directory of Open Access Journals (Sweden)
NA. Pesoa
Full Text Available Prochilodus lineatus is a reophilic migratory species of economical importance for local fisheries which is widely distributed in Brazil. The present study investigated diel and seasonal movement patterns, spawning migration and habitat use of P. lineatus in the Sinos River, Southern Brazil. Between August 2002 and March 2004, 19 grumatãs were tagged internally with digitally coded radio transmitters. Tracking was conducted weekly by boat or aircraft, and six fixed data loggers recorded movements of tagged fish. Results showed that the mean distance covered per fish and day was positively related with fish weight (p = 0.03; n = 19. Grumatã showed preference for river streches surrounded by wetlands (p < 0.001; n = 286. Their diel activity pattern displayed one peak at 7 hours, and a second at 15 hours. During the night, activity was significantly reduced (p = 0.01. The seasonal movements pattern showed increased activity in October 2002 - March 2003 and from October 2003 to January 2004. Multiple regression analysis did not show a significant relationship between distance covered and temperature or water level (p = 0.116; n = 19. No synchronized long distance spawning migrations were observed. The mean distance covered by the individuals/day showed a negative significant relationship with number of tracking days (p = 0.022; n = 19, indicating a higher probability of being captured for more mobile individuals. The preservation of the still existing wetlands and reduction of the fishing pressure are essential for the future conservation of the grumatã population of the Sinos River.
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Application of the aza-Diels-Alder reaction in the synthesis of natural products.
Cao, Min-Hui; Green, Nicholas J; Xu, Sheng-Zhen
2017-04-11
The Diels-Alder reaction that involves a nitrogen atom in the diene or dienophile is termed the aza-Diels-Alder reaction. As well as the powerful all-carbon Diels-Alder reaction, the aza-Diels-Alder reaction has also played an important role in the total synthesis of natural products. Herein, we review various natural products using an aza-Diels-Alder reaction as a key step to their total synthesis, and divide the syntheses into inter- and intra-molecular aza-Diels-Alder reactions and a retro-aza-Diels-Alder reaction. Inter- and intra-molecular aza-Diels-Alder reactions involve an imine as an electron deficient dienophile and an imine as an electron deficient azadiene. The significance of the aza-Diels-Alder reaction for the construction of a six-membered ring containing nitrogen is tremendous, but the development of asymmetric, in particular catalytic enantioselective intramolecular aza-Diels-Alder reaction in the total synthesis of natural products remains highly challenging, and will no doubt see enormous advances in the future.
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Steunou, Anne-Soisig; Jensen, Sheila I; Brecht, Eric; Becraft, Eric D; Bateson, Mary M; Kilian, Oliver; Bhaya, Devaki; Ward, David M; Peters, John W; Grossman, Arthur R; Kühl, Michael
2008-04-01
Nitrogen fixation, a prokaryotic, O2-inhibited process that reduces N2 gas to biomass, is of paramount importance in biogeochemical cycling of nitrogen. We analyzed the levels of nif transcripts of Synechococcus ecotypes, NifH subunit and nitrogenase activity over the diel cycle in the microbial mat of an alkaline hot spring in Yellowstone National Park. The results showed a rise in nif transcripts in the evening, with a subsequent decline over the course of the night. In contrast, immunological data demonstrated that the level of the NifH polypeptide remained stable during the night, and only declined when the mat became oxic in the morning. Nitrogenase activity was low throughout the night; however, it exhibited two peaks, a small one in the evening and a large one in the early morning, when light began to stimulate cyanobacterial photosynthetic activity, but O2 consumption by respiration still exceeded the rate of O2 evolution. Once the irradiance increased to the point at which the mat became oxic, the nitrogenase activity was strongly inhibited. Transcripts for proteins associated with energy-producing metabolisms in the cell also followed diel patterns, with fermentation-related transcripts accumulating at night, photosynthesis- and respiration-related transcripts accumulating during the day and late afternoon, respectively. These results are discussed with respect to the energetics and regulation of N2 fixation in hot spring mats and factors that can markedly influence the extent of N2 fixation over the diel cycle.
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Patterns in diel habitat use of fish covering the littoral and pelagic zones in a reservoir
Czech Academy of Sciences Publication Activity Database
Říha, Milan; Ricard, Daniel; Vašek, Mojmír; Prchalová, Marie; Mrkvička, Tomáš; Jůza, Tomáš; Čech, Martin; Draštík, Vladislav; Muška, Milan; Kratochvíl, Michal; Peterka, Jiří; Tušer, Michal; Seďa, Jaromír; Blabolil, Petr; Bláha, M.; Wanzenbock, J.; Kubečka, Jan
2015-01-01
Roč. 747, č. 1 (2015), s. 111-131 ISSN 0018-8158 R&D Projects: GA MŠk(CZ) EE2.3.20.0204; GA MŠk(CZ) EE2.3.30.0032 Institutional support: RVO:60077344 Keywords : habitat use * diel period * distribution * fish diet * littoral * pelagial * reservoir Subject RIV: EG - Zoology Impact factor: 2.051, year: 2015
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Directory of Open Access Journals (Sweden)
Hamzehloueian Mahshid
2014-01-01
Full Text Available The present study reports a systematic computational analysis of the two possible pathways, fused and bridged, for an intramolecular hetero Diels-Alder (IMHDA and an intramolecular 1,3-dipolar cycloaddition (IMDCA of 2-vinyloxybenzaldehyde derivatives. The potential energy surface analysis for both reactions is in agreement with experimental observations. The activation energies associated with the two regioisomeric channels in IMHDA reaction show that the bridged product is favored, although in IMDCA, the most stable TS results the fused product. The global electronic properties of fragments within each molecule were studied to discuss the reactivity patterns and charge transfer direction in the intramolecular processes. The asynchronicity of the bond formation and aromaticity of the optimized TSs in the Diels-Alder reaction as well as cycloaddition reaction were evaluated. Finally, 1H NMR chemical shifts of the possible regioisomers have been calculated using the GIAO method which of the most stable products are in agreement with the experimental data in the both reaction.
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Rahman, M.M.; Meyer, C.G.
2009-01-01
In order to better understand behaviour patterns of common carp Cyprinus carpio in aquaculture ponds, their diel grazing, swimming, resting and schooling behaviours were observed in six 1 m(2) tanks under simulated pond conditions. Each tank was fertilized to stimulate natural food production before
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Diels-Alder Reactions in Water. Effects of Hydrophobicity and Hydrogen Bonding
Otto, Sijbren; Blokzijl, Wilfried; Engberts, Jan B.F.N.
1994-01-01
In order to check whether the activated complex for the Diels-Alder reactions of 5-substituted 1,4-naphthoquinones with cyclopentadiene is more polar in water than in other solvents, we have determined the substituent effects in seven different solvents. The substituent effects gradually decrease
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Solvent Effects in Asymmetric Hetero Diels-Alder and Ene Reactions
DEFF Research Database (Denmark)
Johannsen, Mogens; Jørgensen, Karl Anker
1996-01-01
The use of polar solvents such as nitromethane or 2-nitropropane leads to a significant improvement of the catalytic properties of a cationic copper-Lewis acid in the hetero Diels-Alder reaction of alkyl glyoxylates with dienes; The scope of a newly developed copper(II)-bisoxazoline catalyst...... for the hetero Diels-Alder reaction is demonstrated by the reaction of different dienes with alkyl glyoxylates in nitroalkane solvents with the formation of the hetero Diels-Alder adduct in high enantiomeric excess as the major product. The synthetic application of the reaction is exemplified by an improved...
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Gieling, Reinerus Gerardus
2003-01-01
This thesis deals with the conceivable transfer of the Diels Alder/retro-Diels Alder concept to the solid phase in order to broaden the scope of the methodology to a combinatorial level. In addition, based on this methodology the development of a traceless thermocleavable linking system for
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Stepwise radical cation Diels-Alder reaction via multiple pathways.
Shimizu, Ryo; Okada, Yohei; Chiba, Kazuhiro
2018-01-01
Herein we disclose the radical cation Diels-Alder reaction of aryl vinyl ethers by electrocatalysis, which is triggered by an oxidative SET process. The reaction clearly proceeds in a stepwise fashion, which is a rare mechanism in this class. We also found that two distinctive pathways, including "direct" and "indirect", are possible to construct the Diels-Alder adduct.
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Zhang, Sheng; Cha, Lide; Li, Lijun; Hu, Yanbin; Li, Yanan; Zha, Zhenggen; Wang, Zhiyong
2016-04-15
A primary amine-catalyzed asymmetric formal aza-Diels-Alder reaction of trifluoromethyl hemiaminals with enones was developed via a chiral gem-diamine intermediate. This novel protocol allowed facile access to structurally diverse trifluoromethyl-substituted piperidine scaffolds with high stereoselectivity. The utility of this method was further demonstrated through a concise approach to biologically active 4-hydroxypiperidine. More importantly, a stepwise mechanism involving an asymmetric induction process was proposed to rationalize the positive correlation between the chirality of the gem-diamine intermediate and the formal aza-Diels-Alder product.
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Diel vertical migration of zooplankton in the Tanzanian waters of ...
African Journals Online (AJOL)
The diel vertical migration of zooplankton was studied in the Southern part of Lake Victoria in January and July 2002. A van dorn water sampler was used to collect zooplankton. In January 2002, zooplankton showed a pronounced diel vertical migration whereby zooplankton were moving upward at around sunset and ...
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Nishikawa, Yasuhiro; Nakano, Saki; Tahira, Yuu; Terazawa, Kanako; Yamazaki, Ken; Kitamura, Chitoshi; Hara, Osamu
2016-05-06
Chiral pyridinium phosphoramide 1·HX was designed to be a new class of chiral Brønsted acid catalyst in which both the pyridinium proton and the adjacent imide-like proton activated by the electron-withdrawing pyridinium moiety could work cooperatively as strong dual proton donors. The potential of 1·HX was shown in the enantioselective Diels-Alder reactions of 1-amino dienes with various dienophiles including N-unsubstituted maleimide, which has yet to be successfully used in an asymmetric Diels-Alder reaction.
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Partial diel migration: A facultative migration underpinned by long-term inter-individual variation.
Harrison, Philip M; Gutowsky, Lee F G; Martins, Eduardo G; Patterson, David A; Cooke, Steven J; Power, Michael
2017-09-01
The variations in migration that comprise partial diel migrations, putatively occur entirely as a consequence of behavioural flexibility. However, seasonal partial migrations are increasingly recognised to be mediated by a combination of reversible plasticity in response to environmental variation and individual variation due to genetic and environmental effects. Here, we test the hypothesis that while partial diel migration heterogeneity occurs primarily due to short-term within-individual flexibility in behaviour, long-term individual differences in migratory behaviour also underpin this migration variation. Specifically, we use a hierarchical behavioural reaction norm approach to partition within- and among-individual variation in depth use and diel plasticity in depth use, across short- and long-term time-scales, in a group of 47 burbot (Lota lota) tagged with depth-sensing acoustic telemetry transmitters. We found that within-individual variation at the among-dates-within-seasons and among-seasons scale, explained the dominant proportion of phenotypic variation. However, individuals also repeatedly differed in their expression of migration behaviour over the 2 year study duration. These results reveal that diel migration variation occurs primarily due to short-term within-individual flexibility in depth use and diel migration behaviour. However, repeatable individual differences also played a key role in mediating partial diel migration. These findings represent a significant advancement of our understanding of the mechanisms generating the important, yet poorly understood phenomena of partial diel migration. Moreover, given the pervasive occurrence of diel migrations across aquatic taxa, these findings indicate that individual differences have an important, yet previously unacknowledged role in structuring the temporal and vertical dynamics of aquatic ecosystems. © 2017 The Authors. Journal of Animal Ecology © 2017 British Ecological Society.
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Intramolecular Diels-Alder reactions of pyrimidines, a synthetic and computational study
Stolle, W.A.W.
1992-01-01
This thesis deals with an investigation on the ringtransformation reactions of 2and 5-(ω-alkynyl)pyrimidine derivatives, which undergo upon heating an intramolecular Diels-Alder reaction and subsequently a spontaneous retro Diels- Alder reaction. To get a better insight into the
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Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system
Gammons, C.H.; Grant, T.M.; Nimick, D.A.; Parker, S.R.; DeGrandpre, M.D.
2007-01-01
Arsenic concentrations are elevated in surface waters of the Warm Springs Ponds Operable Unit (WSPOU), located at the head of the upper Clark Fork River Superfund site, Montana, USA. Arsenic is derived from historical deposition of smelter emissions (Mill and Willow Creeks) and historical mining and milling wastes (Silver Bow Creek). Although long-term monitoring has characterized the general seasonal and flow-related trends in As concentrations in these streams and the pond system used to treat Silver Bow Creek water, little is known about solubility controls and sorption processes that influence diel cycles in As concentrations. Diel (24-h) sampling was conducted in July 2004 and August 2005 at the outlet of the treatment ponds, at two locations along a nearby reconstructed stream channel that diverts tributary water around the ponds, and at Silver Bow Creek 2??km below the ponds. Dissolved As concentration increased up to 51% during the day at most of the stream sites, whereas little or no diel change was displayed at the treatment-pond outlet. The strong cycle in streams is explained by pH- and temperature-dependent sorption of As onto hydrous metal oxides or biofilms on the streambed. Concentrations of dissolved Ca2+ and HCO3- at the stream sites showed a diel temporal pattern opposite to that of As, and geochemical modeling supports the hypothesis that the concentrations of Ca2+ and HCO3- were controlled by precipitation of calcite during the warm afternoon hours when pH rose above 9.0. Nightly increases in dissolved Mn and Fe(II) concentrations were out of phase with concentrations of other divalent cations and are more likely explained by redox phenomena. ?? 2007 Elsevier B.V. All rights reserved.
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The hexadehydro-Diels-Alder reaction.
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.
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Directory of Open Access Journals (Sweden)
Z. Stirn
2016-07-01
Full Text Available The Diels-Alder reaction between N-phenylmaleimide and benzoxazine bearing furan group was investigated for the purpose of successful appliance of self-healing in benzoxazine polymer networks. The reaction as a function of temperature/time was performed in molten state and in a solution, where also the kinetic study was performed. The Diels-Alder reaction leads to a mixture of two diastereomers: endo presented at lower cyclo-reversion temperature and exo at higher. Therefore, the conversion rates and exo/endo ratio were studied in detail for both systems. For instance, in molten state the Diels-Alder reaction was triggered by the temperature of the melting point at 60 °C with exo/endo ratio preferable to the endo adduct. The study of the kinetics in a solution revealed that the Diels-Alder reaction followed typical bimolecular reversible second-order reaction. The activation energies were close to the previous literature data; 48.4 and 51.9 kJ·mol–1 for Diels-Alder reaction, and 91.0 and 102.3 kJ·mol–1 for retro-Diels-Alder reaction, in acetonitrile and chloroform, respectively. The reaction equilibrium in a solution is much more affected by the retro-Diels-Alder reaction than in a molten state. This study shows detailed investigation of DA reaction and provides beneficial knowledge for further use in self-healing polymer networks.
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Directory of Open Access Journals (Sweden)
Maria Raquel de Carvalho
Full Text Available Diel changes in feeding activity and dietary composition of the rough scad Trachurus lathami were investigated through the analysis of stomach contents of 307 fish sampled over a 24-h period on the continental shelf off Ubatuba (23º 35'S 45ºW. Stomach contents were analyzed by frequency of occurrence (O%, percent number (N%, percent mass (M%, and feeding index (FI% = O% * M%. Rough scad fed on mollusks (Gastropoda, Crepidula sp., crustacean (Ostracoda, Copepoda, decapod larvae, chaetognat and teleostean fish. The main items were calanoid copepods (Eucalanus sp. and Centropages sp.. According to the analysis of the stomach fullness and prey digestion, T. lathami is both a diurnal and nocturnal feeder, showing some seasonal variation in feeding time. According to the Chronobiology concept, it was raised the hypothesis of circadian rhythm in feeding of this fish, probably synchronized by light/dark cycle.
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Asymmetric Diels-Alder reactions with 5-menthyloxy-2(5H)-furanones
Jong, Johannes Cornelis de
2006-01-01
At the beginning of the reseach described in this thesis the catalytic asymmetric Diels-Alder reaction had scarcely been investigated. No good catalytic processes with high enantiomeric excess were known at that time. At the same time the Diels-Alder reactions with chiral dienophiles needed further
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Directory of Open Access Journals (Sweden)
Haghdadi Mina
2015-01-01
Full Text Available A DFT study of the reactivity, regio- and stereoselectivity of Diels-Alder reaction between 3-bromo, 5-bromo, and 3,5-dibromo-2(H-pyran-2-ones and some weakly activated and unactivated alkenes has been carried out using density functional theory (DFT. Four possible reaction channels, which are related to the formation of meta- and para- and endo- and exo-cycloadducts have been explored and characterized. The energy and natural bond orbital analysis shows that the meta-regioselectivity on the exo pathway is preferred and follows an asynchronous concerted mechanism with a polar nature in all Diels-Alder cycloadditions. Moreover, the activation free energies of Diels-Alder cycloadditions of 3,5-dibromo-2(H-pyran-2one are lower than 3- bromo-2(H-pyran-2one and 5-bromo-2(H-pyran-2one, which are in line with experimental observation. DFT-based reactivity indices clearly predict the regiochemistry of the isolated cycloadducts.
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Diels-Alder reactions: The effects of catalyst on the addition reaction
Yilmaz, Özgür; Kus, Nermin Simsek; Tunç, Tuncay; Sahin, Ertan
2015-10-01
The reaction between 2,3-dimethyl-1,3-butadiene and dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate is efficiently achieved with small amounts of catalyst, i.e. phenol, AcOH, nafion, and β-cyclodextrin. Exo-diastereoselective cycloaddition reactions were observed both without catalyst and different catalysts for 48 days. As a result, different products (tricyclicmolecule 5, retro-Diels-Alder product 6, and oxidation product 7) were obtained with different catalysts. In addition, we synthesized Diels-Alders product 8 and tricyclocyclitol 10 via Diels-Alder reaction. The structures of these products were characterized by 1H NMR, 13C NMR, MS and IR spectroscopy.
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International Nuclear Information System (INIS)
Castillo, Aylin; Valdes, Juan; Sibaja, Jose; Vega, Ilena; Alfaro, Rosa; Morales, Jose; Esquivel, Germain; Barrantes, Elisa; Black, Paleah; Lean, David
2011-01-01
. With the onset of the wet season TGM increased from typical values near 10 to 905 ng m -3 . Measurements made within 5 km of the Poas volcano were higher than at Heredia at that time. Diel values measured at University site increased until midday along with temperature and radiation. Relative humidity showed a reciprocal pattern. It was found that high values of TGM were not related to wind velocity or direction. The strong diel pattern increased with sunrise, peaked at midday and was lowest during the night time. It would seem that Hg 0 from the volcano is oxidized and is deposited to the soils during the dry season when winds are blowing from the volcano. With the onset of heavy rains in April, Hg in the soil is reduced and re-volatilized resulting in the high levels in the atmosphere. Values at other volcano sites were provided. The role of atmospheric pollutants such as H 2 O 2 and O 3 should be included in future studies as they may result in oxidation of reduced Hg. The instability in the air masses may also be a factor and local pollution sources may result in high levels that is emitted from the volcanoes of Hg being circulated to ground level as radiation intensity increases.
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Energy Technology Data Exchange (ETDEWEB)
Castillo, Aylin; Valdes, Juan; Sibaja, Jose; Vega, Ilena; Alfaro, Rosa; Morales, Jose; Esquivel, Germain; Barrantes, Elisa [Laboratory for Atmospheric Chemistry, LAQAT-UNA, Universidad Nacional, P.O. Box 86-3000, Heredia (Costa Rica); Black, Paleah [Department of Biology, University of Ottawa, P.O. Box 450 Station A, Ottawa, Ontario, K1N 6N5 (Canada); Lean, David, E-mail: drslean@gmail.com [P.O. Box 309, Apsley, Ontario, K0L 1A0 (Canada)
2011-02-15
temperature is 20 deg. C. With the onset of the wet season TGM increased from typical values near 10 to 905 ng m{sup -3}. Measurements made within 5 km of the Poas volcano were higher than at Heredia at that time. Diel values measured at University site increased until midday along with temperature and radiation. Relative humidity showed a reciprocal pattern. It was found that high values of TGM were not related to wind velocity or direction. The strong diel pattern increased with sunrise, peaked at midday and was lowest during the night time. It would seem that Hg{sup 0} from the volcano is oxidized and is deposited to the soils during the dry season when winds are blowing from the volcano. With the onset of heavy rains in April, Hg in the soil is reduced and re-volatilized resulting in the high levels in the atmosphere. Values at other volcano sites were provided. The role of atmospheric pollutants such as H{sub 2}O{sub 2} and O{sub 3} should be included in future studies as they may result in oxidation of reduced Hg. The instability in the air masses may also be a factor and local pollution sources may result in high levels that is emitted from the volcanoes of Hg being circulated to ground level as radiation intensity increases.
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Zhu, Shifa; Guo, Zhengjiang; Huang, Zhipeng; Jiang, Huanfeng
2014-02-24
A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0(2,7) ]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Specificity Responses of Grasshoppers in Temperate Grasslands to Diel Asymmetric Warming
Wu, Tingjuan; Hao, Shuguang; Sun, Osbert Jianxin; Kang, Le
2012-01-01
Background Global warming is characterized by not only an increase in the daily mean temperature, but also a diel asymmetric pattern. However, most of the current studies on climate change have only concerned with the mean values of the warming trend. Although many studies have been conducted concerning the responses of insects to climate change, studies that address the issue of diel asymmetric warming under field conditions are not found in the literature. Methodology/Principal Findings We conducted a field climate manipulative experiment and investigated developmental and demographic responses to diel asymmetric warming in three grasshopper species (an early-season species Dasyhippus barbipes, a mid-season species Oedaleus asiaticus, and a late-season species Chorthippus fallax). It was found that warming generally advanced the development of eggs and nymphs, but had no apparent impacts on the hatching rate of eggs, the emergence rate of nymphs and the survival and fecundity of adults in all the three species. Nighttime warming was more effective in advancing egg development than the daytime warming. The emergence time of adults was differentially advanced by warming in the three species; it was advanced by 5.64 days in C. fallax, 3.55 days in O. asiaticus, and 1.96 days in D. barbipes. This phenological advancement was associated with increases in the effective GDDs accumulation. Conclusions/Significance Results in this study indicate that the responses of the three grasshopper species to warming are influenced by several factors, including species traits, developmental stage, and the thermal sensitivity of the species. Moreover, species with diapausing eggs are less responsive to changes in temperature regimes, suggesting that development of diapausing eggs is a protective mechanism in early-season grasshopper for avoiding the risk of pre-winter hatching. Our results highlight the need to consider the complex relationships between climate change and
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Estudio dieléctrico del envejecimiento físico
Hernández, M. C; Suárez, N; Puma, M
2006-01-01
La influencia del envejecimiento físico en las propiedades dieléctricas de un poliarilato y un policarbonato derivados de la tirosina: Poli(DTH succinato) y poli(DTO carbonato) respectivamente, es estudiada utilizando la técnica de Corrientes de Polarización Estimuladas Térmicamente (TSPC). La caracterización dieléctrica, utilizando electrodos de bloqueo, permite estudiar el efecto de los cambios estructurales del material sobre las relajaciones asociadas con la redistribución de cargas debid...
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Sequential aminodiene Diels-Alder approach to the ergoline skeleton.
Padwa, Albert; Bur, Scott K; Zhang, Hongjun
2005-08-19
Through a novel sequence of aminodiene Diels-Alder reactions, several substituted amidofurans were readily converted to tricyclic ketones in good yield. The formation of the tricyclic ketone system is the result of a ring opening and dehydration of a transient oxabicyclic adduct formed by an intramolecular Diels-Alder cycloaddition of an amidofuran with a cyclohexenone moiety tethered such that it participates in the cycloaddition as the 2pi component. A convenient way to construct the cyclohexenone is to make use of some aminodiene chemistry developed by Rawal. An angular carbomethoxy group is required in order to activate the olefin toward cycloaddition with Rawal's diene. The presence of this activating group not only prevents the isomerization of the advanced ergoline intermediate to a naphthalene but can also be leveraged for an oxidation to provide Uhle's ketone (13). The easily formed Kornfeld ketone analogue 25 was readily transformed into the corresponding triflate 41 by the action of triflic anhydride and a base. Oxidative addition of vinyl triflate 41 to Pd(0) and the ability of the resulting vinyl palladium species to undergo cross-coupling with terminal alkynes prompted us to devise an expeditious route to lysergic acid. Unfortunately, our inability to carry out a regioselective Heck reaction using vinyl triflate 41 and the methylene amino acrylate ester 48 thwarted the completion of the synthesis of lysergic acid.
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Modeling Diel Oxygen Dynamics and Ecosystem Metabolism in a Shallow, Eutrophic Estuary
Weeks Bay is a shallow eutrophic estuary that exhibits frequent summertime diel-cycling hypoxia and periods of dissolved oxygen (DO) oversaturation during the day. Diel DO dynamics in shallow estuaries like Weeks Bay are complex, and may be influenced by wind forcing, vertical an...
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Staby, A; Rø stad, Anders; Kaartvedt, Stein
2011-01-01
. The data revealed known patterns as normal diel vertical migration (DVM), midnight sinking between dusk and dawn, and periods without migrations, as well as novel behaviours consisting of early morning ascents, reverse diel vertical migrations
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Antezana, Tarsicio
2009-12-01
A series of stratified bongo net samples taken over a 2 day period at ca. 18°S, about 20 nm off the coast of Peru, South America, suggest species-specific patterns of diel vertical migration into the Oxygen Minimum Zone (OMZ) of the Humboldt Current Ecosystem (HCE). The OMZ was the most dramatic feature of the water column and seemed to determine the extent of migration: Stylocheiron affine migrated only to the shallow oxycline; whereas Euphausia mucronata, Euphausia eximia, Euphausia distinguenda and Euphausia tenera migrated to the core of the OMZ; and Nematoscelis gracilis to beneath the core of the OMZ. Some differences were also found in the timing and duration of the ascent and descent, and residence times in shallow and deep layers. E. mucronata, N. gracilis and E. distinguenda displayed a normal descent during sunrise, and ascent during sunset. E. eximia and E. tenera also descended during sunrise but seemed to begin their ascent earlier in the afternoon and consequently shortened their deep residence times. S. affine showed the most extended residence times at the shallow layer and the shortest vertical displacement. Day and night vertical stratification and differences in the timing of migration into and out of the OMZ of the HCE suggest a community structure based on habitat partitioning whereby species avoided co-occurrence in time and space. Species-specific patterns of vertical stratification and migratory chronology are examined with regard to body and gill sizes, feeding adaptations of euphausiids, and potential food resources at the OMZ.
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The asymmetric hetero-Diels-Alder reaction in the syntheses of biologically relevant compounds.
Eschenbrenner-Lux, Vincent; Kumar, Kamal; Waldmann, Herbert
2014-10-13
The hetero-Diels-Alder reaction is one of the most powerful transformations in the chemistry toolbox for the synthesis of aza- and oxa-heterocycles embodying multiple stereogenic centers. However, as compared to other cycloadditions, in particular the dipolar cycloadditions and the Diels-Alder reaction, the hetero-Diels-Alder reaction has been much less explored and exploited in organic synthesis. Nevertheless, this powerful transformation has opened up efficient and creative routes to biologically relevant small molecules and different natural products which contain six-membered oxygen or nitrogen ring systems. Recent developments in this field, in particular in the establishment of enantioselectively catalyzed hetero-Diels-Alder cycloadditions steered by a plethora of different catalysts and the application of the resulting small molecules in chemical biology and medicinal chemistry research, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Reaction energetics on long-range corrected density functional theory: Diels-Alder reactions.
Singh, Raman K; Tsuneda, Takao
2013-02-15
The possibility of quantitative reaction analysis on the orbital energies of long-range corrected density functional theory (LC-DFT) is presented. First, we calculated the Diels-Alder reaction enthalpies that have been poorly given by conventional functionals including B3LYP functional. As a result, it is found that the long-range correction drastically improves the reaction enthalpies. The barrier height energies were also computed for these reactions. Consequently, we found that dispersion correlation correction is also crucial to give accurate barrier height energies. It is, therefore, concluded that both long-range exchange interactions and dispersion correlations are essentially required in conventional functionals to investigate Diels-Alder reactions quantitatively. After confirming that LC-DFT accurately reproduces the orbital energies of the reactant and product molecules of the Diels-Alder reactions, the global hardness responses, the halves of highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, along the intrinsic reaction coordinates of two Diels-Alder reactions were computed. We noticed that LC-DFT results satisfy the maximum hardness rule for overall reaction paths while conventional functionals violate this rule on the reaction pathways. Furthermore, our results also show that the HOMO-LUMO gap variations are close to the reaction enthalpies for these Diels-Alder reactions. Based on these results, we foresee quantitative reaction analysis on the orbital energies. Copyright © 2012 Wiley Periodicals, Inc.
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Physicochemical Properties and Fatty Acid Profiles of Elaeagnus mollis Diels Nut Oils.
Liang, Shaohua; Yang, Ruinan; Dong, Caiwen; Yang, Qingping
2015-01-01
The physicochemical properties, fatty acid profiles, content of tocopherol and sterol of the oils extracted from the nuts of Elaeagnus mollis Diels grown in different regions of China were studied in this work. The results indicated that the Elaeagnus mollis Diels nut oils contained about 0.2% sterols and the tocopherol contents were in the range of 119.6-128.6mg/100g. The nut oils were all rich in unsaturated fatty acids, especially oleic acid and linoleic acid. Furthermore, the main triacylglycerols species of the nut oils were all dilinoleoyl-monoolein (LOL), dioleoyl-monolinoleoyl (OLO) and trilinoleate (LLL). This work might be useful for developing applications for Elaeagnus mollis Diels nut oil.
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The first organocatalytic, ortho-regioselective inverse-electron-demand hetero-Diels-Alder reaction.
Hejmanowska, Joanna; Jasiński, Marcin; Wojciechowski, Jakub; Mlostoń, Grzegorz; Albrecht, Łukasz
2017-10-17
The development of the unprecedented ortho-regioselective inverse-electron-demand hetero-Diels-Alder (IEDHDA) reaction is described. It has been demonstrated that by proper choice of reactants and reaction conditions the inverse-electron-demand hetero-Diels-Alder cycloaddition can be realized with unprecedented regioselectivity arising from the reaction between the terminal carbon atom of the dienophile and the heteroatom of the heterodiene.
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Theoretical study of the Diels-Alder reaction between o-benzoquinone and norbornadiene
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.
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Theoretical study of the Diels-Alder reaction between o-benzoquinone and norbornadiene
International Nuclear Information System (INIS)
Quijano-Quiñones, Ramiro F; Quesadas-Rojas, M; Mena-Rejón, Gonzalo J; Cuevas, Gabriel
2013-01-01
The reaction between norbornadiene and o-benzoquinone is an important step in polyalicyclic rigid structures synthesis. It has been considered that this reaction is an example of Diels-Alder (DA) and hetero-Diels-Alder (HDA) cycloadditions with o-benzoquinone acting as diene (forming C-C bonds) and heterodiene (forming O-C bonds). We have performed a Density Functional Theory study of this reaction, employing B3LYP, mPW1PW91, and B1B95 functionals and 6-31G(d,p) and 6-31+G(d,p) Gaussian type basis sets. The results indicate that Diels-Alder is a feasible mechanism for both reactions, but should not be the main route to the formation of products with C-C bonds.
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Diel Variation in Beaked Whale Diving Behavior
National Research Council Canada - National Science Library
Baird, Robin; Webster, Daniel L; Schorr, Gregory S; McSweeney, Daniel J
2008-01-01
...) occurred at similar rates during the day and night for Blainville's beaked whales (daymean=0.38 h-1; nightmean=0.46 h-1), and there were no significant diel differences in depths, durations, ascent or descent rates for deep dives...
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Is it true that polymerization of vegetable oil occurs through Diels-Alder reaction?
Diels-Alder reaction mechanism is known to be one of the major reaction mechanisms to produce dimers and polymers during heating process of vegetable oil. However, our NMR study showed no evidence for Diels-Alder products. Soybean oil oxidized at 180 °C for 24 hrs with 1.45 surface area-to-volume ...
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The Diels-Alder cyclization of ketenimines.
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
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Ueno, Hiroshi; Kawakami, Hiroki; Nakagawa, Koji; Okada, Hiroshi; Ikuma, Naohiko; Aoyagi, Shinobu; Kokubo, Ken; Matsuo, Yutaka; Oshima, Takumi
2014-08-06
We studied the kinetics of the Diels-Alder reaction of Li(+)-encapsulated [60]fullerene with 1,3-cyclohexadiene and characterized the obtained product, [Li(+)@C60(C6H8)](PF6(-)). Compared with empty C60, Li(+)@C60 reacted 2400-fold faster at 303 K, a rate enhancement that corresponds to lowering the activation energy by 24.2 kJ mol(-1). The enhanced Diels-Alder reaction rate was well explained by DFT calculation at the M06-2X/6-31G(d) level of theory considering the reactant complex with dispersion corrections. The calculated activation energies for empty C60 and Li(+)@C60 (65.2 and 43.6 kJ mol(-1), respectively) agreed fairly well with the experimentally obtained values (67.4 and 44.0 kJ mol(-1), respectively). According to the calculation, the lowering of the transition state energy by Li(+) encapsulation was associated with stabilization of the reactant complex (by 14.1 kJ mol(-1)) and the [4 + 2] product (by 5.9 kJ mol(-1)) through favorable frontier molecular orbital interactions. The encapsulated Li(+) ion catalyzed the Diels-Alder reaction by lowering the LUMO of Li(+)@C60. This is the first detailed report on the kinetics of a Diels-Alder reaction catalyzed by an encapsulated Lewis acid catalyst rather than one coordinated to a heteroatom in the dienophile.
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New L-Serine Derivative Ligands as Cocatalysts for Diels-Alder Reaction
Sousa, Carlos A. D.; Rodríguez-Borges, José E.; Freire, Cristina
2013-01-01
New L-serine derivative ligands were prepared and tested as cocatalyst in the Diels-Alder reactions between cyclopentadiene (CPD) and methyl acrylate, in the presence of several Lewis acids. The catalytic potential of the in situ formed complexes was evaluated based on the reaction yield. Bidentate serine ligands showed good ability to coordinate medium strength Lewis acids, thus boosting their catalytic activity. The synthesis of the L-serine ligands proved to be highly efficient and straightforward. PMID:24383009
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The Diels-Alder reaction: A powerful tool for the design of drug delivery systems and biomaterials.
Gregoritza, Manuel; Brandl, Ferdinand P
2015-11-01
Click reactions have the potential to greatly facilitate the development of drug delivery systems and biomaterials. These reactions proceed under mild conditions, give high yields, and form only inoffensive by-products. The Diels-Alder cycloaddition is one of the click reactions that do not require any metal catalyst; it is one of the most useful reactions in synthetic organic chemistry and material design. Herein, we highlight possible applications of the Diels-Alder reaction in pharmaceutics and biomedical engineering. Particular focus is placed on the synthesis of polymers and dendrimers for drug delivery, the preparation of functionalized surfaces, bioconjugation techniques, and applications of the Diels-Alder reaction in nanotechnology. Moreover, applications of the reaction for the preparation of hydrogels for drug delivery and tissue engineering are reviewed. A general introduction to the Diels-Alder reaction is presented, along with a discussion of potential pitfalls and challenges. At the end of the article, we provide a set of tools that may facilitate the application of the Diels-Alder reaction to solve important pharmaceutical or biomedical problems. Copyright © 2015 Elsevier B.V. All rights reserved.
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Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu
2017-03-03
Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.
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Directory of Open Access Journals (Sweden)
Ronald N. Warrener
2000-12-01
Full Text Available Ab initio and DFT quantum chemical calculations have been applied to a study of the Diels-Alder reaction of o-benzoquinone as diene and norbornadiene as dienophile. Transition states for the different reactions are located and activation energies estimated. The prefered exo-À-facial selectivity and exo,endo-stereoselectivity exhibited in this cycloaddition are readily predicted using RHF/3-21G or higher levels of calculations. Differences between experimentally observed results and calculations may be explained by the postulation of a second, nonconcerted biradical mechanism leading to formation of hetero Diels-Alder products.
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von Haden, A.; Marin-Spiotta, E.; Jackson, R. D.; Kucharik, C. J.
2016-12-01
A high proportion of carbon lost from terrestrial ecosystems occurs via soil CO2 respiration. Soil respiration is comprised of two contrasting sources: heterotrophic respiration (RH) from the decomposition of organic matter and autotrophic respiration (RA) from plant root metabolism. Since the two sources of soil respiration vary widely in their origin, the controls of each source are also likely to differ. However, the challenge of partitioning soil respiration sources in situ has limited our mechanistic understanding of RH and RA. Our objective was to evaluate the in situ diurnal controls of RH and RA in maize (Zea mays L.) and switchgrass (Panicum virgatum L.) bioenergy cropping systems. We hypothesized that both RH and RA would follow diurnal soil temperature trends, but that RA would also respond to diel patterns of photosynthetically active radiation (PAR). We also expected that diurnal soil respiration patterns would vary significantly within the growing season. We evaluated our hypothesis with six diurnal soil respiration campaigns during the 2015 and 2016 growing seasons at Arlington, WI, USA. RH showed clear oscillating diel trends, typically peaking in the mid-afternoon when near-surface soil temperatures were highest. Diurnal RA patterns were more nuanced than RH, but were generally highest in the late afternoon and showed the most pronounced diel trends during peak growing season in July. RA also tended to spike in concert with PAR, but this effect was much more prominent in maize than switchgrass. Continuing efforts will attempt to quantitatively separate the effects of soil temperature and PAR on RA.
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Rund, Samuel S C; Yoo, Boyoung; Alam, Camille; Green, Taryn; Stephens, Melissa T; Zeng, Erliang; George, Gary F; Sheppard, Aaron D; Duffield, Giles E; Milenković, Tijana; Pfrender, Michael E
2016-08-18
Marine and freshwater zooplankton exhibit daily rhythmic patterns of behavior and physiology which may be regulated directly by the light:dark (LD) cycle and/or a molecular circadian clock. One of the best-studied zooplankton taxa, the freshwater crustacean Daphnia, has a 24 h diel vertical migration (DVM) behavior whereby the organism travels up and down through the water column daily. DVM plays a critical role in resource tracking and the behavioral avoidance of predators and damaging ultraviolet radiation. However, there is little information at the transcriptional level linking the expression patterns of genes to the rhythmic physiology/behavior of Daphnia. Here we analyzed genome-wide temporal transcriptional patterns from Daphnia pulex collected over a 44 h time period under a 12:12 LD cycle (diel) conditions using a cosine-fitting algorithm. We used a comprehensive network modeling and analysis approach to identify novel co-regulated rhythmic genes that have similar network topological properties and functional annotations as rhythmic genes identified by the cosine-fitting analyses. Furthermore, we used the network approach to predict with high accuracy novel gene-function associations, thus enhancing current functional annotations available for genes in this ecologically relevant model species. Our results reveal that genes in many functional groupings exhibit 24 h rhythms in their expression patterns under diel conditions. We highlight the rhythmic expression of immunity, oxidative detoxification, and sensory process genes. We discuss differences in the chronobiology of D. pulex from other well-characterized terrestrial arthropods. This research adds to a growing body of literature suggesting the genetic mechanisms governing rhythmicity in crustaceans may be divergent from other arthropod lineages including insects. Lastly, these results highlight the power of using a network analysis approach to identify differential gene expression and provide novel
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A dynamic optimization model of the diel vertical distribution of a pelagic planktivorous fish
Rosland, Rune; Giske, Jarl
A stochastic dynamic optimization model for the diel depth distribution of juveniles and adults of the mesopelagic planktivore Maurolicus muelleri (Gmelin) is developed and used for a winter situation. Observations from Masfjorden, western Norway, reveal differences in vertical distribution, growth and mortality between juveniles and adults in January. Juveniles stay within the upper 100m with high feeding rates, while adults stay within the 100-150m zone with very low feeding rates during the diel cycle. The difference in depth profitability is assumed to be caused by age-dependent processes, and are calculated from a mechanistic model for visual feeding. The environment is described as a set of habitats represented by discrete depth intervals along the vertical axis, differing with respect to light intensity, food abundance, predation risk and temperature. The short time interval (24h) allows fitness to be linearly related to growth (feeding), assuming that growth increases the future reproductive output of the fish. Optimal depth position is calculated from balancing feeding opportunity against mortality risk, where the fitness reward gained by feeding is weighted against the danger of being killed by a predator. A basic run is established, and the model is validated by comparing predictions and observations. The sensitivity for different parameter values is also tested. The modelled vertical distributions and feeding patterns of juvenile and adult fish correspond well with the observations, and the assumption of age differences in mortality-feeding trade-offs seems adequate to explain the different depth profitability of the two age groups. The results indicate a preference for crepuscular feeding activity of the juveniles, and the vertical distribution of zooplankton seems to be the most important environmental factor regulating the adult depth position during the winter months in Masfjorden.
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Fourfold Diels-Alder reaction of tetraethynylsilane.
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.
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Directory of Open Access Journals (Sweden)
Hongliang Bu
Full Text Available Understanding the interactions between species and their coexistence mechanisms will help explain biodiversity maintenance and enable managers to make sound conservation decisions. Mesocarnivores are abundant and diverse mid-sized carnivores and can have profound impacts on the function, structure and dynamics of ecosystem after the extirpation of apex predators in many ecosystems. The moist temperate forests of Southwest China harbor a diverse community of mesocarnivores in the absence of apex predators. Sympatric species tend to partition limited resources along time, diet and space to facilitate coexistence. We determined the spatial and temporal patterns for five species of mesocarnivores. We used detection histories from a large camera-trap dataset collected from 2004-2015 with an extensive effort of 23,313 camera-days from 495 camera locations. The five mesocarnivore species included masked palm civet Paguma larvata, leopard cat Prionailurus bengalensis, hog badger Arctonyx collaris, yellow-throated marten Martes flavigula, and Siberian weasel Mustela sibirica. Only the masked palm civet and hog badger tended to avoid each other; while for other pairs of species, they occurred independently of each other, or no clear pattern observed. With regard to seasonal activity, yellow-throated marten was most active in winter, opposite the pattern observed for masked palm civet, leopard cat and hog badger. For diel activity, masked palm civet, leopard cat and hog badger were primarily nocturnal and crepuscular; yellow-throated marten was diurnal, and Siberian weasel had no clear pattern for most of the year (March to November, but was nocturnal in the winter (December to February. The seasonal shift of the Siberian weasel may be due to the high diet overlap among species in winter. Our results provided new facts and insights into this unique community of mesocarnivores of southwest China, and will facilitate future studies on the mechanism
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Synthetic studies on taxanes: A domino-enyne metathesis/Diels ...
Indian Academy of Sciences (India)
Abstract. A domino enyne cross-metathesis/intramolecular Diels-Alder reaction has been successfully used to synthesize a bicyclo[5.3.1] undecene, corresponding to AB-ring of taxol without the gem dimethyl group.
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Modified lignin: Preparation and use in reversible gel via Diels-Alder reaction.
Zhou, Wanpeng; Zhang, Hui; Chen, Fangeng
2018-02-01
In this study, popular soda lignin was modified with either furan or maleimide ring, and the modified lignins were subjected to reversible Diels-Alder reaction. A new process was proposed to prepare the functionalized lignin. A long chain was introduced to the hydroxyl groups of lignin, and then either the furan or maleimide ring was added to the other end of the chain. The test results confirmed that either the furan ring or the maleimide ring was bound to lignin. Furan- and maleimide-functionalized lignins were also combined to generate crosslinking via Diels-Alder [4+2] cycloaddition reaction. Under appropriate conditions, the formation of a gel was identified, which reverted to liquid state after retro Diels-Alder reaction upon heating at 120°C. This study reveals the significant versatility and potential of the developed strategy for the utilization of lignin-based recyclable networks. Copyright © 2017 Elsevier B.V. All rights reserved.
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Diels-Alder cyclo-addition as an efficient tool for linking π-donors onto fullerene C60
International Nuclear Information System (INIS)
Hudhomme, P.
2006-01-01
Diels-Alder reaction of endo-cyclic, acyclic 1,3-dienes or (hetero) o-quinodimethanes with the dienophilic fullerene C 60 is presented as an efficient tool for linking electro-active units giving rise to systems where both the donor and C 60 partners take up well defined volumes and orientations with respect to one another. While porphyrin is the most frequently used electron donor in artificial photosynthetic models, C 60 -based tetrathiafulvalene (TTF) or p-conjugated oligomer adducts remain interesting candidates for the preparation of photovoltaic devices. In this account, we focus on the use of the Diels-Alder cyclo-addition and its use in the synthesis of TTF-C 60 dyads, (TTF) n -C 60 polyads and C 60 -TTF-C 60 dumbbells as part of ongoing research into materials which display efficient photo-induced electron transfer. (author)
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Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath
We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.
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Gorska, Natalia; Kowalska-Duda, Ewa; Pniewski, Filip; Latała, Adam
2018-06-01
The study has been motivated by the development of the hydroacoustic techniques for mapping and classifying the benthic habitats and for the research of the microbenthos photosynthesis in the semi-enclosed Baltic Sea, particularly sensitive to human activity. The investigation of the effect of the benthic microalgal photosynthesis on the echo signal from the Baltic sandy sediments is continuing. The study clarifies the impact of the abiotic and biotic factors on the diel variation of the backscattering caused by the benthic microalgal photosynthetic activity. Five multiday laboratory experiments, different in hydrophysical or biological conditions, were conducted. During each measurement series, the "day" (illumination) and "night" (darkness) conditions (L:D cycle) were simulated and the diel variations of the echo energy of the backscattered signal were analyzed. The hydroacoustic data were acquired along with measuring biological and biooptical parameters and oxygen concentration. The study demonstrated the impact of microphytobenthos photosynthesis on the backscattering properties of the marine sediment which is sensitive to the illumination level, benthic microalgal biomass and macrozoobenthos bioturbation.
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Nico, Leo G.
2010-01-01
Several Pterygoplichthys species, members of the Neotropical catfish family Loricariidae, have been widely introduced outside their native ranges. In this paper, I present observations on the diel activity pattern of non-native Pterygoplichthys, tentatively identified as P. disjunctivus, with respect to their attachment and grazing on endangered Florida manatees, Trichechus manatus latirostris. The study was conducted in December 2009 at Volusia Blue Spring, an artesianal spring system in the St. Johns River basin, Florida (USA). Supplemented by information gathered during previous visits to the spring site, this study revealed that adult Pterygoplichthys are active throughout the diel period (day, twilight and night). However, juvenile Pterygoplichthys were largely nocturnal and only at night did they consistently join adults in attaching to manatees. The juveniles generally remain hidden during the day, probably responding to presence of diurnal predators, mainly birds. Differences in diel behaviors among different Pterygoplichthys size classes in Florida are consistent with published observations on loricariids inhabiting clearwater streams within their native ranges.
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Directory of Open Access Journals (Sweden)
Leo G. Nico
Full Text Available Several Pterygoplichthys species, members of the Neotropical catfish family Loricariidae, have been widely introduced outside their native ranges. In this paper, I present observations on the diel activity pattern of non-native Pterygoplichthys, tentatively identified as P. disjunctivus, with respect to their attachment and grazing on endangered Florida manatees, Trichechus manatus latirostris. The study was conducted in December 2009 at Volusia Blue Spring, an artesianal spring system in the St. Johns River basin, Florida (USA. Supplemented by information gathered during previous visits to the spring site, this study revealed that adult Pterygoplichthys are active throughout the diel period (day, twilight and night. However, juvenile Pterygoplichthys were largely nocturnal and only at night did they consistently join adults in attaching to manatees. The juveniles generally remain hidden during the day, probably responding to presence of diurnal predators, mainly birds. Differences in diel behaviors among different Pterygoplichthys size classes in Florida are consistent with published observations on loricariids inhabiting clearwater streams within their native ranges.
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AFSC/ABL: Gulf of Alaska Diel Trawl Survey, 2005-2006
National Oceanic and Atmospheric Administration, Department of Commerce — Diel epipelagic sampling for juvenile Pacific salmon (Oncorhynchus spp.), rockfish (Sebastes spp.), sablefish (Anoplopoma fimbria), and associated species was...
