Vertical distribution and diel vertical migration of krill beneath snow-covered ice and in ice-free waters

KAUST Repository

Vestheim, Hege; Rø stad, Anders; Klevjer, Thor A.; Solberg, Ingrid; Kaartvedt, Stein

2013-01-01

A bottom mounted upward looking Simrad EK60 120-kHz echo sounder was used to study scattering layers (SLs) and individuals of the krill Meganyctiphanes norvegica. The mooring was situated at 150-m depth in the Oslofjord, connected with an onshore cable for power and transmission of digitized data. Records spanned 5 months from late autumn to spring. A current meter and CTD was associated with the acoustic mooring and a shore-based webcam monitored ice conditions in the fjord. The continuous measurements were supplemented with intermittent krill sampling campaigns and their physical and biological environment.The krill carried out diel vertical migration (DVM) throughout the winter, regardless of the distribution of potential prey. The fjord froze over in mid-winter and the daytime distribution of a mid-water SL of krill immediately became shallower associated with snow fall after freezing, likely related to reduction of light intensities. Still, a fraction of the population always descended all the way to the bottom, so that the krill population by day seemed to inhabit waters with light levels spanning up to six orders of magnitude. Deep-living krill ascended in synchrony with the rest of the population in the afternoon, but individuals consistently reappeared in near-bottom waters already? 1 h after the ascent. Thereafter, the krill appeared to undertake asynchronous migrations, with some krill always being present in near-bottom waters even though the entire population appeared to undertake DVM. The Author 2013. Published by Oxford University Press. All rights reserved.

Vertical distribution and diel vertical migration of krill beneath snow-covered ice and in ice-free waters

KAUST Repository

Vestheim, Hege

2013-11-11

A bottom mounted upward looking Simrad EK60 120-kHz echo sounder was used to study scattering layers (SLs) and individuals of the krill Meganyctiphanes norvegica. The mooring was situated at 150-m depth in the Oslofjord, connected with an onshore cable for power and transmission of digitized data. Records spanned 5 months from late autumn to spring. A current meter and CTD was associated with the acoustic mooring and a shore-based webcam monitored ice conditions in the fjord. The continuous measurements were supplemented with intermittent krill sampling campaigns and their physical and biological environment.The krill carried out diel vertical migration (DVM) throughout the winter, regardless of the distribution of potential prey. The fjord froze over in mid-winter and the daytime distribution of a mid-water SL of krill immediately became shallower associated with snow fall after freezing, likely related to reduction of light intensities. Still, a fraction of the population always descended all the way to the bottom, so that the krill population by day seemed to inhabit waters with light levels spanning up to six orders of magnitude. Deep-living krill ascended in synchrony with the rest of the population in the afternoon, but individuals consistently reappeared in near-bottom waters already? 1 h after the ascent. Thereafter, the krill appeared to undertake asynchronous migrations, with some krill always being present in near-bottom waters even though the entire population appeared to undertake DVM. The Author 2013. Published by Oxford University Press. All rights reserved.

Plankton community composition and vertical migration during polar night in Kongsfjorden

DEFF Research Database (Denmark)

Grenvald, Julie Cornelius; Callesen, Trine Abraham; Daase, Malin

2016-01-01

characterize the plankton community composition during the polar night using water samplers and zooplankton net samples (50, 64, 200, 1500 lm), supplemented by acoustics (ADCPs, 300 kHz), to address a previously unresolved question–which species of zooplankton perform diel vertical migration during the polar...

Feeding habits, daily ration and vertical migration of the cape horse ...

African Journals Online (AJOL)

The feeding periodicity, rate of gut evacuation and vertical migration of horse mackerel were investigated from midwater and bottom trawl collections taken during five diel sampling periods between 1993 and 1995 at fixed positions on the South Coast. Horse mackerel feed only during the day, mostly in late afternoon prior ...

Vertical Distribution of Daily Migrating Mesopelagic Fish in Respect to Nocturnal Lights

KAUST Repository

Prihartato, Perdana

2014-12-01

The nighttime distribution of vertically migrating mesopelagic fish in relation to nocturnal light was studied during a circumglobal survey, in the Red Sea, and in a fjord at high latitude. The study was based on data derived from ship borne echo sounders (circumglobal and the Red Sea) as well as using upward looking echo sounders mounted on the bottom (Masfjorden, Norway). We also applied a numerical model for analyzing diel vertical migration patterns. The effect of the lunar cycle was the focus in studies at low latitudes, while seasonal changes in nocturnal light climate was in focus at high latitude. Lunar phase significantly affected the distribution of mesopelagic fish at the global scale and in the Red Sea. During nights near full moon, scattering layers of mesopelagic fish distributed deeper than during darker phases of the moon. At high latitude, mesopelagic fish switched its behavior along with seasonal changes in nocturnal lights. In autumn, the population of the studied fish (Maurolicus mueleri) formed separated layers. Juveniles performed normal diel vertical migration followed by midnight sinking, with midnight sinking mainly related to temperature minima and also for avoiding predators. Meanwhile the adults did not migrate vertically, reducing foraging but increasing the adult survival. From late winter to mid-Spring, interrupted ascents behavior was noted in the afternoon. Predator avoidance, satiation, and finding temperature optimum might be the reason behind interrupted ascents. At lighter nights in mid-summer, M. muelleri took on schooling behavior, likely as an anti-predator behavior permitting access to the upper waters in the absence of darkness.

Vertical nitrogen flux from the oceanic photic zone by diel migrant zooplankton and nekton

Science.gov (United States)

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.

Inverse vertical migration and feeding in glacier lanternfish (Benthosema glaciale)

KAUST Repository

Dypvik, Eivind

2011-11-08

A bottom-mounted upward-facing 38-kHz echo sounder was deployed at ~400 m and cabled to shore in Masfjorden (~60 52?N, ~5 24?E), Norway. The scattering layers seen during autumn (September-October) 2008 were identified by trawling. Glacier lanternfish (Benthosema glaciale) were mainly distributed below ~200 m and displayed three different diel behavioral strategies: normal diel vertical migration (NDVM), inverse DVM (IDVM) and no DVM (NoDVM). The IDVM group was the focus of this study. It consisted of 2-year and older individuals migrating to ~200-270 m during the daytime, while descending back to deeper than ~270 m during the night. Stomach content analysis revealed increased feeding during the daytime on overwintering Calanus sp. We conclude that visually searching glacier lanternfish performing IDVM benefit from the faint daytime light in mid-waters when preying on overwintering Calanus sp. 2011 The Author(s).

Vertical migrations of a deep-sea fish and its prey.

Directory of Open Access Journals (Sweden)

Pedro Afonso

Full Text Available It has been speculated that some deep-sea fishes can display large vertical migrations and likely doing so to explore the full suite of benthopelagic food resources, especially the pelagic organisms of the deep scattering layer (DSL. This would help explain the success of fishes residing at seamounts and the increased biodiversity found in these features of the open ocean. We combined active plus passive acoustic telemetry of blackspot seabream with in situ environmental and biological (backscattering data collection at a seamount to verify if its behaviour is dominated by vertical movements as a response to temporal changes in environmental conditions and pelagic prey availability. We found that seabream extensively migrate up and down the water column, that these patterns are cyclic both in short-term (tidal, diel as well as long-term (seasonal scales, and that they partially match the availability of potential DSL prey components. Furthermore, the emerging pattern points to a more complex spatial behaviour than previously anticipated, suggesting a seasonal switch in the diel behaviour mode (benthic vs. pelagic of seabream, which may reflect an adaptation to differences in prey availability. This study is the first to document the fine scale three-dimensional behaviour of a deep-sea fish residing at seamounts.

Vertical distributions of autumn spawned larval herring (Clupea harengus L.) in the North Sea

DEFF Research Database (Denmark)

Heath, M.; Brander, Keith; Munk, Peter

1991-01-01

in all stages of development, from yolk-sac to pre-metamorphosis (35 mm). During diel migrations larvae were closer to the surface during daylight than at night. The amplitude of diel vertical migrations increased with the length of the larvae. Semi-diel cycles in the vertical distributions were rare...

Internal wave-mediated shading causes frequent vertical migrations in fishes

KAUST Repository

Kaartvedt, Stein

2012-04-25

We provide evidence that internal waves cause frequent vertical migrations (FVM) in fishes. Acoustic data from the Benguela Current revealed that pelagic scattering layers of fish below ~140 m moved in opposite phases to internal waves, ascending ~20 m towards the wave trough and descending from the wave crest. At the trough, the downward displacement of upper waters and the upward migration of fish created an overlapping zone. Near-bottom fish correspondingly left the benthic boundary zone at the wave trough, ascending into an acoustic scattering layer likely consisting of zooplankton and then descending to the benthic boundary zone at the wave crest. We suggest that this vertical fish migration is a response to fluctuations in light intensity of 3 to 4 orders of magnitude caused by shading from a turbid surface layer that had chlorophyll a values of 3 to 4 mg m−3 and varied in thickness from ~15 to 50 m at a temporal scale corresponding to the internal wave period (30 min). This migration frequency thus is much higher than that of the common and widespread light-associated diel vertical migration. Vertical movements affect prey encounters, growth, and survival. We hypothesize that FVM increase the likelihood of prey encounters and the time for safe visual foraging among planktivorous fish, thereby contributing to efficient trophic transfer in major upwelling areas.

Long-term acoustical observations of the mesopelagic fish Maurolicus muelleri reveal novel and varied vertical migration patterns

KAUST Repository

Staby, A

2011-11-15

We studied the temporal dynamics in the vertical distribution of Maurolicus muelleri scattering layers (SL) by examining continuous acoustic recordings over a 15 mo period in Masfjorden, Norway, complemented by intermittent sampling campaigns. 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, and interrupted ascents in the evening. During the first autumn of the study, adult fish modified their normal DVM behaviour by suspending their migration in the evening, yet ascending toward the surface in the later part of the night to reach upper layers during dawn. This behaviour was not observed during the second autumn of the study. By mid- to end of November (1st autumn), adult fish had suspended the nocturnal ascent entirely, and in the subsequent period until the end of January, a fraction of the population rather performed limited reverse migrations, slightly shifting their vertical distribution upwards during the first part of the day. From January to March 2008, fish interrupted their evening ascent at apparently random intervals and returned to deeper waters, instead of completing a full ascent to the surface. Our study underlines the value of long-term recordings, with the results suggesting that M. muelleri has the capability of changing its behaviour in response to ontogeny and internal state (satiation and hunger) as well as to external stimuli.

Diel vertical migration patterns of three zooplankton populations in a Chilean lake Patrones de migración vertical de tres poblaciones de zooplancton en un lago chileno

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

Tidal Influence on the Diel Vertical Migration Pattern of Zooplankton in a Tropical Monsoonal Estuary

KAUST Repository

Vineetha, G.; Jyothibabu, R.; Madhu, N. V.; Kusum, K. K.; Sooria, P. M.; Shivaprasad, A.; Reny, P. D.; Deepak, M. P.

2015-01-01

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

Hunt warm, rest cool: bioenergetic strategy underlying diel vertical migration of a benthic shark.

Science.gov (United States)

Sims, David W; Wearmouth, Victoria J; Southall, Emily J; Hill, Jacqueline M; Moore, Pippa; Rawlinson, Kate; Hutchinson, Neil; Budd, Georgina C; Righton, David; Metcalfe, Julian D; Nash, Jon P; Morritt, David

2006-01-01

1. Diel vertical migration (DVM) is a widespread phenomenon among marine and freshwater organisms and many studies with various taxa have sought to understand its adaptive significance. Among crustacean zooplankton and juveniles of some fish species DVM is accepted widely as an antipredator behaviour, but little is known about its adaptive value for relatively large-bodied, adult predatory fish such as sharks. Moreover, the majority of studies have focused on pelagic forms, which raises the question of whether DVM occurs in bottom-living predators. 2. To investigate DVM in benthic predatory fish in the marine environment and to determine why it might occur we tracked movements of adult male dogfish (Scyliorhinus canicula) by short- and long-term acoustic and archival telemetry. Movement studies were complemented with measurements of prey abundance and availability and thermal habitat within home ranges. A thermal choice experiment and energy budget modelling was used to investigate trade-offs between foraging and thermal habitat selection. 3. Male dogfish undertook normal DVM (nocturnal ascent) within relatively small home ranges (-100 x 100 m) comprising along-bottom movements up submarine slopes from deeper, colder waters occupied during the day into warmer, shallow prey-rich areas above the thermocline at night. Few daytime vertical movements occurred. Levels of activity were higher during the night above the thermocline compared to below it during the day indicating they foraged in warm water and rested in colder depths. 4. A thermal choice experiment using environmentally realistic temperatures supported the field observation that dogfish positively avoided warmer water even when it was associated with greater food availability. Males in laboratory aquaria moved into warm water from a cooler refuge only to obtain food, and after food consumption they preferred to rest and digest in cooler water. 5. Modelling of energy budgets under different realistic thermal

Species-specific patterns of diel migration into the Oxygen Minimum Zone by euphausiids in the Humboldt Current Ecosystem

Science.gov (United States)

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.

Bio-mixing due to Diel Vertical Migration of Daphnia spp. in a Small Lake

Science.gov (United States)

Simoncelli, Stefano; Wain, Danielle; Thackeray, Stephen

2016-04-01

Bio-turbulence or bio-mixing refers to the contribution of living organisms towards the mixing of waters in oceans and lakes. Experimental measurements in an unstratified tank by Wilhelmus & Dabiri (2014) show that zooplankton can trigger fluid instabilities through collective motions and that energy is imparted to scales bigger than organism's size of few mm. Length scales analysis, for low-Reynolds-number organisms in stratified water by Leshansky & Pismen (2010) and Kunze (2011), estimate eddy diffusivity up two orders of magnitude larger than the molecular thermal diffusivity. Very recently, Wand & Ardekani (2015) showed a maximum diffusivity of 10-5 m2/s for millimetre-sized organisms from numerical simulations in the intermediate Reynolds number regime. Here we focus our attention on turbulence generated by the vertical migration of zooplankton in a small lake, mostly populated by Daphnia spp. This very common species, belonging to Cladocera order, is engaged in a vertical migration (DVM) at sunset, with many organisms crossing the thermocline despite the density stratification. During the ascension they may create hydrodynamic disturbances in the lake interior where the stratification usually suppresses the vertical diffusion. We have conducted five turbulence experiments in Vobster Quay, a small (area ˜ 59,000 m2), deep (40m) man-made basin with small wind fetch and steep sides, located in the South West UK. Turbulence was measured with a temperature microstructure profiler. To asses the zooplankton vertical concentration we used a 100 μm mesh net, by collecting and analyzing samples in 8 layers of the lake. A bottom-mounted acoustic Doppler current profiler was also employed to track their concentration and migration with the measured backscatter strength. Measured dissipation rates ɛ during the day showed low turbulence level (<= 10-8 W/Kg) in the thermocline and in the zooplankton layer. Turbulence, during the DVM in two different days, is highest on

Zooplankton structure and vertical migration: Using acoustics and biomass to compare stratified and mixed fjord systems

Science.gov (United States)

Díaz-Astudillo, Macarena; Cáceres, Mario A.; Landaeta, Mauricio F.

2017-09-01

The patterns of abundance, composition, biomass and vertical migration of zooplankton in short-time scales (ADCP device mounted on the hull of a ship were used to obtain vertical profiles of current velocity data and intensity of the backscattered acoustic signal, which was used to study the migratory strategies and to relate the echo intensity with zooplankton biomass. Repeated vertical profiles of temperature, salinity and density were obtained with a CTD instrument to describe the density patterns during both experiments. Zooplankton were sampled every 3 h using a Bongo net to determine abundance, composition and biomass. Migrations were diel in the stratified station, semi-diel in the mixed station, and controlled by light in both locations, with large and significant differences in zooplankton abundance and biomass between day and night samples. No migration pattern associated with the effect of tides was found. The depth of maximum backscatter strength showed differences of approximately 30 m between stations and was deeper in the mixed station. The relation between mean volume backscattering strength (dB) computed from echo intensity and log10 of total dry weight (mg m-3) of zooplankton biomass was moderate but significant in both locations. Biomass estimated from biological samples was higher in the mixed station and determined by euphausiids. Copepods were the most abundant group in both stations. Acoustic methods were a useful technique to understand the detailed patterns of migratory strategies of zooplankton and to help estimate zooplankton biomass and abundance in the inner waters of southern Chile.

Complex vertical migration of larvae of the ghost shrimp, Nihonotrypaea harmandi, in inner shelf waters of western Kyushu, Japan

Science.gov (United States)

Tamaki, Akio; Mandal, Sumit; Agata, Yoshihiro; Aoki, Ikumi; Suzuki, Toshikazu; Kanehara, Hisao; Aoshima, Takashi; Fukuda, Yasushi; Tsukamoto, Hideshi; Yanagi, Tetsuo

2010-01-01

The position of meroplanktonic larvae in the water column with depth-dependent current velocities determines horizontal transport trajectories. For those larvae occurring in inner shelf waters, little is known about how combined diel and tidally-synchronized vertical migration patterns shift ontogenetically. The vertical migration of larvae of Nihonotrypaea harmandi (Decapoda: Thalassinidea: Callianassidae) was investigated in mesotidal, inner shelf waters of western Kyushu, Japan in July-August 2006. The larval sampling at seven depth layers down to 60 m was conducted every 3 h for 36 h in a 68.5-m deep area 10 km off a major coastal adult habitat. Within a 61-65-m deep area 5-7.5 km off the adult habitat, water temperature, salinity, chlorophyll a concentration, and photon flux density were measured, and water currents there were characterized from harmonic analysis of current meter data collected in 2008. The water column was stratified, with pycnocline, chlorophyll a concentration maximum, and 2% of photon flux density at 2 m, recorded at around 22-24 m. The stratified residual currents were detected in their north component, directed offshore and onshore in the upper and lower mixed layers, respectively. More than 87% of larvae occurred between 20 m and 60 m, producing a net onshore transport of approximately 1.3 km d -1. At the sunset flooding tide, all zoeal-stage larvae ascended, which could further promote retention (1.4-km potential onshore transport in 3 h). The actual onshore transport of larvae was detected by observing their occurrence pattern in a shallow embayment area with the adult habitat for 24 h in October 1994. However, ontogenetic differences in the vertical migration pattern in inner shelf waters were also apparent, with the maximum mean positions of zoeae deepening with increasing stages. Zoeae I and II performed a reverse diel migration, with their minimum and maximum depths being reached around noon and midnight, respectively. Zoeae IV

Moonlight Drives Ocean-Scale Mass Vertical Migration of Zooplankton during the Arctic Winter.