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Siadati, Seyyed Amir; Nami, Navabeh
2016-10-01
C20 fullerene, this novel species with all its pentagonal faces has displayed some unique operations in making fast pericyclic reactions. As an example, the high dienophile character of the C20 fullerene and the ability of this species in making an ultra-fast Diels-Alder reaction with 1,3-butadiene, has been recently reported. Moreover, new experimental reports claim that the C60 fullerene, one of the fullerene family, could make a Diels-Alder reaction with the central ring of anthracene and make the ring non-aromatic. These reports may encourage researchers to do more studies on the properties of this small carbon cage. To address this question, the present research has discussed all the reaction channels of the Diels-Alder cycloaddition of benzene molecule as a 1,3-diene with the C20 fullerene in order to answer this question: ;Is C20fullerene able to make a Diels-Alder reaction with this molecule?;.
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Directory of Open Access Journals (Sweden)
Lucy Satiko Hashimoto Soares
1999-03-01
Full Text Available The diet and diel feeding pattern of the skate Raja agassizii were investigated through analysis of stomach contents. A total of 280 stomachs were collected by a series of hauls during a daily cycle in three periods, 8-10 January 1987, 22-24 July and 2-4 December 1988, from the inner continental shelf of the coastal ecosystem of Ubatuba, São Paulo State, Brazil (25º35'S; 45º00'W. According to the results of the stomach fullness and of the number of fresh prey, it is suggested that this species presents continuity in the feeding activity during a day. The stomach contents were mainly composed of crustaceans. Nematodes, polychaetes and fishes also occurred. No changes were observed in dietary composition between day and night.
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Quinones as dienophiles in the Diels-Alder reaction: history and applications in total synthesis.
Nawrat, Christopher C; Moody, Christopher J
2014-02-17
In the canon of reactions available to the organic chemist engaged in total synthesis, the Diels-Alder reaction is among the most powerful and well understood. Its ability to rapidly generate molecular complexity through the simultaneous formation of two carbon-carbon bonds is almost unrivalled, and this is reflected in the great number of reported applications of this reaction. Historically, the use of quinones as dienophiles is highly significant, being the very first example investigated by Diels and Alder. Herein, we review the application of the Diels-Alder reaction of quinones in the total synthesis of natural products. The highlighted examples span some 60 years from the landmark syntheses of morphine (1952) and reserpine (1956) by Gates and Woodward, respectively, through to the present day examples, such as the tetracyclines. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Kay, R.T.; Groschen, G.E.; Cygan, G.; Dupre, David H.
2011-01-01
Diel variations in the concentrations of a number of constituents have the potential to substantially affect the appropriate sampling regimen in acidic streams. Samples taken once during the course of the day cannot adequately reflect diel variations in water quality and may result in an inaccurate understanding of biogeochemical processes, ecological conditions, and of the threat posed by the water to human health and the associated wildlife. Surface water and groundwater affected by acid drainage were sampled every 60 to 90. min over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, near Hegeler, Illinois. Diel variations related to water quality in the aquifer were not observed in groundwater. Diel variations were observed in the temperature, pH, and concentration of dissolved oxygen, nitrite, barium, iron, lead, vanadium, and possibly uranium in surface water. Temperature, dissolved oxygen, nitrite, barium, lead, and uranium generally attained maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally attained minimum values during the afternoon and maximum values during the night. Concentrations of dissolved oxygen were affected by the intensity of photosynthetic activity and respiration, which are dependent upon insolation. Nitrite, an intermediary in many nitrogen reactions, may have been formed by the oxidation of ammonium by dissolved oxygen and converted to other nitrogen species as part of the decomposition of organic matter. The timing of the pH cycles was distinctly different from the cycles found in Midwestern alkaline streams and likely was the result of the photoreduction of Fe3+ to Fe 2+ and variations in the intensity of precipitation of hydrous ferric oxide minerals. Diel cycles of iron and vanadium also were primarily the result of variations in the intensity of precipitation of hydrous ferric oxide minerals. The diel variation in the concentrations of lead, uranium
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Directory of Open Access Journals (Sweden)
A. C. Ion
2005-01-01
Full Text Available In the present study, we examined PM2.5 continental rural background aerosols, which were collected during a summer field campaign at K-puszta, Hungary (4 June-10 July 2003, a mixed coniferous/deciduous forest site characterized by intense solar radiation during summer. Emphasis was placed on polar oxygenated organic compounds that provide information on aerosol sources and source processes. The major components detected at significant atmospheric concentrations were: (a photo-oxidation products of isoprene including the 2-methyltetrols (2-methylthreitol and 2-methylerythritol and 2-methylglyceric acid, (b levoglucosan, a marker for biomass burning, (c malic acid, an intermediate in the oxidation of unsaturated fatty acids, and (d the sugar alcohols, arabitol and mannitol, markers for fungal spores. Diel patterns with highest concentrations during day-time were observed for the 2-methyltetrols, which can be regarded as supporting evidence for their fast photochemical formation from locally emitted isoprene. In addition, a diel pattern with highest concentrations during day-time was observed for the fungal markers, suggesting that the release of fungal fragments that are associated with the PM2.5 aerosol is enhanced during that time. Furthermore, a diel pattern was also found for levoglucosan with the highest concentrations at night when wood burning may take place in the settlements around the sampling site. In contrast, malic acid did not show day/night differences but was found to follow quite closely the particulate and organic carbon mass. This is interpreted as an indication that malic acid is formed in photochemical reactions which have a much longer overall time-scale than that of isoprene photo-oxidation, and the sources of its precursors are manifold, including both anthropogenic and natural emissions. On the basis of the high concentrations found for the isoprene oxidation products during day-time, it can be concluded that rapid photo
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Directory of Open Access Journals (Sweden)
Fernanda Michalski
2011-12-01
Full Text Available Understanding what influences the activity of organisms is important for both ecological understanding and species conservation. Using data from 2,707 camera trap days distributed across 24 forest sites, we present quantitative analyses of the activity pattern of Cuniculus paca (Linnaeus, 1766 in southern Amazonia. We compared the activity pattern of this species across four designated subsets of the 24-hours diel cycle (dawn, dusk, day and night. Using linear regression models we tested the influence of season, temperature and rainfall on the activity patterns of C. paca (paca. We also evaluated the nocturnal photos of paca (N = 111 as a function of the degree of lunar illumination in order to test the prediction that pacas minimize their activity during moon phase when illumination is brighter. Pacas were not recorded during the day but were active at dawn, dusk and night time. We found differences in the influence of the abiotic variables on the nocturnal activity of pacas in the study area. There was no significant difference between the observed (expressed as the frequency of total counts of independent photos over the five classes of lunar illumination and the expected activity of pacas, based on the frequency of days in the lunar cycle with different classes of lunar illumination, whereas lunar illumination had a weak negative influence on the timing of paca activity (i.e. pacas were active closer to sunset with increasing lunar illumination. However, the timing of nocturnal activity in pacas was not influenced by season, temperature or rainfall. Our findings highlight the ecological plasticity of this Neotropical rodent which has a key function in the maintenance of Neotropical forests.
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Catalytic Asymmetric Total Synthesis of (+)- and (-)-Paeoveitol via a Hetero-Diels-Alder Reaction.
Li, Tian-Ze; Geng, Chang-An; Yin, Xiu-Juan; Yang, Tong-Hua; Chen, Xing-Long; Huang, Xiao-Yan; Ma, Yun-Bao; Zhang, Xue-Mei; Chen, Ji-Jun
2017-02-03
The first catalytic asymmetric total synthesis of (+)- and (-)-paeoveitol has been accomplished in 42% overall yield via a biomimetic hetero-Diels-Alder reaction. The chiral phosphoric acid catalyzed hetero-Diels-Alder reaction showed excellent diastereo- and enantioselectivity (>99:1 dr and 90% ee); two rings and three stereocenters were constructed in a single step to produce (-)-paeoveitol on a scale of 452 mg. This strategy enabled us to selectively synthesize both paeoveitol enantiomers from the same substrates by simply changing the enantiomer of the catalyst.
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Directory of Open Access Journals (Sweden)
C. Teixeira
1991-01-01
Full Text Available A series of experiments with natural phytoplankton populations was carried out to study the diel variation of chlrophyll a, primary production and some environmental factors. Samples were collected from surface over a period of 24 hours and always from one fixed station located in Flamengo Inlet, Ubatuba region, southern Brazil The experiments were performed in situ and simulated conditions to verify the patterns of diel cycles of both biotic and abiotic factors. The results obtained showed that diel variations were markedly pronounced mainly in relation to primary production and chlorophyll a. Diel variations of biological factors seems to be due to exogenous and endogenous phenomena.
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Interpreting diel hysteresis between soil respiration and temperature
C. Phillips; N. Nickerson; D. Risk; B.J. Bond
2011-01-01
Increasing use of automated soil respiration chambers in recent years has demonstrated complex diel relationships between soil respiration and temperature that are not apparent from less frequent measurements. Soil surface flux is often lagged from soil temperature by several hours, which results in semielliptical hysteresis loops when surface flux is plotted as a...
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Vegetation induced diel signal and its meaning in recharge and discharge regions
Gribovszki, Zoltán; Tóth, Tibor; Csáfordi, Péter; Szabó, András; Móricz, Norbert; Kalicz, Péter
2017-04-01
Afforestation, promoted by the European Union is planned in Hungary in the next decades. One of the most important region for afforestation is the Hungarian Great Plain where the precipitation is far below potential ET so forests can not survive without significant water uptake from shallow groundwater. Diel fluctuations of hydrological variables (e.g., soil moisture, shallow groundwater level, streamflow rate) are rarely investigated in the hydrologic literature although these short-term fluctuations may incorporate useful information (like groundwater uptake) about hydro-ecological systems in shallow groundwater areas. Vegetation induced diel fluctuations are rarely compared under varying hydrologic conditions (such as recharge and discharge zones). In this study, the data of soil moisture and shallow groundwater monitoring under different surface covers (forest and neighboring agricultural plots) in discharge and recharge regions were analyzed to gain a better understanding of the vegetation hydrological impact or water uptake in changing climate. The pilot areas of the study are located in Hungarian Great Plain and in Western Hungary. The water table under the forest displayed a typical night-time recovery in the discharge region, indicating a significant groundwater supply. Certainly, the root system of the forest was able to tap the groundwater in depths measuring a few metres, while the shallower roots of the herbaceous vegetation generally did not reach the groundwater reservoir at these depths. In the recharge zone the water table under the forest showed step-like diel pattern that refer to a lack of additional groundwater supply from below. The low groundwater evapotranspiration of the forest in the recharge zone was due to the lack of the groundwater supply in the recharge area. Similar patterns can be detected in the soil moisture of recharge and discharge zones as well. Our results suggest that local estimations of groundwater evapotranspiration from
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Directory of Open Access Journals (Sweden)
J. Antonio Palenzuela
2007-02-01
Full Text Available A route for the preparation of 2,5-disubstituted octahydroquinolin-4-ones, synthetic precursors of the decahydroquinoline-type toxins, is presented. The key steps are an asymmetric epoxidation and an intramolecular hetero Diels-Alder reaction between an activated diene and an imine. The presence of an allylic stereogenic center induces some selectivity and thus only two cycloadducts are obtained in 70:30 ratio and good yield.
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Intramolecular inverse electron demand Diels-Alder reactions of pyrimidines
Frissen, A.E.
1990-01-01
This thesis deals with the intramolecular inverse electron demand Diels-Alder reaction of pyrimidines. The main objective of the study was to investigate the synthetic applicability of this reaction and to get more insight in the electronic and steric effects which determine the reactivity
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Diel feeding rhythm of copepod size-fractions from Coliumo Bay, Central Chile
Directory of Open Access Journals (Sweden)
Danilo Calliari
2001-12-01
Full Text Available The feeding behaviour of the size fractionated copepod assemblage was studied over a diel cycle in Coliumo Bay. In this shallow environment the photic layer reached the bottom and salinity, temperature, and food availability were fairly homogeneous throughout the water column. All four size-fractions (250-500 ?m, 500-1000 ?m, 1000-2000 ?m, >2000 ?m showed a period of high feeding activity during the night and low feeding activity during the day. The persistence of nocturnal feeding in the presence of high food concentration over the 24-h cycle is interpreted as a predator avoidance strategy: empty guts by day make copepods less conspicuous to their visual daytime predators.
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Pessanha, André Luiz Machado; Araújo, Francisco Gerson
2003-08-01
Fish assemblages from two beaches, one in the inner and the other in the outer Sepetiba Bay (latitude: 22°54'-23°04'S; longitude: 43°34'-44°10'W), Southeast Brazil, were sampled by beach seine net, simultaneously, on both seasonal and diel scales, between August 1998 and June 1999. Sites were selected to encompass different environmental conditions which reflect the two bay zones, thus providing a comprehensive assessment of the factors influencing surf zone fish assemblages, and their spatial, seasonal and diel variations. A total of 55 fish species was recorded, mostly young-of-the-year. Anchoa tricolor, Micropogonias furnieri, Gerres aprion, Diapterus rhombeus, Harengula clupeola, Atherinella brasiliensis and Mugil liza were numerically dominant and contributed to 95.2% of the total fish catches. Strong differences in fish assemblages were observed between the two areas, with higher number of species in the outer bay. Increases in fish numbers occurred in winter, while the highest biomass occurred in winter and summer. Transparency, followed by salinity, was responsible for most of the spatial variability and played an important role in structuring fish assemblages. Overall, diel patterns did not reveal any significant trends; however, if we consider each season separately, an increase in fish numbers during the day with peak at sunset was observed in winter, and a higher biomass occurred at night in winter and summer. Species preferences for various combinations of environmental variables are responsible for shifts in the structure and overall abundance of assemblages and dictated some patterns. The sciaenid M. furnieri, the second most abundant species, occurred only in the inner zone, being more abundant in winter. The species of Engraulidae were more abundant in the outer zone in winter/spring during the day. The gerreids G. aprion and D. rhombeus occurred mainly in summer. Overall, temporal fluctuations act more at a specific level than at a structural
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High stereoselectivity on low temperature Diels-Alder reactions
Directory of Open Access Journals (Sweden)
Invernize Paulo
2005-12-01
Full Text Available Abstract We have found that some of the usually poor dienophiles (2-cycloenones can undergo Diels-Alder reaction at -78°C with unusually high stereoselectivity in the presence of niobium pentachloride as a Lewis acid catalyst. A remarkable difference in reaction rates for unsubstituted and α- or β-methyl substituted 2-cycloenones was also observed.
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Niobium(V) chloride as catalyst in Diels-Alder reaction of furan ring
International Nuclear Information System (INIS)
Santos, Deborah A. dos; Rodrigues, Ludmila R.; Arpini, Bruno H.; Lacerda Junior, Valdemar; Greco, Sandro J.; Santos, Reginaldo B. dos; Neto, Alvaro C.; Castro, Eustaquio V.R. de
2014-01-01
According to the relevant literature, the Diels-Alder reaction of furan without a catalyst can last several weeks and shows a low yield due to the diene’s low reactivity. The use of Lewis acid catalysts or high pressures is described as an effective method for improving the reaction yields. This paper describes our recent study on the use of niobium pentachloride as the catalyst in Diels-Alder reactions between furan and several reactive dienophiles, among which methyl acrylate showed good yields, especially at lower temperatures. Other dienophiles have shown lower yields because of problems such as byproduct formation and the high reversibility of the reaction. (author)
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Niobium(V) chloride as catalyst in Diels-Alder reaction of furan ring
Energy Technology Data Exchange (ETDEWEB)
Santos, Deborah A. dos; Rodrigues, Ludmila R.; Arpini, Bruno H.; Lacerda Junior, Valdemar; Greco, Sandro J.; Santos, Reginaldo B. dos; Neto, Alvaro C.; Castro, Eustaquio V.R. de, E-mail: vljuniorqui@gmail.com [Universidade Federal do Espirito Santo (UFES), Vitoria, ES (Brazil). Dept. de Quimica; Romao, Wanderson [Instituto Federal de Educacao, Ciencia e Tecnologia (IFES), Vila Velha, ES (Brazil)
2014-05-15
According to the relevant literature, the Diels-Alder reaction of furan without a catalyst can last several weeks and shows a low yield due to the diene’s low reactivity. The use of Lewis acid catalysts or high pressures is described as an effective method for improving the reaction yields. This paper describes our recent study on the use of niobium pentachloride as the catalyst in Diels-Alder reactions between furan and several reactive dienophiles, among which methyl acrylate showed good yields, especially at lower temperatures. Other dienophiles have shown lower yields because of problems such as byproduct formation and the high reversibility of the reaction. (author)
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DFT studies for the substituent effect on the diels-alder reaction of 1,4-diaza-1,3-butadienes
International Nuclear Information System (INIS)
Lee, Gab Yong
2001-01-01
DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4-DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular orbital) energies for the optimized 1,4-disubstituted-1,4DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively
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Magnetic Field Fluctuations Due to Diel Vertical Migrations of Zooplankton
Dean, C.; Soloviev, A.
2016-12-01
Dean et al. (2016) have indicated that at high zooplankton concentrations, diel vertical migrations (DVM) cause velocity fluctuations and a respective increase of the dissipation rate of turbulent kinetic energy (TKE). In this work, we used a 3D non-hydrostatic computational fluid dynamics model with Lagrangian particle injections (a proxy for migrating organisms) via a discrete phase model to simulate the effect of turbulence generation by DVM. We tested a range of organism concentrations from 1000 to 10,000 organisms/m3. The simulation at an extreme concentration of zooplankton showed an increase in dissipation rate of TKE by two to three orders of magnitude during DVM over background turbulence, 10-8 W kg-1. At lower concentrations (Frank, J. Wood, 2016: Biomixing due to diel vertical migrations of zooplankton. Ocean Modelling 98, 51-64.
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Nocturnality in synapsids predates the origin of mammals by over 100 million years
Angielczyk, K. D.; Schmitz, L.
2014-01-01
Nocturnality is widespread among extant mammals and often considered the ancestral behavioural pattern for all mammals. However, mammals are nested within a larger clade, Synapsida, and non-mammalian synapsids comprise a rich phylogenetic, morphological and ecological diversity. Even though non-mammalian synapsids potentially could elucidate the early evolution of diel activity patterns and enrich the understanding of synapsid palaeobiology, data on their diel activity are currently unavailab...
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A Tri-O-Bridged Diels-Alder Adduct from Cortex Mori Radicis
Directory of Open Access Journals (Sweden)
An-Qi Lu
2018-01-01
Full Text Available Sanggenon X, an unusual tri-O-bridged Diels-Alder adduct, was isolated from Cortex Mori Radicis. Its structure was established by spectroscopic analysis, including NMR and HR-MS (High Resolution Mass Spectrometry. Sanggenon X contained three O-bridged rings, where the oxygenated bridgeheads were all quaternary carbons. Chemical methylation was carried out to deduce the linkages of the three O-bridges. The absolute configuration was determined by calculating the ECD (Electronic Circular Dichroism using the TDDFT (Time-Dependent Density Functional Theory method. Sanggenon X showed significant antioxidant activity against Fe2+-Cys-induced lipid peroxidation in rat liver microsomes, and was as effective as the positive control, curcumin.
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Unsaturated aldehydes as alkene equivalents in the Diels-Alder reaction
DEFF Research Database (Denmark)
Taarning, Esben; Madsen, Robert
2008-01-01
A one-pot procedure is described for using alpha,beta-unsaturated aldehydes as olefin equivalents in the Diels-Alder reaction. The method combines the normal electron demand cycloaddition with aldehyde dienophiles and the rhodium-catalyzed decarbonylation of aldehydes to afford cyclohexenes...
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Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.
Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji
2015-04-07
The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Intramolecular Diels-Alder Reactions in Organic Synthesis
Sizemore, Nicholas Blandford Luke
2014-01-01
Intramolecular Diels-Alder (IMDA) reactions are an important class of reactions in synthetic organic chemistry for the rapid construction of polycyclic frameworks. Three classes of IMDA reactions were investigated synthetically and computationally: 1) all-carbon type 1 IMDA reactions, 2) N-acylnitroso type 2 IMDA reactions, and 3) cyano-azadiene IMDA reactions. The first class was implemented in research toward the total synthesis of maoecrystal Z and isopalhinine A. The second class was stud...
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Johnson, James H.; McKenna, James E.
2015-01-01
Interspecific partitioning of food and habitat resources has been widely studied in stream salmonids. Most studies have examined resource partitioning between two native species or between a native species and one that has been introduced. In this study we examine the diel feeding ecology and habitat use of three species of juvenile salmonids (i.e., Atlantic Salmon Salmo salar, Brown Trout Salmo trutta, and Rainbow Trout Oncorhynchus mykiss) in a tributary of Skaneateles Lake, New York. Subyearling Brown Trout and Rainbow Trout fed more heavily from the drift than the benthos, whereas subyearling Atlantic Salmon fed more from the benthos than either species of trout. Feeding activity of Atlantic Salmon and Rainbow Trout was similar, with both species increasing feeding at dusk, whereas Brown Trout had no discernable feeding peak or trough. Habitat availability was important in determining site-specific habitat use by juvenile salmonids. Habitat selection was greater during the day than at night. The intrastream, diel, intraspecific, and interspecific variation we observed in salmonid habitat use in Grout Brook illustrates the difficulty of acquiring habitat use information for widespread management applications.
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Nocturnality in synapsids predates the origin of mammals by over 100 million years.
Angielczyk, K D; Schmitz, L
2014-10-22
Nocturnality is widespread among extant mammals and often considered the ancestral behavioural pattern for all mammals. However, mammals are nested within a larger clade, Synapsida, and non-mammalian synapsids comprise a rich phylogenetic, morphological and ecological diversity. Even though non-mammalian synapsids potentially could elucidate the early evolution of diel activity patterns and enrich the understanding of synapsid palaeobiology, data on their diel activity are currently unavailable. Using scleral ring and orbit dimensions, we demonstrate that nocturnal activity was not an innovation unique to mammals but a character that appeared much earlier in synapsid history, possibly several times independently. The 24 Carboniferous to Jurassic non-mammalian synapsid species in our sample featured eye morphologies consistent with all major diel activity patterns, with examples of nocturnality as old as the Late Carboniferous (ca 300 Ma). Carnivores such as Sphenacodon ferox and Dimetrodon milleri, but also the herbivorous cynodont Tritylodon longaevus were likely nocturnal, whereas most of the anomodont herbivores are reconstructed as diurnal. Recognizing the complexity of diel activity patterns in non-mammalian synapsids is an important step towards a more nuanced picture of the evolutionary history of behaviour in the synapsid clade. © 2014 The Author(s) Published by the Royal Society. All rights reserved.
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Scholl, Katie; Dillashaw, John; Timpy, Evan; Lam, Yu-Hong; DeRatt, Lindsey; Benton, Tyler R; Powell, Jacqueline P; Houk, Kendall N; Morgan, Jeremy B
2018-05-01
Diels-Alder reactions of tethered vinyl-metal species offer the opportunity to fashion highly functionalized diol intermediates for synthesis. We have developed the first enantioselective boron-tethered Diels-Alder reaction using quinine as a chiral promoter. Quinine recovery, enantioselectivity enhancement, and manipulation of the cyclohexene core are also investigated. DFT modeling calculations confirm the role of quinine as a bidentate ligand enhancing reaction rates. The enantioselectivity of the cycloaddition is proposed to originate from a boron-centered anomeric effect.
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Hadjichristidis, Nikolaos
2015-05-26
A novel strategy towards well-defined polymethylene-based co/terpolymers, by combining anthracene/maleimide Diels-Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: a) synthesis of α-anthracene-ω-hydroxy- polymethylene by polyhomologation using tri (9-anthracene-methyl propyl ether) borane as initiator, b) synthesis of furan-protected-maleimide-terminated poly (ε-caprolactone) or polyethylene glycol and c). Diels-Alder reaction between the anthracene and maleimide-terminated polymers. In the case of triblock terpolymers the α-anthracene-ω-hydroxy-polymethylene was used as macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by Diels-Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. All intermediate and final products were characterized by SEC, 1H NMR, UV-VIS spectroscopy and DSC.
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Total Synthesis of (+)-Cytosporolide A via a Biomimetic Hetero-Diels-Alder Reaction.
Takao, Ken-Ichi; Noguchi, Shuji; Sakamoto, Shu; Kimura, Mizuki; Yoshida, Keisuke; Tadano, Kin-Ichi
2015-12-23
The first total synthesis of (+)-cytosporolide A was achieved by a biomimetic hetero-Diels-Alder reaction of (-)-fuscoatrol A with o-quinone methide generated from (+)-CJ-12,373. The dienophile, highly oxygenated caryophyllene sesquiterpenoid (-)-fuscoatrol A, was synthesized from the synthetic intermediate in our previous total synthesis of (+)-pestalotiopsin A. The o-quinone methide precursor, isochroman carboxylic acid (+)-CJ-12,373, was synthesized through a Kolbe-Schmitt reaction and an oxa-Pictet-Spengler reaction. The hetero-Diels-Alder reaction of these two compounds proceeded with complete chemo-, regio-, and stereoselectivity to produce the complicated pentacyclic ring system of the cytosporolide skeleton. This total synthesis unambiguously demonstrates that natural cytosporolide A has the structure previously suggested.
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Wang, Ben; Zha, Tian Shan; Jia, Xin; Gong, Jin Nan; Bourque, Charles; Feng, Wei; Tian, Yun; Wu, Bin; Qing Zhang, Yu; Peltola, Heli
2017-09-01
Explanations for the occurrence of hysteresis (asynchronicity) between diel soil respiration (Rs) and soil temperature (Ts) have evoked both biological and physical mechanisms. The specifics of these explanations, however, tend to vary with the particular ecosystem or biome being investigated. So far, the relative degree of control of biological and physical processes on hysteresis is not clear for drylands. This study examined the seasonal variation in diel hysteresis and its biological control in a desert-shrub ecosystem in northwest (NW) China. The study was based on continuous measurements of Rs, air temperature (Ta), temperature at the soil surface and below (Tsurf and Ts), volumetric soil water content (SWC), and photosynthesis in a dominant desert shrub (i.e., Artemisia ordosica) over an entire year in 2013. Trends in diel Rs were observed to vary with SWC over the growing season (April to October). Diel variations in Rs were more closely associated with variations in Tsurf than with photosynthesis as SWC increased, leading to Rs being in phase with Tsurf, particularly when SWC > 0.08 m3 m-3 (ratio of SWC to soil porosity = 0.26). However, as SWC decreased below 0.08 m3 m-3, diel variations in Rs were more closely related to variations in photosynthesis, leading to pronounced hysteresis between Rs and Tsurf. Incorporating photosynthesis into a Q10-function eliminated 84.2 % of the observed hysteresis, increasing the overall descriptive capability of the function. Our findings highlight a high degree of control by photosynthesis and SWC in regulating seasonal variation in diel hysteresis between Rs and temperature.
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Synthesis of a Phlorin from a Meso-Fused Anthriporphyrin by a Diels-Alder Strategy.
Aslam, Adil S; Hong, Jung-Ho; Shin, June-Ho; Cho, Dong-Gyu
2017-12-18
An anthracene-containing meso-fused carbaporphyrin, which has extended π-conjugation pathways as compared to the corresponding naphthalene-containing carbaporphyrin, has been synthesized. The weak global aromaticity of the anthriporphyrin also allowed its use as the diene for a Diels-Alder reaction with dimethyl acetylenedicarboxylate (DMAD). The resulting phlorin contains an interesting bicyclic structure. Moreover, to the best of our knowledge, this phlorin is the first Diels-Alder adduct of a diene forming part of the global π-conjugation pathway of an aromatic porphyrinoid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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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.
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Thermally reversible rubber-toughened thermoset networks via Diels-Alder chemistry
Araya-Hermosilla, R.; Fortunato, G.; Pucci, A.; Raffa, P.; Polgar, L.; Broekhuis, A. A.; Pourhossein, P.; Lima, G. M. R.; Beljaars, M.; Picchioni, F.
In this work we present a reversible and toughened thermoset system based on the covalent incorporation of a furane functionalized ethylene-propylene rubber (EPM-Fu) into a thermoset furane functionalized polyketone (PK-Fu) via Diels-Alder (DA) reversible cross-linking with bismaleimide (b-MA).
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Stowe, G. Neil
2010-01-01
Conducting reactions using water as solvent is a highly prized goal for the organic chemist. Based upon recent literature and our continuing interest in the field of aqueous organocatalysis, we tested the scope of an enamine based Diels-Alder reaction using (±)-nornicotine, proline and a proline derivative as aqueous organocatalysts. Unfortunately, none of the examined catalysts under aqueous conditions proved useful, leaving the aqueous Diels-Alder reaction as an elusive goal. PMID:21516231
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Loke, Inga; Bentzinger, Guillaume; Holz, Julia; Raja, Aruna; Bhasin, Aman; Sasse, Florenz; Köhn, Andreas; Schobert, Rainer; Laschat, Sabine
2016-01-21
In order to construct the functionalized AB ring system of clifednamide, member of the class of macrocyclic tetramic acid lactams, a synthesis was developed which utilized an Ireland-Claisen rearrangement and an intramolecular Diels-Alder reaction. Starting from di-O-isopropylidene-d-mannitol the allyl carboxylate precursor for the sigmatropic rearrangement was prepared. This rearrangement proceeded diastereoselectively only in the presence of an allyl silyl ether instead of the parent enone in the side chain, as suggested by deuteration experiments. A subsequent Diels-Alder reaction yielded the target ethyl hexahydro-1H-indene-carboxylate with high diastereoselectivity. Quantum-chemical investigations of this intramolecular Diels-Alder reaction support the proposed configuration of the final product.
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Diel and Lunar Variations in Larval Fish Supply in Malindi Marine ...
African Journals Online (AJOL)
2Department of Fisheries and Aquatic Sciences, University of Eldoret, PO Box 1125, Eldoret, Kenya; ... in fish larval occurrence was thus studied in Malindi Marine Park, Kenya, to assess diel and lunar ..... New South Wales University Press,.
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Brasca, Romina; Kneeteman, María N.; Mancini, Pedro M. E.; Fabian, Walter M. F.
2012-02-01
In this work we studied the capability of several diene/dienophile pairs to undergo Diels-Alder (DA) reactions leading to benzo[b]thiophenes. A variety of synthetically and commercially available nitrothiophenes were chosen as dienophiles. Methyl 5-nitro-3-thiophenecarboxylate was selected as a potential strong electrophilic candidate based on some DFT-based properties and the substitution pattern of the expected product. The mechanistic details concerning the participation of this dienophile in polar DA reactions were investigated through a theoretical point of view. The results were compared with the experimental outcomes. This methodology should allow synthetic chemists to analyze DA reactions in detail in a stage prior to the synthetic job.
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Kaicharla, Trinadh; Bhojgude, Sachin Suresh; Biju, Akkattu T
2012-12-21
A new protocol for the efficient Diels-Alder reaction of 1,2-benzoquinones with arynes is reported. The aryne generated by the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates undergoes a facile Diels-Alder reaction with 1,2-benzoquinones, affording the dioxobenzobicyclooctadienes in moderate to excellent yields. In addition, this methodology has been applied to the one-pot synthesis of benzoquinoxalinobarrelene and naphthalene derivatives.
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Diel cycle of iron, aluminum and other heavy metals in a volcano watershed in northern Taiwan
Kao, S.
2013-12-01
It is well known that heavy metals in surface water show diel (24-hr) changes in concentrations due to diel biogeochemical cycle. Accordingly, it is important to have a better sampling policy for monitoring the environmental impact of heavy metals of surface water, especially volcanic and mining areas. This study investigated Tatun Volcano watershed in northern Taiwan with a 24-h sampling operation to explore the diel cycle of arsenic concentrations and discuss on the corresponding biogeochemical processes. According to the previous studies, solar energy is the main factor of diel cycles, which could have strong effects on temperature, pH, dissolved oxygen, and many other water qualities. These changes produce a series of chain reactions and finally result in the change of heavy metal concentrations. In general, diel cycle of dissolved oxygen is dominated by metabolism of aquatic plants and sunlight photoreduction in acidic stream water; therefore, the Fe and Al contents would be accordingly changed. In addition, the concentrations of heavy metals will be simultaneously modified due to the high adsorption capacity of Fe and Al hydroxides. In this study, the results of hydro chemical analysis show that creek water is characterized by higher temperature, low pH value (3.0-4.5) and high SO4content(60-400 ppm) due to the mixing of hot spring. That the pH dramatically drops in the noon demonstrates that pH is highly dependent on photoreduction. This can be confirmed by the opposite trend of Fe concentration. The high Fe content in the noon also demonstrates that the precipitation of Fe hydroxides is not dominant in the day time and Fe is mainly in dissolved and/or colloid forms. Under the situation, heavy metals are supposed to have a similar trend with Fe. However, arsenic, aluminum and rare earth elements show a quite different diel cycle from Fe and other heavy metals. It concludes that arsenic and rare earth elements may be adsorbed by Al hydroxides instead of Fe
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Saavedra, Diana I; Rencher, Benjamin D; Kwon, Doo-Hyun; Smith, Stacey J; Ess, Daniel H; Andrus, Merritt B
2018-02-16
Deoxypodophyllotoxin is a secondary metabolite lignan possessing potent anticancer activity with potential as a precursor for known anticancer drugs, but its use is limited by scarcity from natural sources. We here report the total synthesis of racemic deoxypodophyllotoxin in seven steps using an intramolecular styryl Diels-Alder reaction strategy uniquely suited to assemble the deoxypodophyllotoxin core. Density functional theory was used to analyze concerted, polar, and singlet-open-shell diradical reaction pathways, which identified a low-energy concerted [4 + 2] Diels-Alder pathway followed by a faster di-t-butylhydroxytoluene assisted [1,3]-formal hydrogen shift.
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Diels-Alder reactions of anthracenes with C-sulfonyldithioformates
DEFF Research Database (Denmark)
El-Sayed, I.; Ali, O.M.; Fischer, A.
2003-01-01
C-Sulfonyldithioformates (2) (R-1 = ArSO2, R 2 = ArS) readily add to anthracene and 9-methylanthracene (1) in a Diels-Alder fashion with formation of 9,10-dihydro-10,9-(epithiomethano)anthracenes (3) which in turn may suffer thermally induced elimination of arenesulfinic acid to yield the 9......-anthracenedithiocarboxylic esters (4). The reactions with the unsymmetrical diene 9-methylanthracene take place in a highly stereoselective fashion....
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Jayakumar, Samydurai; Louven, Kathrin; Strohmann, Carsten; Kumar, Kamal
2017-12-11
The active complexes of chiral N,N'-dioxide ligands with dysprosium and magnesium salts catalyze the hetero-Diels-Alder reaction between 2-aza-3-silyloxy-butadienes and alkylidene oxindoles to selectively form 3,3'- and 3,4'-piperidinoyl spirooxindoles, respectively, in very high yields and with excellent enantioselectivities. The exo-selective asymmetric cycloaddition successfully regaled the construction of sp 3 -rich and highly substituted natural-product-based spirooxindoles supporting many chiral centers, including contiguous all-carbon quaternary centers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Chapin, T.P.; Nimick, D.A.; Gammons, C.H.; Wanty, R.B.
2007-01-01
Recent work has demonstrated that many trace metals undergo dramatic diel (24-h) cycles in near neutral pH streams with metal concentrations reproducibly changing up to 500% during the diel period (Nimick et al., 2003). To examine diel zinc cycles in streams affected by acid rock drainage, we have developed a novel instrument, the Zn-DigiScan, to continuously monitor in situ zinc concentrations in near real-time. Initial results from a 3-day deployment at Fisher Creek, Montana have demonstrated the ability of the Zn-DigiScan to record diel Zn cycling at levels below 100 ??g/l. Longer deployments of this instrument could be used to examine the effects of episodic events such as rainstorms and snowmelt pulses on zinc loading in streams affected by acid rock drainage. ?? Springer Science+Business Media B.V. 2006.
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Carosso, Serena; Miller, Marvin J.
2014-01-01
This review describes the use of nitroso Diels-Alder reactions for the functionalization of complex diene-containing natural products in order to generate libraries of compounds with potential biological activity. The application of this methodology to the structural modification of a series of natural products (thebaine, steroidal dienes, rapamycin, leucomycin, colchicine, isocolchicine and piperine) is discussed using relevant examples from the literature from 1973 onwards. The biological activity of the resulting compounds is also discussed. Additional comments are provided that evaluate the methodology as a useful tool in organic, bioorganic and medicinal chemistry. PMID:25119424
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Hooper, Joel F; James, Natalie C; Bozkurt, Esra; Aviyente, Viktorya; White, Jonathan M; Holland, Mareike C; Gilmour, Ryan; Holmes, Andrew B; Houk, K N
2015-12-18
The intramolecular Diels-Alder reaction has been used as a powerful method to access the tricyclic core of the eunicellin natural products from a number of 9-membered-ring precursors. The endo/exo selectivity of this reaction can be controlled through a remarkable organocatalytic approach, employing MacMillan's imidazolidinone catalysts, although the mechanistic origin of this selectivity remains unclear. We present a combined experimental and density functional theory investigation, providing insight into the effects of medium-ring constraints on the organocatalyzed intramolecular Diels-Alder reaction to form the isobenzofuran core of the eunicellins.
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Li, Yang; Barløse, Casper; Jørgensen, Julie; Carlsen, Bjørn Dreiø; Jørgensen, Karl Anker
2017-01-01
An asymmetric catalytic aza-Diels-Alder/ring-closing cascade reaction between acylhydrazones and in situ formed trienamines is presented. The reaction proceeds through a formal aza-Diels-Alder cycloaddition, followed by a ring-closing reaction forming the hemiaminal ring leading to chiral bicyclic azaheterocycles in moderate to good yield (up to 71 %), good enantio- (up to 92 % ee) and diastereoselectivity (up to >20:1 d.r.). Furthermore, transformations are presented to show the potential application of the formed product. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Computational design of a Diels-Alderase from a thermophilic esterase: the importance of dynamics
Linder, Mats; Johansson, Adam Johannes; Olsson, Tjelvar S. G.; Liebeschuetz, John; Brinck, Tore
2012-09-01
A novel computational Diels-Alderase design, based on a relatively rare form of carboxylesterase from Geobacillus stearothermophilus, is presented and theoretically evaluated. The structure was found by mining the PDB for a suitable oxyanion hole-containing structure, followed by a combinatorial approach to find suitable substrates and rational mutations. Four lead designs were selected and thoroughly modeled to obtain realistic estimates of substrate binding and prearrangement. Molecular dynamics simulations and DFT calculations were used to optimize and estimate binding affinity and activation energies. A large quantum chemical model was used to capture the salient interactions in the crucial transition state (TS). Our quantitative estimation of kinetic parameters was validated against four experimentally characterized Diels-Alderases with good results. The final designs in this work are predicted to have rate enhancements of ≈103-106 and high predicted proficiencies. This work emphasizes the importance of considering protein dynamics in the design approach, and provides a quantitative estimate of the how the TS stabilization observed in most de novo and redesigned enzymes is decreased compared to a minimal, `ideal' model. The presented design is highly interesting for further optimization and applications since it is based on a thermophilic enzyme ( T opt = 70 °C).
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Recent applications of intramolecular Diels-Alder reactions to natural product synthesis
DEFF Research Database (Denmark)
Juhl, M.; Tanner, David Ackland
2009-01-01
This tutorial review presents some recent examples of intramolecular Diels-Alder (IMDA) reactions as key complexity-generating steps in the total synthesis of structurally intricate natural products. The opportunities afforded by transannular (TADA) versions of the IMDA reaction in complex molecu...... comprehensive, reviews....
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Diels-Alder reactions in water : Enforced hydrophobic interaction and hydrogen bonding
Engberts, Jan B.F.N.
1995-01-01
Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of
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DIELS-ALDER REACTIONS IN WATER - ENFORCED HYDROPHOBIC INTERACTION AND HYDROGEN-BONDING
Engberts, J.B.F.N.
Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of
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Czech Academy of Sciences Publication Activity Database
Muška, Milan; Tušer, Michal; Frouzová, Jaroslava; Draštík, Vladislav; Čech, Martin; Jůza, Tomáš; Kratochvíl, Michal; Mrkvička, T.; Peterka, Jiří; Prchalová, Marie; Říha, Milan; Vašek, Mojmír; Kubečka, Jan
2013-01-01
Roč. 707, č. 1 (2013), s. 17-28 ISSN 0018-8158. [Česká ichtyologická konference /13./. Červená nad Vltavou, 24.10.2012-26.10.2012] R&D Projects: GA MZe(CZ) QH81046; GA MŠk(CZ) EE2.3.20.0204 Institutional support: RVO:60077344 Keywords : diel activity * diurnal migration * individual decision making * horizontal hydroacoustics * purse seining * cyprinids Subject RIV: EH - Ecology, Behaviour Impact factor: 2.212, year: 2013
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Flores-Conde, Maria Ines; Reyes, Leonor; Herrera, Rafael; Rios, Hulme; Vazquez, Miguel A.; Miranda, Rene; Tamariz, Joaquin; Delgado, Francisco
2012-01-01
Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17), under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO) calculations. PMID:22489113
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Directory of Open Access Journals (Sweden)
Francisco Delgado
2012-02-01
Full Text Available Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17, under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO calculations.
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Diel and seasonal variation in food habits of Atlantic salmon parr in a small stream
Grader, M.; Letcher, B.H.
2006-01-01
The diel and seasonal food habits of young-of-year (YOY) and post-young-of-year (PYOY) Atlantic salmon (Salmo salar) parr were assayed over the course of 11 months in the West Brook, Massachusetts USA. Gut fullness of YOY salmon did not vary significantly among months. PYOY salmon exhibited significant seasonal differences in gut fullness, with peak fullness occurring in the spring and late fall. Significant diel differences in PYOY gut fullness occurred in June and April, with peak fullness always occurring at dawn. Prey composition varied substantially among months. Dominant prey items of PYOY salmon were baetid mayflies in June, July, and August, limnephilid caddisflies in October and November, and ephemerellid mayflies in February and April. Few differences in prey composition between PYOY and YOY salmon were observed. Fish growth was unrelated to prey availability, but gut fullness explained up to 97% of growth variation across seasons. Results suggest that spring and fall are critical periods of feeding for PYOY salmon and that diel feeding intensity shifts seasonally.
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Directory of Open Access Journals (Sweden)
Andrew J Temple
Full Text Available Understanding temporal patterns in distribution, occurrence and behaviour is vital for the effective conservation of cetaceans. This study used cetacean click detectors (C-PODs to investigate spatial and temporal variation in occurrence and foraging activity of the Indo-Pacific bottlenose (Tursiops aduncus and Indian Ocean humpback (Sousa plumbea dolphins resident in the Menai Bay Conservation Area (MBCA, Zanzibar, Tanzania. Occurrence was measured using detection positive minutes. Inter-click intervals were used to identify terminal buzz vocalisations, allowing for analysis of foraging activity. Data were analysed in relation to spatial (location and temporal (monsoon season, diel phase and tidal phase variables. Results showed significantly increased occurrence and foraging activity of dolphins in southern areas and during hours of darkness. Higher occurrence at night was not explained by diel variation in echolocation rate and so were considered representative of occurrence patterns. Both tidal phase and monsoon season influenced occurrence but results varied among sites, with no general patterns found. Foraging activity was greatest during hours of darkness, High water and Flood tidal phases. Comparisons of echolocation data among sites suggested differences in the broadband click spectra of MBCA dolphins, possibly indicative of species differences. These dolphin populations are threatened by unsustainable fisheries bycatch and tourism activities. The spatial and temporal patterns identified in this study have implications for future conservation and management actions with regards to these two threats. Further, the results indicate future potential for using passive acoustics to identify and monitor the occurrence of these two species in areas where they co-exist.
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Lewis acid catalysis of a Diels-Alder reaction in water
Otto, S; Bertoncin, F; Engberts, JBFN
1996-01-01
Here we report the first detailed study of a Diels-Alder (DA) reaction that is catalyzed by Lewis acids in water. The effect of Co2+, Ni2+, Cu2+ and Zn2+ ions as Lewis acid catalysts on the rate and endo-exo selectivity of the DA reaction between the bidentate dienophiles
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Directory of Open Access Journals (Sweden)
Zhitao Wang
Full Text Available Information on the habitat use of the critically endangered Yangtze finless porpoise (Neophocaena asiaeorientalis asiaeorientalis is critical for its conservation. The diel biosonar behavior of the porpoise in the port areas of the Yangtze River was examined along with simultaneous observations of fish density and boat traffic. Biosonar pulses from the porpoises were detected for 1233 min (5.77% over a 21,380 min duration of effective observations. In total, 190 (5.63% buzzes (an indication of prey capture attempts were recorded among the 3372 identified click trains. Of the 168 echolocation encounters (bouts of click trains less than eight min apart, 150 (89.3% involved single animals, indicating that solitary porpoises were frequently present and feeding in the port areas. Significant diel patterns were evident involving the biosonar behavior of the porpoises (including click trains and buzzes, fish density and boat traffic. The frequencies of the click trains and buzzes were significantly lower during the day than in the evening and at night, which suggests that porpoises in this region are primarily engaged in crepuscular and nocturnal foraging. The lack of a significant diel pattern in the echolocation encounters indicates the importance of the port in porpoise conservation. A forced feeding schedule may be associated with the lack of a significant correlation between porpoise acoustics and boat traffic. Overall, prey availability appears to be the primary factor that attracts porpoises. Additionally, porpoises tend to migrate or remain downstream in the morning and migrate or remain upstream in the evening, most likely to follow their prey. The findings of this study can be used to improve the conservation of the Yangtze finless porpoise.
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Bentley, Kale T; Schindler, Daniel E; Cline, Timothy J; Armstrong, Jonathan B; Macias, Daniel; Ciepiela, Lindsy R; Hilborn, Ray
2014-11-01
Daily movements of mobile organisms between habitats in response to changing trade-offs between predation risk and foraging gains are well established; however, less in known about whether similar tactics are used during reproduction, a time period when many organisms are particularly vulnerable to predators. We investigated the reproductive behaviour of adult sockeye salmon (Oncorhynchus nerka) and the activity of their principal predator, brown bears (Ursus arctos), on streams in south-western Alaska. Specifically, we continuously monitored movements of salmon between lake habitat, where salmon are invulnerable to bears, and three small streams, where salmon spawn and are highly vulnerable to bears. We conducted our study across 2 years that offered a distinct contrast in bear activity and predation rates. Diel movements by adult sockeye salmon between stream and lake habitat were observed in 51.3% ± 17.7% (mean ± SD) of individuals among years and sites. Fish that moved tended to hold in the lake for most of the day and then migrated into spawning streams during the night, coincident with when bear activity on streams tended to be lowest. Additionally, cyclic movements between lakes and spawning streams were concentrated earlier in the spawning season. Individuals that exhibited diel movements had longer average reproductive life spans than those who made only one directed movement into a stream. However, the relative effect was dependent on the timing of bear predation, which varied between years. When predation pressure primarily occurred early in the spawning run (i.e., during the height of the diel movements), movers lived 120-310% longer than non-movers. If predation pressure was concentrated later in the spawning run (i.e. when most movements had ceased), movers only lived 10-60% longer. Our results suggest a dynamic trade-off in reproductive strategies of sockeye salmon; adults must be in the stream to reproduce, but must also avoid predation long
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Micellar Catalysis of Diels-Alder Reactions : Substrate Positioning in the Micelle
Rispens, Theo; Engberts, Jan B.F.N.
2002-01-01
We have studied the kinetics of the Diels-Alder reactions of cyclopentadiene, sorbyl alcohol, and sorbyltrimethylammonium bromide with a series of N-substituted maleimides in micellar media. Micellar rate constants have been determined and were found to be 20-40 times lower than the respective
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New Insights into the Diels-Alder Reaction of Graphene Oxide.
Brisebois, Patrick P; Kuss, Christian; Schougaard, Steen B; Izquierdo, Ricardo; Siaj, Mohamed
2016-04-18
Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Diel Variations in Optical Properties of Micromonas pusilla, a Prasinophyte
DuRand, Michele D.; Green, Rebecca E.; Sosik, Heidi M.; Olson, Robert J.
2001-01-01
A laboratory experiment was conducted on cultures of Micromonas pusilla, a marine prasinophyte, to investigate how cell growth and division affect the optical properties over the light:dark cycle. Measurements were made of cell size and concentration, attenuation and absorption coefficients, flow cytometric light scattering (in forward and side directions), chlorophyll and carbon content. Refractive index was calculated using the anomalous diffraction approximation Cells were about 1.5 micrometers in diameter and exhibited phased division, with the major division burst occurring during the night. Typical diel variations were observed, with cells increasing in size and light scattering during the day as they photosynthesize and decreasing at night upon division. The cells were in ultradian growth, with more than one division per day, at a light level of 120 Mu-mol photons m/sq/sec. Since these cells are similar in size to small phytoplankton that are typically abundant in field samples, these results can be used in the interpretation of diel variations in light scattering in natural populations of phytoplankton.
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Diels-Alder cycloaddition strategy for kinetic resolution of chiral pyrazolidinones.
Sibi, Mukund P; Kawashima, Keisuke; Stanley, Levi M
2009-09-03
A rare example of the application of a catalytic, enantioselective Diels-Alder cycloaddition to affect a kinetic resolution has been developed. Chiral pyrazolidinones are resolved with high selectivity through a process that utilizes a relay of stereochemical information from a permanent chiral center to a fluxional chiral center to enhance the inherent selectivity of the chiral Lewis acid catalyst.
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Metal-catalyzed Asymmetric Hetero-Diels-Alder Reactions of Unactivated Dienes with Glyoxylates
DEFF Research Database (Denmark)
Johannsen, Mogens; Yao, Sulan; Graven, Anette
1998-01-01
The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo...
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Synthesis of 3-Alkenyl-1-azaanthraquinones via Diels-Alder and Electron Transfer Reactions
Directory of Open Access Journals (Sweden)
Patrice Vanelle
2002-12-01
Full Text Available A convenient route to 3-alkenyl-1-azaanthraquinones via a hetero Diels-Alder reaction between an azadiene and naphthoquinone, a free radical chlorination and an electron transfer reaction is reported.
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Palmer, David R. J.
2004-01-01
The Diels-Alder reaction is used as an example for showing the integration of computational and preparative techniques, which help in demonstrating the physical organic concepts in synthetic organic chemistry. These experiments show that the students should not accept the computational results without questioning them and in many Diels-Alder…
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Nimick, D.A.; Harper, D.D.; Farag, A.M.; Cleasby, T.E.; MacConnell, Elizabeth; Skaar, D.
2007-01-01
Extrapolating results of laboratory bioassays to streams is difficult, because conditions such as temperature and dissolved metal concentrations can change substantially on diel time scales. Field bioassays conducted for 96 h in two mining-affected streams compared the survival of hatchery-raised, metal-nai??ve westslope cutthroat trout (Oncorhynchus clarki lewisi) exposed to dissolved (0.1-??m filtration) metal concentrations that either exhibited the diel variation observed in streams or were controlled at a constant value. Cadmium and Zn concentrations in these streams increased each night by as much as 61 and 125%, respectively, and decreased a corresponding amount the next day, whereas Cu did not display a diel concentration cycle. In High Ore Creek (40 km south of Helena, MT, USA), survival (33%) after exposure to natural diel-fluctuating Zn concentrations (range, 214-634 ??g/L; mean, 428 ??g/L) was significantly (p = 0.008) higher than survival (14%) after exposure to a controlled, constant Zn concentration (422 ??g/L). Similarly, in Dry Fork Belt Creek (70 km southeast of Great Falls, MT, USA), survival (75%) after exposure to diel-fluctuating Zn concentrations (range, 266-522 ??g/L; mean, 399 ??g/L) was significantly (p = 0.022) higher than survival (50%) in the constant-concentration treatment (392 ??g/L). Survival likely was greater in these diel treatments, both because the periods of lower metal concentrations provided some relief for the fish and because toxicity during periods of higher metal concentrations was lessened by the simultaneous occurrence each night of lower water temperatures, which reduce the rate of metal uptake. Based on the present study, current water-quality criteria appear to be protective for streams with diel concentration cycles of Zn (and, perhaps, Cd) for the hydrologie conditions tested. ?? 2007 SETAC.
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Directory of Open Access Journals (Sweden)
Felicia Megumi Ito
2009-09-01
Full Text Available The present study aimed to evaluate the ability for biotransformation of the Diels-Alder adduct tricyclo[6.2.1.0(2,7]undeca-4,9-dien-3,6-dione (1 and two synthetic derivatives by the saprobe fungus Mucor ramosissimus Samutsevitsch. Products from oxidation, isomerization and, regioselective and enantioselective reduction were achieved.Neste trabalho avaliou-se a capacidade de biotransformação do aduto de Diels-Alder triciclo[6.2.1.0(2-7]undeca-4,9-dien-3,6-diona (1 e dois derivados sintéticos pelo fungo sapróbio Mucor ramosissimus Samutsevitsch. Produtos de oxidação, isomerização e redução regiosseletiva e enantiosseletiva foram obtidos.
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New 30-Noroleanane Triterpenoid Saponins from Holboellia coriacea Diels
Directory of Open Access Journals (Sweden)
Wenbing Ding
2016-06-01
Full Text Available Three new 30-noroleanane triterpenoid saponins, akebonoic acid 28-O-β-d-glucopyranosyl-(1′′→6′-β-d-glucopyranosyl ester (1, akebonoic acid 28-O-(6′′-O-caffeoyl-β-d-glucopyranosyl-(1′′→6′-β-d-glucopyranosyl ester (Holboelliside A, 2 and 3β,20α,24-trihydroxy-29-norolean-12-en-28-oic acid 3-O-(6′-O-caffeoyl-β-d-glucopyranoside (Holboelliside B, 3 were isolated from the stems of Holboellia coriacea Diels, together with five known compounds, eupteleasaponin VIII (4, 3α-akebonoic acid (5, quinatic acid (6, 3β-hydroxy-30-norhederagenin (7 and quinatoside A (8. The structures of these compounds were determined on the basis of spectral and chemical evidence. Compounds 1–5 were evaluated for their inhibitory activity against three human tumors HepG2, HCT116 and SGC-7901 cell lines in vitro.
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Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine
2015-09-23
Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.
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Comportamiento dieléctrico de compuestos epoxi/aluminio/BaTiO3
Directory of Open Access Journals (Sweden)
Castro, M. S.
2009-06-01
Full Text Available In order to improve the dielectric behaviour of epoxi/BaTiO3, in this work the influence of micrometric aluminum metal flakes (Al, on the dielectric properties of epoxy / BaTiO3 composites was studied. Epoxy resin, Al and BaTiO3 were mixed using an ultrasonic mixer and composites were deposited onto glass substrates by dipping technique. Obtained materials presented good dielectric properties at room temperature, and relaxation process appeared due to the resin behaviour. Obtained results were compared with those reported in literature for similar systems.Con el objetivo de mejorar el comportamiento dieléctrico de los compuestos epoxi/BaTiO3, en este trabajo se estudió la influencia de partículas metálicas de aluminio (Al, con forma de escamas y tamaño micrométrico, sobre las propiedades dieléctricas de sistemas epoxi / BaTiO3. El material compuesto fue obtenido por la técnica de inmersión o “dipping”. La mezcla de los componentes fue llevado a cabo en mezclador ultrasónica y la deposición se realizó sobre sustratos de vidrio. Los materiales obtenidos presentaron buenas propiedades dieléctricas a temperatura ambiente, sin alcanzar el límite de percolación, y los fenómenos de relajación fueron generados por los dominios de la resina. Los valores obtenidos fueron comparados con los reportados en la bibliografía para sistemas similares.
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Sekita, Hiroko; Adachi, Kyohei; Kobayashi, Ippei; Sato, Yusuke; Nakada, Masahisa
2017-05-05
An enantio- and stereoselective construction of the atisane scaffold via organocatalytic intramolecular Michael reaction and Diels-Alder reaction is described. The organocatalytic intramolecular Michael reaction has been found to stereoselectively generate a trans-stereodiad comprising an all-carbon quaternary and a tertiary stereogenic centers. Use of the chiral secondary amine bearing thiourea with benzoic acid as additive is the key to obtaining the desired product with excellent ee in synthetically acceptable yield. The prepared chiral building block has been successfully converted to the compound including the atisane scaffold via the highly stereoselective intramolecular Diels-Alder reaction.
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Moeckel, Claudia; Gasic, Bojan; MacLeod, Matthew; Scheringer, Martin; Jones, Kevin C; Hungerbühler, Konrad
2010-06-01
Diel (24-h) concentration variations of polybrominated diphenyl ethers (PBDEs) in air were measured in the center of Zurich, Switzerland, and on Uetliberg, a hill about 5 km from the city center. Air samples were collected simultaneously at both sites over 4 h time periods for 3 consecutive days during a stable high pressure system in August 2007. Higher PBDE concentrations in the city compared to the Uetliberg site indicate that Zurich is a likely source of PBDEs to the atmosphere. A multimedia mass balance model was used to (i) explain the diel cycling pattern of PBDE concentrations observed at both sites in terms of dominant processes and (ii) estimate emission rates of PBDEs from the city to the atmosphere. We estimate that Zurich emits 0.4, 6.2, 1.6, and 0.4 kg year(-1) of the PBDE congeners 28, 47, 99, and 100, respectively. On a per-capita basis, these estimates are within the range or somewhat above those obtained in other studies using approaches based on emission factors (EF) and PBDE production, usage, and disposal data, or concentration measurements. The present approach complements emission estimates based on the EF approach and can also be applied to source areas where EFs and PBDE material flows are poorly characterized or unknown, such as electronic waste processing plants.
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Using chiral ionic liquid additives to enhance asymmetric induction in a Diels-Alder reaction.
Goodrich, P; Nimal Gunaratne, H Q; Hall, L; Wang, Y; Jin, L; Muldoon, M J; Ribeiro, A P C; Pombeiro, A J L; Pârvulescu, V I; Davey, P; Hardacre, C
2017-01-31
A bis-oxazoline ligand has been complexed using Cu(ii) and Zn(ii) trifluoromethanesulfonate and a range of chiral ionic liquid (CIL) additives based on natural products were used as a co-catalyst for a Diels-Alder reaction. The catalytic performance of these systems was compared for the asymmetric Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene with and without the presence of a CIL additive. In the absence of the CIL, both catalysts resulted in low enantioselectivities in conventional solvents and ionic liquids. However, whilst only a minor effect of the CIL was observed for the Cu based catalyst, in the case of the Zn based catalyst, significant enhancements in endo enantioselectivity of up to 50% were found on the addition of a CIL.
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Linking Activity and Function to Ecosystem Dynamics in a Coastal Bacterioplankton Community
Directory of Open Access Journals (Sweden)
Scott Michael Gifford
2014-04-01
Full Text Available For bacterial communities containing hundreds to thousands of distinct populations, connecting functional processes and environmental dynamics at high taxonomic resolution has remained challenging. Here we use the expression of ribosomal proteins (%RP as a proxy for in situ activity of 200 taxa within 20 metatranscriptomic samples in a coastal ocean time series encompassing both seasonal variability and diel dynamics. %RP patterns grouped the taxa into seven activity clusters with distinct profiles in functional gene expression and correlations with environmental gradients. Clusters 1-3 had their highest potential activity in the winter and fall, and included some of the most active taxa, while Clusters 4-7 had their highest potential activity in the spring and summer. Cluster 1 taxa were characterized by gene expression for motility and complex carbohydrate degradation (dominated by Gammaproteobacteria and Bacteroidetes, and Cluster 2 taxa by transcription of genes for amino acid and aromatic compound metabolism and aerobic anoxygenic phototrophy (Roseobacter. Other activity clusters were enriched in transcripts for proteorhodopsin and methylotrophy (Cluster 4; SAR11 and methylotrophs, photosynthesis and attachment (Clusters 5 and 7; Synechococcus, picoeukaryotes, Verucomicrobia, and Planctomycetes, and sulfur oxidation (Cluster 7; Gammaproteobacteria. The seasonal patterns in activity were overlain, and sometimes obscured, by large differences in %RP over shorter day-night timescales. Seventy-eight taxa, many of them heterotrophs, had a higher %RP activity index during the day than night, indicating strong diel activity at this coastal site. Emerging from these taxonomically- and time-resolved estimates of in situ microbial activity are predictions of specific ecological groupings of microbial taxa in a dynamic coastal environment.
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Weng, Chia-Hao; Hsu, Day-Shin; Liao, Chun-Chen
2016-11-18
Total syntheses of ent-penicillones A (ent-1) and B (ent-2) from 3,5-dimethylcatechol (3) were accomplished in 10 and 9 synthetic steps, respectively. A carbohydrate-templated asymmetric intramolecular Diels-Alder reaction of a masked o-benzoquinone (MOB) 9 and an aqueous acid-catalyzed intramolecular aldol reaction are the key synthetic steps. In addition, the absolute configurations of the bicyclo[2.2.2]oct-5-en-2-one core obtained from the per-O-benzylated α-d-glucopyranosyl as a carbohydrate template in the intramolecular Diels-Alder reaction of MOBs were revised.
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Pfeifer, Johannes; Mielewczik, Michael; Friedli, Michael; Kirchgessner, Norbert; Walter, Achim
2018-01-01
Present-day high-resolution leaf growth measurements provide exciting insights into diel (24-h) leaf growth rhythms and their control by the circadian clock, which match photosynthesis with oscillating environmental conditions. However, these methods are based on measurements of leaf area or elongation and neglect diel changes of leaf thickness. In contrast, the influence of various environmental stress factors to which leaves are exposed to during growth on the final leaf thickness has been studied extensively. Yet, these studies cannot elucidate how variation in leaf area and thickness are simultaneously regulated and influenced on smaller time scales. Only few methods are available to measure the thickness of young, growing leaves non-destructively. Therefore, we evaluated X-ray computed tomography to simultaneously and non-invasively record diel changes and growth of leaf thickness and area. Using conventional imaging and X-ray computed tomography leaf area, thickness and volume growth of young soybean leaves were simultaneously and non-destructively monitored at three cardinal time points during night and day for a period of 80 h under non-stressful growth conditions. Reference thickness measurements on paperboards were in good agreement to CT measurements. Comparison of CT with leaf mass data further proved the consistency of our method. Exploratory analysis showed that measurements were accurate enough for recording and analyzing relative diel changes of leaf thickness, which were considerably different to those of leaf area. Relative growth rates of leaf area were consistently positive and highest during 'nights', while diel changes in thickness fluctuated more and were temporarily negative, particularly during 'evenings'. The method is suitable for non-invasive, accurate monitoring of diel variation in leaf volume. Moreover, our results indicate that diel rhythms of leaf area and thickness show some similarity but are not tightly coupled. These
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Li, Yingzi; Osuna, Sílvia; Garcia-Borràs, Marc; Qi, Xiaotian; Liu, Song; Houk, Kendall N; Lan, Yu
2016-08-26
Diels-Alder cycloaddition is one of the most powerful tools for the functionalization of single-walled carbon nanotubes (SWCNTs). Density functional theory at the B3-LYP level of theory has been used to investigate the reactivity of different-diameter SWCNTs (4-9,5) in Diels-Alder reactions with 1,3-butadiene; the reactivity was found to decrease with increasing SWCNT diameter. Distortion/interaction analysis along the whole reaction pathway was found to be a better way to explore the reactivity of this type of reaction. The difference in interaction energy along the reaction pathway is larger than that of the corresponding distortion energy. However, the distortion energy plots for these reactions show the same trend. Therefore, the formation of the transition state can be determined from the interaction energy. A lower interaction energy leads to an earlier transition state, which indicates a lower activation energy. The computational results also indicate that the original distortion of the SWCNTs leads to an increase in the reactivity of the SWCNTs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Boersma, A.J.; Feringa, B.L.; Roelfes, G.
2007-01-01
alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic
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Mechanistic Insight into the Dehydro-Diels-Alder Reaction of Styrene-Ynes.
Kocsis, Laura S; Kagalwala, Husain N; Mutto, Sharlene; Godugu, Bhaskar; Bernhard, Stefan; Tantillo, Dean J; Brummond, Kay M
2015-12-04
The Diels-Alder reaction represents one of the most thoroughly studied and well-understood synthetic transformations for the assembly of six-membered rings. Although intramolecular dehydro-Diels-Alder (IMDDA) reactions have previously been employed for the preparation of naphthalene and dihydronaphthalene substrates, low yields and product mixtures have reduced the impact and scope of this reaction. Through the mechanistic studies described within, we have confirmed that the thermal IMDDA reaction of styrene-ynes produces a naphthalene product via loss of hydrogen gas from the initially formed cycloadduct, a tetraenyl intermediate. Alternatively, the dihydronaphthalene product is afforded from the same tetraenyl intermediate via a radical isomerization process. Moreover, we have identified conditions that can be used to achieve efficient, high-yielding, and selective IMDDA reactions of styrene-ynes to form either naphthalene or dihydronaphthalene products. The operational simplicity and retrosynthetic orthogonality of this method for the preparation of naphthalenes and dihydronaphthalenes makes this transformation appealing for the synthesis of medicinal and material targets. The mechanistic studies within may impact the development of other thermal transformations.
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The Hexadehydro-Diels-Alder Cycloisomerization Reaction Proceeds by a Stepwise Mechanism.
Wang, Tao; Niu, Dawen; Hoye, Thomas R
2016-06-29
We report here experiments showing that the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction proceeds in a stepwise manner-i.e., via a diradical intermediate. Judicious use of substituent effects was decisive. We prepared (i) a series of triyne HDDA substrates that differed only in the R group present on the remote terminus of the diynophilic alkyne and (ii) an analogous series of dienophilic alkynes (n-C7H15COC≡CR) for use in classical Diels-Alder (DA) reactions (with 1,3-cyclopentadiene). The R groups were CF3, CHO, COMe/Et, CO2Me, CONMe2/Et2, H, and 1-propynyl. The relative rates of both the HDDA cyclization reactions and the simple DA cycloadditions were measured. The reactivity trends revealed a dramatic difference in the behaviors of the CF3 (slowest HDDA and nearly fastest DA) and 1-propynyl (fastest HDDA and slowest DA) containing members of each series. These differences can be explained by invoking radical-stabilizing energies rather than electron-withdrawing effects as the dominating feature of the HDDA reaction.
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Jouha, Jabrane; Buttard, Floris; Lorion, Magali; Berthonneau, Clément; Khouili, Mostafa; Hiebel, Marie-Aude; Guillaumet, Gérald; Brière, Jean-François; Suzenet, Franck
2017-09-15
A straightforward domino aza-Michael-inverse-electron-demand-hetero-Diels-Alder/retro-Diels-Alder reaction between primary and secondary propargylamine derivatives and 3-vinyl-1,2,4-triazines is developed highlighting not only the uniqueness of this dual-heterocyclic platform but also a novel and unprecedented path to polysubstituted tetrahydro-1,6-naphthyridine scaffolds.
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Directory of Open Access Journals (Sweden)
Julio A. Alonso
2013-02-01
Full Text Available Density Functional Theory has been used to model the Diels-Alder reactions of the fullerene fragments triindenetriphenilene and pentacyclopentacorannulene with ethylene and 1,3-butadiene. The purpose is to prove the feasibility of using Diels-Alder cycloaddition reactions to grow fullerene fragments step by step, and to dimerize fullerene fragments, as a way to obtain C60. The dienophile character of the fullerene fragments is dominant, and the reaction of butadiene with pentacyclopentacorannulene is favored.
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Seasonal changes in partial, reverse diel vertical migrations of cisco Coregonus artedi.
Ahrenstorff, T D; Hrabik, T R
2016-09-01
The objectives of this study were to (1) document changes in partial, reverse diel vertical migrations (DVM) patterns of cisco Coregonus artedi in Ten Mile Lake, MN, U.S.A., throughout the year and (2) evaluate the mechanisms that may cause shifts in migration behaviour. Results indicated that C. artedi vertical distributions remained deep in the water column during the day and night of the spring and autumn, which was related to a low risk, low reward strategy. During summer, a partial migration occurred where a portion of the population remained deeper according to the low risk, low reward strategy, while the other portion performed a more extensive high risk, high reward reverse DVM. In winter, C. artedi did not migrate because there were only low risk, low reward conditions present at all depths. The extensive partial, reverse DVM during summer probably increased the growth potential of C. artedi, helping individuals survive in a lake with low zooplankton prey resources. © 2016 The Fisheries Society of the British Isles.
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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.
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Lillis, Ashlee; Mooney, T. Aran
2018-06-01
The rich acoustic environment of coral reefs, including the sounds of a variety of fish and invertebrates, is a reflection of the structural complexity and biological diversity of these habitats. Emerging interest in applying passive acoustic monitoring and soundscape analysis to measure coral reef habitat characteristics and track ecological patterns is hindered by a poor understanding of the most common and abundant sound producers on reefs—the snapping shrimp. Here, we sought to address several basic biophysical drivers of reef sound by investigating acoustic activity patterns of snapping shrimp populations on two adjacent coral reefs using a detailed snap detection analysis routine to a high-resolution 2.5-month acoustic dataset from the US Virgin Islands. The reefs exhibited strong diel and lunar periodicity in snap rates and clear spatial differences in snapping levels. Snap rates peaked at dawn and dusk and were higher overall during daytime versus nighttime, a seldom-reported pattern in earlier descriptions of diel snapping shrimp acoustic activity. Small differences between the sites in snap rate rhythms were detected and illustrate how analyses of specific soundscape elements might reveal subtle between-reef variation. Snap rates were highly correlated with environmental variables, including water temperature and light, and were found to be sensitive to changes in oceanographic forcing. This study further establishes snapping shrimp as key players in the coral reef chorus and provides evidence that their acoustic output reflects a combination of environmental conditions, celestial influences, and spatial habitat variation. Effective application of passive acoustic monitoring in coral reef habitats using snap rates or snapping-influenced acoustic metrics will require a mechanistic understanding of the underlying spatial and temporal variation in snapping shrimp sound production across multiple scales.
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Della Rosa, Claudia D.; Mancini, Pedro M. E.; Kneeteman, Maria N.; Lopez Baena, Anna F.; Suligoy, Melisa A.; Domingo, Luis R.
2015-01-01
The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.
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Regioselectivity of Sc2C2@C3v(8)-C82: Role of the Sumanene-Type Hexagon in Diels-Alder Reaction.
Zhao, Pei; Zhao, Xiang; Ehara, Masahiro
2016-09-16
Recently, several experiments have demonstrated high chemical reactivity of the sumanene-type hexagon in Sc2C2@C82. To further uncover its reactivity, the Diels-Alder reaction to all the nonequivalent C-C bonds of C82 and Sc2C2@C82 has been investigated by density functional theory calculations. For the free fullerene, the [5,6] bond 7 is the thermodynamically most favored, whereas the addition on the [6,6] bond 3 has the lowest activation energy. Diels-Alder reaction has no preference for addition sites in the sumanene-type hexagon. However, in the case of the endohedral fullerene, the [6,6] bond 19 in the special hexagon becomes the most reactive site according to both kinetic and thermodynamic considerations. Further analyses reveal that bond 19 in Sc2C2@C82 exhibits the shortest bond length and third largest π-orbital axis vector. In addition, the LUMOs of bond 19 are also symmetry-allowed to interact with butadiene.
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Ground states of molecules. XLIX. MINDO/3 study of the retro-diels-alder reaction of cyclohexene
International Nuclear Information System (INIS)
Dewar, M.J.S.; Olivella, S.; Rzepa, H.S.
1978-01-01
The retro-Diels-Alder reaction of cyclohexene to form ethylene and butadiene has been studied, using MINDO/3. The transition state is predicted to be very unsymmetric, corresponding to weakening of one of the two breaking CC bonds. The calculated entropy of activation agrees well with experiment and the calculated secondary isotope effects for 4,4-dideuteriocyclohexene and 4,4,5,5-tetradeuteriocyclohexene are similar to those measured for an analogous reaction by Taagepera and Thornton. Discrepancies between the conclusions reached here and those from recent ab-initio calculations are discussed. 4 tables, 3 figures, 53 references
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Radioactive phosphorylation of alcohols to monitor biocatalytic Diels-Alder reactions.
Directory of Open Access Journals (Sweden)
Alexander Nierth
Full Text Available Nature has efficiently adopted phosphorylation for numerous biological key processes, spanning from cell signaling to energy storage and transmission. For the bioorganic chemist the number of possible ways to attach a single phosphate for radioactive labeling is surprisingly small. Here we describe a very simple and fast one-pot synthesis to phosphorylate an alcohol with phosphoric acid using trichloroacetonitrile as activating agent. Using this procedure, we efficiently attached the radioactive phosphorus isotope (32P to an anthracene diene, which is a substrate for the Diels-Alderase ribozyme-an RNA sequence that catalyzes the eponymous reaction. We used the (32P-substrate for the measurement of RNA-catalyzed reaction kinetics of several dye-labeled ribozyme variants for which precise optical activity determination (UV/vis, fluorescence failed due to interference of the attached dyes. The reaction kinetics were analyzed by thin-layer chromatographic separation of the (32P-labeled reaction components and densitometric analysis of the substrate and product radioactivities, thereby allowing iterative optimization of the dye positions for future single-molecule studies. The phosphorylation strategy with trichloroacetonitrile may be applicable for labeling numerous other compounds that contain alcoholic hydroxyl groups.
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Intramolecular and Transannular Diels-Alder Reactions
DEFF Research Database (Denmark)
Tanner, David Ackland; Ascic, Erhad
2014-01-01
Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...
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Diel infection of cyanobacteria by cyanophages
Directory of Open Access Journals (Sweden)
Tianchi eNi
2016-01-01
Full Text Available Cyanobacteria exhibit biological rhythms as an adaptation to the daily light-dark (diel cycle. Light is also crucial for bacteriophages (cyanophages that infect cyanobacteria. As the first step of infection, the adsorption of some cyanophages to their host cells is light-dependent. Moreover, cyanophage replication is affected by light intensity and possibly the host cell cycle. Photosynthesis and carbon metabolism genes have been found in cyanophage genomes. With these genes, cyanophages may affect the host metabolic rhythm. Field studies suggest that cyanophage infection of cyanobacteria in aquatic environments is synchronized directly or indirectly to the light-dark cycle. These discoveries are beginning to reveal how the daily light-dark cycle shapes the interaction of cyanophages and cyanobacteria, which eventually influences matter and energy transformation in aquatic environments.
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Diurnal patterns of methane flux from a seasonal wetland: mechanisms and methodology
Bansal, Sheel; Tangen, Brian; Finocchiaro, Raymond
2018-01-01
Methane emissions from wetlands are temporally dynamic. Few chamber-based studies have explored diurnal variation in methane flux with high temporal replication. Using an automated sampling system, we measured methane flux every 2.5 to 4 h for 205 diel cycles during three growing seasons (2013–2015) from a seasonal wetland in the Prairie Pothole Region of North America. During ponded conditions, fluxes were generally positive (i.e., methanogenesis dominant, 10.1 ± 0.8 mg m−2 h−1), had extreme range of variation (from −1 to 70 mg m−2 h−1), and were highest during late day. In contrast, during dry conditions fluxes were very low and primarily negative (i.e., oxidation dominant, −0.05 ± 0.002 mg m−2 h−1), with the highest (least negative) fluxes occurring at pre-dawn. During semi-saturated conditions, methane fluxes also were very low, oscillated between positive and negative values (i.e., balanced between methanogenesis and methane oxidation), and exhibited no diel pattern. Methane flux was positively correlated with air temperature during ponded conditions (r = 0.57) and negatively during dry conditions (r = −0.42). Multiple regression analyses showed that temperature, light and water-filled pore space explained 72% of variation in methane flux. Methane fluxes are highly temporally dynamic and follow contrasting diel patterns that are dependent on dominant microbial processes influenced by saturation state.
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Diels-Alder reactions onto fluorinated and hydrogenated graphene
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.
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Pattern activation/recognition theory of mind.
du Castel, Bertrand
2015-01-01
In his 2012 book How to Create a Mind, Ray Kurzweil defines a "Pattern Recognition Theory of Mind" that states that the brain uses millions of pattern recognizers, plus modules to check, organize, and augment them. In this article, I further the theory to go beyond pattern recognition and include also pattern activation, thus encompassing both sensory and motor functions. In addition, I treat checking, organizing, and augmentation as patterns of patterns instead of separate modules, therefore handling them the same as patterns in general. Henceforth I put forward a unified theory I call "Pattern Activation/Recognition Theory of Mind." While the original theory was based on hierarchical hidden Markov models, this evolution is based on their precursor: stochastic grammars. I demonstrate that a class of self-describing stochastic grammars allows for unifying pattern activation, recognition, organization, consistency checking, metaphor, and learning, into a single theory that expresses patterns throughout. I have implemented the model as a probabilistic programming language specialized in activation/recognition grammatical and neural operations. I use this prototype to compute and present diagrams for each stochastic grammar and corresponding neural circuit. I then discuss the theory as it relates to artificial network developments, common coding, neural reuse, and unity of mind, concluding by proposing potential paths to validation.
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Rosenblatt, Adam E.; Heithaus, Michael R.; Mazzotti, Frank J.; Cherkiss, Michael; Jeffery, Brian M.
2013-12-01
Movement and habitat use patterns are fundamental components of the behaviors of mobile animals and help determine the scale and types of interactions they have with their environments. These behaviors are especially important to quantify for top predators because they can have strong effects on lower trophic levels as well as the wider ecosystem. Many studies of top predator movement and habitat use focus on general population level trends, which may overlook important intra-population variation in behaviors that now appear to be common. In an effort to better understand the prevalence of intra-population variation in top predator movement behaviors and the potential effects of such variation on ecosystem dynamics, we examined the movement and habitat use patterns of a population of adult American alligators (Alligator mississippiensis) in a subtropical estuary for nearly four years. We found that alligators exhibited divergent behaviors with respect to activity ranges, movement rates, and habitat use, and that individualized behaviors were stable over multiple years. We also found that the variations across the three behavioral metrics were correlated such that consistent behavioral types emerged, specifically more exploratory individuals and more sedentary individuals. Our study demonstrates that top predator populations can be characterized by high degrees of intra-population variation in terms of movement and habitat use behaviors that could lead to individuals filling different ecological roles in the same ecosystem. By extension, one-size-fits-all ecosystem and species-specific conservation and management strategies that do not account for potential intra-population variation in top predator behaviors may not produce the desired outcomes in all cases.
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Hadjichristidis, Nikolaos; Alkayal, Nazeeha
2015-01-01
A novel strategy towards well-defined polymethylene-based co/terpolymers, by combining anthracene/maleimide Diels-Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: a
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Origin of Exo/Endo Selectivity in the Intramolecular Diels-Alder Reaction
International Nuclear Information System (INIS)
Yan, Shihai; Ryu, Do Hyun; Lee, Jin Yong
2010-01-01
The stereoselectivity of the intramolecular Diels-Alder reactions of 1 and its derivatives were investigated by ab initio calculations. The stereoselectivity mainly originates from the steric repulsion and the orbital interactions. The additional s-cis and s-trans conformations by introducing the carbonyl group at the neighbor of diene or dienophile may change the stereoselectivity, hence this kind of substitution can be utilized for stereoselective asymmetric synthesis
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Stefańska, Karolina; Jędrzejewska, Hanna; Wierzbicki, Michał; Szumna, Agnieszka; Iwanek, Waldemar
2016-07-15
The Diels-Alder reaction enables introduction of new functionalities onto the resorcinarene skeleton with simultaneous generation of new stereogenic centers and expansion of the internal cavity. We present highly regio- and diastereoselective inverse electron demand oxa-Diels-Alder reactions of resorcinarene ortho-quinone methide with benzofuran and indene, each generating 12 new stereogenic centers. The mechanism and reasons for regioselectivity and diastereoselectivity were analyzed using theoretical calculations (NBO charges, Fukui functions, transition state energies, and thermodynamic stability of the products). Enantiomers were separated, and their configurations were determined by comparison of experimental and theoretical electronic circular dichroism spectra.
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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.
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Effects of the Hydrophobicity of the Reactants on Diels-Alder Reactions in Water
Meijer, Ale; Otto, Sijbren; Engberts, Jan B.F.N.
1998-01-01
To assess the importance of the hydrophobicity of different parts of diene and dienophile on the aqueous acceleration of Diels-Alder reactions, second-order rate constants have been determined for the reactions of cyclopentadiene (1), 2,3-dimethyl-1,3-butadiene (4), and 1,3-cyclohexadiene (6) with
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Diel and tidal variations in larval fish exchange in the mouth region ...
African Journals Online (AJOL)
Diel and tidal variations in density of larval fishes were monitored over one neap and one spring tidal cycle in the mouth region of the warm temperate Gamtoos Estuary, South Africa. Data were collected over two 24h periods, using mixed method sampling with WP2 nets and a pushnet to sample both channel and margin ...
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Directory of Open Access Journals (Sweden)
LM. Rangel
Full Text Available Phytoplankton vertical and diel dynamics in a small shallow lake (Lake Monte Alegre, Ribeirão Preto, state of São Paulo were investigated in two climatological periods: July 2001 (cool-dry season and March 2002 (warm-rainy season. Monte Alegre is a eutrophic reservoir, with a warm polymictic discontinuous circulation pattern. The lake was thermally stratified in both periods, although dissolved oxygen varied less in the cool-dry period. Phytoplankton biomass was higher in the warm-rainy season and the vertical distribution was stratified in both seasons. Flagellate groups (Lm, Y, W1 and W2 and functional groups typical of shallow eutrophic environments (J, X1 and Sn were important throughout the study period. The lake's thermal pattern strongly influenced the vertical distribution of the phytoplankton community in both periods. Biomass, functional groups and size classes of phytoplankton also were determined by the presence of more efficient herbivores in the lake, especially during the cool-dry period when phytoplankton biomass decreased.
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Rohling, Roderigh Y; Uslamin, Evgeny; Zijlstra, Bart; Tranca, Ionut C; Filot, Ivo A W; Hensen, Emiel J M; Pidko, Evgeny A
2018-02-02
The one-pot Diels-Alder cycloaddition (DAC)/dehydration (D) tandem reaction between 2,5-dimethylfuran and ethylene is a potent pathway toward biomass-derived p -xylene. In this work, we present a cheap and active low-silica potassium-exchanged faujasite (KY, Si/Al = 2.6) catalyst. Catalyst optimization was guided by a computational study of the DAC/D reaction mechanism over different alkali-exchanged faujasites using periodic density functional theory calculations complemented by microkinetic modeling. Two types of faujasite models were compared, i.e., a high-silica alkali-exchanged faujasite model representing isolated active cation sites and a low-silica alkali-exchanged faujasite in which the reaction involves several cations in the proximity. The mechanistic study points to a significant synergetic cooperative effect of the ensemble of cations in the faujasite supercage on the DAC/D reaction. Alignment of the reactants by their interactions with the cationic sites and stabilization of reaction intermediates contribute to the high catalytic performance. Experiments confirmed the prediction that KY is the most active catalyst among low-silica alkali-exchanged faujasites. This work is an example of how the catalytic reactivity of zeolites depends on multiple interactions between the zeolite and reagents.
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Caracterización dieléctrica de la perovskita laminar La1.5Sr0.5CoO4
Directory of Open Access Journals (Sweden)
Rivas, J.
2004-06-01
Full Text Available In this work, the behaviour of the real and imaginary components of the dielectric permittivity of layered perovskite La1.5Sr0.5CoO4 have been studied, in the frequency range 20 Hz-1 MHz and in the temperature range 115-350 K. Polycrystalline samples were prepared by the ceramic method. The powder diffraction results showed the pattern of the desired phase together with a small quantities of La2O3 impurities. A comparative study of the electrical and magnetic properties of this charge-ordered compound (TCO∼750 K has revealed a basically semiconductor behaviour with a complex bidimensional antiferromagnetism which can be explained on the basis of a thermally activated evolution of the spin state of the Co3+ ions. A detailed investigation of the dielectric properties of this system has allowed us to identify two superimposed relaxation processes: the first one in the low frequency range (f En este trabajo se estudia el comportamiento de las componentes real e imaginaria de la permitividad dieléctrica compleja en función de la frecuencia (20 Hz-1 MHz y la temperatura (115-350 K de la perovskita laminar La1.5Sr0.5CoO4. Para realizar este estudio preparamos muestras policristalinas utilizando el método cerámico. El análisis por difracción de rayos X mostró la presencia de la fase deseada y una pequeña impureza de La2O3. Un estudio comparativo de las propiedades eléctricas y magnéticas de este compuesto con orden de carga (TCO∼750 K, reveló que básicamente se trata de un material semiconductor con un complejo antiferromagnetismo bidimensional que evoluciona con la temperatura debido a transiciones del estado de espín del Co3+ activadas térmicamente. Una investigación detallada de las propiedades dieléctricas de este sistema nos permitió identificar dos fenómenos de relajación superpuestos: uno presente a bajas frecuencias (f < 102 Hz que se asocia con los procesos de conducción por “hopping” electrónico en este cristal i
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Directory of Open Access Journals (Sweden)
Perticarrari A.
Full Text Available A comparison between two studies on diel vertical migration of two cyclopoid copepod species, in Lake Monte Alegre, undertaken in 1985/86 and 1999, revealed a change in their migratory behavior. In summer, during a period of marked stratification with low dissolved oxygen near the bottom, the organisms avoided the deepest layers, and migration was nocturnal or undetectable, in both periods. On other occasions, with partial or total circulation in the lake, a weak twilight migration of copepodites and adults in 1985 was replaced by the reverse in 1999. Differences were found among stages, with the weakest or undetectable migration being observed for nauplii. The migratory pattern change for copepodites and adults might be related with a recent predation pressure increase by Chaoborus larvae on copepods, after the virtual disappearance of their main cladoceran prey.
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Directory of Open Access Journals (Sweden)
Mario Katsuragawa
1990-12-01
Full Text Available Fish larvae were collected by neuston and bongo nets, in the Southeastern Brazil, during four océanographie cruises (January 1980; January 1981; October 1981; and March 1982. The results are compared and analyzed in order to study the patterns of diel vertical distributions of fish larvae and to detect sampling problems. Larvae collected with neuston net were quite different in types and size composition, when compared with those collected with bongo net in oblique tows. Clear tendency of stratification in size composition at the uppermost layer can be observed on juveniles ( > 19 mm of Sardinella brasiliensis which also showed day time avoidance. Most of the neustonic taxa were also caught in the deeper layers, although some groups, e.g. Mugilidae, Mullidae, and Gerreidae, were more abundant at the surface. Density of ichthyoneuston is much higher than those observed in the Northwest Atlantic and number of fish larvae collected during the day by neuston net exceeded that of night samples.Larvas de peixes foram coletadas com rede de nêuston e rede bongô, na costa sudeste do Brasil, durante quatro cruzeiros oceanográficos (Jan/1980; Jan/1981; Out/1981; Mar/1982. São estudados os padrões de distribuição diária de larvas e problemas de amostragem. Numa comparação entre coletas de superfície e coletas oblíquas, observam-se diferenças em composição, tanto em termos de espécies como de tamanho de larvas. Pode ser observada uma clara tendência de estratificação por composição de tamanho para Sardinella brasiliensis em que espécimes juvenis (> 19 mm ocorreram preferencialmente na camada superficial. Estes juvenis também apresentaram maior capacidade de fuga da boca da rede durante o período diurno. A maioria dos táxons de ocorrência neustônica foi também capturada em camadas mais profundas, mas alguns grupos como Mugilidae, Mullidae e Gerreidae predomiram na camada superficial. A densidade do ictionêuston é mais elevada na
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Digital Repository Service at National Institute of Oceanography (India)
Patre, R.E.; Gawas, S.; Sen, S.; Parameswaran, P.S.; Tilve, S.G.
A domino Wittig Diels - Alder reaction has been employed in delineating a short and flexible synthetic stratagem for ready access to the AB ring system and the tricyclic framework of furanosesquiterpenes, such as the bioactive natural products...
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Otani, Takashi; Tamai, Yumiko; Seki, Kazunori; Kikuchi, Tomohiro; Miyazawa, Taiichiro; Saito, Takao
2015-06-07
We describe the stereoselective synthesis of polyring-fused heterocyclic compounds based on diene-transmissive hetero-Diels-Alder reactions utilizing β,γ-unsaturated α-keto esters. This protocol involves the initial endo- or exo-selective Diels-Alder (DA) reactions with electron-rich dienophiles, methylenation of the ester carbonyl groups with the Tebbe reagent, and a stereoselective second DA reaction with electron-deficient dienophiles. The use of enantioselective DA reactions in the initial reaction enables access to chiral polyring-fused heterocyclic compounds with multiple chiral centres.
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Diel turbidity cycles in a headwater stream: evidence of nocturnal bioturbation?
Cooper, Richard J.; Outram, Faye; Hiscock, Kevin M.
2016-01-01
Purpose: A small number of recent studies have linked daily cycles in stream turbidity to nocturnal bioturbation by aquatic fauna, principally crayfish, and demonstrated this process can significantly impact upon water quality under baseflow conditions. Adding to this limited body of research, we use high-resolution water quality monitoring data to investigate evidence of diel turbidity cycles in a lowland, headwater stream with a known signal crayfish (Pacifastacus leniusculus) population an...
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The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry
Polgar, Lorenzo Massimo; van Duin, Martin; Picchioni, Francesco
2016-01-01
A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified
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Energy Technology Data Exchange (ETDEWEB)
Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull [Yeungnam University, Gyeongsan (Korea, Republic of)
2016-02-15
Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.
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International Nuclear Information System (INIS)
Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull
2016-01-01
Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.
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Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels-Alder Reaction.
Kumatabara, Yusuke; Kaneko, Shiho; Nakata, Satoshi; Shirakawa, Seiji; Maruoka, Keiji
2016-08-05
A piperidine-derived tetraalkylammonium salt with a non-coordinating counteranion worked as an effective hydrogen-bonding catalyst in an aza-Diels-Alder reaction of imines and a Danishefsky diene. The hydrogen-bonding interaction between the ammonium salt and an imine was observed as part of a (1) H NMR titration study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Gordon H. Reeves; Jon B. Grunbaum; Dirk W. Lang
2009-01-01
The seasonal diel behaviour of age 1+ steelhead from Coast and Cascade Range streams in Oregon was examined in the field and in laboratory streams. During the summer, fish from both areas were active during the day in natural streams: they held position in the water column in moderate velocities and depths. At night, fish were in slower water, closer to the bottom...
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Diel foraging and shelter use of large juvenile brown trout (Salmo trutta) under food satiation
DEFF Research Database (Denmark)
Conallin, J.; Jyde, M.; Filrup, K.
2012-01-01
The diel partitioning of juvenile brown trout Salmo trutta foraging behaviour is controlled by a number of factors including predation risk, competition, temperature and food availability. The present study uses PIT-tagging and visual observation to asses the use of shelter and foraging behaviour...... of Danish wild juvenile brown trout (13.5-15.6 cm). The experiment was conducted in a fluvarium and the fish were fed to satiation. It was hypothesised that food satiation would promote nocturnal foraging and increase daytime shelter use. Our results showed a significant difference in diel shelter use...... between day and night with a significant increase in shelter use during daytime conditions. Visual observations showed a significant preference for nocturnal feeding. Together with the significantly reduced shelter use during the night, our results support the hypothesis that young stream living trout...
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Ory, Nicolas C.; Dudgeon, David; Duprey, Nicolas; Thiel, Martin
2014-09-01
Nonlethal effects of predators on prey behaviour are still poorly understood, although they may have cascading effects through food webs. Underwater observations and experiments were conducted on a shallow fringing coral reef in Malaysia to examine whether predation risks affect diel activity, habitat use, and survival of the rhynchocinetid shrimp Cinetorhynchus hendersoni. The study site was within a protected area where predatory fish were abundant. Visual surveys and tethering experiments were conducted in April-May 2010 to compare the abundance of shrimps and predatory fishes and the relative predation intensity on shrimps during day and night. Shrimps were not seen during the day but came out of refuges at night, when the risk of being eaten was reduced. Shrimp preferences for substrata of different complexities and types were examined at night when they could be seen on the reef; complex substrata were preferred, while simple substrata were avoided. Shrimps were abundant on high-complexity columnar-foliate Porites rus, but tended to make little use of branching Acropora spp. Subsequent tethering experiments, conducted during daytime in June 2013, compared the relative mortality of shrimps on simple (sand-rubble, massive Porites spp.) and complex ( P. rus, branching Acropora spp.) substrata under different predation risk scenarios (i.e., different tether lengths and exposure durations). The mortality of shrimps with short tethers (high risk) was high on all substrata while, under low and intermediate predation risks (long tethers), shrimp mortality was reduced on complex corals relative to that on sand-rubble or massive Porites spp. Overall, mortality was lowest on P. rus. Our study indicates that predation risks constrain shrimp activity and habitat choice, forcing them to hide deep inside complex substrata during the day. Such behavioural responses to predation risks and their consequences for the trophic role of invertebrate mesoconsumers warrant further
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Barthel, Matthias; Hammerle, Albin; Sturm, Patrick; Baur, Thomas; Gentsch, Lydia; Knohl, Alexander
2011-12-01
Recent (13) CO(2) canopy pulse chase labeling studies revealed that photosynthesis influences the carbon isotopic composition of soil respired CO(2) (δ(13) C(SR)) even on a diel timescale. However, the driving mechanisms underlying these short-term responses remain unclear, in particular under drought conditions. The gas exchange of CO(2) isotopes of canopy and soil was monitored in drought/nondrought-stressed beech (Fagus sylvatica) saplings after (13) CO(2) canopy pulse labeling. A combined canopy/soil chamber system with gas-tight separated soil and canopy compartments was coupled to a laser spectrometer measuring mixing ratios and isotopic composition of CO(2) in air at high temporal resolution. The measured δ(13) C(SR) signal was then explained and substantiated by a mechanistic carbon allocation model. Leaf metabolism had a strong imprint on diel cycles in control plants, as a result of an alternating substrate supply switching between sugar and transient starch. By contrast, diel cycles in drought-stressed plants were determined by the relative contributions of autotrophic and heterotrophic respiration throughout the day. Drought reduced the speed of the link between photosynthesis and soil respiration by a factor of c. 2.5, depending on the photosynthetic rate. Drought slows the coupling between photosynthesis and soil respiration and alters the underlying mechanism causing diel variations of δ(13) C(SR). © 2011 The Authors. New Phytologist © 2011 New Phytologist Trust.
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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.
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Unconventional exo selectivity in thermal normal-electron-demand Diels-Alder reactions
Ho, Guo-Ming; Huang, Ci-Jhang; Li, Elise Yu-Tzu; Hsu, Sheng-Kai; Wu, Ti; Zulueta, Medel Manuel L.; Wu, Kevin Binchia; Hung, Shang-Cheng
2016-10-01
The Diels-Alder reaction is a useful tool for generating functionalized chiral molecules through the concerted cycloaddition of dienes and dienophiles leading to six-membered rings. Traditionally, the selective predictions of the products rely heavily on consideration of the secondary orbital interactions that stabilize the endo pathway. However, there remain some basic examples defying this notion and produce the exo-isomer as major product. Here we systematically evaluated of the structural features driving exo selectivity in thermal normal-electron-demand Diels-Alder reactions. Substitution at the Cβ position and the size and electronegativity of the electron-withdrawing group of the dienophile are contributing factors. Experimental and computational studies both point toward the steric and electrostatic forces between the substituents in both the diene and the dienophile that increase the likelihood of the exo pathway. For these substrates, the dominance of the endo pathway is reduced by transition state distortions and poor structural alignments of the reacting partners. We also noted the tilt of the dienophile with respect to the diene causing steric strain on the functionalities at the more advanced bond forming carbon-carbon position of the endo transition state. Insights into such factors may benefit synthetic planning and asserting control over this important named reaction.
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Diel drift of Chironomidae larvae in a pristine Idaho mountain stream
Tilley, L.J.
1989-01-01
Simultaneous hourly net collections in a meadow and canyon reach of a mountain stream determined diel and spatial abundances of drifting Chironomidae larvae. Sixty-one taxa were identified to the lowest practical level, 52 in the meadow and 41 in the canyon. Orthocladiinae was the most abundant subfamily with 32 taxa and a 24 h mean density of 294 individuals 100 m-3 (meadow) and 26 taxa and a mean of 648 individuals 100 m-3 (canyon). Chironominae was the second most abundant subfamily. Nonchironomid invertebrates at both sites and total Chironomidae larvae (meadow) were predominantly night-drifting. Parakiefferiella and Psectrocladius were day-drifting (meadow) whereas 8 other chironomid taxa (meadow) and 2 taxa (canyon) were night-drifting. All others were aperiodic or too rare to test periodicity, Stempellinella cf brevis Edwards exhibited catastrophic drift in the canyon only. The different drift patterns between sites is attributed to greater loss of streambed habitat in the canyon compared to the meadow as streamflow decreased. Consequent crowding of chironomid larvae in the canyon caused catastrophic drift or interfered with drift periodicty. This study adds to knowledge of Chironomidae drift and shows influences on drift of hydrologic and geomorphic conditions. ?? 1989 Kluwer Academic Publishers.