Science.gov (United States)

Last, Kim S; Hobbs, Laura; Berge, Jørgen; Brierley, Andrew S; Cottier, Finlo

2016-01-25

In extreme high-latitude marine environments that are without solar illumination in winter, light-mediated patterns of biological migration have historically been considered non-existent [1]. However, diel vertical migration (DVM) of zooplankton has been shown to occur even during the darkest part of the polar night, when illumination levels are exceptionally low [2, 3]. This paradox is, as yet, unexplained. Here, we present evidence of an unexpected uniform behavior across the entire Arctic, in fjord, shelf, slope and open sea, where vertical migrations of zooplankton are driven by lunar illumination. A shift from solar-day (24-hr period) to lunar-day (24.8-hr period) vertical migration takes place in winter when the moon rises above the horizon. Further, mass sinking of zooplankton from the surface waters and accumulation at a depth of ∼50 m occurs every 29.5 days in winter, coincident with the periods of full moon. Moonlight may enable predation of zooplankton by carnivorous zooplankters, fish, and birds now known to feed during the polar night [4]. Although primary production is almost nil at this time, lunar vertical migration (LVM) may facilitate monthly pulses of carbon remineralization, as they occur continuously in illuminated mesopelagic systems [5], due to community respiration of carnivorous and detritivorous zooplankton. The extent of LVM during the winter suggests that the behavior is highly conserved and adaptive and therefore needs to be considered as "baseline" zooplankton activity in a changing Arctic ocean [6-9]. VIDEO ABSTRACT. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Vertical distribution and migration of euphausiid species in the Red Sea

KAUST Repository

Wiebe, Peter H.

2016-06-01

We addressed how the extreme environmental conditions of the Red Sea impact or alter patterns of vertical distribution and vertical migration of five euphausiid species that are known from other oceans. Euphausia diomedeae was abundant and performed diel vertical migration (DVM) from >200 m in daytime to <100 m at night, similar to its pattern in other ocean regions. Euphausia sibogae and Euphausia sanzoi also showed consistent patterns of DVM across their ranges in the Red Sea and elsewhere. Two species, Stylocheiron affine and Stylocheiron abbreviatum, did not exhibit DVM. DNA barcode sequences for mitochondrial cytochrome oxidase I (COI) were used to confirm species identifications for four species (no previous barcode data exist for E. sanzoi). COI sequence differences averaged 2.8% (SD 3.1%) within species and 16.6% (SD 0.7%) between species, similar to previous studies of euphausiids. Red Sea specimens of S. affine matched morphological descriptions of a western equatorial form and differed 14% from Atlantic and Pacific specimens, suggesting possible cryptic species-level variation within this taxon. Widely distributed species of zooplankton may exhibit broad tolerance ranges for key environmental variables, and have considerable potential to adapt to variable and changing conditions across their geographic range.

To migrate, or not to migrate: partial diel horizontal migration of fish in a temperate freshwater reservoir

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

Diel horizontal migration in streams: juvenile fish exploit spatial heterogeneity in thermal and trophic resources

Science.gov (United States)

Armstrong, Jonathan B.; Schindler, Daniel E.; Ruff, Casey P.; Brooks, Gabriel T.; Bentley, Kale E.; Torgersen, Christian E.

2013-01-01

Vertical heterogeneity in the physical characteristics of lakes and oceans is ecologically salient and exploited by a wide range of taxa through diel vertical migration to enhance their growth and survival. Whether analogous behaviors exploit horizontal habitat heterogeneity in streams is largely unknown. We investigated fish movement behavior at daily timescales to explore how individuals integrated across spatial variation in food abundance and water temperature. Juvenile coho salmon made feeding forays into cold habitats with abundant food, and then moved long distances (350–1300 m) to warmer habitats that accelerated their metabolism and increased their assimilative capacity. This behavioral thermoregulation enabled fish to mitigate trade-offs between trophic and thermal resources by exploiting thermal heterogeneity. Fish that exploited thermal heterogeneity grew at substantially faster rates than did individuals that assumed other behaviors. Our results provide empirical support for the importance of thermal diversity in lotic systems, and emphasize the importance of considering interactions between animal behavior and habitat heterogeneity when managing and restoring ecosystems.

The diel vertical migration patterns and individual swimming behavior of overwintering sprat Sprattus sprattus

KAUST Repository

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

Diel vertical migration and distribution of zooplankton in a tropical Brazilian reservoirlian

Directory of Open Access Journals (Sweden)

Ana M. A. da Silva

2009-08-01

amostradas em quatro profundidades (Sub-superfície, 50% Io, 1% Io e Fundo em uma estação de amostragem com cinco metros de profundidade, em intervalos de quatro horas, ao longo de 24 horas. Duas espécies de Cladocera (Moina minuta e Diaphanosoma spinulosum e uma espécie de Copepoda (Notodiaptomus cearensis apresentaram padrões relativamente semelhantes de migração noturna, permanecendo no fundo durante o dia e se deslocando próximo à superfície no fim da tarde e ao longo da noite. Brachionus falcatus e Hexarthra mira (Rotifera não apresentaram padrões migratórios e as suas distribuições verticais foram relativamente homogêneas. As variáveis ambientais e as distribuições das espécies correlacionaram-se fracamente, sugerindo que outros mecanismos podem ser responsáveis por induzir a migração vertical.

Habitat use and diel vertical migration of bigeye thresher shark: Overlap with pelagic longline fishing gear.

Science.gov (United States)

Coelho, Rui; Fernandez-Carvalho, Joana; Santos, Miguel N

2015-12-01

Pelagic longliners targeting swordfish and tunas in oceanic waters regularly capture sharks as bycatch, including currently protected species as the bigeye thresher, Alopias superciliosus. Fifteen bigeye threshers were tagged with pop-up satellite archival tags (PSATs) in 2012-2014 in the tropical northeast Atlantic, with successful transmissions received from 12 tags for a total of 907 tracking days. Marked diel vertical movements were recorded on all specimens, with most of the daytime spent in deeper colder water (mean depth = 353 m, SD = 73; mean temperature = 10.7 °C, SD = 1.8) and nighttime spent in warmer water closer to the surface (mean depth = 72 m, SD = 54; mean temperature = 21.9 °C, SD = 3.7). The operating depth of the pelagic longline gear was measured with Minilog Temperature and Depth Recorders (TDRs), and the overlap with habitat utilization was calculated. Overlap is taking place mainly during the night and is higher for juveniles. The results presented herein can be used as inputs for Ecological Risk Assessments for bigeye threshers captured in oceanic tuna fisheries, and serve as a basis for efficient management and conservation of this vulnerable shark species. Copyright © 2015 Elsevier Ltd. All rights reserved.

Use of an Autonomous Surface Vehicle reveals small-scale diel vertical migrations of zooplankton and susceptibility to light pollution under low solar irradiance

Science.gov (United States)

Ludvigsen, Martin; Berge, Jørgen; Geoffroy, Maxime; Cohen, Jonathan H.; De La Torre, Pedro R.; Nornes, Stein M.; Singh, Hanumant; Sørensen, Asgeir J.; Daase, Malin; Johnsen, Geir

2018-01-01

Light is a major cue for nearly all life on Earth. However, most of our knowledge concerning the importance of light is based on organisms’ response to light during daytime, including the dusk and dawn phase. When it is dark, light is most often considered as pollution, with increasing appreciation of its negative ecological effects. Using an Autonomous Surface Vehicle fitted with a hyperspectral irradiance sensor and an acoustic profiler, we detected and quantified the behavior of zooplankton in an unpolluted light environment in the high Arctic polar night and compared the results with that from a light-polluted environment close to our research vessels. First, in environments free of light pollution, the zooplankton community is intimately connected to the ambient light regime and performs synchronized diel vertical migrations in the upper 30 m despite the sun never rising above the horizon. Second, the vast majority of the pelagic community exhibits a strong light-escape response in the presence of artificial light, observed down to 100 m. We conclude that artificial light from traditional sampling platforms affects the zooplankton community to a degree where it is impossible to examine its abundance and natural rhythms within the upper 100 m. This study underscores the need to adjust sampling platforms, particularly in dim-light conditions, to capture relevant physical and biological data for ecological studies. It also highlights a previously unchartered susceptibility to light pollution in a region destined to see significant changes in light climate due to a reduced ice cover and an increased anthropogenic activity. PMID:29326985

Use of an Autonomous Surface Vehicle reveals small-scale diel vertical migrations of zooplankton and susceptibility to light pollution under low solar irradiance.

Science.gov (United States)

Ludvigsen, Martin; Berge, Jørgen; Geoffroy, Maxime; Cohen, Jonathan H; De La Torre, Pedro R; Nornes, Stein M; Singh, Hanumant; Sørensen, Asgeir J; Daase, Malin; Johnsen, Geir

2018-01-01

Light is a major cue for nearly all life on Earth. However, most of our knowledge concerning the importance of light is based on organisms' response to light during daytime, including the dusk and dawn phase. When it is dark, light is most often considered as pollution, with increasing appreciation of its negative ecological effects. Using an Autonomous Surface Vehicle fitted with a hyperspectral irradiance sensor and an acoustic profiler, we detected and quantified the behavior of zooplankton in an unpolluted light environment in the high Arctic polar night and compared the results with that from a light-polluted environment close to our research vessels. First, in environments free of light pollution, the zooplankton community is intimately connected to the ambient light regime and performs synchronized diel vertical migrations in the upper 30 m despite the sun never rising above the horizon. Second, the vast majority of the pelagic community exhibits a strong light-escape response in the presence of artificial light, observed down to 100 m. We conclude that artificial light from traditional sampling platforms affects the zooplankton community to a degree where it is impossible to examine its abundance and natural rhythms within the upper 100 m. This study underscores the need to adjust sampling platforms, particularly in dim-light conditions, to capture relevant physical and biological data for ecological studies. It also highlights a previously unchartered susceptibility to light pollution in a region destined to see significant changes in light climate due to a reduced ice cover and an increased anthropogenic activity.

A dynamic optimization model of the diel vertical distribution of a pelagic planktivorous fish

Science.gov (United States)

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.

Periodic swarms of the salp Salpa aspera in the Slope Water off the NE United States: Biovolume, vertical migration, grazing, and vertical flux

Science.gov (United States)

Madin, L. P.; Kremer, P.; Wiebe, P. H.; Purcell, J. E.; Horgan, E. H.; Nemazie, D. A.

2006-05-01

Sampling during four summers over a twenty-seven year period has documented dense populations of Salpa aspera in the Slope Water south of New England, northeastern United States. The salps demonstrated a strong pattern of diel vertical migration, moving to depth (mostly 600-800 m) during the day and aggregating in the epipelagic (salps measured were 5.7lm-2 in 1986 and 1.6lm-2 in 1993. Depending on the year, the sampled salp populations were calculated to clear between 8 and 74% of the upper 50 m during each 8 h night. Total fecal output for the same populations was estimated to be between 5 and 91mgCm-2night-1. These results, and other observations, suggest this region is a salp "hot spot", with swarms of S. aspera developing seasonally on a frequent basis.

Twilight vertical migrations of zooplankton in a Chilean fjord

Science.gov (United States)

Valle-Levinson, Arnoldo; Castro, Leonardo; Cáceres, Mario; Pizarro, Oscar

2014-12-01

Time series of acoustic backscatter and vertical velocity profiles were obtained at three sites along a Chilean fjord with the purpose of determining dominant structures of vertical migrations of the sound scattering layer. Ancillary data obtained with stratified net samples indicated that the sound scattering layer may have been dominated by euphausiids and decapods. Therefore, distributions of acoustic backscatter anomalies and vertical velocities were attributed to vertical migrations of predominantly these organisms. Migration patterns were dominated by twilight excursions in which organisms swam toward the water surface at sunset, spent 100 m). This migration strategy can also be termed 'semidiel migration' as two double excursions were linked to light levels. The reasons for this twilight migration remain uncertain. But it is possible that the up and down motion around sunset was related to predation avoidance, hunger-satiation state, ontogeny, seaward transport evasion, or reaction to the environmental shock from the pycnocline, or a combination of all or some of them. In contrast, the sunrise double excursion was probably linked to feeding requirements by organisms that need to spend the day at great depth with no food available. This study demonstrated the existence of semidiel patterns throughout the fjord and through prolonged periods. In addition, identification of this pattern by acoustic backscatter was complemented by direct vertical velocity measurements. It is proposed that twilight vertical migration is a common strategy in Chilean fjords.

Effects of nitrate on the diurnal vertical migration, carbon to nitrogen ratio, and the photosynthetic capacity of the dinoflagellate Gymnodinium splendens

Energy Technology Data Exchange (ETDEWEB)

Cullen, J.J.; Horrigan, S.G.

1981-01-01

A non-thecate dinoflagellate, Gymnodinium splendens, was studied in a 12 d laboratory experiment in 2.0 x 0.25 m containers in which light, temperature, and nutrients could be manipulated. Under a 12 h light:12 h dark cycle, the dinoflagellates exhibited diurnal vertical migrations, swimming downward before the dark period began and upward before the end of the dark period. This vertical migration probably involved geotaxis and a diel rhythm, as well as light-mediated behavior. The vertical distribution of nitrate affected the behavior and physiology of the dinoflagellate. When nitrate was present throughout the container, the organisms resembled those in exponential batch culture both in C:N ratios and photosynthetic capacity (P/sub max/); moreover, they migrated to the surface during the day. In contrast, when nitrate was depleted, C:N ratios increased, P/sub max/ decreased, and the organisms formed a subsurface layer at a depth corresponding to the light level at which photosynthesis saturated. When nitrate was present only at the bottom of the tank, C:N ratios of the population decreased until similar to those of nutrient-saturated cells and P/sub max/ increased; however, the dinoflagellates behaved the same as nutient-depleted cells, forming a subsurface layer during the light period. Field measurements revealed a migratory subsurface chlorophyll maximum layer dominated by G. splendens. It was just above the nitracline during the day, and in the nitracline during the night, which concurs with our laboratory observations.

Elastic kirchhoff migration for vertical seismic profiles

International Nuclear Information System (INIS)

Keho, T.H.; Wu, R.S.

1987-01-01

Elastic Kirchhoff migration is implemented for the VSP recording geometry. The resulting migration formula requires measurement of the stress as well as the displacement. Since stress is not measured in a VSP, and in many cases the horizontal component of displacement is not measured, approximate migration formulas are given for these cases. The elastic migration formula for the case where only the vertical components are available, is the same as the acoustic migration formula, where the pressure data are replaced by the magnitudes of the elastic data as reconstructed from the vertical components, and the acoustic Green's functions are replaced with either the P or S wave elastic Green's functions. Two expressions for migration of two component displacement data are presented. In the first, the terms involving traction data are simply ignored. In the second, an improved backpropagation operator for the displacement field is obtained by replacing the traction data in the Kirchhoff integral by displacement data using Hooke's law. The migration expressions for the cases where two component data are available produce images which are less contaminated by artifacts than the migration images of one component data

What goes down must come up: symmetry in light-induced migration behaviour of Daphnia

NARCIS (Netherlands)

Van Gool, E.; Ringelberg, J.

2003-01-01

During a short period of the year, Daphnia may perform a phenotypically induced diel vertical migration. For this to happen, light-induced swimming reactions must be enhanced both at dawn and at dusk. Enhanced swimming in response to light intensity increase can be elicited by fish-associated

Vertical distribution of alewife in the Lake Ontario offshore: Implications for resource use

Czech Academy of Sciences Publication Activity Database

Říha, Milan; Walsh, M. G.; Connerton, M. J.; Holden, J.; Weidel, B. C.; Sullivan, P. J.; Holda, T. J.; Rudstam, L. G.

2017-01-01

Roč. 43, č. 5 (2017), s. 823-837 ISSN 0380-1330 R&D Projects: GA MŠk(CZ) LD15021 Institutional support: RVO:60077344 Keywords : diel vertical migration * deep chlorophyll layer * zooplankton * mysids * alewife Subject RIV: DA - Hydrology ; Limnology OBOR OECD: Marine biology, freshwater biology, limnology Impact factor: 1.958, year: 2016

Hydrographic features of anguillid spawning areas: Potential signposts for migrating eels

DEFF Research Database (Denmark)

Schabetsberger, Robert; Miller, Michael J.; Dall'Olmo, Giorgio

2016-01-01

Catadromous anguillid eels (genus Anguilla) migrate from their freshwater or estuarine habitats to marine spawning areas. Evidence from satellite tagging studies indicates that tropical and temperate eel species exhibit pronounced diel vertical migrations, from between 150-300 m nighttime depths...... to 600-800 m during the day. Collections of eggs and larvae of Japanese eels A. japonica suggest they may spawn at these upper nighttime migration depths. How anguillid eels navigate through the ocean and find their spawning areas remains unknown; thus, this study describes the salinity, temperature...

Influence of marine current on vertical migration of Pb in marine bay

Science.gov (United States)

Yu, Chen; Hong, Ai; Danfeng, Yang; Huijuan, Zhao; Dongfang, Yang

2018-02-01

This paper analyzed that vertical migration of Pb contents waters in Jiaozhou Bay, and revealed the influence of marine current on vertical migration process. Results showed that Pb contents in bottom waters of Jiaozhou Bay in April and July 1988 were 1.49-18.53 μg L-1 and 12.68/-27.64 μg L-1, respectively. The pollution level of Pb in bottom waters was moderate to heavy, and were showing temporal variations and spatial heterogeneity. The vertical migration process of Pb in April 1988 included a drifting process from the southwest to the north by means of the marine current was rapid in this region. The vertical migration process of Pb in July 1988 in the open waters included no drifting process since the flow rate of marine current was relative low in this region. The vertical migration process of Pb was jointly determined by vertical water’s effect, source input and water exchange, and the influence of marine current on the vertical migration of Pb in marine bay was significant.

Small scale distribution patterns and vertical migration of North Sea herring larvae (Clupea harengus, Teleostei: Clupeidea in relation to abiotic and biotic factors

Directory of Open Access Journals (Sweden)

Holger Haslob

2009-10-01

Full Text Available The distribution of herring larvae in relation to environmental conditions and the occurrence of possible prey and predator organisms was studied during a 4-day period on a permanent station in the northern North Sea in September 1999. The vertical distribution of herring larvae was sampled in 20-m intervals by means of a multiple-closing net. To resolve the small-scale patchiness of herring larvae and planktonic prey and predator organisms, a towed in-situ video system was used, the Ichthyoplankton Recorder. A diel vertical migration of herring larvae was observed with different intensities depending on their body length. Small larvae ( 16 mm showed the highest abundances in the upper water layers during the day and were concentrated in deeper water layers during the night. The presented results appear to be relevant for individual-based modelling of the fate of larval herring populations.

Vertical migration of motile phytoplankton chains through turbulence

Science.gov (United States)

Climent, Eric; Lovecchio, Salvatore; Durham, William; Stocker, Roman

2017-11-01

Daily, phytoplankton needs to migrate vertically from and towards the ocean surface to find nutrients such as dissolved oxygen. To travel through the water column they need to fight against gravity (by swimming) and fluid turbulence which can make their journey longer. It is often observed that cells migrate across the water column as chains. The first benefit to form chains is that micro-organisms sum up their thrust while reducing their drag. Therefore, upwards swimming is faster for chains in a quiescent fluid with steady vertical orientation. However, as chain length increases their tendency to periodically tumble in turbulent structures increases which reduces orientation stability and limits their capacity to swim upwards. The purpose of our study is to elaborate on this apparent contradiction. We carried out direct numerical simulations and physical analysis of the coupled system of homogeneous isotropic turbulence and chain trajectories through Lagrangian tracking. Formation of chains is indeed favorable for vertical migration through the upper layer of the ocean.

Variation in the diel vertical distributions of larvae and transforming stages of oceanic fishes across the tropical and equatorial Atlantic

Science.gov (United States)

Olivar, M. Pilar; Contreras, Tabit; Hulley, P. Alexander; Emelianov, Mikhail; López-Pérez, Cristina; Tuset, Víctor; Castellón, Arturo

2018-01-01

The vertical distributions of early developmental stages of oceanic fishes were investigated across the tropical and equatorial Atlantic, from oligotrophic waters close to the Brazilian coast to more productive waters close to the Mauritanian Upwelling Region. Stratification of the water column was observed throughout the study region. Fishes were caught with a MOCNESS-1 net with mouth area of 1 m2 at 11 stations. Each station was sampled both during the day and at night within a single 24-h period. The investigation covered both larvae and transforming stages from the surface to 800 m depth. Distribution patterns were analysed, and weighted mean depths for the larvae and transforming stages of each species were calculated for day and night conditions. Forty-seven different species were found. The highest number of species occurred in the three stations south of Cape Verde Islands, characterized by a mixture of South Atlantic Central Water (SACW) and Eastern North Atlantic Central Water (ENACW). There was a marked drop in species richness in the three stations closer to the African upwelling, dominated by ENACW. The highest abundances occurred in the families Myctophidae, Sternoptychidae, Gonostomatidae and Phosichthyidae. Day and night vertical distributions of larvae and transforming stages showed contrasting patterns, both in the depths of the main concentration layers in the water column, and in the diel migration patterns (where these were observed). Larvae generally showed a preference for the upper mixed layer (ca. 0-50 m) and upper thermocline (ca. 50-100 m), except for sternoptychids, which were also abundant in the lower thermocline layer (100-200 m) and even extended into the mesopelagic zone (down to 500 m). Transforming stages showed a more widespread distribution, with main concentrations in the mesopelagic zone (200-800 m). Larvae showed peak concentrations in the more illuminated and zooplankton-rich upper mixed layers during the day and a wider

Modeling Diel Oxygen Dynamics and Ecosystem Metabolism in a Shallow, Eutrophic Estuary

Science.gov (United States)

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...

Diel vertical migration of major fish-species in Lake Victoria, East Africa

NARCIS (Netherlands)

Goudswaard, P.C.; Wanink, J.H.; Witte, F.; Katunzi, E.F.B.; Berger, M.R.; Postma, D.J.

2004-01-01

Understanding of migration patterns is essential in the interpretation of hydro-acoustic stock assessment data of partly demersal partly pelagic fish stocks. In this paper we provide this kind of information for some species that were common in the Mwanza Gulf of Lake Victoria in the 1980s, before

Diel vertical migration of major fish-species in Lake Victoria, East Africa.

NARCIS (Netherlands)

Goudswaard, KPC; Wanink, JH; Witte, F; Katunzi, EFB; Berger, MR; Postma, DJ

2004-01-01

Understanding of migration patterns is essential in the interpretation of hydro-acoustic stock assessment data of partly demersal partly pelagic fish stocks. In this paper we provide this kind of information for some species that were common in the Mwanza Gulf of Lake Victoria in the 1980s, before

Eat and run? The hunger/satiation hypothesis in vertical migration: history, evidence and consequences.

Science.gov (United States)

Pearre, Sifford

2003-02-01

The study of vertical migrations in aquatic organisms has a long and colourful history, much of it to do with the effects of changing sampling technology on our understanding of the phenomenon. However, the overwhelming majority of such studies carried out today still depend on detecting differences in vertical distribution profiles during some course of time, or acoustic echoes of migrating bands of organisms. These can not distinguish migratory activity of individual organisms, but can only assess net results of mass transfers of populations, which may integrate many individual migrations. This is an important distinction, for without knowing the actual movements of individuals it seems unlikely that we will be able to understand their causes, nor the effects of vertical migrations on the environment or on the migrators themselves. This review examines evidence for individual vertical movements gathered from 'tracers', mainly gut contents, and reviews the evidence for the hypothesis that such movements are in fact driven by hunger and satiation. The more recently appreciated vertical migrations of phytoplankters and their similarities in form and driving forces to those of zooplankton and nekton are also discussed. Finally, the role of vertical migrators in vertical fluxes of materials is discussed, along with the consequences of satiation-driven descent for such estimates.

Modelling the transport of common sole larvae in the southern North Sea: Influence of hydrodynamics and larval vertical movements

Science.gov (United States)

Savina, Marie; Lacroix, Geneviève; Ruddick, Kevin

2010-04-01

In the present work we used a particle-tracking model coupled to a 3D hydrodynamic model to study the combined effect of hydrodynamic variability and active vertical movements on the transport of sole larvae in the southern North Sea. Larval transport from the 6 main spawning grounds was simulated during 40 day periods starting on 2 plausible spawning dates, the 15/04 and the 01/05, during 2 years, 1995 and 1996. In addition to a "passive" behaviour, 3 types of active vertical movements inspired from previous studies have been tested: (1) Eggs and early larvae float in the surface waters, late larvae migrate toward the bottom and stay there until the end of the simulation; (2 and 3) Eggs float in the surface waters, early larvae perform diel vertical migrations in the surface waters, and (2) Late larvae perform diel vertical migrations in the bottom waters until the end of the simulation; or (3) Late larvae perform tidally synchronised vertical migrations in the bottom waters until the end of the simulation. These behaviours have been implemented in the model with vertical migration rates, positive or negative, which can account for buoyancy or real swimming activity. Variations in larval transport were analysed in terms of mean trajectories, final larvae distribution, larval retention above nurseries, and connectivity. Results suggest that the variations in larval retention above nurseries due to the varying hydrodynamic conditions are not consistent in space i.e. not the same for all the spawning sites. The effect of active vertical movements on larval transport is also not consistent in space: Effects of active vertical movements include decreased retention above nurseries, decreased transport and/or decreased horizontal dispersion of larvae through reduced vertical shear (depending on the zone). The variability in larval retention due to hydrodynamic variability is higher than variability due to differences in the behaviour of larvae. In terms of connectivity

Reproducing {sup 137}Cs vertical migration in Spanish soils - Reproducing {sup 137}Cs and {sup 90}Sr vertical migration in Spanish mainland

Energy Technology Data Exchange (ETDEWEB)

Olondo, C.; Legarda, F.; Herranz, M.; Idoeta, R. [The University of the Basque Country - UPV/EHU, Nuclear Engineering and Fluid Mechanics Dept. Faculty of Engineering, Alda. Urquijo 48013, Bilbao (Spain)

2014-07-01

As a result of caesium's and strontium's activity migration study developed in Spanish mainland soils, there has been obtained convective - diffusive migration equation that will reproduce adequately the movement that an activity deposit would follow in this land. Taking into account the dependence on rain that apparent convection velocity shows, it has been defined a new migration parameter that depends only on soil's properties. By means of a least square method and fitting the migration equation to experimental activity profiles, the values showed by the migration parameters in the studied soils, characteristics of that area, have been obtained. After that, there have been obtained the mean values of these parameters for each defined group that, depending on soil's texture, have been observed in the study performed about the movement of both radionuclides in soils and to whom these soils belong. Using these mean values and obtained equation, it has been properly reproduce those vertical activity profiles that were experimentally determined. In order to validate these values, a new sampling programme is carrying out in the north of Spain and, with obtained new sampling points' information, is going to verify if, indeed, obtained mean values also reproduce these new sampling points' activity vertical profile. (authors)

Vertical migration of 85Sr, 137Cs and 131I in various arable and undisturbed soils

International Nuclear Information System (INIS)

Palagyi, S.; Palagyiova, J.

2003-01-01

The vertical migration of 85 Sr, 137 Cs and 131 I in some arable and undisturbed single-contaminated soils was studied by gamma-spectrometry measurements under lysimetric laboratory conditions during irrigation of the soil profiles with wet atmospheric precipitation for about one year, except 131 I. A new simple exponential compartment (box) model was derived, which makes it possible to calculate the migration rate constants and migration rates in the individual soil layers (vertical sections) as well as the total vertical migration rate constants and total vertical migration rates of radionuclides in the bulk soil horizon. The relaxation times of radionuclides in respective soil horizons can also be evaluated. (author)

Beyond the average: Diverse individual migration patterns in a population of mesopelagic jellyfish

KAUST Repository

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.

Beyond the average: Diverse individual migration patterns in a population of mesopelagic jellyfish

KAUST Repository

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.

Vertical migration of 85Sr, 137Cs and 131I in various arable and undisturbed soils

International Nuclear Information System (INIS)

Palagyi, S.; Palagyiova, J.

2002-01-01

Vertical migration of 85 Sr, 137 Cs and 131 I in some arable and undisturbed single-contaminated soils was studied by gamma-spectrometry measurements in lysimetric laboratory conditions applying irrigation of the soil profiles with wet atmospheric precipitation for about one year (except radioiodine). A new simple exponential compartment (box) model was derived, allowing us to calculate the migration rate constants and migration rates in the individual soil layers (vertical sections) as well as the total vertical migration rate constants and total vertical migration rates of radionuclides in the bulk soil horizon. The data from the time dependence of the depth activity distribution (radionuclide concentration along the vertical soil profile) were used to test the model. The migration rate constants and migration rates were found to be affected by the contaminating radionuclides as well as by the site, type and depth of the soil. The relaxation times of the radionuclides in the soil horizons were calculated. The effects on the rate parameters of the permanent grass cover and the zeolite applied onto the arable soil surfaces were also investigated

Shark predation on migrating adult American eels (Anguilla rostrata in the Gulf of St. Lawrence.

Directory of Open Access Journals (Sweden)

Mélanie Béguer-Pon

Full Text Available In an attempt to document the migratory pathways and the environmental conditions encountered by American eels during their oceanic migration to the Sargasso Sea, we tagged eight silver eels with miniature satellite pop-up tags during their migration from the St. Lawrence River in Québec, Canada. Surprisingly, of the seven tags that successfully transmitted archived data, six were ingested by warm-gutted predators, as observed by a sudden increase in water temperature. Gut temperatures were in the range of 20 to 25°C-too cold for marine mammals but within the range of endothermic fish. In order to identify the eel predators, we compared their vertical migratory behavior with those of satellite-tagged porbeagle shark and bluefin tuna, the only endothermic fishes occurring non-marginally in the Gulf of St. Lawrence. We accurately distinguished between tuna and shark by using the behavioral criteria generated by comparing the diving behavior of these two species with those of our unknown predators. Depth profile characteristics of most eel predators more closely resembled those of sharks than those of tuna. During the first days following tagging, all eels remained in surface waters and did not exhibit diel vertical migrations. Three eels were eaten at this time. Two eels exhibited inverse diel vertical migrations (at surface during the day during several days prior to predation. Four eels were eaten during daytime, whereas the two night-predation events occurred at full moon. Although tagging itself may contribute to increasing the eel's susceptibility to predation, we discuss evidence suggesting that predation of silver-stage American eels by porbeagle sharks may represent a significant source of mortality inside the Gulf of St. Lawrence and raises the possibility that eels may represent a reliable, predictable food resource for porbeagle sharks.

Vertical distribution and migration of euphausiid species in the Red Sea

KAUST Repository

Wiebe, Peter H.; Bucklin, Ann; Kaartvedt, Stein; Rø stad, Anders; Blanco-Bercial, Leocadio

2016-01-01

We addressed how the extreme environmental conditions of the Red Sea impact or alter patterns of vertical distribution and vertical migration of five euphausiid species that are known from other oceans. Euphausia diomedeae was abundant and performed

Mechanism of vertical migration of Am 241 in peaty-gley soil

International Nuclear Information System (INIS)

Kalinin, V.N.

2002-01-01

Nowadays soil in the Chernobyl zone has become a source from which radionuclides can come to other objects of biosphere. The vertical migration determines distribution of the radionuclides in the soil. For research of vertical migration of Am 241 in soil the distribution of the radionuclide in granulometric fractions of the soil particles was measured, humus was extracted from the soil with the help of a sodium pyrophosphate solution by the accelerated method of Kononova and Beltchikova. For an estimation of a share of a mobile form of radionuclide the soil was dissolved in ammonium acetate solution. The conclusion is made, that nowadays significant part of Am 241 is strongly fixed on a mineral matrix of the soil and migrates together with the soil particles

DIEL AND VERTICAL DYNAMIC OF LIMNOLOGICAL CHARACTERISTICS IN FISH REARING NET-CAGES ENVIROMENT DINÂMICA NICTIMERAL E VERTICAL DAS CARACTERÍSTICAS LIMNOLÓGICAS EM AMBIENTE DE CRIAÇÃO DE PEIXES EM TANQUES-REDE

Directory of Open Access Journals (Sweden)

Odair Diemer

2010-04-01

Full Text Available

This study aimed to verify the diel and vertical dynamic characteristics in limnological environment for rearing native fish in net-cage at the reservoir of Itaipu Binacional. The parameters evaluated were water temperature, dissolved oxygen, electrical conductivity, pH, phosphorus, nitrite and ammonia. It was found that there was diel variation for all parameters, except for ammonia and phosphorus. But the variables are in the recommended limits for aquaculture, with the exception of dissolved oxygen that showed critical rates at night. For the vertical distribution concentrations of physical and chemical parameters of water did not exceed the limit established by CONAMA Resolution 357/05 for fish rearing, however, there was vertical variation for nitrite and phosphorus.

KEY WORDS: Aquaculture, intensive culture, limnology, water quality.

O presente trabalho teve como objetivo verificar a dinâmica nictimeral e vertical das características limnológicas em ambiente de criação de peixes nativos em tanques-rede no reservatório da Itaipu Binacional. Os parâmetros avaliados foram temperatura da água, oxigênio dissolvido, condutividade elétrica, pH, fósforo total, nitrito e amônia. Verificou-se que ocorreu variação nictimeral para todos os parâmetros, exceto para amônia e fósforo total. Entretanto, as variáveis estão dentro dos limites recomendados para a aquicultura, com exceção do oxigênio dissolvido, que apresentou valores críticos à noite. Para a distribuição vertical, as concentrações dos parâmetros físicos e químicos da água não ultrapassaram o limite estabelecido pela resolução do CONAMA 357/05 para criação de peixes. No entanto, houve variação vertical para nitrito e fósforo.

PALAVRAS-CHAVES: Aquicultura, cultivo intensivo, limnologia, qualidade de água.

Seasonal and diel patterns in sedimentary flux of krill fecal pellets recorded by an echo sounder

KAUST Repository

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.

Studies on Horizontal and Vertical Migration of 90Sr in Soil Systems

International Nuclear Information System (INIS)

Solecki, J.; Chibowski, S.

2002-01-01

Here are presented results of studies on vertical and horizontal migration of strontium 90 Sr isotope in soil systems of Bug river valleys. Mean radioactivity of strontium in these soils was 26.15 ± 22.2 Bq/kg. Atmospheric precipitation of strontium on this area was 0.35 kBq/m2/cm. Radioactivity in soil profiles ranged from 17 to 130 Bq/m2/cm and the isotope was detected even at 30 cm depth. Some tendency to vertical migration of strontium towards the river was noticed. Obtained results were compared with concentrations of calcium and strontium in the soil. Any clear influence of these elements on the migration of strontium 90 Sr was noticed. (author)

Internal wave-mediated shading causes frequent vertical migrations in fishes

KAUST Repository

Kaartvedt, Stein; Klevjer, TA; Aksnes, Dag L.

2012-01-01

We provide evidence that internal waves cause frequent vertical migrations (FVM) in fishes. Acoustic data from the Benguela Current revealed that pelagic scattering layers of fish below ~140 m moved in opposite phases to internal waves, ascending

Numerical simulation of the vertical migration of Microcystis (cyanobacteria colonies based on turbulence drag

Directory of Open Access Journals (Sweden)

Hongru Zhao

2016-11-01

Full Text Available The vertical migration and accumulation of Microcystis is an important process in water blooms, and colony migration is influenced by colony size and wind-wave disturbance. The vertical migration of Microcystis colonies in turbulence can be simulated in a numerical model. In this study, we model such migration by coupling the colony size and hydrodynamics, including the gravity, colony buoyancy, and the viscous drag force of turbulence. The turbulence intensity was represented by the turbulent kinetic energy (KZ; the larger the KZ, the stronger the wind-wave disturbance. The simulated vertical distribution of Microcystis well agreed with the measured values in a laboratory experiment indicating that our model can simulate the vertical distribution of Microcystis under different hydrodynamic conditions. We also found a size-dependent critical turbulent kinetic energy (TKZ, such that if the turbulent kinetic energy of water exceeds the critical value (i.e., KZ > TKZ, the colonies sink under the drag forces of turbulence; conversely, if KZ < TKZ, the colonies can overcome the turbulent mixing and float. The TKZ of each colony was linearly related to colony diameter. The model is crucial for prediction and prevention of water blooms. The simulated threshold turbulent kinetic energy, at which water blooms disappear in Lake Taihu (a large freshwater lake in the Yangtze Delta, Jiangsu Province, China, was 55.5 cm2 s−2. 