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Polansky, Leo; Douglas-Hamilton, Iain; Wittemyer, George
2013-01-01
Adaptive movement behaviors allow individuals to respond to fluctuations in resource quality and distribution in order to maintain fitness. Classically, studies of the interaction between ecological conditions and movement behavior have focused on such metrics as travel distance, velocity, home range size or patch occupancy time as the salient metrics of behavior. Driven by the emergence of very regular high frequency data, more recently the importance of interpreting the autocorrelation structure of movement as a behavioral metric has become apparent. Studying movement of a free ranging African savannah elephant population, we evaluated how two movement metrics, diel displacement (DD) and movement predictability (MP - the degree of autocorrelated movement activity at diel time scales), changed in response to variation in resource availability as measured by the Normalized Difference Vegetation Index. We were able to capitalize on long term (multi-year) yet high resolution (hourly) global positioning system tracking datasets, the sample size of which allows robust analysis of complex models. We use optimal foraging theory predictions as a framework to interpret our results, in particular contrasting the behaviors across changes in social rank and resource availability to infer which movement behaviors at diel time scales may be optimal in this highly social species. Both DD and MP increased with increasing forage availability, irrespective of rank, reflecting increased energy expenditure and movement predictability during time periods of overall high resource availability. However, significant interactions between forage availability and social rank indicated a stronger response in DD, and a weaker response in MP, with increasing social status. Relative to high ranking individuals, low ranking individuals expended more energy and exhibited less behavioral movement autocorrelation during lower forage availability conditions, likely reflecting sub-optimal movement
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Assessment of possible diel and sex-related differences in round goby (Neogobius melanostomus) diet
Czech Academy of Sciences Publication Activity Database
Všetičková, Lucie; Janáč, Michal; Roche, Kevin Francis; Jurajda, Pavel
2015-01-01
Roč. 64, č. 2 (2015), s. 104-111 ISSN 0139-7893 R&D Projects: GA ČR(CZ) GAP505/11/1768 Institutional support: RVO:68081766 Keywords : invasive species * diel feeding * inter-sex differences * nest-guarding * breeding season Subject RIV: EG - Zoology Impact factor: 0.592, year: 2015
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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.
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Czech Academy of Sciences Publication Activity Database
Koehler, K. C.; Ďuračková, Andrea; Kloxin, C. J.; Bowman, C. N.
2012-01-01
Roč. 58, č. 11 (2012), s. 3545-3552 ISSN 0001-1541 Institutional research plan: CEZ:AV0Z40500505 Keywords : Diels - Alder reaction s * self-healing polymer networks * thermoreversible reaction s Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.493, year: 2012
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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.
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Cozzi, Gabriele; Broekhuis, Femke; McNutt, John W; Turnbull, Lindsay A; Macdonald, David W; Schmid, Bernhard
2012-12-01
Africa is home to the last intact guild of large carnivores and thus provides the only opportunity to investigate mechanisms of coexistence among large predator species. Strong asymmetric dominance hierarchies typically characterize guilds of large carnivores; but despite this asymmetry, subdominant species may persist alongside their stronger counterparts through temporal partitioning of habitat and resources. In the African guild, the subdominant African wild dogs and cheetahs are routinely described as diurnal and crepuscular. These activity patterns have been interpreted to result from the need to avoid encounters with the stronger, nocturnal spotted hyenas and lions. However, the idea that diel activity patterns of carnivore species are strongly shaped by competition and predation has recently been challenged by new observations. In a three-year study in the Okavango Delta, we investigated daily activity patterns and temporal partitioning for wild dogs, cheetahs, spotted hyenas and lions by fitting radio collars that continuously recorded activity bursts, to a total of 25 individuals. Analysis of activity patterns throughout the 24-h cycle revealed an unexpectedly high degree of temporal overlap among the four species. This was mainly due to the extensive and previously undescribed nocturnal activity of wild dogs and cheetahs. Their nocturnal activity fluctuated with the lunar cycle, represented up to 40% of the diel activity budget and was primarily constrained by moonlight availability. In contrast, the nocturnal activity patterns of lions and hyenas were unaffected by moonlight and remained constant over the lunar cycle. Our results suggest that other ecological factors such as optimal hunting conditions have shaped the diel activity patterns of subdominant, large predators. We suggest that they are "starvation driven" and must exploit every opportunity to obtain a meal. The benefits of activity on moonlit nights therefore offset the risks of encountering
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Diel variation of fish community in sandy beaches of southeastern Brazil
Directory of Open Access Journals (Sweden)
Luiz Ricardo Gaelzer
2008-03-01
Full Text Available Fish living in coastal waters present behavior patterns ruled by environmental light levels. Diel variations in fish community structure were investigated at Arraial do Cabo surf zone (22º58'S, 42º01'W. From September/2001 to August/2002 monthly sampling consisted of 12 hauls of a beach seine during the day and at night at Praia dos Anjos, Praia Grande and Prainha beaches. Different temporal distribution patterns of the ichthyc community were recorded. At Praia dos Anjos, total richness was higher at night while the average number of species, CPUE, Margalef's richness and Shannon diversity were generally higher during the day. We believe that this pattern was caused by the displacement of some species such as Harengula clupeola,Trachinotus carolinus and Umbrina coroides at night to deeper areas searching for food or for predator avoidance. At Praia Grande and Prainha the average number of species, CPUE, richness and diversity indexes were generally higher at night with the dominant species H. clupeola, Pomatomus saltatrix and Sardinella brasiliensis. It is suggested that the main factor to diel variation is the protection against predators due to darkness, making visualization of the prey difficult, besides the presence of seasonal macroalgae beds at Prainha, which might function as a food area for piscivorous fishes due to the proximity of larger individuals in shallower water especially at night.Peixes que vivem em águas costeiras marinhas exibem modelos de comportamento que são regulados pelos níveis de luz do ambiente. A variação nictemeral na estrutura da comunidade de peixes de zona de arrebentação foi investigada na região de Arraial do Cabo (22º58'S, 42º01'W. Desetembro/2001 a agosto/2002 foram realizadas coletas mensais, sendo efetuadas 12 arrastos utilizando cerco de praia nos períodos diurnos e noturnos na Praia dos Anjos, Praia Grande e Prainha. Diferentes padrões de distribuição da comunidade ictíca foram
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Digital Repository Service at National Institute of Oceanography (India)
Goswami, S.C.; KrishnaKumari, L.; Shrivastava, Y.
Diel variations in zooplankton biomass, common groups and proximate composition zooplankton at stations between Vengurla to Ratnagiri, along west coast of India were studied. Higher biomass values were obtained for the night samples (av = 80 ml/100...
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A Computational Experiment of the Endo versus Exo Preference in a Diels-Alder Reaction
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…
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The unexpected product of Diels-Alder reaction between "indanocyclon" and maleimide
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.
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Silvestri, Michael G.; Dills, Charles E.
1989-01-01
Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)
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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.
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Composition of phenolic compounds and antioxidant attributes of Cyclea gracillima Diels extracts
Directory of Open Access Journals (Sweden)
Jau-Tien Lin
2018-01-01
Full Text Available Cyclea gracillima Diels is a Taiwanese native medicinal herb. However, there are currently few relevant reports on its biochemical activity. In this study, the antioxidant attributes of the ethanol and hot water extracts of this herb were assayed using in vitro models, including the following: 2,2-diphenyl-1-(2,4,6-trinitrophenyl-hydrazyl radical scavenging, Trolox equivalent antioxidant capacity, reducing power, and chelating ferrous ions. The following biochemical models were also assayed: inhibition of human low density lipoprotein oxidation, inhibition of human erythrocyte hemolysis, and scavenging oxygen radicals in human blood. The composition and content of flavonoids and phenolic acids in these extracts were also analyzed. The results showed that these extracts with high polyphenol levels presented remarkable antioxidant effects in all assays, especially when extracted with ethanol. Six phenolic acids (mainly ferulic acid, sinapic acid, and syringic acid and 12 flavonoids (mainly narigenin, myricetin, naringin, and apigenin were found in these extracts.
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Diels-Alder Reactions of 12-Hydroxy-9(10®20-5aH-abeo-abieta-1(10,8(9,12(13-triene-11,14-dione
Directory of Open Access Journals (Sweden)
Shougang Hu
2013-06-01
Full Text Available 12-Hydroxy-9(10®20-5aH-abeo-abieta-1(10,8(9,12(13-triene-11,14-dione (quinone 2 served as the dienophile in numerous intermolecular Diels-Alder reactions. These cycloadditions were conducted either thermally (including microwave heating or with Lewis acid activation. While most dienes reacted with quinone 2 in good chemical yield, others were incompatible under the experimental conditions used.
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Kiselev, V. D.; Kornilov, D. A.; Kashaeva, E. A.; Potapova, L. N.; Krivolapov, D. B.; Litvinov, I. A.; Konovalov, A. I.
2014-12-01
The Diels-Alder reaction between substituted anthracenes 1a-1j and 4-phenyl-1,2,4-triazoline-3,5 ( 2) is studied. In all cases except one, the reaction proceeds on the most active 9,10-atoms of substituted anthracenes. The orthogonality of the two phenyl groups at the 9,10-position of diene 1a is found to shield 9,10-reactive centers. No dienophiles with C=C bonds are shown to participate in the Diels-Alder reaction with 1a; however, the reaction 1a + 2 proceeds with the very active dienophile 2,4-phenyl-1,2,4-triazoline-3,5-dione. It is shown that attachment occurs on the less active but sterically accessible 1,4-reactive center of diene 1a. The structure of adduct 3a is proved by 1H and 13C NMR spectroscopy and X-ray diffraction analysis. The following parameters are obtained for reaction 1a + 2 ⇆ 3a in toluene at 25°C: K eq = 2120 M-1, Δ Hf ≠ = 58.6 kJ/mol, Δ Sf ≠ = -97 J/(mol K), Δ Vf ≠ = -17.2 cm3/mol, Δ Hb ≠ = 108.8 kJ/mol, Δ Sb ≠ = 7.3 J/(mol K), Δ Vb ≠ = -0.8 cm3/mol, Δ H r-n = -50.2 kJ/mol, Δ S r-n = -104.3 J/(mol K), Δ V r-n = -15.6 cm3/mol. It is concluded that the values of equilibrium constants of the reactions 1a-1j + 2 ⇆ 3a-3j vary within 4 × 101-1011 M-1.
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DEFF Research Database (Denmark)
Kjær, Katrine Heinsvig; Poiré, Richard; Ottosen, Carl-Otto
2012-01-01
diurnally-regulated parameters related to growth. In this study, chrysanthemum plants were exposed to a change in the time-of-day application of light followed by short days or long days with a night interruption of light. We observed a clear shift in the diel cycle of sucrose turnover and relative leaf......Abstract. Diel (24 h) rhythms are believed to be of great importance to plant growth and carbohydrate metabolism in fluctuating environments. However, it is unclear how plants that have evolved to experience regular day–night patterns will respond to irregular light environments that disturb...... expansion, indicating a resetting of these activities with a temporal trigger in the early morning. The starch pool was relatively stable in long-day plants and marginally affected by the change in the time-of-day application in light followed by long days with a night interruption. This was in contrast...
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Naphthalene Diels-Alder in a self-assembled molecular flask.
Murase, Takashi; Horiuchi, Shinnosuke; Fujita, Makoto
2010-03-10
Despite its inertness toward pericyclic reactions under common conditions, naphthalenes readily undergo Diels-Alder reactions when coencapsulated with a suitable dienophile within the cavity of a self-assembled host. Localization of the reactant pair significantly reduces the entropic cost of the reaction, and preorganization within the host cavity controls both the regio- and stereoselectivity of the reaction: electronically disfavored exo adducts were obtained, and with substituted naphthalenes, the reaction takes place on the less electron-rich, unsubstituted ring. Our findings highlight the fact that judicious tuning of substrate size and shape within molecular flasks can unveil new and unusual reactivities for otherwise unreactive molecules.
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Sulfate Reduction and Thiosulfate Transformations in a Cyanobacterial Mat during a Diel Oxygen Cycle
DEFF Research Database (Denmark)
JØRGENSEN, BB
1994-01-01
Bacterial sulfate reduction and transformations of thiosulfate were studied with radiotracers in a Microcoleus chthono-plastes-dominated microbial mat growing in a hypersaline pond at the Red Sea. The study showed how a diel cycle of oxygen evolution affected respiration by sulfate-reducing bacte......Bacterial sulfate reduction and transformations of thiosulfate were studied with radiotracers in a Microcoleus chthono-plastes-dominated microbial mat growing in a hypersaline pond at the Red Sea. The study showed how a diel cycle of oxygen evolution affected respiration by sulfate......-reducing bacteria and the metabolism of thiosulfate through oxidative and reductive pathways. Sulfate reduction occurred in both oxic and anoxic layers of the mat and varied diurnally, apparently according to temperature rather than to oxygen. Time course experiments showed that the radiotracer method...... underestimated sulfate reduction in the oxic zone due to rapid reoxidation of the produced sulfide. Extremely high reduction rates of up to 10 mu mol cm(-3) d(-1) were measured just below the euphotic zone. Although thiosulfate was simultaneously oxidized, reduced and disproportionated by bacteria in all layers...
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Vertical nitrogen flux from the oceanic photic zone by diel migrant zooplankton and nekton
Longhurst, Alan R.; Glen Harrison, W.
1988-06-01
Where the photic zone is a biological steady-state, the downward flux of organic material across the pycnocline to the interior of the ocean is thought to be balanced by upward turbulent flux of inorganic nitrogen across the nutricline. This model ignores a significant downward dissolved nitrogen flux caused by the diel vertical migration of interzonal zooplankton and nekton that feed in the photic zone at night and excrete nitrogenous compounds at depth by day. In the oligotrophic ocean this flux can be equivalent to the flux of particulate organic nitrogen from the photic zone in the form of faecal pellets and organic flocculates. Where nitrogen is the limiting plant nutrient, and the flux by diel migration of interzonal plankton is significant compared to other nitrogen exports from the photic zone, there must be an upward revision of previous estimates for the ratio of new to total primary production in the photic zone if a nutrient balance is to be maintained. This upward revision is of the order 5-100% depending on the oceanographic regime.
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Energy Technology Data Exchange (ETDEWEB)
Looman, Arún, E-mail: arun.looman@scu.edu.au [National Marine Science Centre, Southern Cross University, Coffs Harbour, New South Wales (Australia); School of Environment, Science, and Engineering, Southern Cross University, Lismore, New South Wales (Australia); Santos, Isaac R.; Tait, Douglas R.; Webb, Jackie R. [National Marine Science Centre, Southern Cross University, Coffs Harbour, New South Wales (Australia); School of Environment, Science, and Engineering, Southern Cross University, Lismore, New South Wales (Australia); Sullivan, Caroline A.; Maher, Damien T. [School of Environment, Science, and Engineering, Southern Cross University, Lismore, New South Wales (Australia)
2016-04-15
Catchment headwaters comprise the majority of all stream length globally, however, carbon (C) dynamics in these systems remains poorly understood. We combined continuous measurements of pCO{sub 2} and radon ({sup 222}Rn, a natural groundwater tracer) with discrete sampling for particulate organic, dissolved organic and inorganic carbon (POC, DOC, and DIC) to assess the short-term carbon dynamics of a pristine subtropical headwater stream in Australia, over contrasting hydrologic regimes of drought, flash-flooding and recovery. Observations over 23 days revealed a shift from carbon losses dominated by CO{sub 2} outgassing under conditions of low flow (66.4 ± 0.4% of carbon export) to downstream exports of carbon during the flood (87.8 ± 9.7% of carbon export). DOC was the dominant form of downstream exports throughout the study (DOC:DIC:POC = 0.82:0.05:0.13). The broadest diel variability among variables occurred during the drought phase, with diel variability up to 662 μatm d{sup −1} (or 27 μM [CO{sub 2}*] d{sup −1}), 17 μM d{sup −1} and 268 Bq m{sup −3} d{sup −1} for pCO{sub 2}, dissolved oxygen and {sup 222}Rn, respectively. Diel dynamics indicated multiple interrelated drivers of stream water chemistry including groundwater seepage and in-stream metabolism. The catchment exported terrestrial carbon throughout the field campaign, with a mean net stream flux of 4.7 ± 7.8 mmol C m{sup −2} (catchment area) d{sup −1} which is equivalent to 1.4 ± 2.3% of the estimated local terrestrial net primary production. Our observations highlight the importance of accounting for hydrological extremes when assessing the carbon budgets and ecosystem metabolism of headwater streams, and provide a first estimate of aquatic carbon exports from a pristine Australian subtropical rainforest. - Highlights: • First carbon export estimates of a pristine Australian subtropical headwater catchment. • Metabolism and hydrology were drivers of aquatic carbon flux.
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International Nuclear Information System (INIS)
Looman, Arún; Santos, Isaac R.; Tait, Douglas R.; Webb, Jackie R.; Sullivan, Caroline A.; Maher, Damien T.
2016-01-01
Catchment headwaters comprise the majority of all stream length globally, however, carbon (C) dynamics in these systems remains poorly understood. We combined continuous measurements of pCO_2 and radon ("2"2"2Rn, a natural groundwater tracer) with discrete sampling for particulate organic, dissolved organic and inorganic carbon (POC, DOC, and DIC) to assess the short-term carbon dynamics of a pristine subtropical headwater stream in Australia, over contrasting hydrologic regimes of drought, flash-flooding and recovery. Observations over 23 days revealed a shift from carbon losses dominated by CO_2 outgassing under conditions of low flow (66.4 ± 0.4% of carbon export) to downstream exports of carbon during the flood (87.8 ± 9.7% of carbon export). DOC was the dominant form of downstream exports throughout the study (DOC:DIC:POC = 0.82:0.05:0.13). The broadest diel variability among variables occurred during the drought phase, with diel variability up to 662 μatm d"−"1 (or 27 μM [CO_2*] d"−"1), 17 μM d"−"1 and 268 Bq m"−"3 d"−"1 for pCO_2, dissolved oxygen and "2"2"2Rn, respectively. Diel dynamics indicated multiple interrelated drivers of stream water chemistry including groundwater seepage and in-stream metabolism. The catchment exported terrestrial carbon throughout the field campaign, with a mean net stream flux of 4.7 ± 7.8 mmol C m"−"2 (catchment area) d"−"1 which is equivalent to 1.4 ± 2.3% of the estimated local terrestrial net primary production. Our observations highlight the importance of accounting for hydrological extremes when assessing the carbon budgets and ecosystem metabolism of headwater streams, and provide a first estimate of aquatic carbon exports from a pristine Australian subtropical rainforest. - Highlights: • First carbon export estimates of a pristine Australian subtropical headwater catchment. • Metabolism and hydrology were drivers of aquatic carbon flux. • Catchment exports ranged between 1.1 and 18.6 mmol C m
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Karunakaran, Jayachandran; Mohanakrishnan, Arasambattu K
2018-02-16
Diels-Alder reaction of 1,3-diarylbenzo[c]furan/cyclopentadienone with TTF followed by triflic acid mediated cleavage of the resulting adducts led to the formation of the respective 1,4-diaryl substituted naphthalenes, fluoranthenes, and fluorenones. The photophysical properties of representative diaryl-substituted hydrocarbons are also reported.
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Czech Academy of Sciences Publication Activity Database
Drahota, P.; Nováková, B.; Matoušek, Tomáš; Mihaljevič, M.; Rohovec, Jan; Filippi, Michal
2013-01-01
Roč. 31, APR (2013), s. 84-93 ISSN 0883-2927 Institutional research plan: CEZ:AV0Z30130516 Institutional support: RVO:68081715 ; RVO:67985831 Keywords : arsenic * molybdenum * antimony * trace elements * diel cycle Subject RIV: CB - Analytical Chemistry, Separation; DD - Geochemistry (GLU-S) Impact factor: 2.021, year: 2013
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Directory of Open Access Journals (Sweden)
Mario Posillico
1995-12-01
Full Text Available Abstract Three stone martens (2 males, 1 female Martes foina Erxleben, 1777, were radio-tracked for 4, 2.5 and 12 months respectively, in a rural hilly area in Siena County, Central Italy. Food habits were assessed by faecal analysis, as percentage of occurrence and estimated volume. Diel, nocturnal, diurnal and crepuscular activity were measured as the proportion of active fixes on a 48 hours/fortnight basis. Seasonal variation of all activities was assessed and correlated to mean T°C, daylength, food and trophic niche breadth. Daily time budgets were also measured and compared between months and seasons. Fruits were the staple food in summer/autumn, followed by vertebrates and invertebrates. Vertebrates and invertebrates were the main food source in winter and spring. No significant difference of activity could be found between the three animals. Diel activity reached its maximum in summer, and decreased significantly throughout the rest of the year. Die1 activity did not differ significantly between subsequent seasons, whereas a statistically significant difference was found between every other season. Nocturnal activity peaked in winter and dropped in summer. It significantly differed between seasons but for spring vs. summer and autumn vs. winter. Diurnal activity differed significantly between seasons, but for spring vs. summer, when it reached its maximum, and for autumn vs. winter when it was at its minimum. Crepuscular activity remained constant throughout the year. The 24-hour distribution of active fixes showed a bimodal pattern in spring and summer, while in autumn and winter the activity pattern was unimodal, with a nocturnal peak. Time budget differed between seasons, but for autumn and winter vs. spring. Significant correlations between activities and abiotical variables (except rainfall were direct, but for nocturnal activity. No significant correlation was found with precipitation. Activity was not
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Wijnen, J.W.; Engberts, Jan B.F.N.
1997-01-01
The retro-Diels-Alder (RDA) reaction of anthracenedione 1a proceeds considerably faster in aqueous solutions than in organic solvents. Addition of organic solvents to water retards the reaction, whereas glucose induces a modest acceleration. SDS micelles induce a considerable retardation, but even
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Koeck, Barbara; Pastor, Jérémy; Saragoni, Gilles; Dalias, Nicolas; Payrot, Jérôme; Lenfant, Philippe
2014-03-01
Temporal movement patterns and spawning behaviour of the dusky grouper Epinephelus marginatus were investigated using depth and temperature sensors combined to acoustic telemetry. Results showed that these fish are year-round resident, remaining inside the fully protected area of the marine reserve of Cerbère-Banyuls (65 ha) and display a diurnal activity pattern. Records from depth sensors revealed that groupers range inside small, distinct, and individual territories. Individual variations in habitat depth are only visible on a seasonal scale, i.e., between the spawning season and the rest of the year. In fact, during summer months when the seawater temperature exceeded 20 °C, tagged groupers made vertical spawning migrations of 4-8 m in amplitude. These vertical migrations are characteristic of the reproductive behaviour of dusky groupers, during which they release their gametes. The results are notable for the implementation of management rules in marine protected areas, such as reduced navigation speed, boating or attendance during spawning season. Copyright © 2013 Elsevier Ltd. All rights reserved.
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The influence of diel period on fish assemblage in the unstructured littoral of reservoirs
Czech Academy of Sciences Publication Activity Database
Říha, Milan; Kubečka, Jan; Prchalová, Marie; Mrkvička, Tomáš; Čech, Martin; Draštík, Vladislav; Frouzová, Jaroslava; Hohausová, Eva; Jůza, Tomáš; Kratochvíl, Michal; Peterka, Jiří; Tušer, Michal; Vašek, Mojmír
2011-01-01
Roč. 18, č. 4 (2011), s. 339-347 ISSN 0969-997X R&D Projects: GA ČR(CZ) GA206/07/1392; GA MZe(CZ) QH81046 Institutional research plan: CEZ:AV0Z60170517 Keywords : beach seining * diel migration * sampling * species composition * Římov Reservoir Subject RIV: EG - Zoology Impact factor: 1.294, year: 2011
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Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph
2017-01-12
We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Borisova, Kseniya K; Kvyatkovskaya, Elizaveta A; Nikitina, Eugeniya V; Aysin, Rinat R; Novikov, Roman A; Zubkov, Fedor I
2018-04-20
A rare example of chemospecificity in the tandem Diels-Alder reaction of activated alkynes and bis-dienes has been revealed. The reaction between bis-furyl dienes and DMAD occurs at 25-80 °C and leads to kinetically controlled "pincer" adducts, 4a,8a-disubstituted 1,4:5,8-diepoxynaphthalenes. On the contrary, only thermodynamically controlled "domino" adducts (2,3-disubstituted 1,4:5,8-diepoxynaphthalenes) are formed in the same reaction at 140 °C. The "pincer" adducts can be transformed to the "domino" adducts at heating. The rate constants for reactions of both types were calculated using dynamic 1 H NMR spectroscopy.
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Stepwise or concerted? DFT study on the mechanism of ionic Diels-Alder reaction of chromanes
Directory of Open Access Journals (Sweden)
Haghdadi Mina
2016-01-01
Full Text Available The stepwise and concerted Ionic Diels-Alder reaction between phenyl (pyridin-2-ylmethylene oxonium and styrene derivatives are explored using theoretical method. The results support using computational method via persistent intermediates. The DFT method was essential to reproduce a reasonable potential energy surface for these challenging systems.
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Yang, Limin; Wang, Fei; Lee, Richmond; Lv, Yunbo; Huang, Kuo-Wei; Zhong, Guofu
2014-01-01
A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study
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Kowalczyk, Marcin; Lupton, David W
2014-05-19
The addition of an N-heterocyclic carbene to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels-Alder reaction, for which mechanistic studies implicate Lewis base catalysis. Preliminary studies into the utility of the products have been undertaken with reductive and oxidative cleavage, giving materials for potential use in complex-target synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Directory of Open Access Journals (Sweden)
Millie T. Olsen
2015-06-01
Full Text Available Genomes were obtained for three closely related strains of Synechococcus that are representative of putative ecotypes that predominate at different depths in the 1 mm-thick, upper-green layer in the 60°C mat of Mushroom Spring, Yellowstone National Park, and exhibit different light adaptation and acclimation responses. The genomes were compared to the published genome of a previously obtained, closely related strain from a neighboring spring, and differences in both gene content and orthologous gene alleles between high-light-adapted and low-light-adapted strains were identified. Evidence of genetic differences that relate to adaptation to light intensity and/or quality, CO2 uptake, nitrogen metabolism, organic carbon metabolism, and uptake of other nutrients were found between strains of the different putative ecotypes. In situ diel transcription patterns of genes, including genes unique to either low-light-adapted or high-light-adapted strains and different alleles of an orthologous photosystem gene, revealed that expression is fine-tuned to the different light environments experienced by ecotypes prevalent at various depths in the mat. This study suggests that strains of closely related putative ecotypes have different genomic adaptations that enable them to inhabit distinct ecological niches while living in close proximity within a microbial community.
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An MM and QM Study of Biomimetic Catalysis of Diels-Alder Reactions Using Cyclodextrins
Directory of Open Access Journals (Sweden)
Wei Chen
2018-01-01
Full Text Available We performed a computational investigation of the mechanism by which cyclodextrins (CDs catalyze Diels-Alder reactions between 9-anthracenemethanol and N-cyclohexylmaleimide. Hydrogen bonds (Hbonds between N-cyclohexylmaleimide and the hydroxyl groups of cyclodextrins were suggested to play an important role in this catalytic process. However, our free energy calculations and molecular dynamics simulations showed that these Hbonds are not stable, and quantum mechanical calculations suggested that the reaction is not promoted by these Hbonds. The binding of 9-anthracenemethanol and N-cyclohexylmaleimide to cyclodextrins was the key to the catalytic process. Cyclodextrins act as a container to hold the two reactants in the cavity, pre-organize them for the reactions, and thus reduce the entropy penalty to the activation free energy. Dimethyl-β-CD was a better catalyst for this specific reaction than β-CD because of its stronger van der Waals interaction with the pre-organized reactants and its better performance in reducing the activation energy. This computational work sheds light on the mechanism of the catalytic reaction by cyclodextrins and introduces new perspectives of supramolecular catalysis.
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Default activity patterns at the neocortical microcircuit level
Directory of Open Access Journals (Sweden)
Artur eLuczak
2012-06-01
Full Text Available Even in absence of sensory stimuli cortical networks exhibit complex, self-organized activity patterns. While the function of those spontaneous patterns of activation remains poorly understood, recent studies both in vivo and in vitro have demonstrated that neocortical neurons activate in a surprisingly similar sequential order both spontaneously and following input into cortex. For example, neurons that tend to fire earlier within spontaneous bursts of activity also fire earlier than other neurons in response to sensory stimuli. These 'default patterns' can last hundreds of milliseconds and are strongly conserved under a variety of conditions. In this paper we will review recent evidence for these default patterns at the local cortical level. We speculate that cortical architecture imposes common constraints on spontaneous and evoked activity flow, which result in the similarity of the patterns.
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A facile avenue to conductive polymer brushes via cyclopentadiene-maleimide Diels-Alder ligation
Czech Academy of Sciences Publication Activity Database
Yameen, B.; Rodriguez-Emmenegger, C.; Preuss, C. M.; Pop-Georgievski, Ognen; Verveniotis, Elisseos; Trouillet, V.; Rezek, Bohuslav; Barner-Kowollik, C.
2013-01-01
Roč. 49, č. 77 (2013), s. 8623-8625 ISSN 1359-7345 R&D Projects: GA ČR GBP205/12/G118; GA ČR GAP108/11/1857; GA ČR(CZ) GBP108/12/G108 Institutional support: RVO:61389013 ; RVO:68378271 Keywords : conductive poly(3-hexylthiophen) brushes * Diels-Alder ligation * Kelvin Probe Force Microscopy (KFM) Subject RIV: CD - Macromolecular Chemistry Impact factor: 6.718, year: 2013
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Intramolecular anionic diels-alder reactions of 1-aryl-4-oxahepta-1,6-diyne systems in DMSO.
Kudoh, Takayuki; Mori, Tomoko; Shirahama, Mitsuhito; Yamada, Masashi; Ishikawa, Teruhiko; Saito, Seiki; Kobayashi, Hisayoshi
2007-04-25
Base-promoted cycloaddition reactions of 1-aryl- or 1-aryl-7-substituted-4-oxahepta-1,6-diyne systems in DMSO have proven to involve an anionic intramolecular Diels-Alder process taking place even at room temperature in spite of the reaction suffering from temporary disruption of aromaticity. Although initially formed alpha-arylallenide anion can be protonated by DMSO, it can be back to the allenide anion probably because of a small acidity difference between alpha-arylallene and DMSO. The alpha-arylallenide anion in combination with the alpha-aryl substituent can constitute an anionic diene structure that undergoes the intramolecular Diels-Alder reaction involving the C(6)-yne part, a very fast process probably because of the increased HOMO-1 level of the anionic diene, as shown by DFT calculations. Diversified substituted naphthalenes, benzofurans, phenanthrenes, and quinolines, including biaryl architectures, are available from 4-oxahepta-1,6-diynes in a highly expeditious way.
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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.
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Directory of Open Access Journals (Sweden)
Xinguo Shi
Full Text Available Gene structure and expression regulation of form II RuBisCO (rbcII in dinoflagellates are still poorly understood. Here we isolated this gene (Pdrbc and investigated its diel expression pattern in a harmful algal bloom forming dinoflagellate Prorocentrum donghaiense. We obtained cDNA sequences with triple tandem repeats of the coding unit (CU; the 5' region has the sequence of a typical dinoflagellate plastid gene, encoding an N-terminus with two transmembrane regions separated by a plastid transit peptide. The CUs (1,455 bp except 1464 bp in last CU are connected through a 63 bp spacer. Phylogenetic analysis showed that rbcII CUs within species formed monophyletic clusters, indicative of intraspecific gene duplication or purifying evolution. Using quantitative PCR (qPCR we estimated 117±40 CUs of Pdrbc in the P. donghaiense genome. Although it is commonly believed that most dinoflagellate genes lack transcriptional regulation, our RT-qPCR analysis on synchronized cultures revealed remarkable diel rhythm of Pdrbc expression, showing significant correlations of transcript abundance with the timing of the dark-to-light transition and cell cycle G2M-phase. When the cultures were shifted to continuous light, Pdrbc expression remained significantly correlated with the G2M-phase. Under continuous darkness the cell cycle was arrested at the G1 phase, and the rhythm of Pdrbc transcription disappeared. Our results suggest that dinoflagellate rbcII 1 undergoes duplication or sequence purification within species, 2 is organized in tandem arrays in most species probably to facilitate efficient translation and import of the encoded enzyme, and 3 is regulated transcriptionally in a cell cycle-dependent fashion at least in some dinoflagellates.
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Jasiński, Radomir
2017-08-01
DFT computational study shows that Diels-Alder (DA) reactions of 1-chloro-1-nitroethene with cyclopentadiene and furan have polar nature. However, their mechanism is substantially different. In particular, 1-chloro-1-nitroethene react with cyclopentadiene according to one-step mechanism. In the same time, more favourable channel associated with the P-DA reaction between furan and 1-chloro-1-nitroethene is a domino process, that comprises an initial hetero-Diels-Alder reaction yielding a [2+4] cycloadduct, which experiences a subsequent [3,3] sigmatropic shift to yield the expected formal [4+2] cycloadduct. This is a consequence of more polar nature of reaction, due to higher nucleophilicity of furan in comparison to cyclopentadiene. Copyright © 2017 Elsevier Inc. All rights reserved.
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DEFF Research Database (Denmark)
Jacobsen, Lene; Berg, Søren; Baktoft, Henrik
2015-01-01
Behaviour of large perch Perca fluviatilis was studied in two lakes differing in environmental state i.e. mesotrophic v. hypereutrophic. A total of 20 adult perch P. fluviatilis (29–42 cm total length) in each lake were tagged with radio-transmitters, tracked and located eight times a day during...... six 24 h tracking periods over a year, enabling detection of differences in diel activity patterns and habitat use during summer and winter under two different environmental regimes. During summer, P. fluviatilis in the mesotrophic lake showed a distinct crepuscular activity pattern and a change from...... factor of large P. fluviatilis did not differ between the two lakes. Thus, it is suggested that P. fluviatilis in the hypereutrophic turbid lake adopted an alternative behaviour for successful foraging, being uniformly active throughout the diel cycle...
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DEFF Research Database (Denmark)
Ishøy, Mette; Petersen, Rico; Petersen, Michael Åxman
2017-01-01
A high-yielding, stereoselective and extraordinarily complexity generatingPetasis 3-component/intramolecular Diels-Alderreaction has been developed. In combination with ROM-RCM, rapid access to complex sp3-rich heterocyclic scaffolds amenableto subsequent functionalization and library synthesis...
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Cove, Michael V.; Gardner, Beth; Simons, Theodore R.; Kays, Roland; O'Connell, Allan F.
2017-01-01
Feral and free-ranging domestic cats (Felis catus) can have strong negative effects on small mammals and birds, particularly in island ecosystems. We deployed camera traps to study free-ranging cats in national wildlife refuges and state parks on Big Pine Key and Key Largo in the Florida Keys, USA, and used spatial capture–recapture models to estimate cat abundance, movement, and activities. We also used stable isotope analyses to examine the diet of cats captured on public lands. Top population models separated cats based on differences in movement and detection with three and two latent groups on Big Pine Key and Key Largo, respectively. We hypothesize that these latent groups represent feral, semi-feral, and indoor/outdoor house cats based on the estimated movement parameters of each group. Estimated cat densities and activity varied between the two islands, with relatively high densities (~4 cats/km2) exhibiting crepuscular diel patterns on Big Pine Key and lower densities (~1 cat/km2) exhibiting nocturnal diel patterns on Key Largo. These differences are most likely related to the higher proportion of house cats on Big Pine relative to Key Largo. Carbon and nitrogen isotope ratios from hair samples of free-ranging cats (n = 43) provided estimates of the proportion of wild and anthropogenic foods in cat diets. At the population level, cats on both islands consumed mostly anthropogenic foods (>80% of the diet), but eight individuals were effective predators of wildlife (>50% of the diet). We provide evidence that cat groups within a population move different distances, exhibit different activity patterns, and that individuals consume wildlife at different rates, which all have implications for managing this invasive predator.
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Beniwal, Vijay; Kumar, Anil
2017-02-08
Organic reactions in general display large rate accelerations when performed under interfacial conditions, such as on water or at ionic liquid interfaces. However, a clear picture of the physicochemical factors responsible for this large rate enhancements is not available. To gain an understanding of the thermodynamic and molecular origin of these large rate enhancements, we performed a Diels-Alder reaction between cyclopentadiene and methyl acrylate at ionic liquid/n-hexane interfaces. This study describes, for the first time, a methodology for the calculation of the activation parameters of an interfacial reaction. It has been seen that the energy of activation for an interfacial reaction is much smaller than that of the corresponding homogeneous reaction, resulting into the large rate acceleration for the interfacial reaction. Furthermore, the study describes the effects of the alkyl chain length of ionic liquid cations, the extent of heterogeneity, and the polarity of ionic liquids on the rate constants and stereoselectivity of the reaction.
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Directory of Open Access Journals (Sweden)
RODRIGO RAMOS-JILIBERTO
2004-03-01
Full Text Available In this work we analyzed the depth-distribution, at noon and midnight, of three zooplankton populations which are common inhabitants of lakes from central Chile and coexist in lake El Plateado. The species were Tumeodiaptomus diabolicus, Diaphanosoma chilense and Bosmina longirostris. Also, we analyzed the association between the depth-specific abundances of the groups and the depth-specific temperature and oxygen values during the sampling period. Our results show that: (1 the three population exhibited diel vertical migration during part of the year; (2 T. diabolicus and D. chilense exhibited the normal pattern of vertical migration, and B. longirostris presented both the normal and the reverse pattern; (3 for all species and most dates, zooplankters experience significant decreases in oxygen exposure as a consequence of downward migration. Temperature costs are less important but present in T. diabolicus and D. chilense during part of the yearEn este trabajo analizamos la distribución en profundidad, a mediodía y medianoche, de tres poblaciones de zooplancton que son habitantes comunes de los lagos de Chile central, y que coexisten en el lago El Plateado. Las especies fueron Tumeodiaptomus diabolicus, Diaphanosoma chilense y Bosmina longirostris. También analizamos la asociación entre las abundancias profundidad-específicas de los grupos y los valores profundidad-específicos de temperatura y oxígeno durante el periodo de muestreo. Nuestros resultados muestran que: (1 las tres poblaciones exhibieron migración vertical durante una parte del año; (2 T. diabolicus y D. chilense exhibieron el patrón normal de migración, y B. longirostris presentó tanto el patrón normal como el inverso; (3 para todas las especies y en la mayoría de las fechas, el zooplancton presentó reducciones significativas en su exposición al oxígeno como consecuencia de la migración descendente. Los costos térmicos son menos importantes pero existentes en T
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Seasonal and daily activity patterns of leopard tortoises ...
African Journals Online (AJOL)
Seasonal and daily activity patterns of leopard tortoises ( Stigmochelys pardalis Bell, 1828) on farmland in the Nama-Karoo, South Africa. ... that activity is also initiated by the time since sunrise. Key words: Stigmochelys pardalis, leopard tortoise, activity patterns, activity behaviour, Nama-Karoo Biome, time of day, season.
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Solberg, Ingrid
2016-11-27
We addressed the behavioral patterns and DVM dynamics of sprat overwintering in a 150 m Norwegian fjord with increasing hypoxia by depth. An upward-facing echosounder deployed at the bottom and cabled to shore provided 4 months of continuous acoustic data. This enabled detailed studies of individual behavior, specifically allowing assessment of individual vertical migrations at dusk and dawn in relation to light, analysis of so-called rise-and-sink swimming, and investigation of the sprat’ swimming activity and behavior in severely hypoxic waters. Field campaigns supplemented the acoustic studies. The acoustic records showed that the main habitat for sprat was the upper ∼ 65 m where oxygen concentrations were ⩾ 0.7 mL O2 L-1. The sprat schooled at ∼ 50 m during daytime and initiated an upward migration about 1 hour prior to sunset. While some sprat migrated to surface waters, other individuals interrupted the ascent when at ∼20-30 m, and returned to deeper waters ∼ 20-50 min after sunset. Sprat at depth was on average larger, yet individuals made excursions to- and from upper layers. Sprat were swimming in a “rise and sink” pattern at depth, likely related to negative buoyancy. Short-term dives into waters with less than 0.45 mL O2 L-1 were interpreted as feeding forays for abundant overwintering Calanus spp. The deep group of sprat initiated a dawn ascent less than 1 hour before sunrise, ending at 20-30 m where they formed schools. They subsequently returned to deeper waters about ∼20 min prior to sunrise. Measurements of surface light intensities indicated that the sprat experienced lower light levels in upper waters at dawn than at dusk. The vertical swimming speed varied significantly between the behavioral tasks. The mixed DVM patterns and dynamic nocturnal behavior of sprat persisted throughout winter, likely shaped by individual strategies involving optimized feeding and predator avoidance, as well as relating to temperature, hypoxia and
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Leisure Activity Patterns and Marital Conflict in Iran.
Ahmadi, Khodabakhsh; Saadat, Hassan; Noushad, Siena
2016-01-01
Over the past few decades, the association between leisure activity patterns and marital conflict or satisfaction has been studied extensively. However, most studies to date have been limited to middle-class families of developed societies, and an investigation of the issue, from a developing country perspective like Iran, is non-existent. In an observational, analytical, cross-sectional study we aimed to investigate the relationship between leisure activity patterns and marital conflict in a nationally representative sample of Iranian married males. Using the cluster sampling method, a representative sample of 400 Iranian married individuals from seven provinces of Iran was surveyed. Self-administered surveys included a checklist collecting demographic and socioeconomic characteristics of the enrolled participants, leisure time questionnaire, and marital conflict questionnaire. The main patterns of leisure activity were derived from principal component analysis. For each pattern, factor scores were calculated. The relationship between factor scores and marital conflict were assessed using multivariate linear regression models accounting for the potential confounding effects of age, education, socioeconomic status, job status, number of children, duration of marriage, and time spent for leisure. Two hundred and ninety-nine respondents completed the leisure time and marital conflict questionnaires. Five major leisure patterns were identified accounting for 60.3% of the variance in data. The most dominant pattern was family-oriented activities (e.g. spending time with family outdoors and spending time with family indoors) and was negatively linked to marital conflict (standardized beta= -0.154, P = 0.013). Of the four remaining patterns, three only included individual activities and one was a family-individual composite. Individual patterns exhibited discrepant behavior; while the pattern involving activities like 'watching TV', 'non-purposive time spending', and
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Leisure Activity Patterns and Marital Conflict in Iran
Ahmadi, Khodabakhsh; Saadat, Hassan; Noushad, Siena
2016-01-01
Background: Over the past few decades, the association between leisure activity patterns and marital conflict or satisfaction has been studied extensively. However, most studies to date have been limited to middle-class families of developed societies, and an investigation of the issue, from a developing country perspective like Iran, is non-existent. Objectives: In an observational, analytical, cross-sectional study we aimed to investigate the relationship between leisure activity patterns and marital conflict in a nationally representative sample of Iranian married males. Patients and Methods: Using the cluster sampling method, a representative sample of 400 Iranian married individuals from seven provinces of Iran was surveyed. Self-administered surveys included a checklist collecting demographic and socioeconomic characteristics of the enrolled participants, leisure time questionnaire, and marital conflict questionnaire. The main patterns of leisure activity were derived from principal component analysis. For each pattern, factor scores were calculated. The relationship between factor scores and marital conflict were assessed using multivariate linear regression models accounting for the potential confounding effects of age, education, socioeconomic status, job status, number of children, duration of marriage, and time spent for leisure. Results: Two hundred and ninety-nine respondents completed the leisure time and marital conflict questionnaires. Five major leisure patterns were identified accounting for 60.3% of the variance in data. The most dominant pattern was family-oriented activities (e.g. spending time with family outdoors and spending time with family indoors) and was negatively linked to marital conflict (standardized beta= −0.154, P = 0.013). Of the four remaining patterns, three only included individual activities and one was a family-individual composite. Individual patterns exhibited discrepant behavior; while the pattern involving activities
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Türkmen, Yunus E; Montavon, Timothy J; Kozmin, Sergey A; Rawal, Viresh H
2012-06-06
A highly effective silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes has been developed. The reactions provide ready access to a wide range of siloxy naphthalenes and anthracenes, which are formed in good to high yields, under mild reaction conditions, using low catalyst loadings.
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Dypvik, Eivind; Kaartvedt, Stein
2012-01-01
The vertical migration and diel feeding periodicity of the skinnycheek lanternfish (Benthosema pterotum) were studied by use of a hull-mounted 38 kHz echo sounder, ROV-deployments and net-sampling at two locations (∼24°48′N, ∼36°15′E and ∼21°27′N
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Patterns and possible mechanisms of soil CO2 uptake in sandy soil.
Fa, Ke-Yu; Zhang, Yu-Qing; Wu, Bin; Qin, Shu-Gao; Liu, Zhen; She, Wei-Wei
2016-02-15
It has been reported that soils in drylands can absorb CO2, although the patterns and mechanisms of such a process remain under debate. To address this, we investigated the relationships between soil CO2 flux and meteorological factors and soil properties in Northwest China to reveal the reasons for "anomalous" soil CO2 flux in a desert ecosystem. Soil CO2 flux increased significantly and exponentially with surficial turbulence at the diel scale under dry conditions (Psoil CO2 flux demonstrated remarkable negative correlation with soil air pressure (Psoil water content was insufficient to dissolve the absorbed CO2 in dry conditions, but was sufficient in wet conditions. The concentration of soil HCO3(-) in the morning was higher than in the evening in dry conditions, but this pattern was reversed in wet conditions. These results imply that CO2 outgassing induced by turbulence, expansion of soil air, CO2 effusion from soil water, and carbonate precipitation during daytime can explain the abiotic diurnal CO2 release. Moreover, CO2 pumping from the atmosphere into the soil, caused mainly by carbonate dissolution, can account for nocturnal CO2 absorption in dry conditions. The abiotic soil CO2 flux pattern (CO2 absorption throughout the diel cycle) in wet conditions can be attributed to downward mass flow of soil CO2 and intensified soil air shrinkage, CO2 dissolving in soil water, and carbonate dissolution. These results provide a basis for determining the location of abiotic fixed carbon within soils in desert ecosystems. Copyright © 2015 Elsevier B.V. All rights reserved.
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Li, Mao; Carreras, Virginie; Jalba, Angela; Ollevier, Thierry
2018-02-16
An asymmetric Fe III -bipyridine diol catalyzed Diels-Alder reaction of α,β-unsaturated oxazolidin-2-ones has been developed. Among various Fe II /Fe III salts, Fe(ClO 4 ) 3 ·6H 2 O was selected as the Lewis acid of choice. The use of a low catalyst loading (2 mol % of Fe(ClO 4 ) 3 ·6H 2 O and 2.4 mol % of Bolm's ligand) afforded high yields (up to 99%) and high enantiomeric excesses (up to 98%) of endo-cycloadducts for the Diels-Alder reaction between cyclopentadiene and substituted acryloyloxazolidin-2-ones. Other noncyclic dienes led to decreased enantioselectivities. A proposed model supports the observed stereoinduction.
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Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium
Directory of Open Access Journals (Sweden)
Pégot Bruce
2006-09-01
Full Text Available Abstract The asymmetric aza-Diels-Alder reaction of chiral imines with Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their efficiency is preserved.
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Fish activity as determined by gillnet catch: A comparison of two reservoirs of different turbidity
Czech Academy of Sciences Publication Activity Database
Prchalová, Marie; Mrkvička, T.; Kubečka, Jan; Peterka, Jiří; Čech, Martin; Muška, Milan; Kratochvíl, Michal; Vašek, Mojmír
2010-01-01
Roč. 102, č. 3 (2010), s. 291-296 ISSN 0165-7836 Grant - others:NFM(CZ) CZ0091 Institutional research plan: CEZ:AV0Z60170517 Keywords : diel pattern * soak time * CPUE Subject RIV: EH - Ecology, Behaviour Impact factor: 1.656, year: 2010
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Pacheco, Joshua J.; Davis, Mark E.
2014-01-01
Terephthalic acid (PTA), a monomer in the synthesis of polyethylene terephthalate (PET), is obtained by the oxidation of petroleum-derived p-xylene. There is significant interest in the synthesis of renewable, biomass-derived PTA. Here, routes to PTA starting from oxidized products of 5-hydroxymethylfurfural (HMF) that can be produced from biomass are reported. These routes involve Diels-Alder reactions with ethylene and avoid the hydrogenation of HMF to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with high pressure ethylene over a pure-silica molecular sieve containing framework tin (Sn-Beta) to produce the Diels-Alder dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with 31% selectivity at 61% HMFA conversion after 6 h at 190 °C. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of Sn-Beta for 2 h to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with 46% selectivity at 28% MMFC conversion or in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) for 6 h to produce MMBC with 81% selectivity at 26% MMFC conversion. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder dehydration product is observed. PMID:24912153
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Guan, Chao; Li, Xinrong; Zhang, Peng; Chen, Yongle
2018-01-01
Soil respiration induced by biological soil crusts (BSCs) is an important process in the carbon (C) cycle in arid and semi-arid ecosystems, where vascular plants are restricted by the harsh environment, particularly the limited soil moisture. However, the interaction between temperature and soil respiration remains uncertain because of the number of factors that control soil respiration, including temperature and soil moisture, especially in BSC-dominated areas. In this study, the soil respiration in moss-dominated crusts and lichen-dominated crusts was continuously measured using an automated soil respiration system over a one-year period from November 2015 to October 2016 in the Shapotou region of the Tengger Desert, northern China. The results indicated that over daily cycles, the half-hourly soil respiration rates in both types of BSC-covered areas were commonly related to the soil temperature. The observed diel hysteresis between the half-hourly soil respiration rates and soil temperature in the BSC-covered areas was limited by nonlinearity loops with semielliptical shapes, and soil temperature often peaked later than the half-hourly soil respiration rates in the BSC-covered areas. The average lag times between the half-hourly soil respiration rates and soil temperature for both types of BSC-covered areas were two hours over the diel cycles, and they were negatively and linearly related to the volumetric soil water content. Our results highlight the diel hysteresis phenomenon that occurs between soil respiration rates and soil temperatures in BSC-covered areas and the negative response of this phenomenon to soil moisture, which may influence total C budget evaluations. Therefore, the interactive effects of soil temperature and moisture on soil respiration in BSC-covered areas should be considered in global carbon cycle models of desert ecosystems.