Large scale patterns in vertical distribution and behaviour of mesopelagic scattering layers

KAUST Repository

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.

Will the application of Ammonium-Ferric-Hexacyano-Ferrate enhance the vertical migration of radiocaesium?

International Nuclear Information System (INIS)

Vandenhove, H.; Bacquoy, C.; Hees, M. van; Lewyckyj, N.; Vandecasteele, C.

1998-01-01

The consideration of a possible enhanced vertical migration of radiocaesium with the application of ammonium-ferric-hexacyano-ferrate (AFCF) as countermeasure, due to the colloidal nature of AFCF, made us set up a series of migration experiments. For the study two soil types were considered, which were either left unplanted or cultivated with ryegrass. Two AFCF concentrations, 1 and 10 g m -2 , and an untreated control were applied. A simple diffusion-convection model was fitted to the data.The application of AFCF did not enhance the downward migration of radiocaesium in the profile. Moreover, for an unplanted sandy soil the application of AFCF significantly retarded the migration: 10 g AFCF m -2 decreased the convection term, V, from 0·78 to 0·42 cm a -1 and the diffusion component, D, from 0·21 to 0·09 cm 2 a -1 . For all other experimental conditions (unplanted loamy soil, ryegrass cultivated sandy and loamy soil), the application of AFCF did not have any effect on radiocaesium migration. Since AFCF does not promote the vertical migration of radiocaesium, enhanced groundwater contamination is improbable. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

UV B-induced vertical migrations of cyanobacteria in a microbial mat

International Nuclear Information System (INIS)

Rebout, B.M.; Garcia-Pichel, F.

1995-01-01

Exposure to moderate doses of UV B (0.35 to 0.79 W m -2 s -1 or 0.98 to 2.2 μmol of photons m -2 s -1 at 310 nm) caused the surface layers of microbial mats from Solar Lake, Sinai, Egypt, to become visibly lighter green. Concurrent with the color change were rapid and dramatic reductions in gross photosynthesis and in the resultant high porewater oxygen concentrations in the surface layers of the mats. The depths at which both maximum gross photosynthesis and maximum oxygen concentrations occurred were displaced downward. In contrast, gross photosynthesis in the deeper layers of the mats increased in response to UV B incident upon the surface. The cessation of exposure to UV B partially reversed all of these changes. Taken together, these responses suggest that photoautotrophic members of the mat community, most likely the dominant cyanobacterium Microcoleus chthonoplastes, were migrating in response to the added UV B. The migration phenomenon was also observed in response to increases in visible radiation and UV A, but UV B was ca. 100-fold more effective than visible radiation and ca. 20-fold more effective than UV A in provoking the response. Migrating microorganisms within this mat are apparently able to sense UV B directly and respond behaviorally to limit their exposure to UV. Because of strong vertical gradients of light and dissolved substances in microbial mats, the migration and the resultant vertical redistribution of photosynthetic activity have important consequences for both the photobiology of the cyanobacteria and the net primary productivity of the mat ecosystem

Small-scale distribution and diel vertical migration of zooplankton in a shallow lake (Lake Naardermeer, the Netherlands)

NARCIS (Netherlands)

Cerbin, S.; Balayla, D.; Van de Bund, W.J.

2003-01-01

Small scale distribution and diurnal migration of zooplankton were investigated in lake Naardermeer, a shallow lake largely covered by uniform Chara beds. For sampling, pattern samplers with a number of inverted funnels facing towards the lake bottom and held in a frame were used. Samplers were

How biophysical interactions associated with sub- and mesoscale structures and migration behavior affect planktonic larvae of the spiny lobster in the Juan Fernández Ridge: A modeling approach

Science.gov (United States)

Medel, Carolina; Parada, Carolina; Morales, Carmen E.; Pizarro, Oscar; Ernst, Billy; Conejero, Carlos

2018-03-01

The Juan Fernández Ridge (JFR) is a chain of topographical elevations in the eastern South Pacific (∼33-35°S, 76-81.5°W). Rich in endemic marine species, this ridge is frequently affected by the arrival of mesoscale eddies originating in the coastal upwelling zone off central-southern Chile. The impacts of these interactions on the structure and dynamics of the JFR pelagic system have, however, not been addressed yet. The present model-based study is focused on the coupled influence of mesoscale-submesoscale processes and biological behavior (i.e., diel vertical migration) on the horizontal distribution of planktonic larvae of the spiny lobster (Jasus frontalis) around the JFR waters. Two case studies were selected from a hydrodynamic Regional Ocean Modeling System to characterize mesoscale and submesoscale structures and an Individual-based model (IBM) to simulate diel vertical migration (DVM) and its impact on the horizontal distribution and the patchiness level. DVM behavior of these larvae has not been clearly characterized, therefore, three types of vertical mechanisms were assessed on the IBM: (1) no migration (LG), (2) a short migration (0-50 m depth, DVM1), and (3) a long migration (10-200 m depth, DVM2). The influence of physical properties (eddy kinetic energy, stretching deformation and divergence) on larval aggregation within meso and submesoscale features was quantified. The patchiness index assessed for mesoscale and submesoscale structures showed higher values in the mesoscale than in the submesoscale. However, submesoscale structures revealed a higher accumulation of particles by unit of area. Both vertical migration mechanisms produced larger patchiness indices compared to the no migration experiment. DVM2 was the one that showed by far the largest aggregation of almost all the aggregation zones. Larval concentrations were highest in the submesoscale structures; these zones were characterized by low eddy kinetic energy, negative stretching

Do predators influence the distribution of age-0 kokanee in a Colorado Reservoir?

Science.gov (United States)

Hardiman, J.M.; Johnson, B.M.; Martinez, P.J.

2004-01-01

Seasonal changes in reservoir conditions such as productivity, light, and temperature create spatiotemporal variation in habitat that may segregate or aggregate predators and prey, producing implications for the distribution, growth, and survival of fishes. We used hydroacoustics to document the diel vertical distribution of age-0 kokanee Oncorhynchus nerka relative to environmental gradients at Blue Mesa Reservoir, Colorado, during May-August of 2002. Temperature, light, and zooplankton density profiles were examined relative to foraging conditions for kokanee and their primary predator, lake trout Salvelinus namaycush. Age-0 kokanee displayed large diel vertical migrations in May despite the lack of an energetic advantage before reservoir stratification. Age-0 kokanee minimized near-surface foraging at this time, perhaps to avoid predation by visual predators, such as lake trout, in the well-lit surface waters. Strong reservoir stratification in midsummer appeared to provide a thermal refuge from lake trout that the kokanee exploited. By August vertical migrations were shallow and most kokanee remained in the epilimnion throughout the day. Although the energetic implications of the late-summer strategy are unclear, it appears that kokanee were responding to changes in their predator environment. A robust model for kokanee diel vertical migration across a range of systems should include a predator avoidance component.

Evidence of cormorant-induced mortality, disparate migration strategies and repeatable circadian rhythm in the endangered North Sea houting (Coregonus oxyrinchus ): A telemetry study mapping the postspawning migration

DEFF Research Database (Denmark)

Jensen, Lasse Fast; Rognon, Paul; Aarestrup, Kim

2017-01-01

constrained navigation through the lakes. The migration into the Wadden Sea correlated with temperature perhaps indicating osmoregulatory constraints of sea entry. Unlike most salmonid species, migration occurred both day and night. Moreover, fish exhibited repeatable individual differences in diel activity...

Assessing the use of magnetic methods to monitor vertical migration of metal pollutants in soil

Science.gov (United States)

Sapkota, B.; Cioppa, M. T.

2010-12-01

In order to assess the use of magnetic methods to study and improve our understanding of the vertical migration behavior of metal pollutants in natural soil, a controlled experiment was performed during August-December 2009, near Belle River, Ontario. The soil is Quaternary in age, consisting primarily of glacial till (Tavistock Till) overlain by localized alluvium deposits of very recent origin. Groundcover vegetation is minimal, consisting only of various grasses. Eighteen PVC tubes (8” wide, 16” long) were inserted vertically into the ground as test capsules, in order to avoid contaminating the surrounding area. Magnetite powder (5µm) was distributed on the surface of the soil inside nine of the tubes (10 grams of magnetite/tube) to simulate anthropogenic contamination, while the others were used as controls. Magnetic Susceptibility (MS) measurements were used for both ongoing surface monitoring and pre- and post-treatment vertical migration assessment. The initial surface MS values in the contaminated tubes were one to two orders of magnitude larger than in the uncontaminated tubes. While the surficial MS remained fairly stable in uncontaminated soil, decreases of 15-60 % were observed in contaminated soil tubes. Susceptibility profiles from soil cores in the contaminated tubes show that the concentration of iron containing particles is highest at depths between 2-7 cm. Energy Dispersive Spectroscopy (EDS) analysis on layers with an enhanced magnetic signal showed high weight% of iron and oxygen, indicating the presence of iron minerals. Scanning Electron Microscopy (SEM) showed that the magnetite powder and the particles from the contaminated tubes had similar morphologies. These results suggest that the magnetite migrated downwards into the soil over the five month period, probably as a result of rainwater infiltration and vertical migration. Some of the soil profiles showed a small enhancement of magnetic signal at 17-18 cm, and SEM-EDS analysis shows

Diel biogeochemical processes in terrestrial waters

Science.gov (United States)

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

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

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

International Nuclear Information System (INIS)

Chandra, Sankhabrata; Bhattacharya, Atanu; Periyasamy, Ganga

2015-01-01

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH 2 , CF 3 , and COOH substituents) molecules paired with NH 3 (referred as ACl:NH 3 complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH 3 complex, the hole is predicted to migrate from the NH 3 -end to the ClCN-end of the NCCl⋯NH 3 complex in approximately 0.5 fs on the D 0 cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H 2 NCl:NH 3 , F 3 CCl:NH 3 , and HOOCCl:NH 3 , exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH 3 and HOCl:NH 3 complexes do not exhibit any charge migration following vertical ionization to the D 0 cation state, pointing to interesting halogen bond strength-dependent charge migration

Vertical and horizontal larval distribution of an offshore brachyuran crab, Monodaeus couchii, off the south coast of Portugal

Directory of Open Access Journals (Sweden)

Patricia N. Pochelon

2014-06-01

Full Text Available A strong understanding of larval distribution and abundance is of major value in delineating the location and size of a breeding population of deep-sea species such as Monodaeus couchii. In this study, vertical distribution of the larvae of a brachyuran crab, M. couchii, was assessed during two week-long cruises conducted at the end of January 2006 and 2007 off the South Coast of Portugal. Larvae were collected by oblique plankton hauls with a Longhurst-Hardy Plankton Recorder from the surface to 300 m. Abundance and distribution of zoeae I and II were correlated during both years. For all stages, abundance decreased with depth during the day while it increased with depth at night; the larvae thus displayed reverse diel vertical migration. Abundance of zoeae I and II was correlated with chlorophyll a levels, whereas those of later stages were correlated with neither physical parameters (chlorophyll a, temperature or salinity nor each other. An ontogenic shift in vertical distribution explained the results; earlier zoeal stages remain in the food-rich upper water column while later stages were not correlated with any physical parameters (i.e. chlorophyll a, salinity or temperature and migrated to the bottom for settlement.

Dynamic optimal foraging theory explains vertical migrations of bigeye tuna

DEFF Research Database (Denmark)

Thygesen, Uffe Høgsbro; Sommer, Lene; Evans, Karen

2016-01-01

Bigeye tuna are known for remarkable daytime vertical migrations between deep water, where food is abundant but the water is cold, and the surface, where water is warm but food is relatively scarce. Here we investigate if these dive patterns can be explained by dynamic optimal foraging theory...... behaves such as to maximize its energy gains. The model therefore provides insight into the processes underlying observed behavioral patterns and allows generating predictions of foraging behavior in unobserved environments...

Application of INAA in monitoring vertical migration of elements in weathering zone

International Nuclear Information System (INIS)

Frana, J.; Mastalka, A.; Henes, J.

1983-01-01

The vertical migration of elements is studied in two types of Czechoslovak soils formed on loess. The INAA method is used to determine the total value of ca 40 elements in soils. Processed are relative errors of determination and the concentrations of elements to depths of 150 cm. Tables show the distribution of elements of rare earths according to genetic horizons, graphically presented is the vertical distribution of elements with concentrations exceeding 0.1 weight %. Soil enrichment or depletion with trace elements as compared with bedrock is shown on the examples of Co, Mn and Zn. (author)

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

Energy Technology Data Exchange (ETDEWEB)

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in [Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore (India); Periyasamy, Ganga [Department of Chemistry, Central College Campus, Bangalore University, Bangalore (India)

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.

Vertically migrating swimmers generate aggregation-scale eddies in a stratified column.

Science.gov (United States)

Houghton, Isabel A; Koseff, Jeffrey R; Monismith, Stephen G; Dabiri, John O

2018-04-01

Biologically generated turbulence has been proposed as an important contributor to nutrient transport and ocean mixing 1-3 . However, to produce non-negligible transport and mixing, such turbulence must produce eddies at scales comparable to the length scales of stratification in the ocean. It has previously been argued that biologically generated turbulence is limited to the scale of the individual animals involved 4 , which would make turbulence created by highly abundant centimetre-scale zooplankton such as krill irrelevant to ocean mixing. Their small size notwithstanding, zooplankton form dense aggregations tens of metres in vertical extent as they undergo diurnal vertical migration over hundreds of metres 3,5,6 . This behaviour potentially introduces additional length scales-such as the scale of the aggregation-that are of relevance to animal interactions with the surrounding water column. Here we show that the collective vertical migration of centimetre-scale swimmers-as represented by the brine shrimp Artemia salina-generates aggregation-scale eddies that mix a stable density stratification, resulting in an effective turbulent diffusivity up to three orders of magnitude larger than the molecular diffusivity of salt. These observed large-scale mixing eddies are the result of flow in the wakes of the individual organisms coalescing to form a large-scale downward jet during upward swimming, even in the presence of a strong density stratification relative to typical values observed in the ocean. The results illustrate the potential for marine zooplankton to considerably alter the physical and biogeochemical structure of the water column, with potentially widespread effects owing to their high abundance in climatically important regions of the ocean 7 .

Use of acoustic backscatter and vertical velocity to estimate concentration and dynamics of suspended solids in Upper Klamath Lake, south-central Oregon: Implications for Aphanizomenon flos-aquae

Science.gov (United States)

Wood, Tamara M.; Gartner, Jeffrey W.

2010-01-01

Vertical velocity and acoustic backscatter measurements by acoustic Doppler current profilers were used to determine seasonal, subseasonal (days to weeks), and diel variation in suspended solids in a freshwater lake where massive cyanobacterial blooms occur annually. During the growing season, the suspended material in the lake is dominated by the buoyancy-regulating cyanobacteria, Aphanizomenon flos-aquae. Measured variables (water velocity, relative backscatter [RB], wind speed, and air and water temperatures) were averaged over the deployment season at each sample time of day to determine average diel cycles. Phase shifts between diel cycles in RB and diel cycles in wind speed, vertical water temperature differences (delta T(degree)), and horizontal current speeds were found by determining the lead or lag that maximized the linear correlation between the respective diel cycles. Diel cycles in RB were more in phase with delta T(degree) cycles, and, to a lesser extent, wind cycles, than to water current cycles but were out of phase with the cycle that would be expected if the vertical movement of buoyant cyanobacteria colonies was controlled primarily by light. Clear evidence of a diel cycle in vertical velocity was found only at the two deepest sites in the lake. Cycles of vertical velocity, where present, were out of phase with expected vertical motion of cyanobacterial colonies based on the theoretical cycle for light-driven vertical movement. This suggests that water column stability and turbulence were more important factors in controlling vertical distribution of colonies than light. Variations at subseasonal time scales were determined by filtering data to pass periods between 1.2 and 15 days. At subseasonal time scales, correlations between RB and currents or air temperature were consistent with increased concentration of cyanobacterial colonies near the surface when water column stability increased (higher air temperatures or weaker currents) and

Importance des phénomènes de migration verticale des hydrocarbures Significance of Vertical Migration Phenomea of Hydrocarbons

Directory of Open Access Journals (Sweden)

Chiarelle A.

2006-11-01

Full Text Available Cette publication a pour but de démonter les mécanismes de migration verticale des hydrocarbures et d'en analyser les conséquences, à partir d'exemples concrets choisis sur les domaines d'activité de la Société Nationale Elf Aquitaine (Production [SNEA (PJ. Les hydrocarbures, huile et gaz, rassemblés en phase individualisée évoluent dans un milieu poreux, fin, généralement mouillé à l'eau. Dans un tel environnement la migration suppose des pressions capillaires élevées. On démontre que cette condition se realise plus particulièrement sur Ies zones hautes fermées où les élements d'hydrocarbures expulses de la roche mère peuvent se rassembler en amas de taille importante, développant une forte poussee d'Archimède. De même le gaz, du fait de sa masse volumique faible par rapport à celle de l'eau, manifestera une grande aptitude à la migration verticale, ce qui conduira souvent à une redistribution verticale des hydrocarbures non conforme au schéma diagénétique classique : présence d'un gisement de gaz en surface et huile en profondeur. Combinés à l'effet Gussow, phénomène de refoulement de l'huile par le gaz hors de la fermeture critique d'une structure, les processus envisagés ici, où tes accidents tectoniques tiennent une place importante, aboutiront généralement à sil: aerer spatialement l'huile et le gaz. Ces transferts semblent s'accompagner fréquemment de modifications dans la composition chimique des huiles : augmentation des teneurs en soufre, en métaux traces, en hydrocarbures aromatiques, et alourdissement des huiles The purpose of this article is ta described the vertical migration mechanisms of hydrocarbons and to analyze their conséquences, on the basis of concrete examples selected in the fields of activities carried on by Société Nationale Elf Aquitaine (SNEA. When hydrocarbons (ai( and gas are gathered in a distinct phase, they evolve in a fine porous medium that is usually water wet. In

Vertical distribution of phytoplankton functional groups in a tropical shallow lake: driving forces on a diel scale Distribuição vertical de grupos funcionais fitoplanctônicos em um lago tropical raso: forças direcionadoras em escala nictemeral

Directory of Open Access Journals (Sweden)

Luciana Gomes Barbosa

2011-03-01

Full Text Available AIM: This study analyzed the vertical distribution of phytoplankton functional groups in two diel cycles in a warm monomictic shallow tropical lake; METHODS: Sampling of the abiotic variables, phytoplankton and zooplankton communities was performed at intervals of 3 hours over 24 hours in vertical profiles, in the stratification (February and circulation (July periods; RESULTS: The high thermal stability and the partial atelomixis favored the coexistence of functional groups that are sensitive to destratification, N A and F, composed by desmids and Chlorophyceae coccoids, and groups S2 and Lo, which persisted during the circulation, and were composed by filamentous cyanobacteria which do not fix N2 and dinoflagellates, respectively. The discontinuity in the vertical distribution of the functional groups, with dominance of N A and F in the epilimnion and R and Lo in the metalimnion and hypolimnion, was characteristic of the stratification, and differences between the daytime and nighttime periods were not significant. CONCLUSIONS: The reduction of 80% of the biomass of the NA group during the mixing period indicates the influence of thermal stability and partial atelomixis as determinant factors in the compartmentalization of functional groups, restricting daytime vertical migration (DVM and loss by sedimentation during the stratification period.OBJETIVO: Analisar a distribuição vertical dos grupos funcionais fitoplanctônicos em dois ciclos nictemerais em um lago tropical monomítico raso; MÉTODOS: As amostragens das variáveis abióticas, comunidades fitoplanctônica e zooplanctônica foram realizadas a intervalos de 3 horas ao longo de 24 horas em perfis verticais, nos períodos de estratificação (fevereiro e de circulação (julho; RESULTADOS: A elevada estabilidade térmica e a atelomixia parcial favoreceram a coexistência de grupos funcionais sensíveis a desestratificação N A e F, compostos por desmidias e clorofícias cocoides e

Vertically averaged approaches for CO 2 migration with solubility trapping

KAUST Repository

Gasda, S. E.

2011-05-20

The long-term storage security of injected carbon dioxide (CO2) is an essential component of geological carbon sequestration operations. In the postinjection phase, the mobile CO2 plume migrates in large part because of buoyancy forces, following the natural topography of the geological formation. The primary trapping mechanisms are capillary and solubility trapping, which evolve over hundreds to thousands of years and can immobilize a significant portion of the mobile CO2 plume. However, both the migration and trapping processes are inherently complex, spanning multiple spatial and temporal scales. Using an appropriate model that can capture both large- and small-scale effects is essential for understanding the role of these processes on the long-term storage security of CO2 sequestration operations. Traditional numerical models quickly become prohibitively expensive for the type of large-scale, long-term modeling that is necessary for characterizing the migration and immobilization of CO2 during the postinjection period. We present an alternative modeling option that combines vertically integrated governing equations with an upscaled representation of the dissolution-convection process. With this approach, we demonstrate the effect of different modeling choices for typical large-scale geological systems and show that practical calculations can be performed at the temporal and spatial scales of interest. Copyright 2011 by the American Geophysical Union.

Diel vertical migration arising in a habitat selection game

DEFF Research Database (Denmark)

Sainmont, Julie; Thygesen, Uffe Høgsbro; Visser, Andre

2013-01-01

, avoiding their predator during their peak performance by finding refuge in deep layers during daylight hours and feeding at the surface during the night. Due to the duality of the interaction between prey and predator, we used a game theory approach to investigate whether DVM can be a suitable strategy...

diel vertical migration of zooplankton in a hypertrophic shallow

African Journals Online (AJOL)

Preferred Customer

attention of limnologists due to their key role in the food web ... the same in order to be safe from visual predation ... line of investigation is anticipated to lead to a ...... Selective advantage: A metabolic model. Limnol. Ocean- ogr. 22(5):856–872.

MHD mixed convection in a vertical annulus filled with Al2O3–water nanofluid considering nanoparticle migration

International Nuclear Information System (INIS)

Malvandi, A.; Safaei, M.R.; Kaffash, M.H.; Ganji, D.D.

2015-01-01

In the current study, an MHD mixed convection of alumina/water nanofluid inside a vertical annular pipe is investigated theoretically. The model used for the nanofluid mixture involves Brownian motion and thermophoretic diffusivities in order to take into account the effects of nanoparticle migration. Since the thermophoresis is the main mechanism of the nanoparticle migration, different temperature gradients have been imposed using the asymmetric heating. Considering hydrodynamically and thermally fully developed flow, the governing equations have been reduced to two-point ordinary boundary value differential equations and they have been solved numerically. It is revealed that the imposed thermal asymmetry would change the direction of nanoparticle migration and distorts the velocity, temperature and nanoparticle concentration profiles. Moreover, it is shown that the advantage of nanofluids in heat transfer enhancement is reduced in the presence of a magnetic field. - Highlights: • MHD mixed convection of alumina/water nanofluid inside a vertical annulus. • The effects of nanoparticle migration on rheological and thermophysical characteristics. • The effects of asymmetric heating on nanoparticle migration. • The effects of asymmetric heating on the heat transfer enhancement. • Inclusion of nanoparticles in presence of a magnetic field has a negative effect on performance

The submarine volcano eruption off El Hierro Island: Effects on the scattering migrant biota and the evolution of the pelagic communities

KAUST Repository

Ariza, Alejandro; Kaartvedt, Stein; Rø stad, Anders; Garijo, Juan Carlos; Arí stegui, Javier; Fraile-Nuez, Eugenio; Herná ndez-Leó n, Santiago

2014-01-01

, acidification, rising temperature and deposition of chemicals in shallow waters resulted in a reduction of epipelagic stocks and a disruption of diel vertical migration (nocturnal ascent) of mesopelagic organisms. Furthermore, decreased light levels at depth

Migration Pathways, Behavioural Thermoregulation and Overwintering Grounds of Blue Sharks in the Northwest Atlantic

Science.gov (United States)

Campana, Steven E.; Dorey, Anna; Fowler, Mark; Joyce, Warren; Wang, Zeliang; Yashayaev, Igor

2011-01-01

The blue shark Prionace glauca is the most abundant large pelagic shark in the Atlantic Ocean. Although recaptures of tagged sharks have shown that the species is highly migratory, migration pathways towards the overwintering grounds remain poorly understood. We used archival satellite pop-up tags to track 23 blue sharks over a mean period of 88 days as they departed the coastal waters of North America in the autumn. Within 1–2 days of entering the Gulf Stream (median date of 21 Oct), all sharks initiated a striking diel vertical migration, taking them from a mean nighttime depth of 74 m to a mean depth of 412 m during the day as they appeared to pursue vertically migrating squid and fish prey. Although functionally blind at depth, calculations suggest that there would be a ∼2.5-fold thermoregulatory advantage to swimming and feeding in the markedly cooler deep waters, even if there was any reduced foraging success associated with the extreme depth. Noting that the Gulf Stream current speeds are reduced at depth, we used a detailed circulation model of the North Atlantic to examine the influence of the diving behaviour on the advection experienced by the sharks. However, there was no indication that the shark diving resulted in a significant modification of their net migratory pathway. The relative abundance of deep-diving sharks, swordfish, and sperm whales in the Gulf Stream and adjacent waters suggests that it may serve as a key winter feeding ground for large pelagic predators in the North Atlantic. PMID:21373198

Inventory and vertical migration of 137Cs in Spanish mainland soils

International Nuclear Information System (INIS)

Legarda, F.; Romero, L.M.; Herranz, M.; Barrera, M.; Idoeta, R.; Valino, F.; Olondo, C.; Caro, A.

2011-01-01

In this study the total activity of 137 Cs deposited per unit area over the Spanish peninsular territory was analysed using a 150 x 150 km 2 mesh grid, with samples taken from 29 points. The deposited activities ranged between 251 and 6074 Bq/m 2 . A linear relationship was obtained between these values and the mean annual rainfall at each sampling point which allowed a map to be drawn, using GIS software, which shows the distribution of total deposited 137 Cs activity across the Spanish mainland. At twelve of these sampling points the vertical migration profile of 137 Cs was obtained. These profiles are separated into two groups with different behaviour, one of which includes clay and loam soils and the other containing sandy soils. For both groups of profiles the parameters of the convective-diffusive model, which describes the vertical migration of 137 Cs in the soil, v (apparent convection velocity) and D (apparent diffusion coefficient) were calculated. - Highlights: → Measured the 137 Cs activity in Spanish mainland, being within a range of [251, 6074] Bq/m 2 , with a mean value of 1726 Bq/m 2 . → Establishment of the 137 Cs background by means of a 137 Cs inventory map showing its distribution in the Spanish mainland. → 137 Cs shows two different behaviour tendencies in soil depending on it. → The parameters which govern the applied model have been obtained for the analysed profiles. → Analysed those parameters, the two tendencies have been reflected in the obtained values.

The pentadehydro-Diels-Alder reaction.

Science.gov (United States)

Wang, Teng; Naredla, Rajasekhar Reddy; Thompson, Severin K; Hoye, Thomas R

2016-04-28

In the classic Diels-Alder [4 + 2] cycloaddition reaction, the overall degree of unsaturation (or oxidation state) of the 4π (diene) and 2π (dienophile) pairs of reactants dictates the oxidation state of the newly formed six-membered carbocycle. For example, in the classic Diels-Alder reaction, butadiene and ethylene combine to produce cyclohexene. More recent developments include variants in which the number of hydrogen atoms in the reactant pair and in the resulting product is reduced by, for example, four in the tetradehydro-Diels-Alder (TDDA) and by six in the hexadehydro-Diels-Alder (HDDA) reactions. Any oxidation state higher than tetradehydro (that is, lacking more than four hydrogens) leads to the production of a reactive intermediate that is more highly oxidized than benzene. This increases the power of the overall process substantially, because trapping of the reactive intermediate can be used to increase the structural complexity of the final product in a controllable and versatile manner. Here we report an unprecedented overall 4π + 2π cycloaddition reaction that generates a different, highly reactive intermediate known as an α,3-dehydrotoluene. This species is in the same oxidation state as a benzyne. Like benzynes, α,3-dehydrotoluenes can be captured by various trapping agents to produce structurally diverse products that are complementary to those arising from the HDDA process. We call this new cycloisomerization process a pentadehydro-Diels-Alder (PDDA) reaction-a nomenclature chosen for chemical taxonomic reasons rather than mechanistic ones. In addition to alkynes, nitriles (RC≡N), although non-participants in aza-HDDA reactions, readily function as the 2π component in PDDA cyclizations to produce, via trapping of the α,3-(5-aza)dehydrotoluene intermediates, pyridine-containing products.

The positively phototactic reaction of daphnia magna straus: A contribution to the understanding of diurnal vertical migration

NARCIS (Netherlands)

Ringelberg, J.

1964-01-01

The present investigation was aimed at gaining more insight into the physiological mechanism underlying the diurnal vertical migration of planktonic animals. The experiments were carried out on Daphnia magna. Only reactions to decreases in light intensity were studied. Kinetical

Genome-wide profiling of 24 hr diel rhythmicity in the water flea, Daphnia pulex: network analysis reveals rhythmic gene expression and enhances functional gene annotation.

Science.gov (United States)

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

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

Science.gov (United States)

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

2017-04-11

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

Do bacteria, not fish, produce 'fish kairomone'?

NARCIS (Netherlands)

Ringelberg, J.; Van Gool, E.

1998-01-01

Fish-associated chemicals enhance phototactic downward swimming in Daphnia. If perch were treated with the antibiotic ampicillin, this enhancement was significantly decreased. Therefore, not fish, but bacteria associated with fish, seem to produce this kairomone. [KEYWORDS: Diel vertical migration;

Patterns of Diel Variation in Nitrate Concentrations in the Potomac River

Science.gov (United States)

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

Modelling transport of chokka squid (Loligo reynaudii) paralarvae off South Africa: reviewing, testing and extending the ‘Westward Transport Hypothesis'

CSIR Research Space (South Africa)

Martins, RS

2013-08-01

Full Text Available hydrodynamic model (ROMS) to test the WTH and assessed four factors that might influence successful transport – Release Area, Month, Specific Gravity (body density) and Diel Vertical Migration (DVM) – in numerical experiments that estimated successful transport...

MHD mixed convection in a vertical annulus filled with Al{sub 2}O{sub 3}–water nanofluid considering nanoparticle migration

Energy Technology Data Exchange (ETDEWEB)

Malvandi, A., E-mail: amirmalvandi@aut.ac.ir [Department of Mechanical Engineering, Neyshabur Branch, Islamic Azad University, Neyshabur (Iran, Islamic Republic of); Safaei, M.R. [Young Researchers and Elite Club, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of); Kaffash, M.H. [Department of Mechanical Engineering, Neyshabur Branch, Islamic Azad University, Neyshabur (Iran, Islamic Republic of); Ganji, D.D. [Mechanical Engineering Department, Babol University of Technology, Babol (Iran, Islamic Republic of)

2015-05-15

In the current study, an MHD mixed convection of alumina/water nanofluid inside a vertical annular pipe is investigated theoretically. The model used for the nanofluid mixture involves Brownian motion and thermophoretic diffusivities in order to take into account the effects of nanoparticle migration. Since the thermophoresis is the main mechanism of the nanoparticle migration, different temperature gradients have been imposed using the asymmetric heating. Considering hydrodynamically and thermally fully developed flow, the governing equations have been reduced to two-point ordinary boundary value differential equations and they have been solved numerically. It is revealed that the imposed thermal asymmetry would change the direction of nanoparticle migration and distorts the velocity, temperature and nanoparticle concentration profiles. Moreover, it is shown that the advantage of nanofluids in heat transfer enhancement is reduced in the presence of a magnetic field. - Highlights: • MHD mixed convection of alumina/water nanofluid inside a vertical annulus. • The effects of nanoparticle migration on rheological and thermophysical characteristics. • The effects of asymmetric heating on nanoparticle migration. • The effects of asymmetric heating on the heat transfer enhancement. • Inclusion of nanoparticles in presence of a magnetic field has a negative effect on performance.

Seasonal and Diel Vocalization Patterns of Antarctic Blue Whale (Balaenoptera musculus intermedia in the Southern Indian Ocean: A Multi-Year and Multi-Site Study.

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.

Inventory and vertical migration of {sup 137}Cs in Spanish mainland soils

Energy Technology Data Exchange (ETDEWEB)

Legarda, F. [Dept. Nuclear Engineering and Fluid Mechanics, University of the Basque Country, Alda Urquijo, s/n, E-48013 Bilbao (Spain); Romero, L.M. [CIEMAT, Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas, Av. Complutense 22, 28040 Madrid (Spain); Herranz, M. [Dept. Nuclear Engineering and Fluid Mechanics, University of the Basque Country, Alda Urquijo, s/n, E-48013 Bilbao (Spain); Barrera, M. [CIEMAT, Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas, Av. Complutense 22, 28040 Madrid (Spain); Idoeta, R. [Dept. Nuclear Engineering and Fluid Mechanics, University of the Basque Country, Alda Urquijo, s/n, E-48013 Bilbao (Spain); Valino, F. [CIEMAT, Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas, Av. Complutense 22, 28040 Madrid (Spain); Olondo, C., E-mail: kontxi.olondo@ehu.es [Dept. Nuclear Engineering and Fluid Mechanics, University of the Basque Country, Alda Urquijo, s/n, E-48013 Bilbao (Spain); Caro, A. [CIEMAT, Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas, Av. Complutense 22, 28040 Madrid (Spain)

2011-06-15

In this study the total activity of {sup 137}Cs deposited per unit area over the Spanish peninsular territory was analysed using a 150 x 150 km{sup 2} mesh grid, with samples taken from 29 points. The deposited activities ranged between 251 and 6074 Bq/m{sup 2}. A linear relationship was obtained between these values and the mean annual rainfall at each sampling point which allowed a map to be drawn, using GIS software, which shows the distribution of total deposited {sup 137}Cs activity across the Spanish mainland. At twelve of these sampling points the vertical migration profile of {sup 137}Cs was obtained. These profiles are separated into two groups with different behaviour, one of which includes clay and loam soils and the other containing sandy soils. For both groups of profiles the parameters of the convective-diffusive model, which describes the vertical migration of {sup 137}Cs in the soil, v (apparent convection velocity) and D (apparent diffusion coefficient) were calculated. - Highlights: > Measured the {sup 137}Cs activity in Spanish mainland, being within a range of [251, 6074] Bq/m{sup 2}, with a mean value of 1726 Bq/m{sup 2}. > Establishment of the {sup 137}Cs background by means of a {sup 137}Cs inventory map showing its distribution in the Spanish mainland. > {sup 137}Cs shows two different behaviour tendencies in soil depending on it. > The parameters which govern the applied model have been obtained for the analysed profiles. > Analysed those parameters, the two tendencies have been reflected in the obtained values.

Latitudinal environmental gradients and diel variability influence abundance and community structure of Chaetognatha in Red Sea coral reefs

KAUST Repository

Al-aidaroos, Ali M.

2016-08-15

at night, demonstrating stage-specific diel vertical migration as a potential predator avoidance strategy.

Lateral and vertical distribution of downstream migrating juvenile sea lamprey

Science.gov (United States)

Sotola, V. Alex; Miehls, Scott M.; Simard, Lee G.; Marsden, J. Ellen

2018-01-01

Sea lamprey is considered an invasive and nuisance species in the Laurentian Great Lakes, Lake Champlain, and the Finger Lakes of New York and is a major focus of control efforts. Currently, management practices focus on limiting the area of infestation using barriers to block migratory adults, and lampricides to kill ammocoetes in infested tributaries. No control efforts currently target the downstream-migrating post-metamorphic life stage which could provide another management opportunity. In order to apply control methods to this life stage, a better understanding of their downstream movement patterns is needed. To quantify spatial distribution of downstream migrants, we deployed fyke and drift nets laterally and vertically across the stream channel in two tributaries of Lake Champlain. Sea lamprey was not randomly distributed across the stream width and lateral distribution showed a significant association with discharge. Results indicated that juvenile sea lamprey is most likely to be present in the thalweg and at midwater depths of the stream channel. Further, a majority of the catch occurred during high flow events, suggesting an increase in downstream movement activity when water levels are higher than base flow. Discharge and flow are strong predictors of the distribution of out-migrating sea lamprey, thus managers will need to either target capture efforts in high discharge areas of streams or develop means to guide sea lamprey away from these areas.