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Polgar, L. M.; Fortunato, G.; Araya-Hermosilla, R.; van Duin, M.; Pucci, A.; Picchioni, F.
Furan-functionalized polyketone (PK-FU) was added to a furan-functionalized ethylene-propylene rubber (EPM-FU). The mixture was subsequently cross-linked with a bismaleimide through Diels-Alder chemistry in order to improve the mechanical properties of the rubber. Infrared spectroscopy showed the
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Effects of diel vertical migration on ephippia production in Daphnia
Directory of Open Access Journals (Sweden)
Victor ALEKSEEV
2004-09-01
Full Text Available Fish presence in experimentally simulated temperature conditions (limno-towers led to diel vertical migration and resulted in a decrease of ephippia production in Daphnia pulicaria. Diel fluctuation of food, temperature and day length similar to those experienced by migrating Daphnia were tested in laboratory experiments with flow-through-systems. Daphnids were kept under these conditions for 15 days and the proportions of females producing an ephippium were determined. In addition, maturation time, survival to maturation, size of the first clutch and female dry weight (without eggs on day 15 were traced. The most important factor affecting ephippia production in migrating Daphnia was photoperiod change, and when mother and embryo are exposed to alternating light conditions, these are thought to have the effect on the mother of acting as a signal to stop ephippia production. Such effects might be explained by the different sensitiveness to light intensity in females carrying an embryo and an embryo itself in broods. Fish presence forced Daphnia to stay in low-light conditions during daytime hours, to avoid attacks by fish. The Daphnia were able to check light intensity constantly by short vertical jumps above a light-threshold that was confirmed experimentally in limno-towers. The dim conditions were possibly light enough for adults to check day length, but were too dark for embryos shaded by the mother's body. Food conditions played a relatively small role in the process, and no effects of temperature on ephippia production were found. As expected, food affected the size of the first clutch, and temperature controlled the time to maturation. Photoperiod had a marginally significant influence on the time to maturation in Daphnia. A hypothesis on the role of photoperiod as the key factor for Daphnia life cyclic recurrence and other seasonal adaptations is proposed.
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The inverse electron demand Diels-Alder click reaction in radiochemistry.
Reiner, Thomas; Zeglis, Brian M
2014-04-01
The inverse electron-demand Diels-Alder (IEDDA) cycloaddition between 1,2,4,5-tetrazines and strained alkene dienophiles is an emergent variety of catalyst-free 'click' chemistry that has the potential to have a transformational impact on the synthesis and development of radiopharmaceuticals. The ligation is selective, rapid, high-yielding, clean, and bioorthogonal and, since its advent in 2008, has been employed in a wide variety of chemical settings. In radiochemistry, the reaction has proven particularly useful with (18) F and has already been utilized to create a number of (18) F-labeled agents, including the PARP1-targeting small molecule (18) F-AZD2281, the αv β3 integrin-targeting peptide (18) F-RGD, and the GLP-1-targeting peptide (18) F-exendin. The inherent flexibility of the ligation has also been applied to the construction of radiometal-based probes, specifically the development of a modular strategy for the synthesis of radioimmunoconjugates that effectively eliminates variability in the construction of these agents. Further, the exceptional speed and biorthogonality of the reaction have made it especially promising in the realm of in vivo pretargeted imaging and therapy, and pretargeted imaging strategies based on the isotopes (111) In, (18) F, and (64) Cu have already proven capable of producing images with high tumor contrast and low levels of uptake in background, nontarget organs. Ultimately, the characteristics of inverse electron-demand Diels-Alder click chemistry make it almost uniquely well-suited for radiochemistry, and although the field is young, this ligation has the potential to make a tremendous impact on the synthesis, development, and study of novel radiopharmaceuticals. Copyright © 2013 John Wiley & Sons, Ltd.
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James, Natalie C.; Um, Joann M.; Padias, Anne B.; Hall, H. K.; Houk, K. N.
2013-01-01
The energetics of the Diels-Alder cycloaddition reactions of several 1,3-dienes with acrylonitrile, and the energetics of formation of diradicals, were investigated with density functional theory (B3LYP and M06-2X) and compared to experimental data. For the reaction of 2,3-dimethyl-1,3-butadiene with acrylonitrile, the concerted reaction is favored over the diradical pathway by 2.5 kcal/mol using B3LYP/6-31G(d); experimentally this reaction gives both cycloadduct and copolymer. The concerted cycloaddition of cyclopentadiene with acrylonitrile is preferred computationally over the stepwise pathway by 5.9 kcal/mol; experimentally, only the Diels-Alder adduct is formed. For the reactions of (E)-1,3-pentadiene and acrylonitrile, both cycloaddition and copolymerization were observed experimentally; these trends were mimicked by the computational results, which showed only a 1.2 kcal/mol preference for the concerted pathway. For the reactions of (Z)-1,3-pentadiene and acrylonitrile, the stepwise pathway is preferred by 3.9 kcal/mol, in agreement with previous experimental findings that only polymerization occurs. M06-2X is known to give more accurate activation and reaction energetics but the energies of diradicals are too high. PMID:23758325
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Kislov, V V; Islamova, N I; Kolker, A M; Lin, S H; Mebel, A M
2005-09-01
Extensive ab initio Gaussian-3-type calculations of potential energy surfaces (PES), which are expected to be accurate within 1-2 kcal/mol, combined with statistical theory calculations of reaction rate constants have been applied to study various possible pathways in the hydrogen abstraction acetylene addition (HACA) mechanism of naphthalene and acenaphthalene formation as well as Diels-Alder pathways to acenaphthalene, phenanthrene, and pyrene. The barrier heights; reaction energies; and molecular parameters of the reactants, products, intermediates, and transition states have been generated for all types of reactions involved in the HACA and Diels-Alder mechanisms, including H abstraction from various aromatic intermediates, acetylene addition to radical sites, ring closures leading to the formation of additional aromatic rings, elimination of hydrogen atoms, H disproportionation, C2H2 cycloaddition, and H2 loss. The reactions participating in various HACA sequences (e.g., Frenklach's, alternative Frenklach's, and Bittner and Howard's routes) are demonstrated to have relatively low barriers and high rate constants under combustion conditions. A comparison of the significance of different HACA mechanisms in PAH growth can be made in the future using PES and molecular parameters obtained in the present work. The results show that the Diels-Alder mechanism cannot compete with the HACA pathways even at high combustion temperatures, because of high barriers and consequently low reaction rate constants. The calculated energetic parameters and rate constants have been compared with experimental and theoretical data available in the literature.
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DEFF Research Database (Denmark)
Steunou, Anne-Soisig; Jensen, Sheila I; Brecht, Eric
2008-01-01
Nitrogen fixation, a prokaryotic, O(2)-inhibited process that reduces N(2) gas to biomass, is of paramount importance in biogeochemical cycling of nitrogen. We analyzed the levels of nif transcripts of Synechococcus ecotypes, NifH subunit and nitrogenase activity over the diel cycle...... in the microbial mat of an alkaline hot spring in Yellowstone National Park. The results showed a rise in nif transcripts in the evening, with a subsequent decline over the course of the night. In contrast, immunological data demonstrated that the level of the NifH polypeptide remained stable during the night...
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Eleftheriadis, Nikolaos; Samatidou, Evanthia; Neochoritis, Constantinos G.
The Lewis acid-catalyzed Diels-Alder reactions of suitably substituted imidazole-2-thiones with dienes were studied. It was found that the electron density of the imidazole core influenced the reaction, since electron withdrawing groups led to the novel spiro-derivatives 2 whereas electron donating
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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…
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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.
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International Nuclear Information System (INIS)
Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling
2017-01-01
Highlights: • Silver nanoparticles were functionalized by furan groups. • The DA reaction of furan with bismaleimide was used to cross-link the particles. • The reverse cross-linking could be controlled by temperature. • The antibacterial activity of silvers could be adjusted by the cross-linking. - Abstract: Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV–vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.
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Energy Technology Data Exchange (ETDEWEB)
Liu, Lian; Yang, Pengfei, E-mail: ypf@qlu.edu.cn; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling
2017-05-01
Highlights: • Silver nanoparticles were functionalized by furan groups. • The DA reaction of furan with bismaleimide was used to cross-link the particles. • The reverse cross-linking could be controlled by temperature. • The antibacterial activity of silvers could be adjusted by the cross-linking. - Abstract: Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV–vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.
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Investigating radical cation chain processes in the electrocatalytic Diels-Alder reaction.
Imada, Yasushi; Okada, Yohei; Chiba, Kazuhiro
2018-01-01
Single electron transfer (SET)-triggered radical ion-based reactions have proven to be powerful options in synthetic organic chemistry. Although unique chain processes have been proposed in various photo- and electrochemical radical ion-based transformations, the turnover number, also referred to as catalytic efficiency, remains unclear in most cases. Herein, we disclose our investigations of radical cation chain processes in the electrocatalytic Diels-Alder reaction, leading to a scalable synthesis. A gram-scale synthesis was achieved with high current efficiency of up to 8000%. The reaction monitoring profiles showed sigmoidal curves with induction periods, suggesting the involvement of intermediate(s) in the rate determining step.
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Liu, Fengli; Pullarkat, Sumod A; Tan, Kien-Wee; Li, Yongxin; Leung, Pak-Hing
2009-12-07
The organoplatinum complex containing ortho-metalated (R)-(1-(dimethylamino)ethyl)-naphthalene as the chiral auxiliary has been used efficiently to promote the asymmetric [4 + 2] Diels-Alder reaction between diphenylvinylphosphine and 3-diphenylphosphinofuran to generate two chelating diphosphine endocycloadducts in the ratio 17:1. The absolute configurations of the three newly generated stereocenters have been assigned by single-crystal X-ray analysis.
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Directory of Open Access Journals (Sweden)
Mujeeb A. Sultan
2016-01-01
Full Text Available Diels-Alder reaction of 10-allyl-1,8-dichloroanthracene (3 with 2-chloroacrylonitrile (4 and 1-cyanovinyl acetate (5 gives exclusively the ortho isomer while its reaction with phenyl vinyl sulfone (10 yields a mixture of two isomeric adducts with priority to ortho isomer. The reactions proceeded under microwave condition in xylene. Configurations of these isomers have been assigned with the help of NMR spectra. The results indicated that the steric effect is dominating toward the isomer regioselectivity in the Diels-Alder reaction of the present compounds.
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Modeling activity patterns of wildlife using time-series analysis.
Zhang, Jindong; Hull, Vanessa; Ouyang, Zhiyun; He, Liang; Connor, Thomas; Yang, Hongbo; Huang, Jinyan; Zhou, Shiqiang; Zhang, Zejun; Zhou, Caiquan; Zhang, Hemin; Liu, Jianguo
2017-04-01
The study of wildlife activity patterns is an effective approach to understanding fundamental ecological and evolutionary processes. However, traditional statistical approaches used to conduct quantitative analysis have thus far had limited success in revealing underlying mechanisms driving activity patterns. Here, we combine wavelet analysis, a type of frequency-based time-series analysis, with high-resolution activity data from accelerometers embedded in GPS collars to explore the effects of internal states (e.g., pregnancy) and external factors (e.g., seasonal dynamics of resources and weather) on activity patterns of the endangered giant panda ( Ailuropoda melanoleuca ). Giant pandas exhibited higher frequency cycles during the winter when resources (e.g., water and forage) were relatively poor, as well as during spring, which includes the giant panda's mating season. During the summer and autumn when resources were abundant, pandas exhibited a regular activity pattern with activity peaks every 24 hr. A pregnant individual showed distinct differences in her activity pattern from other giant pandas for several months following parturition. These results indicate that animals adjust activity cycles to adapt to seasonal variation of the resources and unique physiological periods. Wavelet coherency analysis also verified the synchronization of giant panda activity level with air temperature and solar radiation at the 24-hr band. Our study also shows that wavelet analysis is an effective tool for analyzing high-resolution activity pattern data and its relationship to internal and external states, an approach that has the potential to inform wildlife conservation and management across species.
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Directory of Open Access Journals (Sweden)
B. Biolatto
2000-03-01
Full Text Available Under high pressure conditions, the Diels-Alder reaction involving N,N-diethyl-1-tosyl-3-indoleglyoxylamide and 1-(N-acetyl-N-propylamino-1,3-butadiene produces a highly functionalized intermediate for the synthesis of Indole Alkaloids, in shorter times and higher yields than under thermal conditions.
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Diels-Alder Synthesis of endo-cis-N-phenylbicyclo[2.2.2]oct-5-en-2,3-dicarboximide
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.
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Rodríguez, Yeray A; Gutiérrez, Margarita; Ramírez, David; Alzate-Morales, Jans; Bernal, Cristian C; Güiza, Fausto M; Romero Bohórquez, Arnold R
2016-10-01
New N-allyl/propargyl 4-substituted 1,2,3,4-tetrahydroquinolines derivatives were efficiently synthesized using acid-catalyzed three components cationic imino Diels-Alder reaction (70-95%). All compounds were tested in vitro as dual acetylcholinesterase and butyryl-cholinesterase inhibitors and their potential binding modes, and affinity, were predicted by molecular docking and binding free energy calculations (∆G) respectively. The compound 4af (IC50 = 72 μm) presented the most effective inhibition against acetylcholinesterase despite its poor selectivity (SI = 2), while the best inhibitory activity on butyryl-cholinesterase was exhibited by compound 4ae (IC50 = 25.58 μm) with considerable selectivity (SI = 0.15). Molecular docking studies indicated that the most active compounds fit in the reported acetylcholinesterase and butyryl-cholinesterase active sites. Moreover, our computational data indicated a high correlation between the calculated ∆G and the experimental activity values in both targets. © 2016 The Authors Chemical Biology & Drug Design Published by John Wiley & Sons Ltd.
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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.
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Yang, Baochao; Lin, Kuaikuai; Shi, Yingbo; Gao, Shuanhu
2017-09-20
Stereoselective construction of polycyclic rings with all-carbon quaternary centers, and vicinal all-carbon quaternary stereocenters, remains a significant challenge in organic synthesis. These structures can be found in a wide range of polycyclic natural products and drug molecules. Here we report a Ti(Oi-Pr) 4 -promoted photoenolization/Diels-Alder (PEDA) reaction to construct hydroanthracenol and related polycyclic rings bearing all-carbon quaternary centers. This photolysis proceeds under mild conditions and generates a variety of photo-cycloaddition products in good reaction efficiency and stereoselectivity (48 examples), and has been successfully used in the construction of core skeleton of oncocalyxones, tetracycline and pleurotin. It also provides a reliable method for the late-stage modification of natural products bearing enone groups, such as steroids. The total synthesis of oncocalyxone B was successfully achieved using this PEDA approach.Anthracenols with multiple chiral centres are common motifs in natural products. Here, the authors show a highly stereoselective photoenolization/Diels-Alder methodology involving a key Lewis acid reagent enabling the efficient construction of a family of anthracenol derivatives with quaternary centers.
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Li, Jinling; Jiao, Chongjun; Huang, Kuo-Wei; Wu, Jishan
2011-01-01
Diels-Alder cycloaddition reactions at the bay regions of bisanthene (1) with dienophiles such as 1,4-naphthoquinone have been investigated. The products were submitted to nucleophilic addition followed by reductive aromatization reactions to afford the laterally extended bisanthene derivatives 2 and 3. Attempted synthesis of a larger expanded bisanthene 4 revealed an unexpected hydrogenation reaction at the last reductive aromatization step. Unusual Michael addition was observed on quinone 14, which was obtained by Diels-Alder reaction between 1 and 1,4-anthraquinone. Compounds 1-3 exhibited near-infrared (NIR) absorption and emission with high-to-moderate fluorescent quantum yields. Their structures and absorption spectra were studied by density function theory and non-planar twisted structures were calculated for 2 and 3. All compounds showed amphoteric redox behavior with multiple oxidation/reduction waves. Oxidative titration with SbCl 5 gave stable radical cations, and the process was followed by UV/Vis/NIR spectroscopic measurements. Their photostability was measured and correlated to their different geometries and electronic structures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Li, Jinling
2011-11-14
Diels-Alder cycloaddition reactions at the bay regions of bisanthene (1) with dienophiles such as 1,4-naphthoquinone have been investigated. The products were submitted to nucleophilic addition followed by reductive aromatization reactions to afford the laterally extended bisanthene derivatives 2 and 3. Attempted synthesis of a larger expanded bisanthene 4 revealed an unexpected hydrogenation reaction at the last reductive aromatization step. Unusual Michael addition was observed on quinone 14, which was obtained by Diels-Alder reaction between 1 and 1,4-anthraquinone. Compounds 1-3 exhibited near-infrared (NIR) absorption and emission with high-to-moderate fluorescent quantum yields. Their structures and absorption spectra were studied by density function theory and non-planar twisted structures were calculated for 2 and 3. All compounds showed amphoteric redox behavior with multiple oxidation/reduction waves. Oxidative titration with SbCl 5 gave stable radical cations, and the process was followed by UV/Vis/NIR spectroscopic measurements. Their photostability was measured and correlated to their different geometries and electronic structures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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1 Antibacterial and cytotoxic activities of Terminalia stenostachya ...
African Journals Online (AJOL)
activities of extracts of Terminalia stenostachya Engl. & Diels and Terminalia ... leprosy, nosebleeds, oedema, pneumonia, skin diseases, sore throats, dental caries, ..... Helicobacter pylori and Candida spp. to the east African plant Terminalia ...
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International Nuclear Information System (INIS)
Vesper, Dorothy J.; Smilley, Michael J.
2010-01-01
This study reports changes in coal-mine drainage constituent concentrations through a passive treatment wetland and over diel cycles. The purpose of the study was to determine what physiochemical mechanisms control attenuation of metals and if they varied by location and through time. The source water was slightly acidic (average pH 5.43); downstream degassing of CO 2 contributed to an increase in pH prior to discharge from the site (average pH 7.05). Aluminum, Fe, rare earth elements (REE) and Y were removed to a greater extent than were Mn, Co and Ni. At acidic pH, the REE and Y were generally complexed by SO 4 . At higher pH, carbonate complexes became more important. The REE and Y concentrations were normalized to the North American Shale Composite standard; the normalized patterns were coherent near the source but anomalies of Ce and Y were present further downstream indicating oxidation and sorption processes. Four sets of diel-based samples were collected, one from a shallow, surface-flow wetland and three from a deeper, newly constructed wetland. Well-defined diel cycles were observed for concentrations of Si, Mn, Fe, Co, Ni, As, REE and Y in the shallow wetland. In all cases, the concentrations increased (up to 863%) during night and decreased during the day. These cycles had an inverse relationship with the temperature cycle (pH had no discernable cycle). The consistency of concentration cycles suggests a common mechanism, most likely associated with the formation of Fe oxyhydroxides. The increased rate of Fe 2+ oxidation in warm water can account for the cycles in Fe; scavenging of the other elements by the Fe precipitate can account for the consistency of the cycles even though the elements include cations, anions (H 2 AsO 4 - or HAsO 4 -2 ), and neutral species (H 4 SiO 4 0 ). While REE and Y had clear cycles in the constructed wetland, the other elements did not. This is partially due to the lower elemental concentrations (including Fe) but the cycles
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Polgar, L. M.; van Duin, M.; Broekhuis, A. A.; Picchioni, F.
2015-01-01
A proof of principle for the use of Diels-Alder chemistry as a thermoreversible cross-linking tool for rubber products is demonstrated. A commercial ethylene-propylene rubber grafted with maleic anhydride has been thermoreversibly cross-linked in two steps. The pending anhydride rings were first
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Ervilha, Ulysses Fernandes; Mochizuki, Luis; Figueira, Aylton; Hamill, Joseph
2017-09-01
This study aimed to investigate the activation of lower limb muscles during barefoot and shod running with forefoot or rearfoot footfall patterns. Nine habitually shod runners were asked to run straight for 20 m at self-selected speed. Ground reaction forces and thigh and shank muscle surface electromyographic (EMG) were recorded. EMG outcomes (EMG intensity [iEMG], latency between muscle activation and ground reaction force, latency between muscle pairs and co-activation index between muscle pairs) were compared across condition (shod and barefoot), running cycle epochs (pre-strike, strike, propulsion) and footfall (rearfoot and forefoot) by ANOVA. Condition affected iEMG at pre-strike epoch. Forefoot and rearfoot strike patterns induced different EMG activation time patterns affecting co-activation index for pairs of thigh and shank muscles. All these timing changes suggest that wearing shoes or not is less important for muscle activation than the way runners strike the foot on the ground. In conclusion, the guidance for changing external forces applied on lower limbs should be pointed to the question of rearfoot or forefoot footfall patterns.
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Dypvik, Eivind
2012-11-13
The vertical migration and diel feeding periodicity of the skinnycheek lanternfish (Benthosema pterotum) were studied by use of a hull-mounted 38 kHz echo sounder, ROV-deployments and net-sampling at two locations (∼24°48′N, ∼36°15′E and ∼21°27′N, ∼38°5′E) in the central Red Sea. The mesopelagic zone of the Red Sea represents an unusual environment with very high temperatures (∼22 °C) and low zooplankton concentrations (<10 individuals m−3 below 600 m). The skinnycheek lanternfish performed normal diel vertical migration from ∼500 to 750 m during daytime to the epipelagic zone (upper ∼200 m) at night. A strict feeding periodicity occurred; with the skinnycheek lanternfish foraging on zooplankton throughout the night, while rapidly digesting the preceding nocturnal meal in the warm mesopelagic region. We hypothesize that the constrained epipelagic distribution of zooplankton and the unusual warm waters of the Red Sea force the whole population to ascend and feed in epipelagic waters every night, as the prey-ration eaten each night is fully digested at mesopelagic depths during daytime.
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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.
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Pszenny, A.; Cotter, K.; Deegan, B.; Fischer, E.; Johnson, D.
2007-12-01
PM2.5 aerosol was sampled over nominal 3-hour intervals at the head of Zuma Beach in Malibu, California (USA) from 6 to 24 October 2006 by filtration at 1.13 m3 min-1 (STP) through 20 x 25 cm cellulose fiber (Whatman 41) filters that had been rinsed with deionized water (DIW). Exposed filters were removed from support cartridges as soon as possible after retrieval (usually within 2 hours), immediately sealed in clean polyethylene bags, and stored frozen until further processing. Following the field campaign one quarter of each filter was pressed into a pellet (2.0 cm diameter x 0.5 cm thick) and analyzed by neutron activation for total concentrations of I and several other trace elements. Our preliminary analyses indicate that sodium and iodine show a clear diel variation characterized by higher concentrations from late morning to early evening. We hypothesize that this diel variability is related to a persistent land/sea breeze circulation associated with the nearby coastal region. Other elements are indicative of variability in other aerosol sources such as soil dust (Al, Mn) and fossil fuel combustion (V). Second quarters are currently being extracted in DIW and analyzed in two ways: 1) for iodide by ion chromatography, and 2) for inorganic iodine in higher oxidation states (i.e., V to 0) by chemical reduction with ascorbic acid followed by determination of iodide by ion chromatography. Results of the trace element and speciated iodine analyses will be presented.
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Suboptimal Muscle Synergy Activation Patterns Generalize their Motor Function across Postures.
Sohn, M Hongchul; Ting, Lena H
2016-01-01
We used a musculoskeletal model to investigate the possible biomechanical and neural bases of using consistent muscle synergy patterns to produce functional motor outputs across different biomechanical conditions, which we define as generalizability. Experimental studies in cats demonstrate that the same muscle synergies are used during reactive postural responses at widely varying configurations, producing similarly-oriented endpoint force vectors with respect to the limb axis. However, whether generalizability across postures arises due to similar biomechanical properties or to neural selection of a particular muscle activation pattern has not been explicitly tested. Here, we used a detailed cat hindlimb model to explore the set of feasible muscle activation patterns that produce experimental synergy force vectors at a target posture, and tested their generalizability by applying them to different test postures. We used three methods to select candidate muscle activation patterns: (1) randomly-selected feasible muscle activation patterns, (2) optimal muscle activation patterns minimizing muscle effort at a given posture, and (3) generalizable muscle activation patterns that explicitly minimized deviations from experimentally-identified synergy force vectors across all postures. Generalizability was measured by the deviation between the simulated force direction of the candidate muscle activation pattern and the experimental synergy force vectors at the test postures. Force angle deviations were the greatest for the randomly selected feasible muscle activation patterns (e.g., >100°), intermediate for effort-wise optimal muscle activation patterns (e.g., ~20°), and smallest for generalizable muscle activation patterns (e.g., synergy force vector was reduced by ~45% when generalizability requirements were imposed. Muscles recruited in the generalizable muscle activation patterns had less sensitive torque-producing characteristics to changes in postures. We
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Facile approach to prepare pH and redox-responsive nanogels via Diels-Alder click reaction
Directory of Open Access Journals (Sweden)
C. M. Q. Le
2018-08-01
Full Text Available A novel pH and redox responsive system of sub-100 nm nanogels was prepared by arm-first approach via Diels-Alder click reaction. First, well-defined poly(ethylene glycol-block-poly(styrene-alt-maleic anhydride (PEG-b-PSM was synthesized and subsequently functionalized with furfuryl amine, leading to the formation of the dual-functional block copolymer of PEG-b-PSMf. The furfuryl groups in the PSMf block were employed to incorporate a redox-responsive linkage and the carboxylic acid moieties generated through functionalization acted as a pH-responsive part. The Diels-Alder click reaction between a bismaleimide crosslinker and PEG-b-PSMf was conducted at 60 °C, affording star-like nanogel structures. Doxorubicin, a model anticancer drug, was loaded into to the core of the nanogels primarily by the ionic interaction with carboxylates of core blocks and a highest drug loading capacity of 38.1% was obtained. Furthermore, the in vitro profile showed a low release percentage (11.2% of DOX at PBS pH 7.4, whereas a burst release (62% at pH 5.0 in the presence of 10 mM glutathione, indicating the effective pH and redox responsive characteristic of the PEG-b-PSMf nanogels.
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Qi, Jun; Roush, William R.
2008-01-01
A direct synthesis of the α-hydroxyaldehyde exo-5, a precursor of the exo-spirotetronate subunit o f the quartromicins, was achieved through an exo-selective Lewis acid-catalyzed Diels-Alder reaction of dienophile 12a and diene 1. PMID:16774259
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International Nuclear Information System (INIS)
Silva, Fernando de C. da; Ferreira, Sabrina B.; Ferreira, Vitor F.; Kaiser, Carlos R.; Pinto, Angelo C.
2009-01-01
Methylene and aryl o-quinone methides (o-QMs) generated by Knoevenagel condensation of 2-hydroxy-1,4-naphthoquinone with formaldehyde and arylaldehydes, undergo facile hetero Diels-Alder reaction with some substituted styrenes (as dienophiles) in aqueous ethanol media providing derivatives of α- and β-lapachone (author)
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Mining continuous activity patterns from animal trajectory data
Wang, Y.; Luo, Ze; Baoping, Yan; Takekawa, John Y.; Prosser, Diann J.; Newman, Scott H.
2014-01-01
The increasing availability of animal tracking data brings us opportunities and challenges to intuitively understand the mechanisms of animal activities. In this paper, we aim to discover animal movement patterns from animal trajectory data. In particular, we propose a notion of continuous activity pattern as the concise representation of underlying similar spatio-temporal movements, and develop an extension and refinement framework to discover the patterns. We first preprocess the trajectories into significant semantic locations with time property. Then, we apply a projection-based approach to generate candidate patterns and refine them to generate true patterns. A sequence graph structure and a simple and effective processing strategy is further developed to reduce the computational overhead. The proposed approaches are extensively validated on both real GPS datasets and large synthetic datasets.
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Integration of active pauses and pattern of muscular activity during computer work.
St-Onge, Nancy; Samani, Afshin; Madeleine, Pascal
2017-09-01
Submaximal isometric muscle contractions have been reported to increase variability of muscle activation during computer work; however, other types of active contractions may be more beneficial. Our objective was to determine which type of active pause vs. rest is more efficient in changing muscle activity pattern during a computer task. Asymptomatic regular computer users performed a standardised 20-min computer task four times, integrating a different type of pause: sub-maximal isometric contraction, dynamic contraction, postural exercise and rest. Surface electromyographic (SEMG) activity was recorded bilaterally from five neck/shoulder muscles. Root-mean-square decreased with isometric pauses in the cervical paraspinals, upper trapezius and middle trapezius, whereas it increased with rest. Variability in the pattern of muscular activity was not affected by any type of pause. Overall, no detrimental effects on the level of SEMG during active pauses were found suggesting that they could be implemented without a cost on activation level or variability. Practitioner Summary: We aimed to determine which type of active pause vs. rest is best in changing muscle activity pattern during a computer task. Asymptomatic computer users performed a standardised computer task integrating different types of pauses. Muscle activation decreased with isometric pauses in neck/shoulder muscles, suggesting their implementation during computer work.
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Contrasting activity patterns of sympatric and allopatric black and grizzly bears
Schwartz, C.C.; Cain, S.L.; Podruzny, S.; Cherry, S.; Frattaroli, L.
2010-01-01
The distribution of grizzly (Ursus arctos) and American black bears (U. americanus) overlaps in western North America. Few studies have detailed activity patterns where the species are sympatric and no studies contrasted patterns where populations are both sympatric and allopatric. We contrasted activity patterns for sympatric black and grizzly bears and for black bears allopatric to grizzly bears, how human influences altered patterns, and rates of grizzlyblack bear predation. Activity patterns differed between black bear populations, with those sympatric to grizzly bears more day-active. Activity patterns of black bears allopatric with grizzly bears were similar to those of female grizzly bears; both were crepuscular and day-active. Male grizzly bears were crepuscular and night-active. Both species were more night-active and less day-active when ???1 km from roads or developments. In our sympatric study area, 2 of 4 black bear mortalities were due to grizzly bear predation. Our results suggested patterns of activity that allowed for intra- and inter-species avoidance. National park management often results in convergence of locally high human densities in quality bear habitat. Our data provide additional understanding into how bears alter their activity patterns in response to other bears and humans and should help park managers minimize undesirable bearhuman encounters when considering needs for temporal and spatial management of humans and human developments in bear habitats. ?? 2010 The Wildlife Society.
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Volkmar, E.C.; Dahlgren, R.A.; Stringfellow, W.T.; Henson, S.S.; Borglin, S.E.; Kendall, C.; Van Nieuwenhuyse, E. E.
2011-01-01
To investigate the mechanism for diel (24h) changes commonly observed at fixed sampling locations and how these diel changes relate to downstream transport in hypereutrophic surface waters, we studied a parcel of agricultural drainage water as it traveled for 84h in a concrete-lined channel having no additional water inputs or outputs. Algal fluorescence, dissolved oxygen, temperature, pH, conductivity, and turbidity were measured every 30min. Grab samples were collected every 2h for water quality analyses, including nutrients, suspended sediment, and chlorophyll/pheophytin. Strong diel patterns were observed for dissolved oxygen, pH, and temperature within the parcel of water. In contrast, algal pigments and nitrate did not exhibit diel patterns within the parcel of water, but did exhibit strong diel patterns for samples collected at a fixed sampling location. The diel patterns observed at fixed sampling locations for these constituents can be attributed to algal growth during the day and downstream transport (washout) of algae at night. Algal pigments showed a rapid daytime increase during the first 48h followed by a general decrease for the remainder of the study, possibly due to sedimentation and photobleaching. Algal growth (primarily diatoms) was apparent each day during the study, as measured by increasing dissolved oxygen concentrations, despite low phosphate concentrations (<0.01mgL-1). ?? 2011 Elsevier B.V.
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Mata, D.; Amaral, M.; Fernandes, A. J. S.; Colaço, B.; Gama, A.; Paiva, M. C.; Gomes, P. S.; Silva, R. F.; Fernandes, M. H.
2015-05-01
The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT membranes (p,f-CNTs). The in vivo subcutaneously implanted materials showed a higher biological reactivity, thus inducing a slighter intense inflammatory response compared to non-functionalized CNT membranes (p-CNTs), but still showing a reduced cytotoxicity profile. Moreover, the in vivo biodegradation of CNTs was superior for p,f-CNT membranes, likely mediated by the oxidation-induced myeloperoxidase (MPO) in neutrophil and macrophage inflammatory milieus. This proves the biodegradability faculty of functionalized CNTs, which potentially avoids long-term tissue accumulation and triggering of acute toxicity. On the whole, the proposed Diels-Alder functionalization accounts for the improved CNT biological response in terms of the biocompatibility and biodegradability profiles. Therefore, CNTs can be considered for use in bone tissue engineering without notable toxicological threats.The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT
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DEFF Research Database (Denmark)
Bauman, Adrian E.; Grunseit, Anne C.; Rangul, Vegar
2017-01-01
Background: Most studies of physical activity (PA) epidemiology use behaviour measured at a single time-point. We examined whether 'PA patterns' (consistently low, consistently high or inconsistent PA levels over time) showed different epidemiological relationships for anthropometric and mortality...... and time 3, and sport and active travel at times 1 and 2 with BMI, waist, hip circumference and mortality (death from coronary heart disease (CHD) and cardiovascular disease (CVD)) were compared to 'PA patterns' spanning multiple time points. PA pattern classified participants' PA as either 1) inactive......: The moderately and highly active groups for PA at times 1 and 3 had up to 1.7 cm lower increase in waist circumference compared with the inactive/low active group. Across 'PA patterns', 'active maintainers' had a 2.0 cm lower waist circumference than 'inactive/low maintainers'. Waist circumference was inversely...
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Hoang, Giang T.; Kubo, Tomohiro; Young, Victor G., Jr.; Kautzky, Jacob A.; Wissinger, Jane E.
2015-01-01
Two introductory organic chemistry laboratory experiments are described based on the Diels-Alder reaction of 2,3,4,5-tetraphenylcyclopentadienone, which is synthesized prior to or in a one-pot reaction, with styrene. Students are presented with three possible products, the "endo" and "exo" diastereomers and the decarbonylated…
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Kotha, Sambasivarao; Ravikumar, Ongolu
2015-01-01
Atom efficient processes such as the Diels-Alder reaction (DA) and the ring-rearrangement metathesis (RRM) have been used to design new polycycles. In this regard, ruthenium alkylidene catalysts are effective in realizing the RRM of bis-norbornene derivatives prepared by DA reaction and Grignard addition. Here, fused polycycles are assembled which are difficult to produce by conventional synthetic routes.
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Research of angelica sinensis (Oliv) diels new strain DGA2000-02 selection
International Nuclear Information System (INIS)
Xie Hongmei; Li Wenjian; Hao Jifang; Liu Jing; Liu Xiaorui; Jing Yanming; Shang Hushan; Liu Rongqing; He Baogang; Wang Chunming; Zhang Guoli; Chen Shuzhen
2008-01-01
Angelica sinensis(Oliv)Diets new strain DGA2000-02 was selected successfully by Institute of Modern Physics, Chinese Academy of Sciences, Dryland Farming Research and Extension Center of Dingxi Prefecture, etc. According to the program of new strain selection, this new strain was selected for several year's after the dry seeds of Gansu Angelica sinensis(Oliv)Diels 90-01 was irradiated by ions of 55 MeV/u 40 Ar +15 . During the period of year 2005-2007, region experiments of Angelica sinensis (Oliv)Diels new strain DGA2000-02 were developed in Minxian, Weiyuan, Zhangxian and Longxi etc. Average yield of the fresh DGA2000-02 Angelica was 10 621.5 kg/hm 2 , and 15.0% production was increased more than control (for 1 386.0 kg/hm 2 of 90-01). The growth stage of the DGA2000-02 was 790 d, and it has deep purple stem and yellow-white root. The quality analysis results are as follows: total ash content is 4.2% and acidast ash content is 0.4%, 16% and 33.3% better than control, respectively; the lixivium is 61.4%, i.e., 4.4% more than the standard of Pharmacopoeia of People's Republic of China (2005 edition); the ferullc acid content is 0.148%, i.e., 2.96 times ligher than the standard. All these results showed that the quality of the DGA2000-02 was better significantly than both control and the standard. It can be grown appropriately at the high, cold and dankness regions at the altitude of 2000-2600 m and with a annual precipitation of 500-600 mm. (authors)
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International Nuclear Information System (INIS)
Clark, Catherine D.; De Bruyn, Warren J.; Hirsch, Charlotte M.; Aiona, Paige
2010-01-01
Hydrogen peroxide is photochemically produced in natural waters. It has been implicated in the oxidative-induced mortality of fecal indicator bacteria (FIB), a microbial water quality measure. To assess levels and cycling of peroxide in beach waters monitored for FIB, diel studies were carried out in surf zone waters in July 2009 at Crystal Cove State Beach, Southern California, USA. Maximum concentrations of 160-200 nM were obtained within 1 h of solar noon. Levels dropped at night to 20-40 nM, consistent with photochemical production from sunlight. Day-time production and night-time dark loss rates averaged 16 ± 3 nM h -1 and 12 ± 4 nM h -1 respectively. Apparent quantum yields averaged 0.07 ± 0.02. Production was largely dominated by sunlight, with some dependence on chromophoric dissolved organic matter (CDOM) levels in waters with high absorption coefficients. Peroxide levels measured here are sufficient to cause oxidative-stress-induced mortality of bacteria, affect FIB diel cycling and impact microbial water quality in marine bathing waters.
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Fan, Ming; Ma, Ye; Zhang, Ziwei; Mao, Jiahui; Tan, Huaping; Hu, Xiaohong
2015-11-01
A robust synthetic strategy of biopolymer-based hydrogels has been developed where hyaluronic acid derivatives reacted through aqueous Diels-Alder chemistry without the involvement of chemical catalysts, allowing for control and sustain release of dexamethasone. To conjugate the hydrogel, furan and maleimide functionalized hyaluronic acid were synthesized, respectively, as well as furan functionalized dexamethasone, for the covalent immobilization. Chemical structure, gelation time, morphologies, swelling kinetics, weight loss, compressive modulus and dexamethasone release of the hydrogel system in PBS at 37°C were studied. The results demonstrated that the aqueous Diels-Alder chemistry provides an extremely selective reaction and proceeds with high efficiency for hydrogel conjugation and covalent immobilization of dexamethasone. Cell culture results showed that the dexamethasone immobilized hydrogel was noncytotoxic and preserved proliferation of entrapped human adipose-derived stem cells. This synthetic approach uniquely allows for the direct fabrication of biologically functionalized gel scaffolds with ideal structures for adipose tissue engineering, which provides a competitive alternative to conventional conjugation techniques such as copper mediated click chemistry. Copyright © 2015. Published by Elsevier B.V.
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C2-symmetric bisamidines: Chiral Brønsted bases catalysing the Diels-Alder reaction of anthrones
Directory of Open Access Journals (Sweden)
2008-08-01
Full Text Available C2-symmetric bisamidines 8 have been tested as chiral Brønsted bases in the Diels-Alder reaction of anthrones and N-substituted maleimides. High yields of cycloadducts and significant asymmetric inductions up to 76% ee are accessible. The proposed mechanism involves proton transfer between anthrone and bisamidine, association of the resulting ions and finally a cycloaddition step stereoselectively controlled by the chiral ion pair.
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A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction.
McGee, Philippe; Bétournay, Geneviève; Barabé, Francis; Barriault, Louis
2017-05-22
We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this Au I -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Sexton, Thomas; Kraka, Elfi; Cremer, Dieter
2016-02-25
The Diels-Alder reaction between 1,3-butadiene and ethene is investigated from far-out in the entrance channel to the very last step in the exit channel thus passing two bifurcation points and extending the range of the reaction valley studied with URVA (Unified Reaction Valley Approach) by 300% compared to previous studies. For the first time, the pre- and postchemical steps of the reaction are analyzed at the same level of theory as the actual chemical processes utilizing the path curvature and its decomposition into internal coordinate or curvilinear coordinate components. A first smaller charge transfer to the dienophile facilitates the rotation of gauche butadiene into its cis form. The actual chemical processes are initiated by a second larger charge transfer to the dienophile that facilitates pyramidalization of the reacting carbon centers, bond equalization, and biradicaloid formation of the reactants. The transition state is aromatically stabilized and moved by five path units into the entrance channel in line with the Hammond-Leffler postulate. The pseudorotation of the boat form into the halfchair of cyclohexene is analyzed. Predictions are made for the Diels-Alder reaction based on a 11-phase mechanism obtained by the URVA analysis.
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Muscle activity pattern dependent pain development and alleviation
DEFF Research Database (Denmark)
Sjøgaard, Gisela; Søgaard, Karen
2014-01-01
Muscle activity is for decades considered to provide health benefits irrespectively of the muscle activity pattern performed and whether it is during e.g. sports, transportation, or occupational work tasks. Accordingly, the international recommendations for public health-promoting physical activity...... do not distinguish between occupational and leisure time physical activity. However, in this body of literature, attention has not been paid to the extensive documentation on occupational physical activity imposing a risk of impairment of health - in particular musculoskeletal health in terms...... during physical activities at leisure and sport the motor recruitment patterns are more dynamic including regularly relatively high muscle forces - also activating type 2 muscles fibers - as well as periods of full relaxation even of the type 1 muscle fibers. Such activity is unrelated to muscle pain...
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Mono- and polyadducts of C60 with anthracenes by Diels-Alder-reactions
International Nuclear Information System (INIS)
Duarte-Ruiz, A.
2000-09-01
This work describes the synthesis and characterization of seven new mono-adducts of 9-methylanthracene, 9,10-dimethylanthracene, 9-bromoanthracene. 2,3,6,7-tetramethylanthracene, 1-methylanthracene, 2,6-di-tert-butylanthracen, as well as 2-methylanthracene to fullerene C60 in solution at r.t. by means of [4+2] Diels-Alder reactions. It could be shown that the mono-adducts with 9-methylanthracene, 9,10-dimethylanthracene, and 1-methylanthracene form the corresponding antipodal bis-adduct 'trans-1' on heating the solid to 180 o C. Furthermore the functionalization of fullerene C60 anthracene mono-adduct (C60C14H10) with anthracene through [4+2] Diels-Alder reactions was investigated which made it possible to separate and to characterize the five possible bis-adducts ('trans-1', 'trans-2', 'trans-3', 'trans-4', and 'e') that can form when the second anthracene adds either 'trans' to the opposite hemisphere (compared to the first addition of anthracene) or to an equatorial position. An exact identification of the bis-adducts 'trans-2' and 'trans-4' could only be acquired with spectroscopic methods, fortunately the bis-adducts 'trans-4', 'trans-3', and 'e' could also be examined by x-ray, thus all five could be fully characterized. No bis-adducts on the same hemisphere ('cis') were found. UV/VIS-spectra of the bis-adducts opened up the possibility to identify other [4+2] Diels-Alder products in the future. It has been noticed that the eluation sequence of the bis-adducts ('trans-1' before 'trans-2' before 'trans-4' before 'trans-3' before 'e') doesn't strictly correlate with the dipole moments. Furthermore six new tris-adducts ('t4t4t2', 't3t3t3', 't3t3t4', 'et3t2', 'et3t4', and 'eee') and one tetra-adduct ('eeet3') were separated and characterized. The tris-adduct 't3t3t3' was additionally characterized by x-ray which showed that the crystal contains only one enatiomer. All bis- and tris-adducts form the antipodal bis-adduct 'trans-1' on heating to 180 o C for 10 min
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Al-aidaroos, Ali M.
2016-08-15
The Red Sea has been recognized as a unique region to study the effects of ecohydrographic gradients at a basin-wide scale. Its gradient of temperature and salinity relates to the Indian Ocean monsoon and associated wind-driven transport of fertile and plankton-rich water in winter from the Gulf of Aden into the Red Sea. Subsequent evaporation and thermohaline circulation increase the salinity and decrease water temperatures toward the North. Compared with other ocean systems, however, relatively little is known about the zooplankton biodiversity of the Red Sea and how this relates to Red Sea latitudinal gradients. Among the most abundant zooplankton taxa are Chaetognatha, which play an important role as secondary consumers in most marine food webs. Since Chaetognatha are sensitive to changes in temperature and salinity, we surmised latitudinal changes in their biodiversity, community structure and diel variability along the coast of Saudi Arabia. Samples were collected at nine coral reefs spanning approximately 1500km, from the Gulf of Aqaba in the northern Red Sea to the Farasan Archipelago in the southern Red Sea. Thirteen Chaetognatha species belonging to two families (Sagittidae and Krohnittidae) were identified. Latitudinal environmental changes and availability of prey (i.e. Copepoda, Crustacea) altered Chaetognatha density and distribution. The cosmopolitan epiplanktonic Flaccisagitta enflata (38.1%) dominated the Chaetognatha community, and its abundance gradually decreased from South to North. Notable were two mesopelagic species (Decipisagitta decipiens and Caecosagitta macrocephala) in the near-reef surface mixed layers at some sites. This was related to wind-induced upwelling of deep water into the coral reefs providing evidence of trophic oceanic subsidies. Most Sagittidae occurred in higher abundances at night, whereas Krohnittidae were more present during the day. Chaetognatha with developing (stage II) or mature ovaries (stage III) were more active
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Physical activity patterns in Greenland: a country in transition.
Dahl-Petersen, Inger K; Jørgensen, Marit E; Bjerregaard, Peter
2011-11-01
To examine differences in physical activity patterns among Inuit in Greenland in relation to social transition. The Inuit in Greenland are an indigenous population in the circumpolar north who are experiencing rapid social transition. Physical activity patterns were assessed by the International Physical Activity Questionnaire (long version). The population was divided into six groups according to different stages of social change, measured on the basis of education, current residence and occupation. Data were collected in a country-wide cross-sectional population survey among adult Inuit in Greenland from 2005 to 2009. Men with long vocational or academic education living in towns (latest stage of social change) spent significantly less time on occupational physical activity (p = 0.001) compared with hunters and fishermen in villages (earliest stage of social change) (trend test p = 0.01). Women in the latest stage of change spent significantly less time on domestic physical activity (p physical activity during transportation (p = 0.02 and p = 0.01 for men and women, respectively). No significant difference was found for leisure time physical activity. Men and women in the latest stage of social change spent more time on sedentary activity (p physical activity patterns among Inuit in Greenland included decreasing time spent on domestic and occupational physical activity and increasing time spent on sedentary activities along with social change. Knowledge of changes in physical activity patterns in relation to social transition is important in prevention of obesity, type 2 diabetes and lifestyle diseases.
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Surface confined retro Diels-Alder reaction driven by the swelling of weak polyelectrolytes.
Lyu, Beier; Cha, Wenli; Mao, Tingting; Wu, Yuanzi; Qian, Hujun; Zhou, Yitian; Chen, Xiuli; Zhang, Shen; Liu, Lanying; Yang, Guang; Lu, Zhongyuan; Zhu, Qiang; Ma, Hongwei
2015-03-25
Recently, the type of reactions driven by mechanical force has increased significantly; however, the number of methods for activating those mechanochemical reactions stays relatively limited. Furthermore, in situ characterization of a reaction is usually hampered by the inherent properties of conventional methods. In this study, we report a new platform that utilizes mechanical force generated by the swelling of surface tethered weak polyelectrolytes. An initiator with Diels-Alder (DA) adduct structure was applied to prepare the polyelectrolyte-carboxylated poly(OEGMA-r-HEMA), so that the force could trigger the retro DA reaction. The reaction was monitored in real time by quartz crystal microbalance and confirmed with atomic force microscopy and X-ray photoelectron spectroscopy. Compared with the conventional heating method, the swelling-induced retro DA reaction proceeded rapidly with high conversion ratio and selectivity. A 23.61 kcal/mol theoretical energy barrier supported the practicability of this retro DA reaction being triggered mechanically at ambient temperature. During swelling, the tensile force was controllable and persistent. This unique feature imparts this mechanochemical platform the potential to "freeze" an intermediate state of a reaction for in situ spectroscopic observations, such as surface-enhanced Raman spectroscopy and frequency generation spectroscopy.