Density and depth variations of Daphnia multilocus genotypes during a summer period in Lake Maarsseveen

NARCIS (Netherlands)

Ringelberg, J.; van Gool, E.; Brehm, Michaela

2004-01-01

The genotype composition of a Daphnia population complex during a summer period in Lake Maarsseveen (The Netherlands) was determined by allozyme analysis. The depth distribution, diel vertical migration and several parameters of the total population were measured. Young-of-the-year (0+) perch (Perca

Pulsed remineralisation in the northwestern Mediterranean Sea: a hypothesis

Science.gov (United States)

Denis, Michel; Martin, Valérie; Momzikoff, André; Gondry, Geneviève; Stemmann, Lars; Demers, Serge; Gorsky, Gaby; Andersen, Valérie

2003-02-01

A general study of biogeochemical processes (DYNAPROC cruise) was conducted in May 1995 at a time-series station in the open northwestern Mediterranean Sea where horizontal advection was weak. Short-term variations of the vertical distributions of pico- and nanophytoplankton were investigated over four 36-h cycles, along with parallel determinations of metabolic CO 2 production rates and amino acid-containing colloid (AACC) concentrations at the chlorophyll maximum depth. The vertical (0-1000-m depth) distributions of (i) AACC, (ii) suspended particles and (iii) metabolic CO 2 production rate were documented during the initial and final stages of these 36-h cycles. This study was concerned with diel vertical migration (DVM) of zooplankton, which provided periodic perturbations. Accordingly, the time scale of the experimental work varied from a few hours to a few days. Although all distributions exhibited a periodic behaviour, AACC distributions were generally not linked to diel vertical migrations. In the subsurface layer, Synechococcus made the most abundant population and large variations in concentration were observed both at day and at night. The corresponding integrated (over the upper 90 m) losses of Synechococcus during one night pointed to a potential source of exported organic matter amounting to 534 mg C m -2. This study stresses the potential importance of organic matter export from the euphotic zone through the daily grazing activity of vertically migrating organisms, which would not be accounted for by measurements at longer time scales. The metabolic CO 2 production exhibited a peak of activity below 500 m that was shifted downward, apparently in a recurrent way and independently of the vertical distributions of AACC or of suspended particulate material. To account for this phenomenon, a «sustained wave train» hypothesis is proposed that combines the effect of the diel superficial faecal pellet production by swarming migrators and the repackaging

Generalization of some results of a vertical radionuclide migration study in soils of 30-km zone

International Nuclear Information System (INIS)

Ziborov, A.M.; Sadol'ko, I.V.; Sushchik, Yu.Ya.; Tikhanov, Eh.K.; Proskuryakov, A.G.; Kuz'michev, V.N.; Shcheglov, A.I.

1992-01-01

Results of radionuclide distribution study in a vertical profile of soils are presented under different landscape geochemical conditions in 1989-1991. It is ascertained that radionuclide migration process in geochemical profile of soils of 30-km zone is in early stage of development. More than 90% of radioactivity concentrates in the upper 5-10 cm layer whereas measurable radioactivity fixes at a depth up to 1 m. The process of deepening of radioactivity reserve center takes place in the surface soil layer. Now it equals 1,5-3 cm. Peculiarities of the vertical radionuclide distribution haven't brightly pronounced character depending on soil types and are at the formation stage. 12 figs.; 2 tabs

137Cs vertical migration in a deciduous forest soil following the Fukushima Dai-ichi Nuclear Power Plant accident

International Nuclear Information System (INIS)

Nakanishi, Takahiro; Matsunaga, Takeshi; Koarashi, Jun; Atarashi-Andoh, Mariko

2014-01-01

The large amount of 137 Cs deposited on the forest floor because of the Fukushima Dai-ichi Nuclear Power Plant accident represents a major potential long-term source for mobile 137 Cs. To investigate 137 Cs mobility in forest soils, we investigated the vertical migration of 137 Cs through seepage water, using a lysimetric method. The study was conducted in a deciduous forest soil over a period spanning 2 month to 2 y after the Fukushima nuclear accident. Our observations demonstrated that the major part of 137 Cs in the litter layer moved into the mineral soil within one year after the accident. On the other hand, the topsoil prevented migration of 137 Cs, and only 2% of 137 Cs in the leachate from litter and humus layer penetrated below a 10 cm depth. The annual migration below a 10 cm depth accounted for 0.1% of the total 137 Cs inventory. Therefore, the migration of 137 Cs by seepage water comprised only a very small part of the total 137 Cs inventory in the mineral soil, which was undetectable from the vertical distribution of 137 Cs in the soil profile. In the present and immediate future, most of the 137 Cs deposited on the forest floor will probably remain in the topsoil successively, although a small but certain amount of bioavailable 137 Cs exists in forest surface soil. -- Highlights: • Lysimeter captured 137 Cs mobility in a forest soil after the Fukushima accident. • Major part of 137 Cs in the litter layer moved into the mineral soil within a year. • Litter-leachate 137 Cs was predominantly adsorbed within the topsoil. • The annual migration below a 10 cm depth was 0.1% of the total 137 Cs inventory

Important role of vertical migration of compressed gas, oil and water in formation of AVPD (abnormally high pressure gradient) zones

Energy Technology Data Exchange (ETDEWEB)

Anikiyev, K.A.

1980-01-01

The principal role of vertical migration of compressed gases, gas-saturated petroleum and water during formation of abnormally high pressure gradients (AVPD) is confirmed by extensive factual data on gas production, grifons, blowouts and gushers that accompany drilling formations with AVPD from early history to the present time; the sources of vertical migration of compressed fluids, in accordance with geodynamic AVPD theory, are the deep degasified centers of the earth mantle. Among the various types of AVPD zones especially notable are the large (often massive or massive-layer) deposits and the intrusion aureoles that top them in the overlapping covering layers. Prediction of AVPD zones and determining their field and energy potential must be based on field-baric simulation of the formations being drilled in light of laws regarding the important role of the vertical migration of compressed fluids. When developing field-baric models, it is necessary to utilize the extensive and valuable data on grifons, gas production and blowouts that has been collected and categorized by drilling engineers and production geologists. To further develop data on field-baric conditions of the earth, it is necessary to collect and study signals of AVPD. First of all, there is a need to evaluate potential elastic resources of compressed fluids which can move from the bed into the well. Thus it is necessary to study and standardize intrusion aureoles and other AVPD zones within the aspect of fieldbaric modeling.

Zooplankton associated with the oxygen minimum zone system in the northern upwelling region of Chile during March 2000

Science.gov (United States)

Escribano, Ruben; Hidalgo, Pamela; Krautz, Cristina

2009-07-01

Zooplankton in the coastal upwelling region off northern Chile may play a significant biogeochemical role by promoting carbon flux into the subsurface OMZ (oxygen minimum zone). This work identifies the dominant zooplankton species inhabiting the area influenced by the OMZ in March 2000 off Iquique (20°S, northern Chile). Abundance and vertical distribution studies revealed 17 copepod and 9 euphausiid species distributed between the surface and 600 m at four stations sampled both by day and by night. Some abundant species remained in the well-oxygenated upper layer (30 m), with no evidence of diel vertical migration, apparently restricted by a shallow (40-60 m) oxycline. Other species, however, were found closely associated with the OMZ. The large-sized copepod Eucalanus inermis was found below the oxycline and performed diel vertical migrations into the OMZ, whereas the very abundant Euphausia mucronata performed extensive diel vertical migrations between the surface waters and the core of the OMZ (200 m), even crossing it. A complete assessment of copepods and euphausiids revealed that the whole sampled water column (0-600 m) is occupied by distinct species having well-defined habitats, some of them within the OMZ. Ontogenetic migrations were evident in Eucalanidae and E. mucronata. Estimates of species biomass showed a substantial (>75% of total zooplankton biomass) daily exchange of C between the photic layer and the OMZ. Both E. inermis and E. mucronata can actively exchange about 37.8 g C m -2 d -1 between the upper well-oxygenated (0-60 m) layer and the deeper (60-600 m) OMZ layer. This migrant biomass may contribute about 7.2 g C m -2 d -1 to the OMZ system through respiration, mortality, and production of fecal pellets within the OMZ. This movement of zooplankton in and out of the OMZ, mainly as a result of the migratory behavior of E. mucronata, suggests a very efficient mechanism for introducing large amounts of freshly produced carbon into the OMZ

The effect of radial migration on galactic disks

International Nuclear Information System (INIS)

Vera-Ciro, Carlos; D'Onghia, Elena; Navarro, Julio; Abadi, Mario

2014-01-01

We study the radial migration of stars driven by recurring multi-arm spiral features in an exponential disk embedded in a dark matter halo. The spiral perturbations redistribute angular momentum within the disk and lead to substantial radial displacements of individual stars, in a manner that largely preserves the circularity of their orbits and that results, after 5 Gyr (∼40 full rotations at the disk scale length), in little radial heating and no appreciable changes to the vertical or radial structure of the disk. Our results clarify a number of issues related to the spatial distribution and kinematics of migrators. In particular, we find that migrators are a heavily biased subset of stars with preferentially low vertical velocity dispersions. This 'provenance bias' for migrators is not surprising in hindsight, for stars with small vertical excursions spend more time near the disk plane, and thus respond more readily to non-axisymmetric perturbations. We also find that the vertical velocity dispersion of outward migrators always decreases, whereas the opposite holds for inward migrators. To first order, newly arrived migrators simply replace stars that have migrated off to other radii, thus inheriting the vertical bias of the latter. Extreme migrators might therefore be recognized, if present, by the unexpectedly small amplitude of their vertical excursions. Our results show that migration, understood as changes in angular momentum that preserve circularity, can strongly affect the thin disk, but cast doubts on models that envision the Galactic thick disk as a relic of radial migration.

Trade-offs in Daphnia habitat selection

NARCIS (Netherlands)

Winder, M.; Spaak, P.; Mooij, W.M.

2004-01-01

Diel vertical migration (DVM) is a dynamic behavioral pattern found extensively in the world's oceans and lakes, yet the role of food and temperature distribution on DVM is still unclear. While DVM has been mostly studied in systems with surface food maxima, deep-water food maxima are quite common

Solvent Effects in Asymmetric Hetero Diels-Alder and Ene Reactions

DEFF Research Database (Denmark)

Johannsen, Mogens; Jørgensen, Karl Anker

1996-01-01

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

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

NARCIS (Netherlands)

Gieling, Reinerus Gerardus

2003-01-01

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

Vertical Migration of Radionuclides in Soils on the Chernobyl Nuclear Power Plant (ChNPP) Exclusion Zone (1987-2007)

Science.gov (United States)

Jannik, G. T.; Ivanov, Y. A.; Kashparov, V. A.; Levchuk, S. E.; Bondarkov, M. D.; Maksymenko, A. M.; Farfan, E. B.; Marra, J. C.

2009-12-01

In 1986-1987, a set of experimental sites for studies of vertical migration of radionuclides released from the ChNPP was established in the ChNPP Exclusion Zone for various fallout plumes. The sites were selected considering local terrain and geo-chemical conditions, as well as physical and chemical characteristics of the fallout. The experimental sites included grasslands, and pre-Chernobyl cultivated meadows and croplands. Vertical migration of radionuclides in the ChNPP Exclusion Zone grasslands was evaluated. Parameters of 137Cs, 90Sr, and 239,240Pu transfer were calculated and the periods during which these radionuclides reach their ecological half-life in the upper 5 cm soil layer were estimated. Migration capabilities of these radionuclides in the grassland soils tend to decrease as follows: 90Sr >137Cs ≥ 239,240Pu. A significant retardation of the 137Cs vertical migration was shown in the grasslands long after the Chernobyl accident. During the 21st year after the fallout, average Tecol values for 137Cs (the period of time it takes in the environment for 137Cs to reach half the value of its original concentration in the upper 5 cm soil layer, regardless of physical decay) are as follows: 180 - 320 years for grassland containing automorphous mineral soils of a light granulometric composition; and 90 - 100 years for grassland containing hydromorphous organogenic soils. These values are significantly higher than those estimated for the period of 6-9 years after the fallout: 60 - 150 years and 11 - 20 years, respectively. The absolute 137Cs Tecol values are by factors of 3-7 higher than 137Cs radiological decay values long after the accident. Changes in the exposure dose resulting from the soil deposited 137Cs only depend on its radiological decay. This factor should necessarily be considered for development of predictive assessments, including dose exposures for the hypothetical population in case of their re-evacuation to the exclusion areas. The obtained

Stepwise radical cation Diels-Alder reaction via multiple pathways.

Science.gov (United States)

Shimizu, Ryo; Okada, Yohei; Chiba, Kazuhiro

2018-01-01

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

Optimal foraging and diel vertical migration in a life history model

DEFF Research Database (Denmark)

Sainmont, Julie; Andersen, Ken Haste; Visser, Andre

in the model, unsuited for life history modeling. We propose a method based on optimal foraging theory to take into account the emergent feeding rates as a function of the copepod metabolic cost, latitude, time and predation. We predict that copepods will balance their growth rate and mortality, playing a safe...

Use of X-ray fluorescence analysis in studying vertical element migration in weathering zone

International Nuclear Information System (INIS)

Houdkova, Z.; Hally, J.

1980-01-01

The vertical migration of elements was studied in a model area of the Zelivka river basin. The VRS 2 Zeiss GDR analyzer, connected to automatic processor KSR 4 100, were used for the study of concentration variations. Soil samples were taken from bore holes drilled to a depth of the solid bedrock (0 to 6 m). The contents of SiO 2 , Al 2 O 3 , Fe 2 O 3 , K 2 O, CaO, TiO 2 , P 2 O 5 and MnO were determined in concentration ranges from 10 -2 to 10 1 %. The method was tested in comparative measurements against conventional methods of chemical analysis. (author)

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

NARCIS (Netherlands)

Stolle, W.A.W.

1992-01-01

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

The hexadehydro-Diels-Alder reaction.

Science.gov (United States)

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

2012-10-11

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

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

Science.gov (United States)

Horiuchi, Shinnosuke; Murase, Takashi; Fujita, Makoto

2011-07-04

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

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

NARCIS (Netherlands)

Jong, Johannes Cornelis de

2006-01-01

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

Diel dualism in the energy consumption of the European catfish Silurus glanis.

Science.gov (United States)

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.

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

Science.gov (United States)

Yilmaz, Özgür; Kus, Nermin Simsek; Tunç, Tuncay; Sahin, Ertan

2015-10-01

The reaction between 2,3-dimethyl-1,3-butadiene and dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate is efficiently achieved with small amounts of catalyst, i.e. phenol, AcOH, nafion, and β-cyclodextrin. Exo-diastereoselective cycloaddition reactions were observed both without catalyst and different catalysts for 48 days. As a result, different products (tricyclicmolecule 5, retro-Diels-Alder product 6, and oxidation product 7) were obtained with different catalysts. In addition, we synthesized Diels-Alders product 8 and tricyclocyclitol 10 via Diels-Alder reaction. The structures of these products were characterized by 1H NMR, 13C NMR, MS and IR spectroscopy.

The possibilities of least-squares migration of internally scattered seismic energy

KAUST Repository

Aldawood, Ali

2015-05-26

Approximate images of the earth’s subsurface structures are usually obtained by migrating surface seismic data. Least-squares migration, under the single-scattering assumption, is used as an iterative linearized inversion scheme to suppress migration artifacts, deconvolve the source signature, mitigate the acquisition fingerprint, and enhance the spatial resolution of migrated images. The problem with least-squares migration of primaries, however, is that it may not be able to enhance events that are mainly illuminated by internal multiples, such as vertical and nearly vertical faults or salt flanks. To alleviate this problem, we adopted a linearized inversion framework to migrate internally scattered energy. We apply the least-squares migration of first-order internal multiples to image subsurface vertical fault planes. Tests on synthetic data demonstrated the ability of the proposed method to resolve vertical fault planes, which are poorly illuminated by the least-squares migration of primaries only. The proposed scheme is robust in the presence of white Gaussian observational noise and in the case of imaging the fault planes using inaccurate migration velocities. Our results suggested that the proposed least-squares imaging, under the double-scattering assumption, still retrieved the vertical fault planes when imaging the scattered data despite a slight defocusing of these events due to the presence of noise or velocity errors.

The possibilities of least-squares migration of internally scattered seismic energy

KAUST Repository

Aldawood, Ali; Hoteit, Ibrahim; Zuberi, Mohammad; Turkiyyah, George; Alkhalifah, Tariq Ali

2015-01-01

Approximate images of the earth’s subsurface structures are usually obtained by migrating surface seismic data. Least-squares migration, under the single-scattering assumption, is used as an iterative linearized inversion scheme to suppress migration artifacts, deconvolve the source signature, mitigate the acquisition fingerprint, and enhance the spatial resolution of migrated images. The problem with least-squares migration of primaries, however, is that it may not be able to enhance events that are mainly illuminated by internal multiples, such as vertical and nearly vertical faults or salt flanks. To alleviate this problem, we adopted a linearized inversion framework to migrate internally scattered energy. We apply the least-squares migration of first-order internal multiples to image subsurface vertical fault planes. Tests on synthetic data demonstrated the ability of the proposed method to resolve vertical fault planes, which are poorly illuminated by the least-squares migration of primaries only. The proposed scheme is robust in the presence of white Gaussian observational noise and in the case of imaging the fault planes using inaccurate migration velocities. Our results suggested that the proposed least-squares imaging, under the double-scattering assumption, still retrieved the vertical fault planes when imaging the scattered data despite a slight defocusing of these events due to the presence of noise or velocity errors.

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

Science.gov (United States)

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

2014-02-24

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

Estudio dieléctrico del envejecimiento físico

OpenAIRE

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...

Assessing diel variation of CH4 flux from rice paddies through temperature patterns

Science.gov (United States)

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.

Diel and seasonal movements of grumatã Prochilodus lineatus (Valenciennes 1836 (Characiformes: Prochilodontidae in the Sinos River, Southern Brazil

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.

Net ground speed of downstream migrating radio-tagged Atlantic salmon ( Salmo salar L.) and brown trout ( Salmo trutta L.) smolts in relation to environmental factors

DEFF Research Database (Denmark)

Aarestrup, Kim; Nielsen, C.; Koed, Anders

2002-01-01

tagged and released in the Danish River Lilleaa. The downstream migration of the different groups of fish was monitored by manual tracking and by three automatic listening stations. The downstream migration of radio tagged smolts of both species occurred concurrently with their untagged counterparts....... The diel migration pattern of the radio tagged smolts was predominantly nocturnal in both species. Wild sea trout smolt migrated significantly faster than both the F1 trout and the introduced salmon. There was no correlation between net ground speed, gill Na+, K+-ATPase activity or fish length in any...

Driving forces of the diel distribution of phytoplankton functional groups in a shallow tropical lake (Lake Monte Alegre, Southeast Brazil

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.

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

Science.gov (United States)

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

2014-10-13

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

Spawning migration of brown trout, Salmo trutta in the Morávka reservoir

Czech Academy of Sciences Publication Activity Database

Piecuch, J.; Lojkásek, B.; Lusk, Stanislav; Marek, T.

2007-01-01

Roč. 56, č. 2 (2007), s. 201-212 ISSN 0139-7893 R&D Projects: GA AV ČR IAA6093105; GA AV ČR 1QS500450513 Institutional research plan: CEZ:AV0Z60930519 Keywords : reproductive migration * tributary * trap * diel activity * environmental factors Subject RIV: EH - Ecology, Behaviour Impact factor: 0.376, year: 2007 http://www.ivb.cz/folia/56/2/201-212_MS1292.pdf

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

Directory of Open Access Journals (Sweden)

Gil Valdo José da Silva

2002-05-01

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

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

Science.gov (United States)

Singh, Raman K; Tsuneda, Takao

2013-02-15

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

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

Science.gov (United States)

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

2016-01-01

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

Sampling of deep benthic perch fry: insight into the diel vertical migrations.

Czech Academy of Sciences Publication Activity Database

Čech, Martin; Frouzová, Jaroslava; Peterka, Jiří; Jůza, Tomáš; Draštík, Vladislav; Vašek, Mojmír; Kubečka, Jan

2017-01-01

Roč. 784, č. 1 (2017), s. 1-8 ISSN 0018-8158 R&D Projects: GA ČR GA206/06/1371; GA ČR GP206/09/P266; GA MŠk(CZ) EE2.3.20.0204; GA MŠk(CZ) 7F14316 Institutional support: RVO:60077344 Keywords : bathypelagic perch fry * Breder trap * Fulton's condition factor * Perca fluviatilis * Římov Reservoir * SCUBA diving Subject RIV: EG - Zoology OBOR OECD: Zoology Impact factor: 2.056, year: 2016

The diel rhythms of biosonar behavior in the Yangtze finless porpoise (Neophocaena asiaeorientalis asiaeorientalis in the port of the Yangtze River: The correlation between prey availability and boat traffic.

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.

Regional-scale brine migration along vertical pathways due to CO2 injection - Part 1: The participatory modeling approach

Science.gov (United States)

Scheer, Dirk; Konrad, Wilfried; Class, Holger; Kissinger, Alexander; Knopf, Stefan; Noack, Vera

2017-06-01

Saltwater intrusion into potential drinking water aquifers due to the injection of CO2 into deep saline aquifers is one of the potential hazards associated with the geological storage of CO2. Thus, in a site selection process, models for predicting the fate of the displaced brine are required, for example, for a risk assessment or the optimization of pressure management concepts. From the very beginning, this research on brine migration aimed at involving expert and stakeholder knowledge and assessment in simulating the impacts of injecting CO2 into deep saline aquifers by means of a participatory modeling process. The involvement exercise made use of two approaches. First, guideline-based interviews were carried out, aiming at eliciting expert and stakeholder knowledge and assessments of geological structures and mechanisms affecting CO2-induced brine migration. Second, a stakeholder workshop including the World Café format yielded evaluations and judgments of the numerical modeling approach, scenario selection, and preliminary simulation results. The participatory modeling approach gained several results covering brine migration in general, the geological model sketch, scenario development, and the review of the preliminary simulation results. These results were included in revised versions of both the geological model and the numerical model, helping to improve the analysis of regional-scale brine migration along vertical pathways due to CO2 injection.

Physicochemical Properties and Fatty Acid Profiles of Elaeagnus mollis Diels Nut Oils.

Science.gov (United States)

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.

Vertical distribution, composition and migratory patterns of acoustic scattering layers in the Canary Islands

KAUST Repository

Ariza, A.

2016-01-21

Diel vertical migration (DVM) facilitates biogeochemical exchanges between shallow waters and the deep ocean. An effective way of monitoring the migrant biota is by acoustic observations although the interpretation of the scattering layers poses challenges. Here we combine results from acoustic observations at 18 and 38 kHz with limited net sampling in order to unveil the origin of acoustic phenomena around the Canary Islands, subtropical northeast Atlantic Ocean. Trawling data revealed a high diversity of fishes, decapods and cephalopods (152 species), although few dominant species likely were responsible for most of the sound scattering in the region. We identified four different acoustic scattering layers in the mesopelagic realm: (1) at 400–500 m depth, a swimbladder resonance phenomenon at 18 kHz produced by gas-bearing migrant fish such as Vinciguerria spp. and Lobianchia dofleini, (2) at 500–600 m depth, a dense 38 kHz layer resulting primarily from the gas-bearing and non-migrant fish Cyclothone braueri, and to a lesser extent, from fluid-like migrant fauna also inhabiting these depths, (3) between 600 and 800 m depth, a weak signal at both 18 and 38 kHz ascribed either to migrant fish or decapods, and (4) below 800 m depth, a weak non-migrant layer at 18 kHz which was not sampled. All the dielly migrating layers reached the epipelagic zone at night, with the shorter-range migrations moving at 4.6 ± 2.6 cm s − 1 and the long-range ones at 11.5 ± 3.8 cm s − 1. This work reduces uncertainties interpreting standard frequencies in mesopelagic studies, while enhances the potential of acoustics for future research and monitoring of the deep pelagic fauna in the Canary Islands.

Vertical distribution, composition and migratory patterns of acoustic scattering layers in the Canary Islands

KAUST Repository

Ariza, A.; Landeira, J.M.; Escá nez, A.; Wienerroither, R.; Aguilar de Soto, N.; Rø stad, Anders; Kaartvedt, S.; Herná ndez-Leó n, S.

2016-01-01

Diel vertical migration (DVM) facilitates biogeochemical exchanges between shallow waters and the deep ocean. An effective way of monitoring the migrant biota is by acoustic observations although the interpretation of the scattering layers poses challenges. Here we combine results from acoustic observations at 18 and 38 kHz with limited net sampling in order to unveil the origin of acoustic phenomena around the Canary Islands, subtropical northeast Atlantic Ocean. Trawling data revealed a high diversity of fishes, decapods and cephalopods (152 species), although few dominant species likely were responsible for most of the sound scattering in the region. We identified four different acoustic scattering layers in the mesopelagic realm: (1) at 400–500 m depth, a swimbladder resonance phenomenon at 18 kHz produced by gas-bearing migrant fish such as Vinciguerria spp. and Lobianchia dofleini, (2) at 500–600 m depth, a dense 38 kHz layer resulting primarily from the gas-bearing and non-migrant fish Cyclothone braueri, and to a lesser extent, from fluid-like migrant fauna also inhabiting these depths, (3) between 600 and 800 m depth, a weak signal at both 18 and 38 kHz ascribed either to migrant fish or decapods, and (4) below 800 m depth, a weak non-migrant layer at 18 kHz which was not sampled. All the dielly migrating layers reached the epipelagic zone at night, with the shorter-range migrations moving at 4.6 ± 2.6 cm s − 1 and the long-range ones at 11.5 ± 3.8 cm s − 1. This work reduces uncertainties interpreting standard frequencies in mesopelagic studies, while enhances the potential of acoustics for future research and monitoring of the deep pelagic fauna in the Canary Islands.

Diel variation in the catch of fishes and penaeid shrimps in a tropical estuary

Science.gov (United States)

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.

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

NARCIS (Netherlands)

BLOKZIJL, W; BLANDAMER, MJ; ENGBERTS, JBFN

1991-01-01

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

Temporal Variability in Vertical Groundwater Fluxes and the Effect of Solar Radiation on Streambed Temperatures Based on Vertical High Resolution Distributed Temperature Sensing

Science.gov (United States)

Sebok, E.; Karan, S.; Engesgaard, P. K.; Duque, C.

2013-12-01

and heat transport model (HydroGeoSphere). Subsequently, time series of vertical groundwater fluxes were computed based on the high-resolution vertical streambed sediment temperature profiles by coupling the model with PEST. The calculated vertical flux time series show spatial differences in discharge between the two HR-DTS sites. A similar temporal variability in vertical fluxes at the two test sites can also be observed, most likely linked to rainfall-runoff processes. The effect of solar radiation as streambed conduction is visible both at the exposed and shaded test site in form of increased diel temperature oscillations up to 14 cm depth from the streambed surface, with the test site exposed to solar radiation showing larger diel temperature oscillations.

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

Science.gov (United States)

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

2017-10-17

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

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

Science.gov (United States)

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

2013-06-01

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

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

International Nuclear Information System (INIS)

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

2013-01-01

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

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...

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

Science.gov (United States)

Diels-Alder reaction mechanism is known to be one of the major reaction mechanisms to produce dimers and polymers during heating process of vegetable oil. However, our NMR study showed no evidence for Diels-Alder products. Soybean oil oxidized at 180 °C for 24 hrs with 1.45 surface area-to-volume ...

The Diels-Alder cyclization of ketenimines.

Science.gov (United States)

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

2012-04-20

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

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

Science.gov (United States)

Gregoritza, Manuel; Brandl, Ferdinand P

2015-11-01

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

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

Science.gov (United States)

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

2017-03-03

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

Inventory and vertical migration of {sup 90}Sr fallout and {sup 137}Cs/{sup 90}Sr ratio in Spanish mainland soils

Energy Technology Data Exchange (ETDEWEB)

Herranz, M. [Department Nuclear Engineering and Fluid Mechanics, University of the Basque, Country (UPV/EHU), Alda Urquijo s/n, E-48013 Bilbao (Spain); Romero, L.M. [CIEMAT, Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas, Av. Complutense 22, 28040 Madrid (Spain); Idoeta, R. [Department Nuclear Engineering and Fluid Mechanics, University of the Basque, Country (UPV/EHU), Alda Urquijo s/n, E-48013 Bilbao (Spain); Olondo, C., E-mail: kontxi.olondo@ehu.es [Department Nuclear Engineering and Fluid Mechanics, University of the Basque, Country (UPV/EHU), Alda Urquijo s/n, E-48013 Bilbao (Spain); Valino, F. [CIEMAT, Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas, Av. Complutense 22, 28040 Madrid (Spain); Legarda, F. [Department Nuclear Engineering and Fluid Mechanics, University of the Basque, Country (UPV/EHU), Alda Urquijo s/n, E-48013 Bilbao (Spain)

2011-11-15

In this paper the inventory of {sup 90}Sr in 34 points distributed along the Spanish peninsular territory is presented. Obtained values range between 173 Bq/m{sup 2} and 2047 Bq/m{sup 2}. From these data set and those {sup 137}Cs data obtained in a previous work the {sup 137}Cs/{sup 90}Sr activity ratio has been established, laying this value between 0.9 and 3.6. Also the migration depth of both radionuclides has been analysed obtaining for {sup 137}Cs an average value 57% lower than that obtained for {sup 90}Sr. Additionally, this paper presents the results obtained in 11 sampling points in which the activity vertical profile has been measured. These profiles have been analysed to state the behaviour of strontium in soils and after, by using a convective-diffusive model, the parameters of the model which governs the vertical migration of {sup 90}Sr in the soil, v (apparent convection velocity) and D (apparent diffusion coefficient) have been evaluated. Mean values obtained are 0.20 cm/year and 3.67 cm{sup 2}/year, respectively. - Highlights: > Measured {sup 90}Sr activity in Spanish mainland, being within a range of [173, 2047] Bq/m{sup 2}, with a mean value of 793 Bq/m{sup 2}. > Compared the migration capacity of {sup 137}Cs and {sup 90}Sr in the same soils. > {sup 90}Sr shows a unique behaviour tendency in soil. > The parameters which govern the applied model have been obtained for the analysed profiles. > Analysed those parameters' values also reflects this unique tendency.

Ontogenetic behavior, migration, and social behavior of pallid sturgeon, Scaphirhynchus albus, and shovelnose sturgeon, S. platorynchus, with notes on the adaptive significance of body color

Science.gov (United States)

Kynard, B.; Henyey, E.; Horgan, M.

2002-01-01

We conducted laboratory studies on the ontogenetic behavior of free embryos (first life interval after hatching) and larvae (first feeding interval) of pallid and shovelnose sturgeon. Migration styles of both species were similar for timing of migration (initiation by embryos on day 0 after hatching and cessation by larvae on days 12-13 at 236-243 cumulative temperature degree units), migration distance (about 13 km), life interval when most distance was moved (embryo), and diel behavior of embryos (diurnal). However, the species differed for two behaviors: movement characteristics of embryos (peak movement rate of pallid sturgeon was only one-half the peak rate of shovelnose sturgeon, but pallid sturgeon continued the lower rate for twice as long) and diel behavior of larvae (pallid sturgeon were diurnal and shovelnose sturgeon were nocturnal). Thus, the species used different methods to move the same distance. Migrating as poorly developed embryos suggests a migration style to avoid predation at the spawning site, but moving from spawning habitat to rearing habitat before first feeding could also be important. Migrants of both species preferred bright habitat (high illumination intensity and white substrate), a behavioral preference that may characterize the migrants of many species of sturgeon. Both species were remarkably similar for swimming height above the bottom by age, and day 7 and older migrants may swim far above the bottom and move far downstream. A migration of 12 or 13 days will probably not distribute larvae throughout the population's range, so an older life interval likely initiates a second longer downstream migration (2-step migration). By day 2, individuals of both species were a black-tail phenotype (light grey body with a black-tail that moved conspicuously during swimming). Aggregation behavior suggests that black-tail is a visual signal used for group cohesion.

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.

Acceleration of vertical migration of corneal epithelial cells in albino rats during chronic immobilization stress

International Nuclear Information System (INIS)

Timoshin, S.S.; Berezhnova, N.I.

1986-01-01

This paper studies the effect of chronic immobilization stress on the kinetics of corneal epithelial cells from the basal layer into higher layers. Experiments were carried out on 49 male rats. The animals were given an intraperitoneal injection of tritium-thymidine and an additional application of 5 microCi of tritium-thymidine was made to its surface because the cornea has no blood supply. The animals were killed and the cornea removed for investigation. Values of the index of labeled nuclei and intensity of thymidine labeling, characterizing DNA synthesis in the corneas of the control and experimental animals showed no significant change compared with their values in a pervious series of experiments. Chronic exposure to stress increased the velocity of vertical migration of the cells from the basal layer toward the outer layers of the cornea

Diel vertical migrations of age 0+ percids in a shallow, well-mixed reservoir

Czech Academy of Sciences Publication Activity Database

Kratochvíl, M.; Čech, Martin; Vašek, Mojmír; Kubečka, Jan; Hejzlar, Josef; Matěna, Josef; Peterka, Jiří; Macháček, Jiří; Seďa, Jaromír

2010-01-01

Roč. 69, č. 2 (2010), s. 305-310 ISSN 1129-5767 R&D Projects: GA ČR(CZ) GA206/06/1371; GA ČR(CZ) GP206/09/P266; GA AV ČR(CZ) 1QS600170504 Institutional research plan: CEZ:AV0Z60170517 Keywords : Perca fluviatilis * Sander lucioperca * DVM * juvenile Subject RIV: EH - Ecology, Behaviour Impact factor: 1.140, year: 2010

Effects of habitat type on short- and long-term growth parameters of the European perch (Perca fluviatilis L.)

Czech Academy of Sciences Publication Activity Database

Petrtýl, M.; Kalous, L.; Frouzová, Jaroslava; Čech, Martin

2015-01-01

Roč. 100, č. 1 (2015), s. 13-20 ISSN 1434-2944 R&D Projects: GA ČR(CZ) GA206/06/1371; GA ČR(CZ) GP206/09/P266; GA MŠk(CZ) EE2.3.20.0204 Institutional support: RVO:60077344 Keywords : diel vertical migrations * RNA/DNA ratio * bathypelagic perch fry * growth rate * fish larvae * Římov Reservoir Subject RIV: GL - Fishing Impact factor: 1.459, year: 2015

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

Science.gov (United States)

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

2018-02-02

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

Fourfold Diels-Alder reaction of tetraethynylsilane.

Science.gov (United States)

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

2014-12-08

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

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.

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

Science.gov (United States)

Zhou, Wanpeng; Zhang, Hui; Chen, Fangeng

2018-02-01

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

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

NARCIS (Netherlands)

Rosati, F.; Roelfes, J.G.

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

Phosphorus vertical migration in aquic brown soil and light chernozem under different phosphorous application rate: a soil column leaching experiment.

Science.gov (United States)

Zhao, Muqiu; Chen, Xin; Shi, Yi; Zhou, Quanlai; Lu, Caiyan

2009-01-01

A soil column leaching experiment was conducted to study the vertical migration of phosphorus in aquic brown soil and light chernozem under different phosphorus fertilization rates. The results showed that total dissolved phosphorus concentration in the leachates from the two soils was nearly the same, but dissolved inorganic phosphorus concentration was obviously different. In all fertilization treatments, aquic brown soil had a higher content of phosphorus in calcium chloride extracts compared with light chernozem. But Olsen phosphorus content was higher at the soil depth beneath 0-20 cm, and increased with increasing phosphorus application rate.

Measurement and modeling of diel variability of polybrominated diphenyl ethers and chlordanes in air.

Science.gov (United States)

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.

AFSC/ABL: Gulf of Alaska Diel Trawl Survey, 2005-2006

Data.gov (United States)

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...

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

Science.gov (United States)

Siadati, Seyyed Amir; Nami, Navabeh

2016-10-01

C20 fullerene, this novel species with all its pentagonal faces has displayed some unique operations in making fast pericyclic reactions. As an example, the high dienophile character of the C20 fullerene and the ability of this species in making an ultra-fast Diels-Alder reaction with 1,3-butadiene, has been recently reported. Moreover, new experimental reports claim that the C60 fullerene, one of the fullerene family, could make a Diels-Alder reaction with the central ring of anthracene and make the ring non-aromatic. These reports may encourage researchers to do more studies on the properties of this small carbon cage. To address this question, the present research has discussed all the reaction channels of the Diels-Alder cycloaddition of benzene molecule as a 1,3-diene with the C20 fullerene in order to answer this question: ;Is C20fullerene able to make a Diels-Alder reaction with this molecule?;.