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Modeling Patterns of Activities using Activity Curves.
Dawadi, Prafulla N; Cook, Diane J; Schmitter-Edgecombe, Maureen
2016-06-01
Pervasive computing offers an unprecedented opportunity to unobtrusively monitor behavior and use the large amount of collected data to perform analysis of activity-based behavioral patterns. In this paper, we introduce the notion of an activity curve , which represents an abstraction of an individual's normal daily routine based on automatically-recognized activities. We propose methods to detect changes in behavioral routines by comparing activity curves and use these changes to analyze the possibility of changes in cognitive or physical health. We demonstrate our model and evaluate our change detection approach using a longitudinal smart home sensor dataset collected from 18 smart homes with older adult residents. Finally, we demonstrate how big data-based pervasive analytics such as activity curve-based change detection can be used to perform functional health assessment. Our evaluation indicates that correlations do exist between behavior and health changes and that these changes can be automatically detected using smart homes, machine learning, and big data-based pervasive analytics.
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A Multiscale Survival Process for Modeling Human Activity Patterns.
Zhang, Tianyang; Cui, Peng; Song, Chaoming; Zhu, Wenwu; Yang, Shiqiang
2016-01-01
Human activity plays a central role in understanding large-scale social dynamics. It is well documented that individual activity pattern follows bursty dynamics characterized by heavy-tailed interevent time distributions. Here we study a large-scale online chatting dataset consisting of 5,549,570 users, finding that individual activity pattern varies with timescales whereas existing models only approximate empirical observations within a limited timescale. We propose a novel approach that models the intensity rate of an individual triggering an activity. We demonstrate that the model precisely captures corresponding human dynamics across multiple timescales over five orders of magnitudes. Our model also allows extracting the population heterogeneity of activity patterns, characterized by a set of individual-specific ingredients. Integrating our approach with social interactions leads to a wide range of implications.
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Longitudinal Physical Activity Patterns Among Older Adults: A Latent Transition Analysis.
Mooney, Stephen J; Joshi, Spruha; Cerdá, Magdalena; Kennedy, Gary J; Beard, John R; Rundle, Andrew G
2018-05-14
Most epidemiologic studies of physical activity measure either total energy expenditure or engagement in a single activity type, such as walking. These approaches may gloss over important nuances in activity patterns. We performed a latent transition analysis to identify patterns of activity types as well as neighborhood and individual determinants of changes in those activity patterns over two years in a cohort of 2,023 older adult residents of New York City, NY, surveyed between 2011 and 2013. We identified seven latent classes: 1) Mostly Inactive, 2) Walking, 3) Exercise, 4) Household Activities and Walking, 5) Household Activities and Exercise, 6) Gardening and Household Activities, and 7) Gardening, Household Activities, and Exercise. The majority of subjects retained the same activity patterns between waves (54% unchanged between waves 1 and 2, 66% unchanged between waves 2 and 3).Most latent class transitions were between classes distinguished only by one form of activity, and only neighborhood unemployment was consistently associated with changing between activity latent classes. Future latent transition analyses of physical activity would benefit from larger cohorts and longer follow-up periods to assess predictors of and long-term impacts of changes in activity patterns.
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Hayashi, Yujiro; Bondzic, Bojan P; Yamazaki, Tatsuya; Gupta, Yogesh; Ogasawara, Shin; Taniguchi, Tohru; Monde, Kenji
2016-10-24
The asymmetric Diels-Alder reaction of α-substituted acrolein proceeds in the presence of the trifluoroacetic acid salt of trifluoromethyl-substituted diarylprolinol silyl ether to afford the exo-isomer with both excellent diastereoselectivity and high enantioselectivity. In the Diels-Alder reaction of a β,β-disubstituted α,β-unsaturated aldehyde, good exo-selectivity and excellent enantioselectivity was obtained when the perchloric acid salt of the bulky triisopropyl silyl ether of trifluoromethyl substituted diarylprolinol was employed as an organocatalyst in the presence of water. In both cases, all-carbon quaternary stereocenters are constructed enantioselectively. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Patterns and predictors of physical activity among pregnant women ...
African Journals Online (AJOL)
The patterns and predictors of physical activity (PA) in pregnant women is poorly understood. This study described the patterns of physical activity (PA) in specific domains (home, occupation, transport and exercise/sport) and intensities (light, moderate and vigorous), and determined the factors associated with achieving ...
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Directory of Open Access Journals (Sweden)
Dongfeng Yang
Full Text Available Plants of the genus Salvia produce various types of phenolic compounds and tanshinones which are effective for treatment of coronary heart disease. Salvia miltiorrhiza and S. castanea Diels f. tomentosa Stib are two important members of the genus. In this study, metabolic profiles and cDNA-AFLP analysis of four samples were employed to identify novel genes potentially involved in phenolic compounds and tanshinones biosynthesis, including the red roots from the two species and two tanshinone-free roots from S. miltiorrhiza. The results showed that the red roots of S. castanea Diels f. tomentosa Stib produced high contents of rosmarinic acid (21.77 mg/g and tanshinone IIA (12.60 mg/g, but low content of salvianolic acid B (1.45 mg/g. The red roots of S. miltiorrhiza produced high content of salvianolic acid B (18.69 mg/g, while tanshinones accumulation in this sample was much less than that in S. castanea Diels f. tomentosa Stib. Tanshinones were not detected in the two tanshinone-free samples, which produced high contents of phenolic compounds. A cDNA-AFLP analysis with 128 primer pairs revealed that 2300 transcript derived fragments (TDFs were differentially expressed among the four samples. About 323 TDFs were sequenced, of which 78 TDFs were annotated with known functions through BLASTX searching the Genbank database and 14 annotated TDFs were assigned into secondary metabolic pathways through searching the KEGGPATHWAY database. The quantitative real-time PCR analysis indicated that the expression of 9 TDFs was positively correlated with accumulation of phenolic compounds and tanshinones. These TDFs additionally showed coordinated transcriptional response with 6 previously-identified genes involved in biosynthesis of tanshinones and phenolic compounds in S. miltiorrhiza hairy roots treated with yeast extract. The sequence data in the present work not only provided us candidate genes involved in phenolic compounds and tanshinones biosynthesis
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Directory of Open Access Journals (Sweden)
Özgür Yılmaz
2017-10-01
Full Text Available The reaction between 1,3-cyclohexadiene and dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate both without a catalyst and with different catalysts, in both atmospheric and at high pressure, over 20 days were studied. At the end of the reactions, different products (retro Diels-Alder addition product 5 and Diels-Alder addition product 6 were obtained in different yields. When we look at the percentage of the addition product, it is observed that the yield of reaction at high pressure in water is the highest. All structures of these products were characterized by 1H-NMR, 13C-NMR, MS, and IR spectroscopy.
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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.
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Sultan, Mujeeb A; Karama, Usama; Almansour, Abdulrahman I; Soliman, Saied M
2016-09-23
A theoretical study of the regioselectivity of the Diels-Alder reaction between 1,8-dichloroanthracene and acrolein is performed using DFT at the B3LYP/6-31G(d,p) level of theory. The FMO analysis, global and local reactivity indices confirmed the reported experimental results. Potential energy surface analysis showed that the cycloadditions (CAs) favor the formation of the anti product. These results are in good agreement with the reported results obtained experimentally where the anti is the major product.
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Feng, Wei; Jiang, Danfeng; Kee, Choon-Wee; Liu, Hongjun; Tan, Choon-Hong
2016-02-04
Hydroisoquinoline derivatives were prepared in moderate to good enantioselectivities via a bicyclic guanidine-catalyzed tandem isomerization intramolecular-Diels-Alder (IMDA) reaction of alkynes. With this synthetic method, the first enantioselective synthesis of (+)-alpha-yohimbine was completed in 9 steps from the IMDA products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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It has been generally accepted that the Diels-Alder reaction mechanism is one of the major reaction mechanisms to produce dimers and polymers during heating process of vegetable oil. Soybean oil oxidized at 180 °C for 24 hrs with 1.45 surface area-to-volume ratio showed 36.1% polymer peak area in g...
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Demas, James A; Payne, Hannah; Cline, Hollis T
2012-04-01
Developing amphibians need vision to avoid predators and locate food before visual system circuits fully mature. Xenopus tadpoles can respond to visual stimuli as soon as retinal ganglion cells (RGCs) innervate the brain, however, in mammals, chicks and turtles, RGCs reach their central targets many days, or even weeks, before their retinas are capable of vision. In the absence of vision, activity-dependent refinement in these amniote species is mediated by waves of spontaneous activity that periodically spread across the retina, correlating the firing of action potentials in neighboring RGCs. Theory suggests that retinorecipient neurons in the brain use patterned RGC activity to sharpen the retinotopy first established by genetic cues. We find that in both wild type and albino Xenopus tadpoles, RGCs are spontaneously active at all stages of tadpole development studied, but their population activity never coalesces into waves. Even at the earliest stages recorded, visual stimulation dominates over spontaneous activity and can generate patterns of RGC activity similar to the locally correlated spontaneous activity observed in amniotes. In addition, we show that blocking AMPA and NMDA type glutamate receptors significantly decreases spontaneous activity in young Xenopus retina, but that blocking GABA(A) receptor blockers does not. Our findings indicate that vision drives correlated activity required for topographic map formation. They further suggest that developing retinal circuits in the two major subdivisions of tetrapods, amphibians and amniotes, evolved different strategies to supply appropriately patterned RGC activity to drive visual circuit refinement. Copyright © 2011 Wiley Periodicals, Inc.
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Fast Hetero-Diels-Alder Reactions Using 4-Phenyl-1,2,4-Triazoline-3,5-Dione (PTAD) as the Dienophile
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…
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Rong, Zi-Qiang; Wang, Min; Chow, Chi Hao Eugene; Zhao, Yu
2016-07-04
Highly efficient and diastereodivergent aza-Diels-Alder reactions have been developed to access either diastereomeric series of benzofuran-fused δ-lactams and dihydropyridines in nearly perfect stereoselectivity (d.r. >20:1, >99 % ee for all examples). The complementarity of N-heterocyclic carbene and chiral amine as the catalyst was demonstrated for the first time, together with an excellent level of catalytic efficiency (1 mol % loading). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Directory of Open Access Journals (Sweden)
Mujeeb A. Sultan
2016-09-01
Full Text Available A theoretical study of the regioselectivity of the Diels-Alder reaction between 1,8-dichloroanthracene and acrolein is performed using DFT at the B3LYP/6-31G(d,p level of theory. The FMO analysis, global and local reactivity indices confirmed the reported experimental results. Potential energy surface analysis showed that the cycloadditions (CAs favor the formation of the anti product. These results are in good agreement with the reported results obtained experimentally where the anti is the major product.
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Brulíková, Lucie; Harrison, Aidan; Miller, Marvin J; Hlaváč, Jan
2016-01-01
The hetero-Diels-Alder reaction between a nitroso dienophile and a conjugated diene to give the 3,6-dihydro-2 H -1,2-oxazine scaffold is useful for the synthesis of many biologically interesting molecules due to the diverse opportunities created by subsequent transformations of the resulting 1,2-oxazine ring. This review discusses the rationale for the observed regio- and stereoselectivity and the methods developed in recent years used to control and improve the stereo- and regioselectivity for the synthesis of 1,2-oxazine scaffolds.
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Spectacular Rate Enhancement of the Diels-Alder Reaction at the Ionic Liquid/n-Hexane Interface.
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.
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Guaresti, O; García-Astrain, C; Aguirresarobe, R H; Eceiza, A; Gabilondo, N
2018-03-01
Stimuli-responsive chitosan-based hydrogels for biomedical applications using the Diels-Alder reaction were prepared. Furan modified chitosan (Cs-Fu) was cross-linked with polyetheramine derived bismaleimide at different equivalent ratios in order to determine the effect in the swelling and release properties on the final CsFu:BMI hydrogels. The Diels Alder cross-linking reaction was monitored by UV-vis spectroscopy and rheological measurements. Both the sol-gel transition value and the final storage modulus for the different formulations were similar and close to 40 min and 400 Pa, respectively. On the contrary, the swelling degree was found to be strongly dependent on the amount of bismaleimide, mainly in acidic medium, where the increased cross-linking reduced the swelling value in 25%, but maintaining the sustained drug release in the simulated gastrointestinal environment. Our study suggested that these DA-cross-linked chitosan hydrogels could be potential carriers for targeted drug administration. Copyright © 2017 Elsevier Ltd. All rights reserved.
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George, Kelly A; Archer, Melanie S; Toop, Tes
2015-01-01
This study explored the molecular mechanisms potentially underlying blow fly nocturnal oviposition. A behavioral study revealed that Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae) possesses a diel rhythm of oviposition in light under 12:12 light/dark conditions. Reversal to 12:12 dark/light resulted in oviposition behavior changing to align with the adjusted regime in most females, but four of 59 experimental females lacked a diel rhythm of oviposition (were arrhythmic). Real-time PCR was used to monitor the molecular expression levels of known circadian genes per and tim in C. vicina to determine whether gene expression and behavior correlated. As with behavior, reversing light/dark conditions changed rhythmic gene expression to align with an adjusted light regime. This suggests that although it is unlikely that C. vicina will colonize dead bodies at night, arrhythmic females and oviposition in the dark was demonstrated. © 2014 American Academy of Forensic Sciences.
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Food deprivation and drinking in two African rodents, Mastomys ...
African Journals Online (AJOL)
1986-02-12
Feb 12, 1986 ... sumption of the two speCies may have been partially the result of their different patterns of diel activity. Free- living M. nataJensis are nocturnal, while R. pumilio is diurnal with crepuscular activity peaks (De Graaff 1981;. Smithers 1983). In captivity, M. nataJensis remains strictly nocturnal, and R. pumilio ...
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Physical Activity, Sedentary Behavior, and Dietary Patterns among Children
Gubbels, Jessica S.; van Assema, Patricia; Kremers, Stef P. J.
2013-01-01
Energy balance-related behavioral patterns find their origin in early childhood. The current paper provides an overview of studies that have examined such behavioral patterns, i.e., the clustering of dietary behaviors, physical activity, and/or sedentary behavior. The paper discusses the importance of examining energy balance-related behavioral patterns in children, outlines methods to examine these patterns, and provides examples of patterns that have been found (e.g., the universal sedentar...
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Physical Activity, Sedentary Behavior, and Dietary Patterns among Children.
Gubbels, Jessica S; van Assema, Patricia; Kremers, Stef P J
2013-06-01
Energy balance-related behavioral patterns find their origin in early childhood. The current paper provides an overview of studies that have examined such behavioral patterns, i.e., the clustering of dietary behaviors, physical activity, and/or sedentary behavior. The paper discusses the importance of examining energy balance-related behavioral patterns in children, outlines methods to examine these patterns, and provides examples of patterns that have been found (e.g., the universal sedentary-snacking and healthy intake patterns, as well as more unique or local patterns), child and parental characteristics predicting such patterns (e.g., child gender and maternal educational level), and the relationship of these patterns with overweight and related measures.
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A computational study of the Diels Alder reactions involving acenes: reactivity and aromaticity
Cheng, Mei-Fun; Li, Wai-Kee
2003-01-01
Ab initio and DFT methods have been used to study the Diels-Alder reactivity and the aromaticity of four linear acenes, namely, naphthalene, anthracene, tetracene and pentacene. In total, eight additional pathways between ethylene and four acenes have been studied and all of them are concerted and exothermic reactions. It is found that the most reactive sites on the acenes are the center ring's meso-carbons. Also, reactivity decreases along the series pentacene > tetracene > anthracene > naphthalene. In addition, the NICS results indicate that the most reactive rings in the acenes are those with the highest aromaticity. These results are consistent with those of other theoretical studies and experiments.
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Lezama-Ochoa, A
2011-10-20
Macrozooplankton plays a key role in pelagic ecosystems as a link between lower trophic levels and fish. However, although its ecological role is usually considered in polar ecosystems, it is rarely considered in temperate ones. To obtain comprehensive information on the macrozooplankton distribution in the Bay of Biscay we adapted a bi-frequency acoustic method developed for the Humboldt Current system. This method can be used to extract continuous and simultaneous high-resolution information on the spatiotemporal patterns of biomass distributions of macrozooplankton and pelagic fish throughout the diel cycle. The 2 distributions were mapped using geostatistical techniques. We applied kriging with external drifts, which accounts for both diel and across-shore changes in macrozooplankton biomass. We then used a cross-variogram to determine the scale-dependent relationships between macrozooplankton and fish. The results show how macrozooplankton and fish are distributed according to the different ecological domains (coast, shelf, shelf-break and offshore) along the Spanish and French coasts. Specific macrozooplankton hotspots were observed, but macrozooplankton was generally more abundant offshore than inshore, whereas fish showed the opposite trend. This pattern was confirmed by the aggregation sizes, which increased towards oceanic waters for macrozooplankton and decreased for fish. Finally, the correlation between fish and macrozooplankton was positive on a small scale (<30 nautical miles) and negative on a large scale (>30 nautical miles).
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Yang, Limin
2014-08-01
A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations. © 2014 American Chemical Society.
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Changing patterns of brain activation during maze learning.
Van Horn, J D; Gold, J M; Esposito, G; Ostrem, J L; Mattay, V; Weinberger, D R; Berman, K F
1998-05-18
Recent research has found that patterns of brain activation involving the frontal cortex during novel task performance change dramatically following practice and repeat performance. Evidence for differential left vs. right frontal lobe activation, respectively, during episodic memory encoding and retrieval has also been reported. To examine these potentially related issues regional cerebral blood flow (rCBF) was measured in 15 normal volunteers using positron emission tomography (PET) during the naive and practiced performance of a maze task paradigm. SPM analysis indicated a largely right-sided, frontal lobe activation during naive performance. Following training and practice, performance of the same maze task elicited a more posterior pattern of rCBF activation involving posterior cingulate and precuneus. The change in the pattern of rCBF activation between novel and practiced task conditions agrees with results found in previous studies using repeat task methodology, and indicates that the neural circuitry required for encoding novel task information differs from that required when the same task has become familiar and information is being recalled. The right-sided preponderance of activation during naive performance may relate to task novelty and the spatially-based nature of the stimuli, whereas posterior areas activated during repeat performance are those previously found to be associated with visuospatial memory recall. Activation of these areas, however, does not agree with previously reported findings of left-sided activation during verbal episodic memory encoding and right-sided activation during retrieval, suggesting different neural substrates for verbal and visuospatial processing within memory. Copyright 1998 Elsevier Science B.V.
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Spontaneous Plasticity of Multineuronal Activity Patterns in Activated Hippocampal Networks
Directory of Open Access Journals (Sweden)
Atsushi Usami
2008-01-01
Full Text Available Using functional multineuron imaging with single-cell resolution, we examined how hippocampal networks by themselves change the spatiotemporal patterns of spontaneous activity during the course of emitting spontaneous activity. When extracellular ionic concentrations were changed to those that mimicked in vivo conditions, spontaneous activity was increased in active cell number and activity frequency. When ionic compositions were restored to the control conditions, the activity level returned to baseline, but the weighted spatial dispersion of active cells, as assessed by entropy-based metrics, did not. Thus, the networks can modify themselves by altering the internal structure of their correlated activity, even though they as a whole maintained the same level of activity in space and time.
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Time activity patterns: a case of south Durban, South Africa
CSIR Research Space (South Africa)
Matooane, M
2010-08-01
Full Text Available Exposure modelling in south Durban is constrained by a lack of population specific time-activity patterns data. We argue that the application of time-activity patterns from elsewhere in the world in exposure modelling in south Durban would...
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Seasonal and diel variation in xylem CO2 concentration and sap pH in sub-Mediterranean oak stems.
Salomón, Roberto; Valbuena-Carabaña, María; Teskey, Robert; McGuire, Mary Anne; Aubrey, Doug; González-Doncel, Inés; Gil, Luis; Rodríguez-Calcerrada, Jesús
2016-04-01
Since a substantial portion of respired CO2 remains within the stem, diel and seasonal trends in stem CO2 concentration ([CO2]) are of major interest in plant respiration and carbon budget research. However, continuous long-term stem [CO2] studies are scarce, and generally absent in Mediterranean climates. In this study, stem [CO2] was monitored every 15min together with stem and air temperature, sap flow, and soil water storage during a growing season in 16 stems of Quercus pyrenaica to elucidate the main drivers of stem [CO2] at different temporal scales. Fluctuations in sap pH were also assessed during two growing seasons to evaluate potential errors in estimates of the concentration of CO2 dissolved in xylem sap ([CO2*]) calculated using Henry's law. Stem temperature was the best predictor of stem [CO2] and explained more than 90% and 50% of the variability in stem [CO2] at diel and seasonal scales, respectively. Under dry conditions, soil water storage was the main driver of stem [CO2]. Likewise, the first rains after summer drought caused intense stem [CO2] pulses, suggesting enhanced stem and root respiration and increased resistance to radial CO2 diffusion. Sap flow played a secondary role in controlling stem [CO2] variations. We observed night-time sap pH acidification and progressive seasonal alkalinization. Thus, if the annual mean value of sap pH (measured at midday) was assumed to be constant, night-time sap [CO2*] was substantially overestimated (40%), and spring and autumn sap [CO2*] were misestimated by 25%. This work highlights that diel and seasonal variations in temperature, tree water availability, and sap pH substantially affect xylem [CO2] and sap [CO2*]. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.
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Estimating repetitive spatiotemporal patterns from resting-state brain activity data.
Takeda, Yusuke; Hiroe, Nobuo; Yamashita, Okito; Sato, Masa-Aki
2016-06-01
Repetitive spatiotemporal patterns in spontaneous brain activities have been widely examined in non-human studies. These studies have reported that such patterns reflect past experiences embedded in neural circuits. In human magnetoencephalography (MEG) and electroencephalography (EEG) studies, however, spatiotemporal patterns in resting-state brain activities have not been extensively examined. This is because estimating spatiotemporal patterns from resting-state MEG/EEG data is difficult due to their unknown onsets. Here, we propose a method to estimate repetitive spatiotemporal patterns from resting-state brain activity data, including MEG/EEG. Without the information of onsets, the proposed method can estimate several spatiotemporal patterns, even if they are overlapping. We verified the performance of the method by detailed simulation tests. Furthermore, we examined whether the proposed method could estimate the visual evoked magnetic fields (VEFs) without using stimulus onset information. The proposed method successfully detected the stimulus onsets and estimated the VEFs, implying the applicability of this method to real MEG data. The proposed method was applied to resting-state functional magnetic resonance imaging (fMRI) data and MEG data. The results revealed informative spatiotemporal patterns representing consecutive brain activities that dynamically change with time. Using this method, it is possible to reveal discrete events spontaneously occurring in our brains, such as memory retrieval. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.
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Wijnen, J.W; Engberts, J.B.F.N.
The adduct of the Diels-Alder reaction of nitrosobenzene with cyclopentadiene is not stable in solution. The equilibrium constant for the reaction depends strongly on the medium and water induces a spectacular shift to the adduct. Comparison with the bimolecular addition of nitrosobenzene to
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Czech Academy of Sciences Publication Activity Database
Dejmek, Milan; Hřebabecký, Hubert; Šála, Michal; Dračínský, Martin; Nencka, Radim
-, č. 24 (2011), s. 4077-4083 ISSN 0039-7881 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : Diels - Alder reaction * polychlorinated norbornanes * norbornene Subject RIV: CC - Organic Chemistry Impact factor: 2.466, year: 2011
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Kotha, Sambasivarao; Gunta, Rama
2015-01-01
Here, we describe a new and simple synthetic strategy to various polycyclic sulfones via Diels-Alder reaction and ring-rearrangement metathesis (RRM) as the key steps. This approach delivers tri- and tetracyclic sulfones with six (n = 1), seven (n = 2) or eight-membered (n = 3) fused-ring systems containing trans-ring junctions unlike the conventional all cis-ring junctions generally obtained during the RRM sequence. Interestingly the starting materials used are simple and commercially available.
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Spatial and Temporal Patterns In Ecohydrological Separation
Jarvis, S. K.; Barnard, H. R.; Singha, K.; Harmon, R. E.; Szutu, D.
2017-12-01
The model of ecohydrological separation suggests that trees source water from a different subsurface pool than what is contributing to stream flow during dry periods, however diel fluctuations in stream flow and transpiration are tightly coupled. To better understand the mechanism of this coupling, this study examines spatiotemporal patterns in water isotopic relationships between tree, soil, and stream water. Preliminary analysis of data collected in 2015 show a trend in δ18O enrichment in xylem water, suggesting an increased reliance on enriched soil water not flowing to the stream as the growing season progresses, while xylem samples from 2016, a particularly wet year, do not have this trend. Variations in these temporal trends are explored with regard to distance from stream, aspect of hillslope, position in the watershed, size of the tree, and soil depth. Additionally, a near-stream site is examined at high resolution using water isotope data, sap flow, and electrical resistivity surveying to examine soil moisture and water use patterns across the riparian-hillslope transition.
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Individual, Social, and Environmental Correlates of Active Transportation Patterns in French Women.
Perchoux, Camille; Enaux, Christophe; Oppert, Jean-Michel; Menai, Mehdi; Charreire, Hélène; Salze, Paul; Weber, Christiane; Hercberg, Serge; Feuillet, Thierry; Hess, Franck; Roda, Célina; Simon, Chantal; Nazare, Julie-Anne
2017-01-01
The objectives were (1) to define physical activity (PA) and sedentary behaviors (SB) patterns in daily life contexts (work, leisure, and transportation) in French working women from NutriNet-Santé web-cohort and (2) to identify pattern(s) of active transportation and their individual, social, and environmental correlates. 23,432 participants completed two questionnaires to evaluate PA and SB in daily life contexts and individual representations of residential neighborhood and transportation modes. Hierarchical cluster analysis was performed which identified 6 distinct movement behavior patterns: (i) active occupation, high sedentary leisure, (ii) sedentary occupation, low leisure, (iii) sedentary transportation, (iv) sedentary occupation and leisure, (v) active transportation, and (vi) active leisure. Multinomial logistic regressions were performed to identify correlates of the "active transportation" cluster. The perceived environmental characteristics positively associated with "active transportation" included "high availability of destinations around home," "presence of bicycle paths," and "low traffic." A "positive image of walking/cycling," the "individual feeling of being physically active," and a "high use of active transport modes by relatives/friends" were positively related to "active transportation," identified as a unique pattern regarding individual and environmental correlates. Identification of PA and SB context-specific patterns will help to understand movement behaviors' complexity and to design interventions to promote active transportation in specific subgroups.
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Mining Emerging Sequential Patterns for Activity Recognition in Body Sensor Networks
DEFF Research Database (Denmark)
Gu, Tao; Wang, Liang; Chen, Hanhua
2010-01-01
Body Sensor Networks oer many applications in healthcare, well-being and entertainment. One of the emerging applications is recognizing activities of daily living. In this paper, we introduce a novel knowledge pattern named Emerging Sequential Pattern (ESP)|a sequential pattern that discovers...... signicant class dierences|to recognize both simple (i.e., sequential) and complex (i.e., interleaved and concurrent) activities. Based on ESPs, we build our complex activity models directly upon the sequential model to recognize both activity types. We conduct comprehensive empirical studies to evaluate...
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Kopchuk, Dmitry S; Nikonov, Igor L; Khasanov, Albert F; Giri, Kousik; Santra, Sougata; Kovalev, Igor S; Nosova, Emiliya V; Gundala, Sravya; Venkatapuram, Padmavathi; Zyryanov, Grigory V; Majee, Adinath; Chupakhin, Oleg N
2018-05-02
The interactions between substituted 5-R-3-(pyridyl-2)-1,2,4-triazines with in situ generated substituted aryne intermediates have been studied. The reaction afforded either inverse demand (ID) aza-Diels-Alder products or 1,2,4-triazine ring rearrangement (domino) products as major ones depending on the nature of both the substituents at the C5 position of the 1,2,4-triazine core or in the aryne moiety. The structures of the key products were confirmed based on X-ray data. Based on the density functional theoretical (DFT) studies of the Diels-Alder transition state geometries, the influence of the nature of arynes on the direction of the 1,2,4-triazine transformation has been proposed.
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PHYSIOLOGIC PATTERNS OF SLEEP ON EEG, MASKING OF EPILEPTIFORM ACTIVITY
Directory of Open Access Journals (Sweden)
L. Yu. Glukhova
2013-01-01
Full Text Available Physiologic patterns of sleep on EEG can sometimes be similar to epileptiform activity and even to the EEG pattern of epileptic seizures, but they have no connection to epilepsy and their incorrect interpretation may lead to overdiagnosis of epilepsy. These sleep patterns include vertex transients, K-complexes, hypnagogic hypersynchrony, 14 and 6 Hz positive bursts, wicket-potentials, etc. The main distinctive features of acute physiological phenomena of sleep unlike epileptiform activity are stereotyped, monomorphic morphology of waves, which frequently has rhythmic, arcuate pattern, often with change of lateralization, mainly dominated in the first stages of sleep (N1-N2, with their reduction in the deeper stages and transition to delta sleep (N3. The correct interpretation of physiological sharp-wave phenomena of sleep on EEG requires considerable training and experience of the physician. Our review includes a variety of physiological sleep patterns, which can mimic epileptiform activity on EEG, their criteria of diagnostic with demonstration of own illustrations of EEG.
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Exploring Human Activity Patterns Using Taxicab Static Points
Directory of Open Access Journals (Sweden)
Bin Jiang
2012-06-01
Full Text Available This paper explores the patterns of human activities within a geographical space by adopting the taxicab static points which refer to the locations with zero speed along the tracking trajectory. We report the findings from both aggregated and individual aspects. Results from the aggregated level indicate the following: (1 Human activities exhibit an obvious regularity in time, for example, there is a burst of activity during weekend nights and a lull during the week. (2 They show a remarkable spatial drifting pattern, which strengthens our understanding of the activities in any given place. (3 Activities are heterogeneous in space irrespective of their drifting with time. These aggregated results not only help in city planning, but also facilitate traffic control and management. On the other hand, investigations on an individual level suggest that (4 activities witnessed by one taxicab will have different temporal regularity to another, and (5 each regularity implies a high level of prediction with low entropy by applying the Lempel-Ziv algorithm.
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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…
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Shiramizu, Mika; Toste, F Dean
2011-10-24
Polyethylene terephthalate (PET) is a polymeric material with high global demand. Conventionally, PET is produced from fossil-fuel-based materials. Herein, we explored the feasibility of a sustainable method for PET production by using solely bio-renewable resources. Specifically, 2,5-dimethylfuran (derived from lignocellulosic biomass through 5-(hydroxymethyl)furfural) and acrolein (produced from glycerol, a side product of biodiesel production) were converted into the key intermediate p-xylene (a precursor of terephthalic acid). This synthesis consists of a sequential Diels-Alder reaction, oxidation, dehydration, and decarboxylation. In particular, the pivotal first step, the Diels-Alder reaction, was studied in detail to provide useful kinetic and thermodynamic data. Although it was found that this reaction requires low temperature to proceed efficiently, which presents a limitation on economic feasibility on an industrial scale, the concept was realized and bio-derived p-xylene was obtained in 34% overall yield over four steps. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Individual, Social, and Environmental Correlates of Active Transportation Patterns in French Women
Directory of Open Access Journals (Sweden)
Camille Perchoux
2017-01-01
Full Text Available The objectives were (1 to define physical activity (PA and sedentary behaviors (SB patterns in daily life contexts (work, leisure, and transportation in French working women from NutriNet-Santé web-cohort and (2 to identify pattern(s of active transportation and their individual, social, and environmental correlates. 23,432 participants completed two questionnaires to evaluate PA and SB in daily life contexts and individual representations of residential neighborhood and transportation modes. Hierarchical cluster analysis was performed which identified 6 distinct movement behavior patterns: (i active occupation, high sedentary leisure, (ii sedentary occupation, low leisure, (iii sedentary transportation, (iv sedentary occupation and leisure, (v active transportation, and (vi active leisure. Multinomial logistic regressions were performed to identify correlates of the “active transportation” cluster. The perceived environmental characteristics positively associated with “active transportation” included “high availability of destinations around home,” “presence of bicycle paths,” and “low traffic.” A “positive image of walking/cycling,” the “individual feeling of being physically active,” and a “high use of active transport modes by relatives/friends” were positively related to “active transportation,” identified as a unique pattern regarding individual and environmental correlates. Identification of PA and SB context-specific patterns will help to understand movement behaviors’ complexity and to design interventions to promote active transportation in specific subgroups.
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Physical activity patterns in Greenland: A country in transition
DEFF Research Database (Denmark)
Dahl-Petersen, Inger; Jørgensen, Marit E; Bjerregaard, Peter
2011-01-01
To examine differences in physical activity patterns among Inuit in Greenland in relation to social transition. The Inuit in Greenland are an indigenous population in the circumpolar north who are experiencing rapid social transition.......To examine differences in physical activity patterns among Inuit in Greenland in relation to social transition. The Inuit in Greenland are an indigenous population in the circumpolar north who are experiencing rapid social transition....
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Correlations between human mobility and social interaction reveal general activity patterns.
Mollgaard, Anders; Lehmann, Sune; Mathiesen, Joachim
2017-01-01
A day in the life of a person involves a broad range of activities which are common across many people. Going beyond diurnal cycles, a central question is: to what extent do individuals act according to patterns shared across an entire population? Here we investigate the interplay between different activity types, namely communication, motion, and physical proximity by analyzing data collected from smartphones distributed among 638 individuals. We explore two central questions: Which underlying principles govern the formation of the activity patterns? Are the patterns specific to each individual or shared across the entire population? We find that statistics of the entire population allows us to successfully predict 71% of the activity and 85% of the inactivity involved in communication, mobility, and physical proximity. Surprisingly, individual level statistics only result in marginally better predictions, indicating that a majority of activity patterns are shared across our sample population. Finally, we predict short-term activity patterns using a generalized linear model, which suggests that a simple linear description might be sufficient to explain a wide range of actions, whether they be of social or of physical character.
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Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando; Del Pozo, Carlos; Fustero, Santos
2015-01-01
A new tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM-IMDAR protocols.
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International Nuclear Information System (INIS)
Müller, Claudia E.; Gerecke, Andreas C.; Bogdal, Christian; Wang, Zhanyun; Scheringer, Martin; Hungerbühler, Konrad
2012-01-01
Poly- and perfluorinated alkyl substances (PFASs) are anthropogenic pollutants ubiquitously found in the environment. Volatile PFASs are likely transported atmospherically over long ranges, but identification and quantification of emission sources is a challenging task. In this work, special meteorological conditions were utilized to quantify atmospheric emissions of Zurich City, Switzerland with a dual approach of modeling and field measurements. During high pressure systems in summer, a stable nocturnal boundary layer is formed in which pollutants are enriched. For volatile PFASs, a diel pattern of high concentrations in the night and low concentrations during the day was observed in Zurich, which is likely due to the atmospheric boundary layer dynamics. These results enable to model the emission source strength of Zurich City with a multimedia mass balance model in an accompanying paper. Cluster analyses suggested that perfluorocarboxylates (PFCAs) are a result of degradation of volatile precursors and direct emissions. - Highlights: ► Atmospheric PFAS concentrations in Zurich increase during the night. ► Diel concentration dynamics are likely due to stable nocturnal boundary layer. ► City is a source of PFASs to the atmosphere. ► 8:2 FTOH concentrations are high: up to 1200 pg/m 3 . ► PFAA concentrations are correlated with ozone, not particulate matter. - Semivolatile PFAS concentrations follow a diel trend in Zurich City in stable summer conditions likely due to atmospheric boundary layer effects and urban emissions.
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Solberg, Ingrid; Kaartvedt, Stein
2016-01-01
We addressed the behavioral patterns and DVM dynamics of sprat overwintering in a 150 m Norwegian fjord with increasing hypoxia by depth. An upward-facing echosounder deployed at the bottom and cabled to shore provided 4 months of continuous
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Mining Emerging Patterns for Recognizing Activities of Multiple Users in Pervasive Computing
DEFF Research Database (Denmark)
Gu, Tao; Wu, Zhanqing; Wang, Liang
2009-01-01
Understanding and recognizing human activities from sensor readings is an important task in pervasive computing. Existing work on activity recognition mainly focuses on recognizing activities for a single user in a smart home environment. However, in real life, there are often multiple inhabitants...... activity models, and propose an Emerging Pattern based Multi-user Activity Recognizer (epMAR) to recognize both single-user and multiuser activities. We conduct our empirical studies by collecting real-world activity traces done by two volunteers over a period of two weeks in a smart home environment...... sensor readings in a home environment, and propose a novel pattern mining approach to recognize both single-user and multi-user activities in a unified solution. We exploit Emerging Pattern – a type of knowledge pattern that describes significant changes between classes of data – for constructing our...
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Directory of Open Access Journals (Sweden)
Bojan Tamburic
Full Text Available A matrix of photobioreactors integrated with metabolic sensors was used to examine the combined impact of light and temperature variations on the growth and physiology of the biofuel candidate microalgal species Nannochloropsis oculata. The experiments were performed with algal cultures maintained at a constant 20 °C versus a 15 °C to 25 °C diel temperature cycle, where light intensity also followed a diel cycle with a maximum irradiance of 1920 µmol photons m(-2 s(-1. No differences in algal growth (Chlorophyll a were found between the two environmental regimes; however, the metabolic processes responded differently throughout the day to the change in environmental conditions. The variable temperature treatment resulted in greater damage to photosystem II due to the combined effect of strong light and high temperature. Cellular functions responded differently to conditions before midday as opposed to the afternoon, leading to strong hysteresis in dissolved oxygen concentration, quantum yield of photosystem II and net photosynthesis. Overnight metabolism performed differently, probably as a result of the temperature impact on respiration. Our photobioreactor matrix has produced novel insights into the physiological response of Nannochloropsis oculata to simulated environmental conditions. This information can be used to predict the effectiveness of deploying Nannochloropsis oculata in similar field conditions for commercial biofuel production.
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Sow-activity classification from acceleration patterns
DEFF Research Database (Denmark)
Escalante, Hugo Jair; Rodriguez, Sara V.; Cordero, Jorge
2013-01-01
sow-activity classification can be approached with standard machine learning methods for pattern classification. Individual predictions for elements of times series of arbitrary length are combined to classify it as a whole. An extensive comparison of representative learning algorithms, including......This paper describes a supervised learning approach to sow-activity classification from accelerometer measurements. In the proposed methodology, pairs of accelerometer measurements and activity types are considered as labeled instances of a usual supervised classification task. Under this scenario...... neural networks, support vector machines, and ensemble methods, is presented. Experimental results are reported using a data set for sow-activity classification collected in a real production herd. The data set, which has been widely used in related works, includes measurements from active (Feeding...
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Barber-Meyer, Shannon M.; Mech, L. David
2014-01-01
Because many white-tailed deer (Odocoileus virginianus) home-range and habitat-use studies rely only on daytime radio-tracking data, we were interested in whether diurnal data sufficiently represented diel home ranges. We analyzed home-range and core-use size and overlap of 8 adult-female Global-Positioning-System-collared deer during May and June 2001 and 2002 in the Superior National Forest, Minnesota, USA. We used 2 traditional means of analysis: minimum-convex polygons (MCP) and fixed kernels (95% FK, home range and 50% FK, core use) and two methods to partition day and night location data: (1) daytime = 0800-2000 h versus nighttime = 2000-0800 h and (2) sunup versus sundown. We found no statistical difference in size of home-range and core-use areas across day and night comparisons; however, in terms of spatial overlap, approximately 30% of night-range areas on average were not accounted for using daytime locations, with even greater differences between core-use areas (on average approximately 50%). We conclude that diurnal data do not adequately describe diel adult-female-deer, May-June home-ranges due to differences in spatial overlap (location). We suggest research to determine (1) if our findings hold in other circumstances (e.g., exclusive of the parturition period, other age classes, etc.), (2) if our conclusions generalize under other conditions (e.g., across deer range, varying seasons, etc.), (3) if habitat-use conclusions are affected by the incomplete overlap between diurnal and diel data, (4) how many nocturnal locations must be included to generate sufficient overlap, and (5) the influence of using other kernel sizes (e.g., 75%, 90%).
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Directory of Open Access Journals (Sweden)
Jack A Gilbert
Full Text Available How microbial communities change over time in response to the environment is poorly understood. Previously a six-year time series of 16S rRNA V6 data from the Western English Channel demonstrated robust seasonal structure within the bacterial community, with diversity negatively correlated with day-length. Here we determine whether metagenomes and metatranscriptomes follow similar patterns. We generated 16S rRNA datasets, metagenomes (1.2 GB and metatranscriptomes (157 MB for eight additional time points sampled in 2008, representing three seasons (Winter, Spring, Summer and including day and night samples. This is the first microbial 'multi-omic' study to combine 16S rRNA amplicon sequencing with metagenomic and metatranscriptomic profiling. Five main conclusions can be drawn from analysis of these data: 1 Archaea follow the same seasonal patterns as Bacteria, but show lower relative diversity; 2 Higher 16S rRNA diversity also reflects a higher diversity of transcripts; 3 Diversity is highest in winter and at night; 4 Community-level changes in 16S-based diversity and metagenomic profiles are better explained by seasonal patterns (with samples closest in time being most similar, while metatranscriptomic profiles are better explained by diel patterns and shifts in particular categories (i.e., functional groups of genes; 5 Changes in key genes occur among seasons and between day and night (i.e., photosynthesis; but these samples contain large numbers of orphan genes without known homologues and it is these unknown gene sets that appear to contribute most towards defining the differences observed between times. Despite the huge diversity of these microbial communities, there are clear signs of predictable patterns and detectable stability over time. Renewed and intensified efforts are required to reveal fundamental deterministic patterns in the most complex microbial communities. Further, the presence of a substantial proportion of orphan
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Predesigned surface patterns and topological defects control the active matter.
Turiv, Taras; Peng, Chenhui; Guo, Yubing; Wei, Qi-Huo; Lavrentovich, Oleg
Active matter exhibits remarkable patterns of never-ending dynamics with giant fluctuations of concentration, varying order, nucleating and annihilating topological defects. These patterns can be seen in active systems of both biological and artificial origin. A fundamental question is whether and how one can control this chaotic out-of-equilibrium behavior. We demonstrate a robust control of local concentration, trajectories of active self-propelled units and the net flows of active bacteria Bacillus Substilis by imposing pre-designed surface patterns of orientational order in a water-based lyotropic chromonic liquid crystal. The patterns force the bacteria to gather into dynamic swarms with spatially modulated concentration and well-defined polarity of motion. Topological defects produce net motion of bacteria with a unidirectional circulation, while pairs of defects induce a pumping action. The qualitative features of the dynamics can be explained by interplay of curvature and activity, in particular, by ability of mixed splay-bend curvatures to generate threshold-less active flows. The demonstrated level of control opens opportunities in engineering materials and devices that mimic rich functionality of living systems. This work was supported by NSF Grants DMR-1507637, DMS-1434185, CMMI-1436565, by the Petroleum Research Grant PRF# 56046-ND7 administered by the American Chemical Society.
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Molina-Espíritu, Moyocoyani; Esquivel, Rodolfo O; Kohout, Miroslav; Angulo, Juan Carlos; Dobado, José A; Dehesa, Jesús S; LópezRosa, Sheila; Soriano-Correa, Catalina
2014-08-01
The course of the Diels-Alder reactions of cyclopentadiene and maleic anhydride were studied. Two reaction paths were modelled: endo- and exo-selective paths. All structures within the transient region were characterized and analyzed by means of geometrical descriptors, physicochemical parameters and information-theoretical measures in order to observe the linkage between chemical behavior and the carriage of information. We have shown that the information-theoretical characterization of the chemical course of the reaction is in complete agreement with its phenomenological behavior in passing from reactants to products. In addition, we were able to detect the main differences between the two reaction mechanisms. This type of informational analysis serves to provide tools to help understand the chemical reactivity of the two simplest Diels-Alder reactions, which permits the establishment of a connection between the quantum changes that molecular systems exert along reaction coordinates and standard physicochemical phenomenology. In the present study, we have shown that every reaction stage has a family of subsequent structures that are characterized not solely by their phenomenological behavior but also by informational properties of their electronic density distribution (localizability, order, uniformity). Moreover, we were able to describe the main differences between endo-adduct and exo-adduct pathways. With the advent of new experimental techniques, it is in principle possible to observe the structural changes in the transient regions of chemical reactions. Indeed, through this work we have provided the theoretical concepts needed to unveil the concurrent processes associated with chemical reactions.
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Ahrenstorff, Tyler D.; Hrabik, Thomas R.; Stockwell, Jason D.; Yule, Daniel L.; Sass, Greg G.
2011-01-01
Diel vertical migrations are common among many aquatic species and are often associated with changing light levels. The underlying mechanisms are generally attributed to optimizing foraging efficiency or growth rates and avoiding predation risk (μ). The objectives of this study were to (1) assess seasonal and interannual changes in vertical migration patterns of three trophic levels in the Lake Superior pelagic food web and (2) examine the mechanisms underlying the observed variability by using models of foraging, growth, and μ. Our results suggest that the opossum shrimp Mysis diluviana, kiyi Coregonus kiyi, and siscowet lake trout Salvelinus namaycush migrate concurrently during each season, but spring migrations are less extensive than summer and fall migrations. In comparison with M. diluviana, kiyis, and siscowets, the migrations by ciscoes C. artedi were not as deep in the water column during the day, regardless of season. Foraging potential and μ probably drive the movement patterns of M. diluviana, while our modeling results indicate that movements by kiyis and ciscoes are related to foraging opportunity and growth potential and receive a lesser influence from μ. The siscowet is an abundant apex predator in the pelagia of Lake Superior and probably undertakes vertical migrations in the water column to optimize foraging efficiency and growth. The concurrent vertical movement patterns of most species are likely to facilitate nutrient transport in this exceedingly oligotrophic ecosystem, and they demonstrate strong linkages between predators and prey. Fishery management strategies should use an ecosystem approach and should consider how altering the densities of long-lived top predators produces cascading effects on the nutrient cycling and energy flow in lower trophic levels.
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Agricultural activity shapes the communication and migration patterns in Senegal
Martin-Gutierrez, S.; Borondo, J.; Morales, A. J.; Losada, J. C.; Tarquis, A. M.; Benito, R. M.
2016-06-01
The communication and migration patterns of a country are shaped by its socioeconomic processes. The economy of Senegal is predominantly rural, as agriculture employs over 70% of the labor force. In this paper, we use mobile phone records to explore the impact of agricultural activity on the communication and mobility patterns of the inhabitants of Senegal. We find two peaks of phone calls activity emerging during the growing season. Moreover, during the harvest period, we detect an increase in the migration flows throughout the country. However, religious holidays also shape the mobility patterns of the Senegalese people. Hence, in the light of our results, agricultural activity and religious holidays are the primary drivers of mobility inside the country.
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Instabilities and patterns in an active nematic film
Srivastava, Pragya; Marchetti, Cristina
2015-03-01
Experiments on microtubule bundles confined to an oil-water interface have motivated extensive theoretical studies of two-dimensional active nematics. Theoretical models taking into account the interplay between activity, flow and order have remarkably reproduced several experimentally observed features of the defect-dynamics in these ``living'' nematics. Here, we derive minimal description of a two-dimensional active nematic film confined between walls. At high friction, we eliminate the flow to obtain closed equations for the nematic order parameter, with renormalized Frank elastic constants. Active processes can render the ``Frank'' constants negative, resulting in the instability of the uniformly ordered nematic state. The minimal model yields emergent patterns of growing complexity with increasing activity, including bands and turbulent dynamics with a steady density of topological defects, as obtained with the full hydrodynamic equations. We report on the scaling of the length scales of these patterns and of the steady state number of defects with activity and system size. National Science Foundation grant DMR-1305184 and Syracuse Soft Matter Program.
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Patterns of adolescent physical activity and dietary behaviours
Directory of Open Access Journals (Sweden)
Gorely Trish
2009-07-01
Full Text Available Abstract Background The potential synergistic effects of multiple dietary and physical activity behaviours on the risk of chronic conditions and health outcomes is a key issue for public health. This study examined the prevalence and clustering patterns of multiple health behaviours among a sample of adolescents in the UK. Methods Cross-sectional survey of 176 adolescents aged 12–16 years (49% boys. Adolescents wore accelerometers for seven days and completed a questionnaire assessing fruit, vegetable, and breakfast consumption. The prevalence of adolescents meeting the physical activity (≥ 60 minutes moderate-to-vigorous physical activity/day, fruit and vegetable (≥ 5 portions of FV per day and breakfast recommendations (eating breakfast on ≥ 5 days per week, and clustering patterns of these health behaviours are described. Results Boys were more active than girls (p Conclusion Many adolescents fail to meet multiple diet and physical activity recommendations, highlighting that physical activity and dietary behaviours do not occur in isolation. Future research should investigate how best to achieve multiple health behaviour change in adolescent boys and girls.
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Yaghoobi, Fereshteh; Sohrabi Mahboub, Mahdi
2018-03-15
The reaction mechanism of the Aza-Diels-Alder (A-D-A) cycloaddition reaction between X 2 C═NNH 2 , where X = H, F, Cl, Br, and 1,3-butadiene catalyzed by a PHCl 2 Lewis acid was characterized using density functional theory calculations. The influences of various substituents of X on the studied reaction were analyzed using the activation strain model (ASM), which is also termed as the distortion-interaction model. Calculations showed that the smallest and largest values of the activation energies belong to the substituents of F and Br, respectively. The activation energy of the studied reactions was decreased within 8.6 kcal·mol -1 in the presence of PHCl 2 catalyst. Investigations showed that the pnicogen bonding is adequately capable of activating the A-D-A reaction. The quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis were implemented to understand the nature of C 4,Cbut ···C XIm and C 1,Cbut ···N XIm bonds at the TS structures. Additionally, the energy decomposition analysis (EDA) based on the ETS-NOCV scheme was used to characterize the nature of C 4,Cbut ···C XIm and C 1,Cbut ···N XIm bond. The results of the study mirror the fact that the PHCl 2 Lewis acid may be suggested as a simple suitable catalyst for experimental studies on the A-D-A reactions.
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Momiyama, Norie; Tabuse, Hideaki; Noda, Hirofumi; Yamanaka, Masahiro; Fujinami, Takeshi; Yamanishi, Katsunori; Izumiseki, Atsuto; Funayama, Kosuke; Egawa, Fuyuki; Okada, Shino; Adachi, Hiroaki; Terada, Masahiro
2016-09-07
A chiral Brønsted acid containing two different acidic sites, chiral carboxylic acid-monophosphoric acid 1a, was designed to be a new and effective concept in catalytic asymmetric hetero-Diels-Alder reactions of azopyridinecarboxylate with amidodienes. The multipoint hydrogen-bonding interactions among the carboxylic acid, monophosphoric acid, azopyridinecarboxylate, and amidodiene achieved high catalytic and chiral efficiency, producing substituted 1,2,3,6-tetrahydropyridazines with excellent stereocontrol in a single step. This constitutes the first example of regio-, diastereo-, and enantioselective azo-hetero-Diels-Alder reactions by chiral Brønsted acid catalysis.
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Neural Activity Patterns in the Human Brain Reflect Tactile Stickiness Perception
Kim, Junsuk; Yeon, Jiwon; Ryu, Jaekyun; Park, Jang-Yeon; Chung, Soon-Cheol; Kim, Sung-Phil
2017-01-01
Our previous human fMRI study found brain activations correlated with tactile stickiness perception using the uni-variate general linear model (GLM) (Yeon et al., 2017). Here, we conducted an in-depth investigation on neural correlates of sticky sensations by employing a multivoxel pattern analysis (MVPA) on the same dataset. In particular, we statistically compared multi-variate neural activities in response to the three groups of sticky stimuli: A supra-threshold group including a set of sticky stimuli that evoked vivid sticky perception; an infra-threshold group including another set of sticky stimuli that barely evoked sticky perception; and a sham group including acrylic stimuli with no physically sticky property. Searchlight MVPAs were performed to search for local activity patterns carrying neural information of stickiness perception. Similar to the uni-variate GLM results, significant multi-variate neural activity patterns were identified in postcentral gyrus, subcortical (basal ganglia and thalamus), and insula areas (insula and adjacent areas). Moreover, MVPAs revealed that activity patterns in posterior parietal cortex discriminated the perceptual intensities of stickiness, which was not present in the uni-variate analysis. Next, we applied a principal component analysis (PCA) to the voxel response patterns within identified clusters so as to find low-dimensional neural representations of stickiness intensities. Follow-up clustering analyses clearly showed separate neural grouping configurations between the Supra- and Infra-threshold groups. Interestingly, this neural categorization was in line with the perceptual grouping pattern obtained from the psychophysical data. Our findings thus suggest that different stickiness intensities would elicit distinct neural activity patterns in the human brain and may provide a neural basis for the perception and categorization of tactile stickiness. PMID:28936171
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Physical Activity, Sedentary Behavior, and Dietary Patterns among Children
Gubbels, J.S.; van Assema, P.; Kremers, S.P.
2013-01-01
Energy balance-related behavioral patterns find their origin in early The current paper provides an overview of studies that have examined behavioral patterns, i.e., the clustering of dietary behaviors, physical activity, and/or sedentary behavior. The paper discusses the importance examining energy
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Osipov, Dmitry V; Osyanin, Vitaly A; Khaysanova, Guzel' D; Masterova, Elvira R; Krasnikov, Pavel E; Klimochkin, Yuri N
2018-04-20
We have studied the reactions of o-quinone methide precursors with imino ethers. The reaction provides a versatile route to substituted 1,3-benzoxazines. The proposed reaction mechanism involves the generation of the o-quinone methide intermediates, imino-Diels-Alder reaction, and elimination. This cascade process is a rare example of the participation of imino ethers as dienophiles.
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Categorizing Pedagogical Patterns by Teaching Activities and Pedagogical Value
DEFF Research Database (Denmark)
Eriksen, Ole
2006-01-01
The main contribution of this paper is a proposal for a universal pedagogical pattern categorization based on teaching values and activities. This categorization would be more sustainable than the arbitrary categorization implied by pedagogical pattern language themes. Pedagogical patterns from two...... central patterns languages are analyzed and categorized, and the result is a catalogue theoretically founded and practical in its application. The teaching values are derived from learning theories, implying the theoretical foundation of the catalogue. In order to increase the usability of the value...
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Physical Activity and Pattern of Blood Pressure
African Journals Online (AJOL)
GB
2014-04-02
Apr 2, 2014 ... This study investigated physical activity (PA) and pattern of blood ... values of SBP, DBP, BMI and WHR were higher among participants with low PA compared to those ..... nervous system is associated with abdominal visceral ...
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Heintzelman, Geoffrey R.; Weinreb, Steven M.; Parvez, Masood
1996-07-12
The synthesis of a piperidine A-ring precursor to the alkaloid cylindrospermopsin (1) is described. The initial approach to the A-ring precursor focused on the imino Diels-Alder reaction of diene 8 with ethyl (N-tosylimino)acetate (9) to form the cycloadduct 10 as a single stereoisomer. However, all attempts to convert ester 10 to a requisite diene such as 5 were unsuccessful. An alternative strategy involved the Diels-Alder cycloaddition of N-tosylimine 9 with oxygenated diene 19 under either thermal or Lewis acid-catalyzed conditions to produce a mixture of cis and trans enones 20 and 21. Although the undesired cis-enone 20 was the major product under all reaction conditions, it could be converted to the desired trans enone 21 by acid-catalyzed isomerization. Copper-mediated conjugate addition of vinylmagnesium bromide to cis-enone 20 followed by stereoselective ketone reduction with L-Selectride produced alcohol 23, whose structure was confirmed by X-ray crystallography. Similarly, trans-enone 21 was converted to alcohol 25 whose structure and stereochemistry were also established by X-ray analysis. Alcohol 25 was then protected as the silyl ether 26, which was hydroborated at the terminal olefin to produce primary alcohol ester 28having the stereochemistry and functionality needed for cylindrospermopsin.
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Kusano, Toshiki; Kurashige, Hiroki; Nambu, Isao; Moriguchi, Yoshiya; Hanakawa, Takashi; Wada, Yasuhiro; Osu, Rieko
2015-08-01
It has been suggested that resting-state brain activity reflects task-induced brain activity patterns. In this study, we examined whether neural representations of specific movements can be observed in the resting-state brain activity patterns of motor areas. First, we defined two regions of interest (ROIs) to examine brain activity associated with two different behavioral tasks. Using multi-voxel pattern analysis with regularized logistic regression, we designed a decoder to detect voxel-level neural representations corresponding to the tasks in each ROI. Next, we applied the decoder to resting-state brain activity. We found that the decoder discriminated resting-state neural activity with accuracy comparable to that associated with task-induced neural activity. The distribution of learned weighted parameters for each ROI was similar for resting-state and task-induced activities. Large weighted parameters were mainly located on conjunctive areas. Moreover, the accuracy of detection was higher than that for a decoder whose weights were randomly shuffled, indicating that the resting-state brain activity includes multi-voxel patterns similar to the neural representation for the tasks. Therefore, these results suggest that the neural representation of resting-state brain activity is more finely organized and more complex than conventionally considered.
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Mild and modular surface modification of cellulose via hetero Diels-Alder (HDA) cycloaddition.
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.
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An epidemiological study of physical activity patterns and weight ...
African Journals Online (AJOL)
Physical activity during pregnancy has been investigated for its potential benefits which includes weight control. Physical activity patterns of pregnant women in Tshwane, South Africa, were investigated using the EPIC–Norfolk Physical Activity Questionnaire (EPAQ-2) in an epidemiological cross-sectional study. Differences ...
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Directory of Open Access Journals (Sweden)
Márcio Silva Araújo
2002-06-01
Full Text Available Seven nests of T. fuscus Emery, 1834 have been studied for their structure. These nests, which opened at the soil surface, had two to four chambers located one above the other. Externally all of these nests presented a heap of brownish-yellow debris that was constituted basically by remains of vegetable material. The total nest population was, on average, 1,048 individuais. The diel pattern of foraging of this species was studied for four consecuti ve months on two nests. This activity occurred predominantly in the night period, and the workers transported, mainly, dry vegetation to the nest.
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Directory of Open Access Journals (Sweden)
Carolina C. Sokolowicz
Full Text Available O objetivo do presente trabalho foi caracterizar o ritmo de atividade e tempo de digestão em Aegla longirostri Bond-Buckup & Buckup, 1994. Os animais foram coletados em Santa Maria, RS, Brasil. Em laboratório, os animais foram transferidos para aquários individuais (5L. Para testar a atividade locomotora e alimentar dos aeglídeos um grupo de animais permaneceu sob luminosidade constante durante 12 horas, enquanto outro grupo permanecia no escuro, essa condição sendo invertida a cada 12 horas. As observações foram realizadas a cada 6 horas. Para determinar o tempo de digestão os animais foram alimentados e a cada 30 minutos um indivíduo era sacrificado. Aegla longirostri mostrou menor atividade em períodos de luminosidade, o que aconteceu nos dois grupos de animais. Essa espécie leva aproximadamente 5 horas para concluir a digestão extracelular. Os resultados sugerem que A. longirostri possui hábitos noturnos e provavelmente se alimenta sempre que há recursos disponíveis.The aim of this work was to characterize the diel activity rhythm and time of digestion in Aegla longirostri Bond-Buckup & Buckup, 1994. The individuals were collected in Santa Maria, RS, Brazil. In laboratory, the animals were kept in individuals glass aquariums (5L. To test locomotor and feeding activity of the aeglids, a group remained under constant luminosity for 12 hours, while another group was mantained in the dark, this condition being reversed at each 12 hours. The observations were taken at every 6 hours. For the determination of digestion's time the animals were fed, and one individual was sacrificed at each 30 minutes. Aegla longirostri showed lower activity in periods of light time. This condition was recorded for both groups of animals. This species takes approximately 5 hours to conclude its extracellular digestion. The results suggest that A. longirostri has nocturnal habits and probably feeds whenever resources are available.
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Relationships between hippocampal activity and breathing patterns
DEFF Research Database (Denmark)
Harper, R M; Poe, G R; Rector, D M
1998-01-01
Single cell discharge, EEG activity, and optical changes accompanying alterations in breathing patterns, as well as the knowledge that respiratory musculature is heavily involved in movement and other behavioral acts, implicate hippocampal regions in some aspects of breathing control. The control...... is unlikely to reside in oscillatory breathing movements, because such patterns emerge in preparations retaining only the medulla (and perhaps only the spinal cord). However, momentary changes in breathing patterns induced by affect, startle, whole-body movement changes, or compensatory ventilatory changes...... of hippocampal contributions to breathing control should be viewed in the context that significant interactions exist between blood pressure changes and ventilation, and that modest breathing challenges, such as exposure to hypercapnia or to increased resistive loads, bring into action a vast array of brain...
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Zhou, Y.; Fang, Z.
2017-09-01
There existing a significant social and spatial differentiation in the residential communities in urban city. People live in different places have different socioeconomic background, resulting in various geographically activity patterns. This paper aims to label the characteristics of residential communities in a city using collective activity patterns derived from taxi trip data. Specifically, we first present a method to allocate the O/D (Origin/Destination) points of taxi trips to the land use parcels where the activities taken place in. Then several indices are employed to describe the collective activity patterns, including both activity intensity, travel distance, travel time, and activity space of residents by taking account of the geographical distribution of all O/Ds of the taxi trip related to that residential community. Followed by that, an agglomerative hierarchical clustering algorithm is introduced to cluster the residential communities with similar activity patterns. In the case study of Wuhan, the residential communities are clearly divided into eight clusters, which could be labelled as ordinary communities, privileged communities, old isolated communities, suburban communities, and so on. In this paper, we provide a new perspective to label the land use under same type from people's mobility patterns with the support of big trajectory data.
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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.
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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.
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Patterns of muscle activity underlying object-specific grasp by the macaque monkey.
Brochier, T; Spinks, R L; Umilta, M A; Lemon, R N
2004-09-01
During object grasp, a coordinated activation of distal muscles is required to shape the hand in relation to the physical properties of the object. Despite the fundamental importance of the grasping action, little is known of the muscular activation patterns that allow objects of different sizes and shapes to be grasped. In a study of two adult macaque monkeys, we investigated whether we could distinguish between EMG activation patterns associated with grasp of 12 differently shaped objects, chosen to evoke a wide range of grasping postures. Each object was mounted on a horizontal shuttle held by a weak spring (load force 1-2 N). Objects were located in separate sectors of a "carousel," and inter-trial rotation of the carousel allowed sequential presentation of the objects in pseudorandom order. EMG activity from 10 to 12 digit, hand, and arm muscles was recorded using chronically implanted electrodes. We show that the grasp of different objects was characterized by complex but distinctive patterns of EMG activation. Cluster analysis shows that these object-related EMG patterns were specific and consistent enough to identify the object unequivocally from the EMG recordings alone. EMG-based object identification required a minimum of six EMGs from simultaneously recorded muscles. EMG patterns were consistent across recording sessions in a given monkey but showed some differences between animals. These results identify the specific patterns of activity required to achieve distinct hand postures for grasping, and they open the way to our understanding of how these patterns are generated by the central motor network.
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Directory of Open Access Journals (Sweden)
Beáta Fekete
2017-04-01
Full Text Available From 2-aminonorbornene hydroxamic acids, a simple and efficient method for the preparation of pyrrolo[1,2-a]pyrimidine enantiomers is reported. The synthesis is based on domino ring-closure followed by microwave-induced retro Diels-Alder (RDA protocols, where the chirality of the desired products is transferred from norbornene derivatives. The stereochemistry of the synthesized compounds was proven by X-ray crystallography. The absolute configuration of the product is determined by the configuration of the starting amino hydroxamic acid.
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Zhou, Zhi; Wang, Zhou-Xiang; Ouyang, Qin; Xiao, Wei; Du, Wei; Chen, Ying-Chun
2017-02-24
Endo-type cross-conjugated trienamines between highly congested α'-alkylidene 2-cyclohexenones and a chiral primary amine catalyst serve as HOMO-raised dienophiles in inverse-electron-demand aza-Diels-Alder cycloadditions with a number of 1-azadiene substrates. The reactions exhibit exclusive β,γ-regioselectivity, and multifunctional products with high molecular complexity are efficiently constructed in excellent diastereo- and enantioselectivity (>19:1 d.r., up to 99 % ee). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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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.
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Finding purchase activity patterns in small & medium enterprises
Vegter, Geert J.
2015-01-01
Finding purchase activity patterns in Small & Medium Enterprises in a research program to enable SMEs to improve their purchase and company performance. Posterpresentatie KCO conferentie, 16 november 2015.
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Marino Claverie, Lucila; Knobel, Elizabeth; Takashima, Lorena; Techera, Lorena; Oliver, Marina; Gonzalez, Paula; Romanini, Félix E; Fonseca, María L; Mamani, Marta N
2013-06-01
Changes in nailfold capillaroscopy in systemic sclerosis patients could be related to the disease severity. The aim of this study was to investigate whether patients with "late" scleroderma (SD) pattern have more organ involvement than patients with "early/active" SD pattern. Forty-six Argentinian patients (44 women and 2 men), with a diagnosis of systemic sclerosis, were distributed in two groups based on the presence of late and early/active patterns. Organ involvement was assessed as follows: pulmonary function by chest radiography, high-resolution chest tomography (HRCT), lung volume tests, and diffusing capacity for carbon monoxide (DLCO); esophageal involvement by manometry; and pulmonary arterial hypertension (PAH) by Doppler echocardiography and six-minute walk test. Honeycombing of the lungs evaluated by HRCT was more frequently present in patients with late pattern compared with early/active patients (p = 0.01). We also found statistically significant differences in lung volume tests (p = 0.03) and DLCO (p = 0.02) between the two SD pattern groups. Esophageal manometry showed a significantly higher frequency of motility disorders in the group with late pattern (p = 0.0024). In this study, patients with late pattern had higher frequency of pulmonary and esophageal involvement compared with patients with early/active pattern.
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Optimizing human activity patterns using global sensitivity analysis.
Fairchild, Geoffrey; Hickmann, Kyle S; Mniszewski, Susan M; Del Valle, Sara Y; Hyman, James M
2014-12-01
Implementing realistic activity patterns for a population is crucial for modeling, for example, disease spread, supply and demand, and disaster response. Using the dynamic activity simulation engine, DASim, we generate schedules for a population that capture regular (e.g., working, eating, and sleeping) and irregular activities (e.g., shopping or going to the doctor). We use the sample entropy (SampEn) statistic to quantify a schedule's regularity for a population. We show how to tune an activity's regularity by adjusting SampEn, thereby making it possible to realistically design activities when creating a schedule. The tuning process sets up a computationally intractable high-dimensional optimization problem. To reduce the computational demand, we use Bayesian Gaussian process regression to compute global sensitivity indices and identify the parameters that have the greatest effect on the variance of SampEn. We use the harmony search (HS) global optimization algorithm to locate global optima. Our results show that HS combined with global sensitivity analysis can efficiently tune the SampEn statistic with few search iterations. We demonstrate how global sensitivity analysis can guide statistical emulation and global optimization algorithms to efficiently tune activities and generate realistic activity patterns. Though our tuning methods are applied to dynamic activity schedule generation, they are general and represent a significant step in the direction of automated tuning and optimization of high-dimensional computer simulations.
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Activity patterns of free-ranging koalas (Phascolarctos cinereus revealed by accelerometry.
Directory of Open Access Journals (Sweden)
Michelle A Ryan
Full Text Available An understanding of koala activity patterns is important for measuring the behavioral response of this species to environmental change, but to date has been limited by the logistical challenges of traditional field methodologies. We addressed this knowledge gap by using tri-axial accelerometer data loggers attached to VHF radio collars to examine activity patterns of adult male and female koalas in a high-density population at Cape Otway, Victoria, Australia. Data were obtained from 27 adult koalas over two 7-d periods during the breeding season: 12 in the early-breeding season in November 2010, and 15 in the late-breeding season in January 2011. Multiple 15 minute observation blocks on each animal were used for validation of activity patterns determined from the accelerometer data loggers. Accelerometry was effective in distinguishing between inactive (sleeping, resting and active (grooming, feeding and moving behaviors. Koalas were more active during the early-breeding season with a higher index of movement (overall dynamic body acceleration [ODBA] for both males and females. Koalas showed a distinct temporal pattern of behavior, with most activity occurring from mid-afternoon to early morning. Accelerometry has potential for examining fine-scale behavior of a wide range of arboreal and terrestrial species.
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Activity patterns of free-ranging koalas (Phascolarctos cinereus) revealed by accelerometry.
Ryan, Michelle A; Whisson, Desley A; Holland, Greg J; Arnould, John P Y
2013-01-01
An understanding of koala activity patterns is important for measuring the behavioral response of this species to environmental change, but to date has been limited by the logistical challenges of traditional field methodologies. We addressed this knowledge gap by using tri-axial accelerometer data loggers attached to VHF radio collars to examine activity patterns of adult male and female koalas in a high-density population at Cape Otway, Victoria, Australia. Data were obtained from 27 adult koalas over two 7-d periods during the breeding season: 12 in the early-breeding season in November 2010, and 15 in the late-breeding season in January 2011. Multiple 15 minute observation blocks on each animal were used for validation of activity patterns determined from the accelerometer data loggers. Accelerometry was effective in distinguishing between inactive (sleeping, resting) and active (grooming, feeding and moving) behaviors. Koalas were more active during the early-breeding season with a higher index of movement (overall dynamic body acceleration [ODBA]) for both males and females. Koalas showed a distinct temporal pattern of behavior, with most activity occurring from mid-afternoon to early morning. Accelerometry has potential for examining fine-scale behavior of a wide range of arboreal and terrestrial species.
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Influence of the active layer pattern on the electrical characteristics of organic inverters
Energy Technology Data Exchange (ETDEWEB)
Kim, Jae-Hyun; Kwon, Jin-Hyuk; Bae, Jin-Hyuk [Kyungpook National University, Daegu (Korea, Republic of); Park, Jae-Hoon; Baang, Sung-Keun [Hallym University, Chuncheon (Korea, Republic of)
2014-12-15
We describe the importance of a patterned active layer for the fine driving of organic inverters. In the case of a non-patterned inverter, the capacitance as a function of the applied bias in an organic capacitor structure exhibits a slow saturation nature due to the slow movement of charge carriers. Hence, during the operation of organic inverters with non-patterned active layers, the voltage gains inevitably exhibit lower values whereas higher gains are achieved in the case of sharply-patterned pentacene layers. These results suggest that the patterning of the active layer can be a decisive factor for realizing high-performance electronic circuits based on organic semiconductors.
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a Three-Step Spatial-Temporal Clustering Method for Human Activity Pattern Analysis
Huang, W.; Li, S.; Xu, S.
2016-06-01
How people move in cities and what they do in various locations at different times form human activity patterns. Human activity pattern plays a key role in in urban planning, traffic forecasting, public health and safety, emergency response, friend recommendation, and so on. Therefore, scholars from different fields, such as social science, geography, transportation, physics and computer science, have made great efforts in modelling and analysing human activity patterns or human mobility patterns. One of the essential tasks in such studies is to find the locations or places where individuals stay to perform some kind of activities before further activity pattern analysis. In the era of Big Data, the emerging of social media along with wearable devices enables human activity data to be collected more easily and efficiently. Furthermore, the dimension of the accessible human activity data has been extended from two to three (space or space-time) to four dimensions (space, time and semantics). More specifically, not only a location and time that people stay and spend are collected, but also what people "say" for in a location at a time can be obtained. The characteristics of these datasets shed new light on the analysis of human mobility, where some of new methodologies should be accordingly developed to handle them. Traditional methods such as neural networks, statistics and clustering have been applied to study human activity patterns using geosocial media data. Among them, clustering methods have been widely used to analyse spatiotemporal patterns. However, to our best knowledge, few of clustering algorithms are specifically developed for handling the datasets that contain spatial, temporal and semantic aspects all together. In this work, we propose a three-step human activity clustering method based on space, time and semantics to fill this gap. One-year Twitter data, posted in Toronto, Canada, is used to test the clustering-based method. The results show that the
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Exotic high activity surface patterns in PtAu nanoclusters
Mokkath, Junais Habeeb; Schwingenschlö gl, Udo
2013-01-01
of the truncated octahedron cluster motif. Exotic surface patterns are obtained particularly for Pt-rich compositions, where Pt atoms are being surrounded by Au atoms. These surface arrangements boost the catalytic activity by creating a large number of active
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Mojica, Martha; Méndez, Francisco; Alonso, Julio A
2016-02-12
The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH₂, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF₃, CHO, CN, NO₂). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO₂ substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.
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Weighted Local Active Pixel Pattern (WLAPP for Face Recognition in Parallel Computation Environment
Directory of Open Access Journals (Sweden)
Gundavarapu Mallikarjuna Rao
2013-10-01
Full Text Available Abstract - The availability of multi-core technology resulted totally new computational era. Researchers are keen to explore available potential in state of art-machines for breaking the bearer imposed by serial computation. Face Recognition is one of the challenging applications on so ever computational environment. The main difficulty of traditional Face Recognition algorithms is lack of the scalability. In this paper Weighted Local Active Pixel Pattern (WLAPP, a new scalable Face Recognition Algorithm suitable for parallel environment is proposed. Local Active Pixel Pattern (LAPP is found to be simple and computational inexpensive compare to Local Binary Patterns (LBP. WLAPP is developed based on concept of LAPP. The experimentation is performed on FG-Net Aging Database with deliberately introduced 20% distortion and the results are encouraging. Keywords — Active pixels, Face Recognition, Local Binary Pattern (LBP, Local Active Pixel Pattern (LAPP, Pattern computing, parallel workers, template, weight computation.
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Knol, Joop; Meetsma, Auke; Feringa, Bernard
1995-01-01
The Diels Alder reaction of 1-vinyl-2,2,6-trimethylcyclohexene and 3-((E)-3-(methoxycarbonyl)propenoyl)-1,3-oxazolidin-2-one under high pressure, catalyzed by a chiral bis-imine copper(II) complex, yields a drimane sesquiterpene precursor in a highly regio- and diastereoselective manner with
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Activities pattern of planned settlement’s residence and its influence toward settlement design
Nirfalini Aulia, Dwira
2018-03-01
Everyday activity of residents in a housing area will create activities pattern. Utilization of public spaces in a housing area with repeating activities pattern will affect the design of public spaces. Changes in public space usage in a housing area happen as a result of residents’ activities pattern. The goal of this paper is to identify residents’ activity pattern and connect its influence towards public spaces utilization in planned housing in micro and urban area in macro. Housing residents classified into four respondent groups based on marriage status which is unmarried, single parents, the family without child and family with a child. The method used in this research is the qualitative descriptive approach. Research finding showed that housing area with housing facilities capable of creating happiness and convenience for its residents doing their activities in public spaces.
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Activity Patterns and Pollution Exposure. A Case Study of Melbourne
International Nuclear Information System (INIS)
Marquez, L.; Smith, N.; Trinidad, G.; Guo, J.
2001-01-01
In recent times there has been increasing interest in modelling policies to limit impacts of air pollution due to motor vehicles. Impacts of air pollution on human health and comfort depend on the relationship between the distribution of pollutants and the spatial distribution of the urban population. As emissions, weather conditions and the location of the population vary with time of day, day of month and season of the year, the problem is complex. Travel demand models with activity-based approaches and a focus on the overall structure of activity/travel relations, not only spatially, but temporally can make a valuable contribution. They are often used to estimate emissions due to the travel patterns of city populations but may equally be used to provide distributions of urban populations during the day. A case study for Melbourne, Australia demonstrates the use of activity data in the estimation of population exposure. Additionally the study shows some marked differences in activity between seasons and even greater the differences in effect of that activity on exposure to air pollution. Numbers of cities will have seasonal pollutant patterns similar to Melbourne and others will benefit from exploring such patterns
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Groba, H F; Martínez, G; Rossini, C; González, A
2018-02-07
The bronze bug, Thaumastocoris peregrinus Carpintero & Dellapé (Heteroptera: Thaumastocoridae), is an exotic emerging pest in Eucalyptus commercial forests in South America, Africa, and southern Europe. Information on the chemical communication system and reproductive ecology of this insect is scant, and it may be relevant for designing management strategies for eucalypt plantations. Males emit large amounts of 3-methyl-2-butenyl butyrate, which attracts conspecific adult males but not females. To learn more about the biological function of this putative male-produced pheromone, we quantified this compound in volatile emissions collected from males, females, and couples, in three 4-h collecting periods during the morning, afternoon, and night of a single 24-h cycle. Our results showed that virgin males emit 3-methyl-2-butenyl butyrate in a diel time pattern, with an almost sevenfold difference between the afternoon emission peak compared to morning or night hours. In addition, we show that in the presence of females, males emit the compound in the same amounts throughout the photocycle. While a definite function cannot yet be attributed to the emission of 3-methyl-2-butenyl butyrate by T. peregrinus males, our findings point to an intraspecific function, possibly one related to male-male competition.
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Daily physical activity patterns from hip- and wrist-worn accelerometers
DEFF Research Database (Denmark)
Shiroma, Eric J; Schepps, M A; Harezlak, J
2016-01-01
Accelerometer wear location may influence physical activity estimates. This study investigates this relationship through the examination of activity patterns throughout the day. Participants from the aging research evaluating accelerometry (AREA) study (n men = 37, n women = 47, mean age (SD) = 78...... activity accrual provide support that each location is capable of estimating total physical activity volume. The examination of activity patterns over time may provide a more detailed way to examine differences in wear location and different subpopulations. © 2016 Institute of Physics and Engineering.......9 (5.5) years) were asked to wear accelerometers in a free-living environment for 7 d at three different wear locations; one on each wrist and one on the right hip. During waking hours, wrist-worn accelerometers consistently produced higher median activity counts, about 5 × higher, as well as wider...
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Muscle activity pattern dependent pain development and alleviation.
Sjøgaard, Gisela; Søgaard, Karen
2014-12-01
Muscle activity is for decades considered to provide health benefits irrespectively of the muscle activity pattern performed and whether it is during e.g. sports, transportation, or occupational work tasks. Accordingly, the international recommendations for public health-promoting physical activity do not distinguish between occupational and leisure time physical activity. However, in this body of literature, attention has not been paid to the extensive documentation on occupational physical activity imposing a risk of impairment of health - in particular musculoskeletal health in terms of muscle pain. Focusing on muscle activity patterns and musculoskeletal health it is pertinent to elucidate the more specific aspects regarding exposure profiles and body regional pain. Static sustained muscle contraction for prolonged periods often occurs in the neck/shoulder area during occupational tasks and may underlie muscle pain development in spite of rather low relative muscle load. Causal mechanisms include a stereotype recruitment of low threshold motor units (activating type 1 muscle fibers) characterized by a lack of temporal as well as spatial variation in recruitment. In contrast during physical activities at leisure and sport the motor recruitment patterns are more dynamic including regularly relatively high muscle forces - also activating type 2 muscles fibers - as well as periods of full relaxation even of the type 1 muscle fibers. Such activity is unrelated to muscle pain development if adequate recovery is granted. However, delayed muscle soreness may develop following intensive eccentric muscle activity (e.g. down-hill skiing) with peak pain levels in thigh muscles 1-2 days after the exercise bout and a total recovery within 1 week. This acute pain profile is in contrast to the chronic muscle pain profile related to repetitive monotonous work tasks. The painful muscles show adverse functional, morphological, hormonal, as well as metabolic characteristics. Of
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Blue-Emitting Arylalkynyl Naphthalene Derivatives via a Hexadehydro-Diels-Alder Cascade Reaction.
Xu, Feng; Hershey, Kyle W; Holmes, Russell J; Hoye, Thomas R
2016-10-05
We describe here three alkynyl substituted naphthalenes that display promising luminescence characteristics. Each compound is easily and efficiently synthesized in three steps by capitalizing on the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction in which an intermediate benzyne is captured by tetraphenylcyclopentadienone, a classical trap for benzyne itself. These compounds luminesce in the deep blue when stimulated either optically (i.e., photoluminescence in both solution and solid films) or electrically [in a light-emitting diode (LED)]. The photophysical properties are relatively insensitive to the electronic nature of the substituents (H, OMe, CO 2 Me) that define these otherwise identical compounds. Overall, our observations suggest that the twisted nature of the five adjacent aryl groups serves to minimize the intermolecular interaction between core naphthalene units in different sample morphologies. These compounds represent promising leads for the identification of others of value as the emissive component of organic LEDs (OLEDs).
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Directory of Open Access Journals (Sweden)
Yu Guang
2011-01-01
Full Text Available Angelica sinensis (Oliv. Diels (Umbelliferae is a well-known medicinal plant mainly distributed in Gansu Province of China. Its local and global demand is significant because of its food and medicinal applications. However, the early bolting rate of Angelica sinensis (Oliv. Diels reaches 20%-60%, which seriously affects its food and medicinal qualities. Thus, differences in gene expression between the flower bud and sprout-shoot apical meristem underwent analysis, by means of cDNA-amplified restriction fragment length polymorphism, to better understand the flowering mechanism. 64 primer sets, each of which amplified to 60 transcript-derived fragments (TDFs, were used. Among these TDFs, 26 were expressed specifically in the flower bud. After cloning and sequencing, 32 distinct sequences were obtained from these 26 TDFs, and 25 were found with homologous sequences in databases. Confirmation of differential expression of 13 sequences was obtained by semi-quantitative RT-PCR, their showing higher expression levels in flower buds. These homologous sequences encode transposable elements, pentatricopeptide repeat-containing proteins, DNA-binding transcription factors, zinc finger (B-box type family proteins, NADP-dependent sorbitol 6-phosphate dehydrogenase (S6PDH, amongst others.
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Inverse-Electron-Demand Diels-Alder Reactions: Principles and Applications.
Png, Zhuang Mao; Zeng, Huining; Ye, Qun; Xu, Jianwei
2017-09-05
Inverse-electron-demand Diels-Alder (iEDDA) reactions are an intriguing class of cycloaddition reactions that have attracted increasing attention for their application in bioorthogonal chemistry, the total synthesis of natural products, and materials science. In many cases, the application of the iEDDA reaction has been demonstrated as an innovative approach to achieve target structures. The theoretical aspects of this class of reactions are of particular interest for scientists as a means to understand the various factors, such as steric strain and electron density of the attached groups, that govern the reaction and thus to elucidate the reaction mechanism. This review aims to summarize both theoretical investigations and application-driven research work on the iEDDA reaction. First, the historical aspects and the theoretical basis of the reaction, especially recent advances in time-dependent density functional theory (TD-DFT) calculations, as well as catalysis strategies will be highlighted and discussed. Second, the applications of this novel reaction in the context of materials science, bioorthogonal chemistry, and total synthesis of natural products will be elaborated with selected recent examples. The challenges and opportunities of the iEDDA reaction will be highlighted to give more insight into its potential applications in many other research areas. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Unsupervised classification of neocortical activity patterns in neonatal and pre-juvenile rodents
Directory of Open Access Journals (Sweden)
Nicole eCichon
2014-05-01
Full Text Available Flexible communication within the brain, which relies on oscillatory activity, is not confined to adult neuronal networks. Experimental evidence has documented the presence of discontinuous patterns of oscillatory activity already during early development. Their highly variable spatial and time-frequency organization has been related to region specificity. However, it might be equally due to the absence of unitary criteria for classifying the early activity patterns, since they have been mainly characterized by visual inspection. Therefore, robust and unbiased methods for categorizing these discontinuous oscillations are needed for increasingly complex data sets from different labs. Here, we introduce an unsupervised detection and classification algorithm for the discontinuous activity patterns of rodents during early development. For this, firstly time windows with discontinuous oscillations vs. epochs of network silence were identified. In a second step, the major features of detected events were identified and processed by principal component analysis for deciding on their contribution to the classification of different oscillatory patterns. Finally, these patterns were categorized using an unsupervised cluster algorithm. The results were validated on manually characterized neonatal spindle bursts, which ubiquitously entrain neocortical areas of rats and mice, and prelimbic nested gamma spindle bursts. Moreover, the algorithm led to satisfactory results for oscillatory events that, due to increased similarity of their features, were more difficult to classify, e.g. during the pre-juvenile developmental period. Based on a linear classification, the optimal number of features to consider increased with the difficulty of detection. This algorithm allows the comparison of neonatal and pre-juvenile oscillatory patterns in their spatial and temporal organization. It might represent a first step for the unbiased elucidation of activity patterns
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[Mammals' camera-trapping in Sierra Nanchititla, Mexico: relative abundance and activity patterns].
Monroy-Vilchis, Octavio; Zarco-González, Martha M; Rodríguez-Soto, Clarita; Soria-Díaz, Leroy; Urios, Vicente
2011-03-01
Species conservation and their management depend on the availability of their population behavior and changes in time. This way, population studies include aspects such as species abundance and activity pattern, among others, with the advantage that nowadays new technologies can be applied, in addition to common methods. In this study, we used camera-traps to obtain the index of relative abundance and to establish activity pattern of medium and large mammals in Sierra Nanchititla, Mexico. The study was conducted from December 2003 to May 2006, with a total sampling effort of 4 305 trap-days. We obtained 897 photographs of 19 different species. Nasua narica, Sylvilagus floridanus and Urocyon cinereoargenteus were the most abundant, in agreement with the relative abundance index (RAI, number of independent records/100 trap-days), and according to previous studies with indirect methods in the area. The activity patterns of the species showed that 67% of them are nocturnal, except Odocoileus virginianus, Nasua narica and others. Some species showed differences with previously reported patterns, which are related with seasonality, resources availability, organism sex, principally. The applied method contributed with reliable data about relative abundance and activity patterns.
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Changes in shoulder muscle activity pattern on surface electromyography after breast cancer surgery.
Yang, Eun Joo; Kwon, YoungOk
2018-02-01
Alterations in muscle activation and restricted shoulder mobility, which are common in breast cancer patients, have been found to affect upper limb function. The purpose of this study was to determine muscle activity patterns, and to compare the prevalence of abnormal patterns among the type of breast surgery. In total, 274 breast cancer patients were recruited after surgery. Type of breast surgery was divided into mastectomy without reconstruction (Mastectomy), reconstruction with tissue expander/implant (TEI), latissimus dorsi (LD) flap, or transverse rectus abdominis flap (TRAM). Activities of shoulder muscles were measured using surface electromyography. Experimental analysis was conducted using a Gaussian filter smoothing method with regression. Patients demonstrated different patterns of muscle activation, such as normal, lower muscle electrical activity, and tightness. After adjusting for BMI and breast surgery, the odds of lower muscle electrical activity and tightness in the TRAM are 40.2% and 38.4% less than in the Mastectomy only group. The prevalence of abnormal patterns was significantly greater in the ALND than SLNB in all except TRAM. Alterations in muscle activity patterns differed by breast surgery and reconstruction type. For breast cancer patients with ALND, TRAM may be the best choice for maintaining upper limb function. © 2017 Wiley Periodicals, Inc.
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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.
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A mechanochemical study of the effects of compression on a Diels-Alder reaction
Jha, Sanjiv K.; Brown, Katie; Todde, Guido; Subramanian, Gopinath
2016-08-01
We examine the effects of compressive external forces on the mechanisms of the parent Diels-Alder (DA) reaction between butadiene and ethylene. Reaction pathways and transition states were calculated using the nudged elastic band method within a mechanochemical framework at the CASSCF(6,6)/6-31G**, as well as the B3LYP/6-311++G** levels of theory. Our results suggest that compressive hydrostatic pressure lowers the energy barrier for the parent DA reaction while suppressing the undesirable side reaction, thereby leading to a direct increase in the yield of cyclohexene. Compressive pressure also increases the exothermicity of the parent DA reaction, which would lead to increased temperatures in a reaction vessel and thereby indirectly increase the yield of cyclohexene. Our estimates indicate that the compression used in our study corresponds to a range of 68 MPa-1410 MPa.
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Evolution of Daily Activity Patterns from 1971 to 1981: A Study of the Halifax Activity Panel Survey
Directory of Open Access Journals (Sweden)
Andrew S. Harvey
2001-12-01
similarity measures between character strings, which can be used to measure the similarity of two persons’ daily activities, to measure change over time, or to determine the relative similarity of three or more activity diaries. The results of the research showed that both pure activities and activity-settings identified broadly the same behvioural groupings: employed workers, domestic workers, and weekend activities. The similarity of activity patterns of individuals was greater over the ten-year analysis period than the average similarity of the sample in either 1971 or 1981. The average similarity of activity and activitysetting patterns rose from 1971 to 1981, which contradicts observations that daily routines are becoming more complex and diverse.
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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.
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Correlations between human mobility and social interaction reveal general activity patterns
DEFF Research Database (Denmark)
Mollgaard, Anders; Jørgensen, Sune Lehmann; Mathiesen, Joachim
2017-01-01
activity types, namely communication, motion, and physical proximity by analyzing data collected from smartphones distributed among 638 individuals. We explore two central questions: Which underlying principles govern the formation of the activity patterns? Are the patterns specific to each individual...... or shared across the entire population? We find that statistics of the entire population allows us to successfully predict 71% of the activity and 85% of the inactivity involved in communication, mobility, and physical proximity. Surprisingly, individual level statistics only result in marginally better...... they be of social or of physical character....
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Estimating Activity Patterns Using Spatio-temporal Data of Cellphone Networks
Directory of Open Access Journals (Sweden)
Zahedi Seyedmostafa
2016-01-01
Full Text Available The tendency towards using activity-based models to predict trip demand has increased dramatically over recent years, but these models have suffered insufficient data for calibration. This paper discusses ways to process the cellphone spatio-temporal data in a manner that makes it comprehensible for traffic interpretations and proposes methods on how to infer urban mobility and activity patterns from the aforementioned data. Movements of each subscriber is described by a sequence of stays and trips and each stay is labeled by an activity. The type of activities are estimated using features such as land use, duration of stay, frequency of visit, arrival time to that activity and its distance from home. Finally, the chains of trips are identified and different patterns that citizens follow to participate in activities are determined. The data comprises 144 million records of the location of 300,000 citizens of Shiraz at five-minute intervals.
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Directory of Open Access Journals (Sweden)
Qi Liu
2015-01-01
Full Text Available Background. Pattern differentiation is the foundation of traditional Chinese medicine (TCM treatment for erectile dysfunction (ED. This study aims to investigate the differences in cerebral activity in ED patients with different TCM patterns. Methods. 27 psychogenic ED patients and 27 healthy subjects (HS were enrolled in this study. Each participant underwent an fMRI scan in resting state. The fractional amplitude of low-frequency fluctuation (fALFF was used to detect the brain activity changes in ED patients with different patterns. Results. Compared to HS, ED patients showed an increased cerebral activity in bilateral cerebellum, insula, globus pallidus, parahippocampal gyrus, orbitofrontal cortex (OFC, and middle cingulate cortex (MCC. Compared to the patients with liver-qi stagnation and spleen deficiency pattern (LSSDP, the patients with kidney-yang deficiency pattern (KDP showed an increased activity in bilateral brainstem, cerebellum, hippocampus, and the right insula, thalamus, MCC, and a decreased activity in bilateral putamen, medial frontal gyrus, temporal pole, and the right caudate nucleus, OFC, anterior cingulate cortex, and posterior cingulate cortex (P<0.005. Conclusions. The ED patients with different TCM patterns showed different brain activities. The differences in cerebral activity between LSSDP and KDP were mainly in the emotion-related regions, including prefrontal cortex and cingulated cortex.
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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.…
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Beyond the average: Diverse individual migration patterns in a population of mesopelagic jellyfish
Kaartvedt, Stein; Titelman, Josefin; Rø stad, Anders; Klevjer, Thor A.
2011-01-01
We examined the diel behavior among the jellyfish Periphylla periphylla in Lurefjorden, Norway in a sampling campaign and by a > 3-month continuous acoustic study. Jellyfish distribution and behavior were recorded by an upward-facing, bottom-mounted echo sounder at 280-m depth. The population was typically divided into four groups, each with different behavior. Individuals of behavioral Mode 1 undertook synchronous diel vertical migrations (DVM) within the upper 100 m. Individuals of behavioral Mode 2, stayed at ~ 160-200-m depth during the day, and also exhibited synchronized DVM, ascending at dusk and descending at dawn. The smaller individuals of behavioral Mode 3 swam continuously up and down throughout both day and night, yet occurred below Mode 2 individuals in daytime (~ 200 m-bottom), while their vertical range encompassed the entire water column during night. Mode 4 behavior was displayed by large jellyfish located between ~ 130 m and the bottom. These animals shifted between remaining motionless and relocating in rapid steps during both day and night. These four main behavioral patterns persisted throughout the registration period, although the synchronously migrating Mode 2 behavior became weaker in spring. This acoustic study has unveiled more diverse migration behaviors than previously derived from net sampling and remote-operated vehicles methods and emphasizes the importance of studying individuals. DVM is complex because individuals in a plankton population may simultaneously engage in a range of various contrasting behaviors.
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Beyond the average: Diverse individual migration patterns in a population of mesopelagic jellyfish
Kaartvedt, Stein
2011-11-01
We examined the diel behavior among the jellyfish Periphylla periphylla in Lurefjorden, Norway in a sampling campaign and by a > 3-month continuous acoustic study. Jellyfish distribution and behavior were recorded by an upward-facing, bottom-mounted echo sounder at 280-m depth. The population was typically divided into four groups, each with different behavior. Individuals of behavioral Mode 1 undertook synchronous diel vertical migrations (DVM) within the upper 100 m. Individuals of behavioral Mode 2, stayed at ~ 160-200-m depth during the day, and also exhibited synchronized DVM, ascending at dusk and descending at dawn. The smaller individuals of behavioral Mode 3 swam continuously up and down throughout both day and night, yet occurred below Mode 2 individuals in daytime (~ 200 m-bottom), while their vertical range encompassed the entire water column during night. Mode 4 behavior was displayed by large jellyfish located between ~ 130 m and the bottom. These animals shifted between remaining motionless and relocating in rapid steps during both day and night. These four main behavioral patterns persisted throughout the registration period, although the synchronously migrating Mode 2 behavior became weaker in spring. This acoustic study has unveiled more diverse migration behaviors than previously derived from net sampling and remote-operated vehicles methods and emphasizes the importance of studying individuals. DVM is complex because individuals in a plankton population may simultaneously engage in a range of various contrasting behaviors.
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Prediction of Human Activity by Discovering Temporal Sequence Patterns.
Li, Kang; Fu, Yun
2014-08-01
Early prediction of ongoing human activity has become more valuable in a large variety of time-critical applications. To build an effective representation for prediction, human activities can be characterized by a complex temporal composition of constituent simple actions and interacting objects. Different from early detection on short-duration simple actions, we propose a novel framework for long -duration complex activity prediction by discovering three key aspects of activity: Causality, Context-cue, and Predictability. The major contributions of our work include: (1) a general framework is proposed to systematically address the problem of complex activity prediction by mining temporal sequence patterns; (2) probabilistic suffix tree (PST) is introduced to model causal relationships between constituent actions, where both large and small order Markov dependencies between action units are captured; (3) the context-cue, especially interactive objects information, is modeled through sequential pattern mining (SPM), where a series of action and object co-occurrence are encoded as a complex symbolic sequence; (4) we also present a predictive accumulative function (PAF) to depict the predictability of each kind of activity. The effectiveness of our approach is evaluated on two experimental scenarios with two data sets for each: action-only prediction and context-aware prediction. Our method achieves superior performance for predicting global activity classes and local action units.
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It's about time: a comparison of Canadian and American time-activity patterns.
Leech, Judith A; Nelson, William C; Burnett, Richard T; Aaron, Shawn; Raizenne, Mark E
2002-11-01
This study compares two North American time-activity data bases: the National Human Activity Pattern Survey (NHAPS) of 9386 interviewees in 1992-1994 in the continental USA with the Canadian Human Activity Pattern Survey (CHAPS) of 2381 interviewees in 1996-1997 in four major Canadian cities. Identical surveys and methodology were used to collect this data: random sample telephone selection within the identified telephone exchanges, computer-assisted telephone interviews, overselection of children and weekends in the 24-h recall diary and the same interviewers. Very similar response rates were obtained: 63% (NHAPS) and 64.5% (CHAPS). Results of comparisons by age within major activity and location groups suggest activity and location patterns are very similar (most differences being less than 1% or 14 min in a 24-h day) with the exception of seasonal differences. Canadians spend less time outdoors in winter and less time indoors in summer than their U.S. counterparts. When exposure assessments use time of year or outdoor/indoor exposure gradients, these differences may result in significant differences in exposure assessments. Otherwise, the 24-h time activity patterns of North Americans are remarkably similar and use of the combined data set for some exposure assessments may be feasible.
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A THREE-STEP SPATIAL-TEMPORAL-SEMANTIC CLUSTERING METHOD FOR HUMAN ACTIVITY PATTERN ANALYSIS
Directory of Open Access Journals (Sweden)
W. Huang
2016-06-01
Full Text Available How people move in cities and what they do in various locations at different times form human activity patterns. Human activity pattern plays a key role in in urban planning, traffic forecasting, public health and safety, emergency response, friend recommendation, and so on. Therefore, scholars from different fields, such as social science, geography, transportation, physics and computer science, have made great efforts in modelling and analysing human activity patterns or human mobility patterns. One of the essential tasks in such studies is to find the locations or places where individuals stay to perform some kind of activities before further activity pattern analysis. In the era of Big Data, the emerging of social media along with wearable devices enables human activity data to be collected more easily and efficiently. Furthermore, the dimension of the accessible human activity data has been extended from two to three (space or space-time to four dimensions (space, time and semantics. More specifically, not only a location and time that people stay and spend are collected, but also what people “say” for in a location at a time can be obtained. The characteristics of these datasets shed new light on the analysis of human mobility, where some of new methodologies should be accordingly developed to handle them. Traditional methods such as neural networks, statistics and clustering have been applied to study human activity patterns using geosocial media data. Among them, clustering methods have been widely used to analyse spatiotemporal patterns. However, to our best knowledge, few of clustering algorithms are specifically developed for handling the datasets that contain spatial, temporal and semantic aspects all together. In this work, we propose a three-step human activity clustering method based on space, time and semantics to fill this gap. One-year Twitter data, posted in Toronto, Canada, is used to test the clustering-based method. The
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Matz, Carlyn J.; Stieb, David M.; Davis, Karelyn; Egyed, Marika; Rose, Andreas; Chou, Benedito; Brion, Orly
2014-01-01
Estimation of population exposure is a main component of human health risk assessment for environmental contaminants. Population-level exposure assessments require time-activity pattern distributions in relation to microenvironments where people spend their time. Societal trends may have influenced time-activity patterns since previous Canadian data were collected 15 years ago. The Canadian Human Activity Pattern Survey 2 (CHAPS 2) was a national survey conducted in 2010–2011 to collect time-...
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Vegter, Geert
2015-01-01
This survey is about recognizing patterns in the way Small and Medium Enterprises (SMEs) organize their procurement activities. The scope of the survey is limited to the key commodities of the SME. A key commodity is defined as the purchased product or service group which is essential for realizing
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Czech Academy of Sciences Publication Activity Database
Točík, Zdeněk; Krásný, Libor; Kovačková, Soňa; Rejman, Dominik; Rosenberg, Ivan
2007-01-01
Roč. 6, č. 5 (2007), s. 357 ISSN 1535-3508. [International Conference of the European Society for Molecular Imaging /2./. 14.06.2007-15.06.2007, Naples] Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50520701 Keywords : UTP derivative * Diels - Alder reaction * diene * spacer arm Subject RIV: CC - Organic Chemistry
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Electrostatic catalysis of a Diels-Alder reaction
Aragonès, Albert C.; Haworth, Naomi L.; Darwish, Nadim; Ciampi, Simone; Bloomfield, Nathaniel J.; Wallace, Gordon G.; Diez-Perez, Ismael; Coote, Michelle L.
2016-03-01
It is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could affect the outcomes of a range of chemical reactions, regardless of whether a redox system is involved. This possibility arises because many formally covalent species can be stabilized via minor charge-separated resonance contributors. When an applied electric field is aligned in such a way as to electrostatically stabilize one of these minor forms, the degree of resonance increases, resulting in the overall stabilization of the molecule or transition state. This means that it should be possible to manipulate the kinetics and thermodynamics of non-redox processes using an external electric field, as long as the orientation of the approaching reactants with respect to the field stimulus can be controlled. Here, we provide experimental evidence that the formation of carbon-carbon bonds is accelerated by an electric field. We have designed a surface model system to probe the Diels-Alder reaction, and coupled it with a scanning tunnelling microscopy break-junction approach. This technique, performed at the single-molecule level, is perfectly suited to deliver an electric-field stimulus across approaching reactants. We find a fivefold increase in the frequency of formation of single-molecule junctions, resulting from the reaction that occurs when the electric field is present and aligned so as to favour electron flow from the dienophile to the diene. Our results are qualitatively consistent with those predicted by quantum-chemical calculations in a theoretical model of this system, and herald a new approach to chemical catalysis.
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Patterns of adolescent physical activity and dietary behaviours
Pearson, Natalie; Atkin, Andrew J; Biddle, Stuart JH; Gorely, Trish; Edwardson, Charlotte
2009-01-01
Background The potential synergistic effects of multiple dietary and physical activity behaviours on the risk of chronic conditions and health outcomes is a key issue for public health. This study examined the prevalence and clustering patterns of multiple health behaviours among a sample of adolescents in the UK. Methods Cross-sectional survey of 176 adolescents aged 12–16 years (49% boys). Adolescents wore accelerometers for seven days and completed a questionnaire assessing fruit, vegetable, and breakfast consumption. The prevalence of adolescents meeting the physical activity (≥ 60 minutes moderate-to-vigorous physical activity/day), fruit and vegetable (≥ 5 portions of FV per day) and breakfast recommendations (eating breakfast on ≥ 5 days per week), and clustering patterns of these health behaviours are described. Results Boys were more active than girls (p < 0.001) and younger adolescents were more active than older adolescents (p < 0.01). Boys ate breakfast on more days per week than girls (p < 0.01) and older adolescents ate more fruit and vegetables than younger adolescents (p < 0.01). Almost 54% of adolescents had multiple risk behaviours and only 6% achieved all three of the recommendations. Girls had significantly more risk factors than boys (p < 0.01). For adolescents with two risk behaviours, the most prevalent cluster was formed by not meeting the physical activity and fruit and vegetable recommendations. Conclusion Many adolescents fail to meet multiple diet and physical activity recommendations, highlighting that physical activity and dietary behaviours do not occur in isolation. Future research should investigate how best to achieve multiple health behaviour change in adolescent boys and girls. PMID:19624822
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Children's organized physical activity patterns from childhood into adolescence.
Findlay, Leanne C; Garner, Rochelle E; Kohen, Dafna E
2009-11-01
Few longitudinal studies of physical activity have included young children or used nationally representative datasets. The purpose of the current study was to explore patterns of organized physical activity for Canadian children aged 4 through 17 years. Data from 5 cycles of the National Longitudinal Survey of Children and Youth were analyzed separately for boys (n = 4463) and girls (n = 4354) using multiple trajectory modeling. Boys' and girls' organized physical activity was best represented by 3 trajectory groups. For boys, these groups were labeled: high stable, high decreasing, and low decreasing participation. For girls, these groups were labeled: high decreasing, moderate stable, and low decreasing participation. Risk factors (parental education, household income, urban/rural dwelling, and single/dual parent) were explored. For boys and girls, having a parent with postsecondary education and living in a higher income household were associated with a greater likelihood of weekly participation in organized physical activity. Living in an urban area was also significantly associated with a greater likelihood of weekly participation for girls. Results suggest that Canadian children's organized physical activity is best represented by multiple patterns of participation that tend to peak in middle childhood and decline into adolescence.
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Evidence of Diel Vertical Migration of Mesopelagic Sound-Scattering Organisms in the Arctic
Directory of Open Access Journals (Sweden)
Harald Gjøsæter
2017-10-01
Full Text Available While sound scattering layers (SSLs have been described previously from ice-covered waters in the Arctic, the existence of a viable mesopelagic community that also includes mesopelagic fishes in the Arctic has been questioned. In addition, it has been hypothesized that vertical migration would hardly exist in these areas. We wanted to check if deep scattering layers (DSLs was found to the west and north of Svalbard (79°30′N−82°10′N during autumn 2015, and if present; whether organisms in such DSLs undertook vertical migrations. Our null hypothesis was that there would be no evidence of diel vertical migration. Multi-frequency acoustic observations by hull mounted echo sounder (18, 38, and 120 kHz revealed a DSL at depths ~210–510 m in areas with bottom depths exceeding ~600 m. Investigating eight geographical locations that differed with respect to time periods, light cycle and sea ice conditions, we show that the deeper layer of DSL displayed a clear ascending movement during night time and a descending movement during daytime. The high-light weighted mean depth (WMD (343–514 m with respect to backscattered energy was statistically deeper than the low-light WMD (179–437 m for the locations studied. This behavior of the DSL was found to be consistent both when the sun was continuously above the horizon and after it started to set on 1 September, and both in open water and sea ice covered waters. The WMD showed an increasing trend, while the nautical area backscattering strength from the DSL showed a decreasing trend from south to north among the studied locations. Hydrographic observations revealed that the diel migration was found in the lower part of the north-flowing Atlantic Water, and was disconnected from the surface water masses above the Atlantic Water during day and night. The organisms conducting vertical migrations were studied by vertical and oblique hauls with zooplankton nets and pelagic trawls. These data suggest
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fMRI activation patterns in an analytic reasoning task: consistency with EEG source localization
Li, Bian; Vasanta, Kalyana C.; O'Boyle, Michael; Baker, Mary C.; Nutter, Brian; Mitra, Sunanda
2010-03-01
Functional magnetic resonance imaging (fMRI) is used to model brain activation patterns associated with various perceptual and cognitive processes as reflected by the hemodynamic (BOLD) response. While many sensory and motor tasks are associated with relatively simple activation patterns in localized regions, higher-order cognitive tasks may produce activity in many different brain areas involving complex neural circuitry. We applied a recently proposed probabilistic independent component analysis technique (PICA) to determine the true dimensionality of the fMRI data and used EEG localization to identify the common activated patterns (mapped as Brodmann areas) associated with a complex cognitive task like analytic reasoning. Our preliminary study suggests that a hybrid GLM/PICA analysis may reveal additional regions of activation (beyond simple GLM) that are consistent with electroencephalography (EEG) source localization patterns.
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West African spatial patterns of economic activities
DEFF Research Database (Denmark)
Walther, Olivier; Howard, Allen; Retaillé, Denis
2015-01-01
Over the last 30 years, two different bodies of literature developed by both US historians and francophone geographers have moved toward similar conclusions regarding West African economic spatial patterns. Despite their different backgrounds, both the ‘spatial factor’ approach promoted by histor......Over the last 30 years, two different bodies of literature developed by both US historians and francophone geographers have moved toward similar conclusions regarding West African economic spatial patterns. Despite their different backgrounds, both the ‘spatial factor’ approach promoted...... by historians and the ‘mobile space’ approach developed by geographers view exchange centres as nodes of transnational trade networks and places in production territories, and perceive spatial dynamics as highly dependent on shifts of trade flows and production activities. The objective of this article...
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Byun, Yearin; Coskun, Ali
2018-03-12
The synthesis of highly microporous, epoxy-functionalized porous organic polymers (ep-POPs) by a one-pot, catalyst-free Diels-Alder cycloaddition polymerization is reported. The high oxygen content of ep-POPs offer efficient hydrogen-bonding sites for water molecules, thus leading to high water-uptake capacities up to 39.2-42.4 wt % under a wide temperature range of 5-45 °C, which covers the span of climatic conditions and manufacturing applications in which such materials might be used. Importantly, ep-POPs demonstrated regeneration temperatures as low as 55 °C, as well as excellent water stability, recyclability, and high specific surface areas up to 852 m 2 g -1 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Directory of Open Access Journals (Sweden)
Lynn Bar-On
Full Text Available The definition of spasticity as a velocity-dependent activation of the tonic stretch reflex during a stretch to a passive muscle is the most widely accepted. However, other mechanisms are also thought to contribute to pathological muscle activity and, in patients post-stroke and spinal cord injury can result in different activation patterns. In the lower-limbs of children with spastic cerebral palsy (CP these distinct activation patterns have not yet been thoroughly explored. The aim of the study was to apply an instrumented assessment to quantify different muscle activation patterns in four lower-limb muscles of children with CP. Fifty-four children with CP were included (males/females n = 35/19; 10.8 ± 3.8 yrs; bilateral/unilateral involvement n = 32/22; Gross Motor Functional Classification Score I-IV of whom ten were retested to evaluate intra-rater reliability. With the subject relaxed, single-joint, sagittal-plane movements of the hip, knee, and ankle were performed to stretch the lower-limb muscles at three increasing velocities. Muscle activity and joint motion were synchronously recorded using inertial sensors and electromyography (EMG from the adductors, medial hamstrings, rectus femoris, and gastrocnemius. Muscles were visually categorised into activation patterns using average, normalized root mean square EMG (RMS-EMG compared across increasing position zones and velocities. Based on the visual categorisation, quantitative parameters were defined using stretch-reflex thresholds and normalized RMS-EMG. These parameters were compared between muscles with different activation patterns. All patterns were dominated by high velocity-dependent muscle activation, but in more than half, low velocity-dependent activation was also observed. Muscle activation patterns were found to be both muscle- and subject-specific (p<0.01. The intra-rater reliability of all quantitative parameters was moderate to good. Comparing RMS-EMG between
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Directory of Open Access Journals (Sweden)
Malcolm P Francis
Full Text Available Juvenile rig (Mustelus lenticulatus were internally tagged with acoustic transmitters and tracked with acoustic receivers deployed throughout two arms of Porirua Harbour, a small (7 km(2 estuary in New Zealand. Ten rig were tracked for up to four months during summer-autumn to determine their spatial and temporal use of the habitat. The overall goal was to estimate the size of Marine Protected Areas required to protect rig nursery areas from direct human impacts. Rig showed clear site preferences, but those preferences varied among rig and over time. They spent most of their time in large basins and on shallow sand and mud flats around the margins, and avoided deep channels. Habitat range increased during autumn for many of the rig. Only one shark spent time in both harbour arms, indicating that there was little movement between the two. Rig home ranges were 2-7 km(2, suggesting that an effective MPA would need to cover the entire Porirua Harbour. They moved to outer harbour sites following some high river flow rates, and most left the harbour permanently during or soon after a river spike, suggesting that they were avoiding low salinity water. Rig showed strong diel movements during summer, although the diel pattern weakened in autumn. Persistent use of the same day and night sites indicates that diel movements are directed rather than random. Further research is required to determine the sizes of rig home ranges in larger harbours where nursery habitat is more extensive. Marine Protected Areas do not control land-based impacts such as accelerated sedimentation and heavy metal pollution, so integration of marine and terrestrial management tools across a range of government agencies is essential to fully protect nursery areas.
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Francis, Malcolm P
2013-01-01
Juvenile rig (Mustelus lenticulatus) were internally tagged with acoustic transmitters and tracked with acoustic receivers deployed throughout two arms of Porirua Harbour, a small (7 km(2)) estuary in New Zealand. Ten rig were tracked for up to four months during summer-autumn to determine their spatial and temporal use of the habitat. The overall goal was to estimate the size of Marine Protected Areas required to protect rig nursery areas from direct human impacts. Rig showed clear site preferences, but those preferences varied among rig and over time. They spent most of their time in large basins and on shallow sand and mud flats around the margins, and avoided deep channels. Habitat range increased during autumn for many of the rig. Only one shark spent time in both harbour arms, indicating that there was little movement between the two. Rig home ranges were 2-7 km(2), suggesting that an effective MPA would need to cover the entire Porirua Harbour. They moved to outer harbour sites following some high river flow rates, and most left the harbour permanently during or soon after a river spike, suggesting that they were avoiding low salinity water. Rig showed strong diel movements during summer, although the diel pattern weakened in autumn. Persistent use of the same day and night sites indicates that diel movements are directed rather than random. Further research is required to determine the sizes of rig home ranges in larger harbours where nursery habitat is more extensive. Marine Protected Areas do not control land-based impacts such as accelerated sedimentation and heavy metal pollution, so integration of marine and terrestrial management tools across a range of government agencies is essential to fully protect nursery areas.
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Zhang, Mingrui; Zhang, Junliang
2014-01-07
Angularly fused carbocyclic frameworks and their heteroatom-substituted analogues exist in many natural products that display a broad and interesting range of biological activities. Preparation of polycyclic products by cycloaddition reactions have been the long-standing hot topic in the synthetic community. Dehydro-Diels-Alder (DDA) reactions are one class of dehydropericyclic reactions that are derived conceptually by systematic removal of hydrogen atom pairs. A base-promoted tandem Michael addition and DDA reaction of α,α-dicyanoolefins with electron-deficient 1,3-conjugated enynes was realized in which a DDA reaction takes place between the arylalkynes and electron-deficient tetrasubstituted olefin. The control experiments support the stepwise anionic reaction pathway rather than the concerted reaction pathway. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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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.
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Parker, S.R.; Gammons, C.H.; Jones, Clain A.; Nimick, D.A.
2007-01-01
Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column. ?? 2006 Springer Science+Business Media B.V.
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Oka, Yasunori; Suzuki, Shuhei; Inoue, Yuich
2008-01-01
Bedtime activities, sleep environment, and their impact on sleep/wake patterns were assessed in 509 elementary school children (6-12 years of age; 252 males and 257 females). Television viewing, playing video games, and surfing the Internet had negative impact on sleep/wake parameters. Moreover, presence of a television set or video game in the child's bedroom increased their activity before bedtime. Time to return home later than 8 p.m. from after-school activity also had a negative impact on sleep/wake patterns. Health care practitioners should be aware of the potential negative impact of television, video games, and the Internet before bedtime, and also the possibility that late after-school activity can disturb sleep/wake patterns.
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A cluster analysis of patterns of objectively measured physical activity in Hong Kong.
Lee, Paul H; Yu, Ying-Ying; McDowell, Ian; Leung, Gabriel M; Lam, T H
2013-08-01
The health benefits of exercise are clear. In targeting interventions it would be valuable to know whether characteristic patterns of physical activity (PA) are associated with particular population subgroups. The present study used cluster analysis to identify characteristic hourly PA patterns measured by accelerometer. Cross-sectional design. Objectively measured PA in Hong Kong adults. Four-day accelerometer data were collected during 2009 to 2011 for 1714 participants in Hong Kong (mean age 44?2 years, 45?9% male). Two clusters were identified, one more active than the other. The ‘active cluster’ (n 480) was characterized by a routine PA pattern on weekdays and a more active and varied pattern on weekends; the other, the ‘less active cluster’ (n 1234), by a consistently low PA pattern on both weekdays and weekends with little variation from day to day. Demographic, lifestyle, PA level and health characteristics of the two clusters were compared. They differed in age, sex, smoking, income and level of PA required at work. The odds of having any chronic health conditions was lower for the active group (adjusted OR50?62, 95% CI 0?46, 0?84) but the two groups did not differ in terms of specific chronic health conditions or obesity. Implications are drawn for targeting exercise promotion programmes at the population level.
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Matsumoto, Suzuka; Kanazawa, Arihiro; Kanaoka, Shokyoku; Aoshima, Sadahito
2017-06-14
A unique tandem reaction of sequence-controlled cationic copolymerization and site-specific hetero-Diels-Alder (DA) reaction is demonstrated. In the controlled cationic copolymerization of furfural and 2-acetoxyethyl vinyl ether (AcOVE), only the furan ring adjacent to the propagating carbocation underwent the hetero-DA reaction with the aldehyde moiety of another furfural molecule. A further and equally important feature of the copolymerization is that the obtained copolymers had unprecedented 2:(1 + 1)-type alternating structures of repeating sequences of two VE and one furfural units in the main chain and one furfural unit in the side chain. The specific DA reaction is attributed to the delocalization of the positive charge to the side furan ring.
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Operant conditioning of synaptic and spiking activity patterns in single hippocampal neurons.
Ishikawa, Daisuke; Matsumoto, Nobuyoshi; Sakaguchi, Tetsuya; Matsuki, Norio; Ikegaya, Yuji
2014-04-02
Learning is a process of plastic adaptation through which a neural circuit generates a more preferable outcome; however, at a microscopic level, little is known about how synaptic activity is patterned into a desired configuration. Here, we report that animals can generate a specific form of synaptic activity in a given neuron in the hippocampus. In awake, head-restricted mice, we applied electrical stimulation to the lateral hypothalamus, a reward-associated brain region, when whole-cell patch-clamped CA1 neurons exhibited spontaneous synaptic activity that met preset criteria. Within 15 min, the mice learned to generate frequently the excitatory synaptic input pattern that satisfied the criteria. This reinforcement learning of synaptic activity was not observed for inhibitory input patterns. When a burst unit activity pattern was conditioned in paired and nonpaired paradigms, the frequency of burst-spiking events increased and decreased, respectively. The burst reinforcement occurred in the conditioned neuron but not in other adjacent neurons; however, ripple field oscillations were concomitantly reinforced. Neural conditioning depended on activation of NMDA receptors and dopamine D1 receptors. Acutely stressed mice and depression model mice that were subjected to forced swimming failed to exhibit the neural conditioning. This learning deficit was rescued by repetitive treatment with fluoxetine, an antidepressant. Therefore, internally motivated animals are capable of routing an ongoing action potential series into a specific neural pathway of the hippocampal network.
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Micro-flock patterns and macro-clusters in chiral active Brownian disks
Levis, Demian; Liebchen, Benno
2018-02-01
Chiral active particles (or self-propelled circle swimmers) feature a rich collective behavior, comprising rotating macro-clusters and micro-flock patterns which consist of phase-synchronized rotating clusters with a characteristic self-limited size. These patterns emerge from the competition of alignment interactions and rotations suggesting that they might occur generically in many chiral active matter systems. However, although excluded volume interactions occur naturally among typical circle swimmers, it is not yet clear if macro-clusters and micro-flock patterns survive their presence. The present work shows that both types of pattern do survive but feature strongly enhance fluctuations regarding the size and shape of the individual clusters. Despite these fluctuations, we find that the average micro-flock size still follows the same characteristic scaling law as in the absence of excluded volume interactions, i.e. micro-flock sizes scale linearly with the single-swimmer radius.
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Soto-Delgado, Jorge; Tapia, Ricardo A; Torras, Juan
2016-10-11
Thermodynamics and the solvent role in the acceleration of the Diels-Alder reaction between cyclopentadiene (CPD) and methyl vinyl ketone (MVK) have been revisited. In this work we use an ab initio hybrid QM/MM-MD scheme combined with multiple steered molecular dynamics to extract the free energy pofile in water and methanol using the bidirectional Minh-Adib estimator. We obtain 18.7 kcal mol -1 and 20.8 kcal mol -1 free energy barrier for the reaction in water and methanol, respectively. This methodology reproduces experimental values with an absolute error of about 0.8 kcal mol -1 . The experimental difference between the activation free-energy barriers of water and methanol is also reproduced with an absolute error of about 0.1 kcal mol -1 . We explore the charge transfer evolution along reaction coordinates to characterize the electronic behavior for this reaction. It is shown that the solvent molecules around the reaction system produce a global polarization along the reaction coordinate which is consistent with the solvent polarity. The results highlight the role of hydrogen bonding formed in the transition state to stabilize the system charge reorganization in the reaction process.
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International Nuclear Information System (INIS)
Nair, Preetha; Padmini, S.; Diwakar, M.P.; Gohel, Nilesh
2013-01-01
Computer based systems for power plant and research reactors are expected to have high availability. Redundancy is a common approach to improve the availability of a system. In redundant configuration the challenge is to select one node as active, and in case of failure of current active node provide automatic fast switchover by electing another node to function as active and restore normal operation. Additional constraints include: exactly one node should be elected as active in an n-way redundant architecture. This paper discusses various high availability configurations developed by Electronics Division and deployed in power and research reactors and patterns followed to elect active nodes of distributed data acquisition systems. The systems are categorized into two: Active/Passive where changeover takes effect only on the failure of Active node, and Active/Active, where changeover is effective in alternate cycles. A novel concept of priority driven state based Active (Master) node election pattern is described for Active/Passive systems which allows multiple redundancy and dynamic election of single master. The paper also discusses the Active/Active pattern, which uncovers failure early by activating all the nodes alternatively in a redundant system. This pattern can be extended to multiple redundant nodes. (author)
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He, Y; Li, Y; Lai, J; Wang, D; Zhang, J; Fu, P; Yang, X; Qi, L
2013-10-01
To examine the nationally-representative dietary patterns and their joint effects with physical activity on the likelihood of metabolic syndrome (MS) among 20,827 Chinese adults. CNNHS was a nationally representative cross-sectional observational study. Metabolic syndrome was defined according to the Joint Interim Statement definition. The "Green Water" dietary pattern, characterized by high intakes of rice and vegetables and moderate intakes in animal foods was related to the lowest prevalence of MS (15.9%). Compared to the "Green Water" dietary pattern, the "Yellow Earth" dietary pattern, characterized by high intakes of refined cereal products, tubers, cooking salt and salted vegetable was associated with a significantly elevated odds of MS (odds ratio 1.66, 95%CI: 1.40-1.96), after adjustment of age, sex, socioeconomic status and lifestyle factors. The "Western/new affluence" dietary pattern characterized by higher consumption of beef/lamb, fruit, eggs, poultry and seafood also significantly associated with MS (odds ratio: 1.37, 95%CI: 1.13-1.67). Physical activity showed significant interactions with the dietary patterns in relation to MS risk (P for interaction = 0.008). In the joint analysis, participants with the combination of sedentary activity with the "Yellow Earth" dietary pattern or the "Western/new affluence" dietary pattern both had more than three times (95%CI: 2.8-6.1) higher odds of MS than those with active activity and the "Green Water" dietary pattern. Our findings from the large Chinese national representative data indicate that dietary patterns affect the likelihood of MS. Combining healthy dietary pattern with active lifestyle may benefit more in prevention of MS. Copyright © 2012 Elsevier B.V. All rights reserved.
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Post-fire recovery of torpor and activity patterns of a small mammal.
Stawski, Clare; Hume, Taylor; Körtner, Gerhard; Currie, Shannon E; Nowack, Julia; Geiser, Fritz
2017-05-01
To cope with the post-fire challenges of decreased availability of food and shelter, brown antechinus ( Antechinus stuartii ), a small marsupial mammal, increase the use of energy-conserving torpor and reduce activity. However, it is not known how long it takes for animals to resume pre-fire torpor and activity patterns during the recovery of burnt habitat. Therefore, we tested the hypothesis that antechinus will adjust torpor use and activity after a fire depending on vegetation recovery. We simultaneously quantified torpor and activity patterns for female antechinus from three adjacent areas: (i) the area of a management burn 1 year post-fire, (ii) an area that was burned 2 years prior, and (iii) a control area. In comparison to shortly after the management burn, antechinus in all three groups displayed less frequent and less pronounced torpor while being more active. We provide the first evidence that only 1 year post-fire antechinus resume pre-fire torpor and activity patterns, probably in response to the return of herbaceous ground cover and foraging opportunities. © 2017 The Author(s).
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Diele-Dornse - в саду "Меритона" / Любовь Маклеренко
Маклеренко, Любовь
2010-01-01
Diele-dornse tüüpi elamust Tallinna vanalinnas Pikk 29/Lai 24 ja selle renoveerimisest hotelliks Meriton Old Town Garden. Ümberehitusprojekti tegi arhitektuuribüroo Kalle Rõõmus, sisekujundus on firmalt Vaikla Disain
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Theories of Person Perception Predict Patterns of Neural Activity During Mentalizing.
Thornton, Mark A; Mitchell, Jason P
2017-08-22
Social life requires making inferences about other people. What information do perceivers spontaneously draw upon to make such inferences? Here, we test 4 major theories of person perception, and 1 synthetic theory that combines their features, to determine whether the dimensions of such theories can serve as bases for describing patterns of neural activity during mentalizing. While undergoing functional magnetic resonance imaging, participants made social judgments about well-known public figures. Patterns of brain activity were then predicted using feature encoding models that represented target people's positions on theoretical dimensions such as warmth and competence. All 5 theories of person perception proved highly accurate at reconstructing activity patterns, indicating that each could describe the informational basis of mentalizing. Cross-validation indicated that the theories robustly generalized across both targets and participants. The synthetic theory consistently attained the best performance-approximately two-thirds of noise ceiling accuracy--indicating that, in combination, the theories considered here can account for much of the neural representation of other people. Moreover, encoding models trained on the present data could reconstruct patterns of activity associated with mental state representations in independent data, suggesting the use of a common neural code to represent others' traits and states. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.
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Sugiyama, Koji; Kawanishi, Shinji; Oki, Yasuhiro; Kamiya, Marin; Hanada, Ryosuke; Egi, Masahiro; Akai, Shuji
2018-04-01
One-pot sequential reactions using the acyl moieties installed by enzymatic dynamic kinetic resolution of alcohols have been little investigated. In this work, the acryloyl moiety installed via the lipase/oxovanadium combo-catalyzed dynamic kinetic resolution of a racemic dienol [4-(cyclohex-1-en-1-yl)but-3-en-2-ol or 1-(cyclohex-1-en-1-yl)but-2-en-1-ol] with a (Z)-3-(phenylsulfonyl)acrylate underwent an intramolecular Diels-Alder reaction in a one-pot procedure to produce an optically active naphtho[2,3-c]furan-1(3H)-one derivative (98% ee). This method was successfully applied to the asymmetric total synthesis of (-)-himbacine. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Thoracic posture, shoulder muscle activation patterns and isokinetic ...
African Journals Online (AJOL)
Background. Shoulder injuries are the most severe injuries in rugby union players, accounting for almost 20% of injuries related to the sport and resulting in lost playing hours. Objective. To profile the thoracic posture, scapular muscle activation patterns and rotator cuff muscle isokinetic strength of semi-professional
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Activity patterns of elderly men and women.
Sidney, K H; Shephard, R J
1977-01-01
The activity patterns of elderly men and women (greater than 60 years) were examined by diaries, ECG taperecorders, and electro-chemical integrators. Although the subjects thought that they were active relative to others of their age, both activity measurements and initial assessments of fitness indicated an inactive life style. At different periods of the day, the heart rate averaged 70-90 beats per minute, and the physical training threshold was rarely approached. During the week, the women engaged in 90 min. more physical activity than the men. However, at the weekend the men added an average of 100 min. of physical activity, whereas the women carried out 30 min. less physical work. Introduction of a 1-hour physical activity class four times per week increased the average daily energy expenditure by 150-200 kCal, to 2500 kCal in the men and 2200 kCal in the women. The added activity was sufficient to augment aerobic power, to induce favorable changes in body composition and to initiate change in other areas of life style, including a diminished use of the car.
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Acoustic and temporal partitioning of cicada assemblages in city and mountain environments.
Directory of Open Access Journals (Sweden)
Bao-Sen Shieh
Full Text Available Comparing adaptations to noisy city environments with those to natural mountain environments on the community level can provide significant insights that allow an understanding of the impact of anthropogenic noise on invertebrates that employ loud calling songs for mate attraction, especially when each species has its distinct song, as in the case of cicadas. In this study, we investigated the partitioning strategy of cicada assemblages in city and mountain environments by comparing the acoustic features and calling activity patterns of each species, recorded using automated digital recording systems. Our comparison of activity patterns of seasonal and diel calling revealed that there was no significant temporal partitioning of cicada assemblages in either environment. In addition, there was no correlation between the acoustic distance based on spectral features and temporal segregation. Heterospecific spectral overlap was low in both city and mountain environments, although city and mountain cicada assemblages were subject to significantly different levels of anthropogenic or interspecific noise. Furthermore, for the common species found in both environments, the calling activity patterns at both seasonal and diel time scales were significantly consistent across sites and across environments. We suggest that the temporal calling activity is constrained by endogenous factors for each species and is less flexible in response to external factors, such as anthropogenic noise. As a result, cicada assemblages in city environments with low species diversity do not demonstrate a more significant temporal partitioning than those in mountain environments with high species diversity.
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Biotransformation of isofraxetin-6-O-β-d-glucopyranoside by Angelica sinensis (Oliv.) Diels callus.
Zhou, Di; Zhang, Yuhua; Jiang, Zhe; Hou, Yue; Jiao, Kun; Yan, Chunyan; Li, Ning
2017-01-15
Isofraxetin-6-O-β-d-glucopyranoside, identified from traditional medicinal herbal Xanthoceras sorbifolia Bunge, has been demonstrated to be a natural neuroinflammatory inhibitor. In order to obtain more derivatives with potential anti-neuroinflammatory effects, biotransformation was carried out. According to the characteristics of coumarin skeleton, suspension cultures of Angelica sinensis (Oliv.) Diels callus (A. sinensis callus) were employed because of the presence of diverse phenylpropanoids biosynthetic enzymes. As a result, 15 products were yielded from the suspension cultures, including a new coumarin: 8'-dehydroxymethyl cleomiscosin A (1), together with 14 known compounds. Their structures were elucidated by extensive spectroscopic analysis. Furthermore, the biotransformed pathways were discussed. Among them, compound 13 was transformed from isofraxetin-6-O-β-d-glucopyranoside, while compounds 1-6, 10-12, 14-15 were derived from the culture medium stimulated by the substrate. The biotransformation processes include hydroxylation, oxidation and esterification. Furthermore, their inhibitory effects on lipopolysaccharide (LPS)-activated nitric oxide (NO) production were evaluated in BV2 microglial cells. It is worth noting that, 1, 1'-methanediylbis(4-methoxybenzene) (3), obtucarbamates A (5), 2-nonyl-4-hydroxyquinoline N-oxide (10) and 1H-indole-3-carbaldehyde (11) exhibited significant inhibitory effect against neuroinflammation with IC 50 values at 1.22, 10.57, 1.02 and 0.76μM respectively, much stronger than that of the positive control minocycline (IC 50 35.82μM). Copyright © 2016 Elsevier Ltd. All rights reserved.
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Liu, Qi; Zhang, Peihai; Pan, Junjie; Li, Zhengjie; Liu, Jixin; Li, Guangsen; Qin, Wei; You, Yaodong; Yu, Xujun; Sun, Jinbo; Dong, Minghao; Gong, Qiyong; Guo, Jun; Chang, Degui
2015-01-01
Background. Pattern differentiation is the foundation of traditional Chinese medicine (TCM) treatment for erectile dysfunction (ED). This study aims to investigate the differences in cerebral activity in ED patients with different TCM patterns. Methods. 27 psychogenic ED patients and 27 healthy subjects (HS) were enrolled in this study. Each participant underwent an fMRI scan in resting state. The fractional amplitude of low-frequency fluctuation (fALFF) was used to detect the brain activity changes in ED patients with different patterns. Results. Compared to HS, ED patients showed an increased cerebral activity in bilateral cerebellum, insula, globus pallidus, parahippocampal gyrus, orbitofrontal cortex (OFC), and middle cingulate cortex (MCC). Compared to the patients with liver-qi stagnation and spleen deficiency pattern (LSSDP), the patients with kidney-yang deficiency pattern (KDP) showed an increased activity in bilateral brainstem, cerebellum, hippocampus, and the right insula, thalamus, MCC, and a decreased activity in bilateral putamen, medial frontal gyrus, temporal pole, and the right caudate nucleus, OFC, anterior cingulate cortex, and posterior cingulate cortex (P emotion-related regions, including prefrontal cortex and cingulated cortex.
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Physical activity patterns of youth with Down syndrome.
Esposito, Phil E; MacDonald, Megan; Hornyak, Joseph E; Ulrich, Dale A
2012-04-01
The purpose of this study was to examine the physical activity patterns of children with Down syndrome. A cross-sectional approach and accelerometry were used to measure the time children with Down syndrome (N = 104) spent in sedentary, light, and moderate-to-vigorous physical activity. Results indicated that adolescents from ages 14 to 15 years were the most sedentary and spent the least amount of time in light and moderate-to-vigorous physical activity. A general trend of decreasing physical activity as children increase in age was found. This trend is similar to that found among typically developing youth. Participants in this study were found to spend a majority of their day engaged in sedentary activities. Results indicate that most participants were not accumulating the recommended 60 minutes of moderate or vigorous physical activity.
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Stafford, Ben K; Sher, Alexander; Litke, Alan M; Feldheim, David A
2009-10-29
During development, retinal axons project coarsely within their visual targets before refining to form organized synaptic connections. Spontaneous retinal activity, in the form of acetylcholine-driven retinal waves, is proposed to be necessary for establishing these projection patterns. In particular, both axonal terminations of retinal ganglion cells (RGCs) and the size of receptive fields of target neurons are larger in mice that lack the beta2 subunit of the nicotinic acetylcholine receptor (beta2KO). Here, using a large-scale, high-density multielectrode array to record activity from hundreds of RGCs simultaneously, we present analysis of early postnatal retinal activity from both wild-type (WT) and beta2KO retinas. We find that beta2KO retinas have correlated patterns of activity, but many aspects of these patterns differ from those of WT retina. Quantitative analysis suggests that wave directionality, coupled with short-range correlated bursting patterns of RGCs, work together to refine retinofugal projections.
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Listening to sound patterns as a dynamic activity
Jones, Mari Riess
2003-04-01
The act of listening to a series of sounds created by some natural event is described as involving an entrainmentlike process that transpires in real time. Some aspects of this dynamic process are suggested. In particular, real-time attending is described in terms of an adaptive synchronization activity that permits a listener to target attending energy to forthcoming elements within an acoustical pattern (e.g., music, speech, etc.). Also described are several experiments that illustrate features of this approach as it applies to attending to musiclike patterns. These involve listeners' responses to changes in either the timing or the pitch structure (or both) of various acoustical sequences.
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Möller, Tobias; Wonneberger, Peter; Sárosi, Menyhárt B; Coburger, Peter; Hey-Hawkins, Evamarie
2016-02-07
The principle of stereotopic face differentiation was successfully applied to 2H-phospholes which undergo a very efficient and highly stereoselective Diels-Alder reaction giving phosphorus-chiral 1-phosphanorbornenes with up to 87% yield. The observed reaction pathway has been supported by theoretical calculations showing that the cycloaddition reaction between 2H-phosphole 3a and the dienophile (5R)-(-)-menthyloxy-2(5H)-furanone (8) is of normal electron demand. Optically pure phosphanes were obtained by separation of the single diastereomers and subsequent desulfurisation of the sulfur-protected phosphorus atom. Finally, divergent ligand synthesis is feasible by reduction of the chiral auxiliary, subsequent stereospecific intramolecular Michael addition, and various functionalisations of the obtained key compound 13a. Furthermore, the unique structural properties of phospanorbornenes are presented and compared to those of phosphanorbornanes.
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Bogdan, Vlastimil; Jůnek, Tomáš; Jůnková Vymyslická, Pavla
2016-01-01
The vertebrate fauna of the Philippines, known for its diversity and high proportion of endemic species, comprises mainly small- to medium-sized forms with a few large exceptions. As with other tropical ecosystems, the major threats to wildlife are habitat loss, hunting and invasive species, of which the feral cat (Felis catus) is considered the most damaging. Our camera-trapping study focused on a terrestrial vertebrate species inventory on Bohol Island and tempo-spatial co-occurrences of feral cats with their prey and competitors. The survey took place in the Rajah Sikatuna Protected Landscape, and we examined the primary rainforest, its border with agricultural land, and rural areas in the vicinity of villages. Altogether, over 2,885 trap days we captured 30 species of vertebrates-10 mammals (including Sus philippensis), 19 birds and one reptile, Varanus cumingi. We trapped 81.8% of expected vertebrates. Based on the number of events, the most frequent native species was the barred rail (Gallirallus torquatus). The highest overlap in diel activity between cats and potential prey was recorded with rodents in rural areas (Δ = 0.62); the lowest was in the same habitat with ground-dwelling birds (Δ = 0.40). Cat activity was not recorded inside the rainforest; in other habitats their diel activity pattern differed. The cats' activity declined in daylight in the proximity of humans, while it peaked at the transition zone between rainforest and fields. Both rodents and ground-dwelling birds exhibited a shift in activity levels between sites where cats were present or absent. Rodents tend to become active by day in cat-free habitats. No cats' temporal response to co-occurrences of civets (Paradoxurus hermaphroditus and Viverra tangalunga) was found but cats in diel activity avoided domestic dogs (Canis lupus familiaris). Our first insight into the ecology of this invasive predator in the Philippines revealed an avoidance of homogeneous primary rainforest and a
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International Nuclear Information System (INIS)
Carlucci, A.F.; Craven, D.B.; Henrichs, S.M.
1984-01-01
Diel patterns of dissolved free amino acid (DFAA) concentration and microheterotrophic utilization were examined in the spring and fall of 1981 in euphotic waters from the base of the mixed layer off the southern California coast. The average depths of the isotherms sampled were 19.2 m for spring and 9.0 for fall. Total DFAA levels were generally higher in the spring than in the fall, 18 to 66 nM and 14 to 20 nM, respectively. Two daily concentration maxima and minima were observed for total DFAAs as well as for most individual DFAAs. Maxima were usually measured in the mid-dark period and in the early afternoon; minima were typically observed in early morning and late afternoon. Bacterial cell numbers reached maximal values near midnight in both seasons. The increases coincided with one of the total DFAA maxima. The second total DFAA maximum occurred in early to midafternoon, during the time of maximum photosynthetic carbon production and rapid dissolved amino acid utilization. Microbial metabolism (incorporation plus respiration) of selected 3 H-amino acids was 2.7 to 4.1 times greater during the daylight hours. DFAA turnover times, based on these metabolic measurements, ranged between 11 and 36 h for the amino acids tested, and rates were 1.7 to 3.7 times faster in the daylight hours than at night. DFAA distributions were related to primary production and chlorophyll a concentrations. Amino acids were estimated to represent 9 to 45% of the total phytoplankton exudate. Microheterotrophic utilization or production of total protein amino acids was estimated as 3.6 μg of C liter -1 day -1 in spring and 1.9 μg of C liter -1 day -1 in the fall. Assimilation efficiency for dissolved amino acids averaged 65% for marine microheterotrophs
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DEFF Research Database (Denmark)
Pundhir, Sachin; Bagger, Frederik Otzen; Lauridsen, Felicia Kathrine Bratt
2016-01-01
Formation of nucleosome free region (NFR) accompanied by specific histone modifications at flanking nucleosomes is an important prerequisite for enhancer and promoter activity. Due to this process, active regulatory elements often exhibit a distinct shape of histone signal in the form of a peak......-valley-peak (PVP) pattern. However, different features of PVP patterns and their robustness in predicting active regulatory elements have never been systematically analyzed. Here, we present PARE, a novel computational method that systematically analyzes the H3K4me1 or H3K4me3 PVP patterns to predict NFRs. We show...... four ENCODE cell lines and four hematopoietic differentiation stages, we identified several enhancers whose regulatory activity is stage specific and correlates positively with the expression of proximal genes in a particular stage. In conclusion, our results demonstrate that PVP patterns delineate...
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Motor control patterns during an active straight leg raise in pain-free subjects.
Beales, Darren John; O'Sullivan, Peter Bruce; Briffa, N Kathryn
2009-01-01
Repeated measures. To investigate motor control (MC) patterns of normal subjects during the low level physical load of the active straight leg raise (ASLR). Aberrant MC patterns, as observed with the ASLR test, are considered to be a mechanism for ongoing pain and disability in subjects with chronic musculoskeletal pelvic girdle pain. These patterns may not only affect the provision of lumbopelvic stability, but also respiration and the control of continence. Greater understanding of MC patterns in pain-free subjects may improve the management of pelvic girdle pain. METHODS.: Fourteen pain-free nulliparous women were examined during the ASLR. Electromyography of the anterior abdominal wall, right chest wall and the anterior scaleni, intraabdominal pressure (IAP), intrathoracic pressure (ITP), respiratory rate, pelvic floor kinematics, and downward leg pressure of the nonlifted leg were compared between a left and right ASLR. There was greater activation of obliquus internus abdominis and obliquus externus abdominis on the side of the ASLR. The predominant pattern of activation for the chest wall was tonic activation during an ipsilateral ASLR, and phasic respiratory activation lifting the contralateral leg. Respiratory fluctuation of both IAP and ITP did not differ lifting either leg. The baseline shifts of these pressure variables in response to the physical demand of lifting the leg was also the same either side. There was no difference in respiratory rate, pelvic floor kinematics, or downward leg pressure. Pain-free subjects demonstrate a predominant pattern of greater ipsilateral tonic activation of the abdominal wall and chest wall on the side of the ASLR. This was achieved with minimal apparent disruption to IAP and ITP. The findings of this study demonstrate the plastic nature of the abdominal cylinder and the flexibility of the neuromuscular system in controlling load transference during an ASLR.
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Precise shape reconstruction by active pattern in total-internal-reflection-based tactile sensor.
Saga, Satoshi; Taira, Ryosuke; Deguchi, Koichiro
2014-03-01
We are developing a total-internal-reflection-based tactile sensor in which the shape is reconstructed using an optical reflection. This sensor consists of silicone rubber, an image pattern, and a camera. It reconstructs the shape of the sensor surface from an image of a pattern reflected at the inner sensor surface by total internal reflection. In this study, we propose precise real-time reconstruction by employing an optimization method. Furthermore, we propose to use active patterns. Deformation of the reflection image causes reconstruction errors. By controlling the image pattern, the sensor reconstructs the surface deformation more precisely. We implement the proposed optimization and active-pattern-based reconstruction methods in a reflection-based tactile sensor, and perform reconstruction experiments using the system. A precise deformation experiment confirms the linearity and precision of the reconstruction.
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Diel variation of larval fish abundance in the Amazon and Rio Negro
Directory of Open Access Journals (Sweden)
ARAUJO-LIMA C. A. R. M.
2001-01-01
Full Text Available Many streams and large rivers present higher ichthyoplankton densities at night. However, in some rivers this does not occur and larvae are equally abundant during the day. Larval drift diel variation is an important information for planning sampling programs for evaluating larval distribution and production. The aim of this study was to test whether the abundance of larval fish was different at either period. We tested it by comparing day and night densities of characiform, clupeiform and siluriform larvae during five years in the Amazon and one year in Rio Negro. We found that larvae of three species of characiform and larvae of siluriform were equally abundant during day and night in the Amazon. Conversely, the catch of Pellona spp. larvae was significantly higher during the day. In Rio Negro, however, larval abundance was higher during the night. These results imply that day samplings estimate adequately the abundance of these characiform and siluriform larvae in the Amazon, but not Pellona larvae. Evaluations of larved densities of Rio Negro will have to consider night sampling.
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Diel variation of larval fish abundance in the Amazon and Rio Negro
Directory of Open Access Journals (Sweden)
C. A. R. M. ARAUJO-LIMA
Full Text Available Many streams and large rivers present higher ichthyoplankton densities at night. However, in some rivers this does not occur and larvae are equally abundant during the day. Larval drift diel variation is an important information for planning sampling programs for evaluating larval distribution and production. The aim of this study was to test whether the abundance of larval fish was different at either period. We tested it by comparing day and night densities of characiform, clupeiform and siluriform larvae during five years in the Amazon and one year in Rio Negro. We found that larvae of three species of characiform and larvae of siluriform were equally abundant during day and night in the Amazon. Conversely, the catch of Pellona spp. larvae was significantly higher during the day. In Rio Negro, however, larval abundance was higher during the night. These results imply that day samplings estimate adequately the abundance of these characiform and siluriform larvae in the Amazon, but not Pellona larvae. Evaluations of larved densities of Rio Negro will have to consider night sampling.
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Root activity patterns of some tree crops
International Nuclear Information System (INIS)
1975-01-01
A coordinated research programme was followed using a soil injection method which employed 32 P-labelled superphosphate solution. The technique was applied for determining the root activity distribution of various crops. Field experiments were carried out in Uganda on bananas, Spain and Taiwan on citrus, Ghana on cocoa, Columbia and Kenya on coffee, and Ivory Coast and Malaysia on oil palms, to study the patterns of root activity as a function of depth and distance from the tree base, soil type, tree age and season. A few weeks after injection, leaf samples of similar age were taken from well-defined morphological positions on the tree and analyzed for 32 P. The activity of the label in the sample reflects the root activity at the various positions in the soil. Some preliminary experiments were also carried out using 32 P-superphosphate to evaluate the efficiency of different methods of fertilizer placement in relation to phosphate uptake by the plantation as a whole
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Large scale patterns in vertical distribution and behaviour of mesopelagic scattering layers
Klevjer, Thor Aleksander
2016-01-27
Recent studies suggest that previous estimates of mesopelagic biomasses are severely biased, with the new, higher estimates underlining the need to unveil behaviourally mediated coupling between shallow and deep ocean habitats. We analysed vertical distribution and diel vertical migration (DVM) of mesopelagic acoustic scattering layers (SLs) recorded at 38 kHz across oceanographic regimes encountered during the circumglobal Malaspina expedition. Mesopelagic SLs were observed in all areas covered, but vertical distributions and DVM patterns varied markedly. The distribution of mesopelagic backscatter was deepest in the southern Indian Ocean (weighted mean daytime depth: WMD 590 m) and shallowest at the oxygen minimum zone in the eastern Pacific (WMD 350 m). DVM was evident in all areas covered, on average ~50% of mesopelagic backscatter made daily excursions from mesopelagic depths to shallow waters. There were marked differences in migrating proportions between the regions, ranging from ~20% in the Indian Ocean to ~90% in the Eastern Pacific. Overall the data suggest strong spatial gradients in mesopelagic DVM patterns, with implied ecological and biogeochemical consequences. Our results suggest that parts of this spatial variability can be explained by horizontal patterns in physical-chemical properties of water masses, such as oxygen, temperature and turbidity.