Full Wavefield Migration of Vertical Seismic Profiling data

NARCIS (Netherlands)

Soni, A.K.

2014-01-01

Until now, in most seismic imaging technologies, both surface and internal multiples are considered as noise. In today’s industrial practice, we see various methods for suppressing multiples before migration. This means that only a fraction of the recorded wavefield is used in imaging. In this

Theories on migration processes of Cd in Jiaozhou Bay

Science.gov (United States)

Yang, Dongfang; Li, Haixia; Wang, Qi; Ding, Jun; Zhang, Longlei

2018-03-01

Understanding the migration progress is essential to pollution control, while developing theories for the migration progress is the scientific basis. This paper further developed five key theories on migration processes of Cd including homogeneous theory, environmental dynamic theory, horizontal loss theory, migration trend theory and vertical migration theory, respectively. The performance and practical values of these theories were demonstrated in the application of these on analyzing the migration process of Cd in Jiaozhou Bay. Results these theory helpful to better understand the migration progress of pollutants in marine bay.

Phytoplankton can actively diversify their migration strategy in response to turbulent cues.

Science.gov (United States)

Sengupta, Anupam; Carrara, Francesco; Stocker, Roman

2017-03-23

Marine phytoplankton inhabit a dynamic environment where turbulence, together with nutrient and light availability, shapes species fitness, succession and selection. Many species of phytoplankton are motile and undertake diel vertical migrations to gain access to nutrient-rich deeper layers at night and well-lit surface waters during the day. Disruption of this migratory strategy by turbulence is considered to be an important cause of the succession between motile and non-motile species when conditions turn turbulent. However, this classical view neglects the possibility that motile species may actively respond to turbulent cues to avoid layers of strong turbulence. Here we report that phytoplankton, including raphidophytes and dinoflagellates, can actively diversify their migratory strategy in response to hydrodynamic cues characteristic of overturning by Kolmogorov-scale eddies. Upon experiencing repeated overturning with timescales and statistics representative of ocean turbulence, an upward-swimming population rapidly (5-60 min) splits into two subpopulations, one swimming upward and one swimming downward. Quantitative morphological analysis of the harmful-algal-bloom-forming raphidophyte Heterosigma akashiwo together with a model of cell mechanics revealed that this behaviour was accompanied by a modulation of the cells' fore-aft asymmetry. The minute magnitude of the required modulation, sufficient to invert the preferential swimming direction of the cells, highlights the advanced level of control that phytoplankton can exert on their migratory behaviour. Together with observations of enhanced cellular stress after overturning and the typically deleterious effects of strong turbulence on motile phytoplankton, these results point to an active adaptation of H. akashiwo to increase the chance of evading turbulent layers by diversifying the direction of migration within the population, in a manner suggestive of evolutionary bet-hedging. This migratory behaviour

Tectonic control in source rock maturation and oil migration in Trinidad

Energy Technology Data Exchange (ETDEWEB)

Persad, K.M.; Talukdar, S.C.; Dow, W.G. (DGSI, The Woodlands, TX (United States))

1993-02-01

Oil accumulation in Trinidad were sourced by the Upper Cretaceous calcareous shales deposited along the Cretaceous passive margin of northern South America. Maturation of these source rocks, oil generation, migration and re-migration occurred in a foreland basin setting that resulted from interaction between Caribbean and South American plates during Late Oligocene to recent times. During Middle Miocene-Recent times, the foreland basin experienced strong compressional events, which controlled generation, migration, and accumulation of oil in Trinidad. A series of mature source rock kitchens formed in Late Miocene-Recent times in the Southern and Colombus Basins to the east-southeast of the Central Range Thrust. This thrust and associated fratured developed around 12 m.y.b.p. and served as vertical migration paths for the oil generated in Late Miocene time. This oil migrated into submarine fans deposited in the foreland basin axis and older reservoirs deformed into structural traps. Further generation and migration of oil, and re-migration of earlier oil took place during Pliocene-Holocene times, when later thrusting and wrench faulting served as vertical migration paths. Extremely high sedimentation rates in Pliocene-Pleistocene time, concurrent with active faulting, was responsible for very rapid generation of oil and gas. Vertically migrating gas often mixed with earlier migrated oil in overlying reservoirs. This caused depletion of oil in light hydrocarbons with accompanied fractionation among hydrocarbon types resulting in heavier oil in lower reservoirs, enrichment of light hydrocarbons and accumulation of gas-condensates in upper reservoirs. This process led to an oil-gravity stratification within about 10,000 ft of section.

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

Science.gov (United States)

Nawrat, Christopher C; Moody, Christopher J

2014-02-17

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

Vertical soil migration of radionuclide fallout from the Chernobyl' accident

International Nuclear Information System (INIS)

Silant'ev, A.N.; Shkuratova, I.G.; Bobovnikova, T.I.

1989-01-01

The most suitable model for describing the behavior of radionuclide fallout on a soil surface is quasidiffusion transfer with directional transfer taken into account. The parameter values for this have been determined previously and are supplemented by the results of this work. To investigate the initial radionuclide distribution along the soil profile, monolithic soil samples 5 cm thick were taken in June-September 1986 in areas which had been subjected to contamination due to the Chernobyl' accident. The samples taken were cut up into layers. The first layer, 0.5 cm thick, was cut off from the surface of the soil monolith together with the grass. The next layer cut off was also 0.5 cm thick. Then two layers, each 1 cm in thickness, were cut off. The thickness of the last layer was 2 cm. The vertical distribution of radionuclides along the soil profile which was examined may be called the initial distribution, which will then change due to nonimmediate migration of radionuclides in the soil. Based on the research which has been performed, the following conclusions may be drawn. One portion of the radionuclides resulting from fallout is trapped by plant cover, while the other enters immediately into the soil. For a thick plant covering, about 80% of the radionuclide fallout is sorbed by the grass; for sparse cover, about 40%. The radionuclides entering the soil along with rainwater penetrate into the soil depths, producing contamination which falls off exponentially with depth. The exponent index is close to 1 cm -1 . In a forest, the main amount of radionuclide fallout is trapped by litter. Approximately 10% of the contamination fallout penetrates beneath the litter

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

Science.gov (United States)

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

2017-02-03

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

Interpreting diel hysteresis between soil respiration and temperature

Science.gov (United States)

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...

Predator avoidance during reproduction: diel movements by spawning sockeye salmon between stream and lake habitats.

Science.gov (United States)

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

Intramolecular inverse electron demand Diels-Alder reactions of pyrimidines

NARCIS (Netherlands)

Frissen, A.E.

1990-01-01

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

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.

Vertical Movements and Patterns in Diving Behavior of Whale Sharks as Revealed by Pop-Up Satellite Tags in the Eastern Gulf of Mexico.

Directory of Open Access Journals (Sweden)

John P Tyminski

Full Text Available The whale shark (Rhincodon typus is a wide-ranging, filter-feeding species typically observed at or near the surface. This shark's sub-surface habits and behaviors have only begun to be revealed in recent years through the use of archival and satellite tagging technology. We attached pop-up satellite archival transmitting tags to 35 whale sharks in the southeastern Gulf of Mexico off the Yucatan Peninsula from 2003-2012 and three tags to whale sharks in the northeastern Gulf off Florida in 2010, to examine these sharks' long-term movement patterns and gain insight into the underlying factors influencing their vertical habitat selection. Archived data were received from 31 tags deployed on sharks of both sexes with total lengths of 5.5-9 m. Nine of these tags were physically recovered facilitating a detailed long-term view into the sharks' vertical movements. Whale sharks feeding inshore on fish eggs off the northeast Yucatan Peninsula demonstrated reverse diel vertical migration, with extended periods of surface swimming beginning at sunrise followed by an abrupt change in the mid-afternoon to regular vertical oscillations, a pattern that continued overnight. When in oceanic waters, sharks spent about 95% of their time within epipelagic depths (500 m that largely occurred during daytime or twilight hours (max. depth recorded 1,928 m, had V-shaped depth-time profiles, and comprised more rapid descents (0.68 m sec-1 than ascents (0.50 m sec-1. Nearly half of these extreme dives had descent profiles with brief but conspicuous changes in vertical direction at a mean depth of 475 m. We hypothesize these stutter steps represent foraging events within the deep scattering layer, however, the extreme dives may have additional functions. Overall, our results demonstrate complex and dynamic patterns of habitat utilization for R. typus that appear to be in response to changing biotic and abiotic conditions influencing the distribution and abundance of their

Vertical Movements and Patterns in Diving Behavior of Whale Sharks as Revealed by Pop-Up Satellite Tags in the Eastern Gulf of Mexico

Science.gov (United States)

Tyminski, John P.; de la Parra-Venegas, Rafael; González Cano, Jaime; Hueter, Robert E.

2015-01-01

The whale shark (Rhincodon typus) is a wide-ranging, filter-feeding species typically observed at or near the surface. This shark’s sub-surface habits and behaviors have only begun to be revealed in recent years through the use of archival and satellite tagging technology. We attached pop-up satellite archival transmitting tags to 35 whale sharks in the southeastern Gulf of Mexico off the Yucatan Peninsula from 2003–2012 and three tags to whale sharks in the northeastern Gulf off Florida in 2010, to examine these sharks’ long-term movement patterns and gain insight into the underlying factors influencing their vertical habitat selection. Archived data were received from 31 tags deployed on sharks of both sexes with total lengths of 5.5–9 m. Nine of these tags were physically recovered facilitating a detailed long-term view into the sharks’ vertical movements. Whale sharks feeding inshore on fish eggs off the northeast Yucatan Peninsula demonstrated reverse diel vertical migration, with extended periods of surface swimming beginning at sunrise followed by an abrupt change in the mid-afternoon to regular vertical oscillations, a pattern that continued overnight. When in oceanic waters, sharks spent about 95% of their time within epipelagic depths (500 m) that largely occurred during daytime or twilight hours (max. depth recorded 1,928 m), had V-shaped depth-time profiles, and comprised more rapid descents (0.68 m sec-1) than ascents (0.50 m sec-1). Nearly half of these extreme dives had descent profiles with brief but conspicuous changes in vertical direction at a mean depth of 475 m. We hypothesize these stutter steps represent foraging events within the deep scattering layer, however, the extreme dives may have additional functions. Overall, our results demonstrate complex and dynamic patterns of habitat utilization for R. typus that appear to be in response to changing biotic and abiotic conditions influencing the distribution and abundance of their prey

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

International Nuclear Information System (INIS)

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

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-05-15

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

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

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

Directory of Open Access Journals (Sweden)

Z. Stirn

2016-07-01

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

The diel vertical migration patterns and individual swimming behavior of overwintering sprat Sprattus sprattus

KAUST Repository

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

Subsurface migration of petroleum hydrocarbons: A case study of immiscible migration and chromatographic separation

International Nuclear Information System (INIS)

Dawson, H.E.

1991-01-01

The subsurface distribution of a leaked crude oil illustrates the combined influence of both the chemical and physical properties of soil and free product on the migration of petroleum hydrocarbons. Immiscible phase behavior was observed, as well as chromatographic-like separation of the lighter constituents of the crude oil from the heavier constituents. After downward migration through approximately 50 ft of unsaturated, heterogeneous alluvial sediments, the crude oil formed a horizontal plume on top of a perched, saturated zone. Immiscible phase trapping is evident from the occurrence of very high concentration of hydrocarbons in both the vertical and horizontal plumes. Samples taken from the vertical zone of contamination indicate a transition from heavier hydrocarbons near the surface to lighter hydrocarbons at depth. This phenomenon is attributed to chromatographic-like separation of the heavier hydrocarbons by the soil, possibly due to preferential solubility of the lighter hydrocarbons in percolating ran water

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...

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

Science.gov (United States)

Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

2015-04-07

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

Investigation of Vertical Migration of Pollutants through the Unsaturated Zone Using Stable Isotopes and Trace Elements

International Nuclear Information System (INIS)

Ahmed, M.A.

2012-01-01

Vertical migration of pollutants through unsaturated zone is a complicated process and is affected by a number of factors like type of soil, its chemical properties, or organic matter content, in addition to climatic conditions and biological activity of microorganisms in soil. Soil properties that influence water movement through unsaturated zone are important for determining flow paths, reactions between soil and pollutants and the ultimate destination of these pollutants, and may improve the diagnosis of the potential pollution risk. Three soil cores were sampled to a depth up to 100 cm from cultivated clayey soil, sewage irrigated sandy soil and fertilized sandy soil. The samples were collected at intervals of 5 or 10 cm. The δ 13 C signature of the soil shifted significantly towards that of C 3 -type vegetation in soil cores. The general trend toward heavier 13 C enrichment with depth could be due to isotopic fractionation occurring during decomposition of soil organic matters. Increased δ 15 N with depth in the soil cores suggests that microbial mineralization, denitrification, or volatilization processes caused the enriched δ 15 N signatures. Decreasing nitrogen percent and nitrate values with depth also help support the idea of microbiological processes. The results indicate that concentrations of major and trace elements varied widely among the different soil types and decreased with depths in the studied soil profile. The accumulation pattern for these elements in the soil profiles follows the order: Co < Ni < Mo < Ag < Sr < V < Cu < Cr < Zn < Mn < B < Mg < Al < Fe. The relationships between element concentrations against ph and organic matter contents show antithetical relationships and suggest evidence that these elements arise from anthropogenic input. The results of this study show that there exists risk for the environment due to notable migration of pollutants through the unsaturated zone and that the migrations were also observed to be highly

Intramolecular Diels-Alder Reactions in Organic Synthesis

OpenAIRE

Sizemore, Nicholas Blandford Luke

2014-01-01

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

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

Science.gov (United States)

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

2018-05-01

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

Prestack exploding reflector modeling and migration in TI media

KAUST Repository

Wang, H.

2014-01-01

Prestack depth migration in anisotropic media, especially those that exhibit tilt, can be costly using reverse time migration (RTM). We present two-way spectral extrapolation of prestack exploding reflector modeling and migration (PERM) in acoustic transversely isotropic (TI) media. We construct systematic ways to evaluate phase angles and phase velocities in dip oriented TI (DTI), vertical TI (VTI) and tilted TI (TTI) media. Migration results from the Marmousi VTI model and the BP2007 TTI model show the feasibility of our approach.

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

KAUST Repository

Hadjichristidis, Nikolaos

2015-05-26

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

Vertical gradients in species richness and community composition across the twilight zone in the North Pacific Subtropical Gyre.

Science.gov (United States)

Sommer, Stephanie A; Van Woudenberg, Lauren; Lenz, Petra H; Cepeda, Georgina; Goetze, Erica

2017-11-01

Although metazoan animals in the mesopelagic zone play critical roles in deep pelagic food webs and in the attenuation of carbon in midwaters, the diversity of these assemblages is not fully known. A metabarcoding survey of mesozooplankton diversity across the epipelagic, mesopelagic and upper bathypelagic zones (0-1500 m) in the North Pacific Subtropical Gyre revealed far higher estimates of species richness than expected given prior morphology-based studies in the region (4,024 OTUs, 10-fold increase), despite conservative bioinformatic processing. Operational taxonomic unit (OTU) richness of the full assemblage peaked at lower epipelagic-upper mesopelagic depths (100-300 m), with slight shoaling of maximal richness at night due to diel vertical migration, in contrast to expectations of a deep mesopelagic diversity maximum as reported for several plankton groups in early systematic and zoogeographic studies. Four distinct depth-stratified species assemblages were identified, with faunal transitions occurring at 100 m, 300 m and 500 m. Highest diversity occurred in the smallest zooplankton size fractions (0.2-0.5 mm), which had significantly lower % OTUs classified due to poor representation in reference databases, suggesting a deep reservoir of poorly understood diversity in the smallest metazoan animals. A diverse meroplankton assemblage also was detected (350 OTUs), including larvae of both shallow and deep living benthic species. Our results provide some of the first insights into the hidden diversity present in zooplankton assemblages in midwaters, and a molecular reappraisal of vertical gradients in species richness, depth distributions and community composition for the full zooplankton assemblage across the epipelagic, mesopelagic and upper bathypelagic zones. © 2017 The Authors. Molecular Ecology Published by John Wiley & Sons Ltd.

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

Science.gov (United States)

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

2015-12-23

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

Soil water regulates the control of photosynthesis on diel hysteresis between soil respiration and temperature in a desert shrubland

Science.gov (United States)

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.

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

Science.gov (United States)

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

2017-12-18

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

Modification of meander migration by bank failures

Science.gov (United States)

Motta, D.; Langendoen, E. J.; Abad, J. D.; García, M. H.

2014-05-01

Meander migration and planform evolution depend on the resistance to erosion of the floodplain materials. To date, research to quantify meandering river adjustment has largely focused on resistance to erosion properties that vary horizontally. This paper evaluates the combined effect of horizontal and vertical floodplain material heterogeneity on meander migration by simulating fluvial erosion and cantilever and planar bank mass failure processes responsible for bank retreat. The impact of stream bank failures on meander migration is conceptualized in our RVR Meander model through a bank armoring factor associated with the dynamics of slump blocks produced by cantilever and planar failures. Simulation periods smaller than the time to cutoff are considered, such that all planform complexity is caused by bank erosion processes and floodplain heterogeneity and not by cutoff dynamics. Cantilever failure continuously affects meander migration, because it is primarily controlled by the fluvial erosion at the bank toe. Hence, it impacts migration rates and meander shapes through the horizontal and vertical distribution of erodibility of floodplain materials. Planar failures are more episodic. However, in floodplain areas characterized by less cohesive materials, they can affect meander evolution in a sustained way and produce preferential migration patterns. Model results show that besides the hydrodynamics, bed morphology and horizontal floodplain heterogeneity, floodplain stratigraphy can significantly affect meander evolution, both in terms of migration rates and planform shapes. Specifically, downstream meander migration can either increase or decrease with respect to the case of a homogeneous floodplain; lateral migration generally decreases as result of bank protection due to slump blocks; and the effect on bend skewness depends on the location and volumes of failed bank material caused by cantilever and planar failures along the bends, with possible achievement of

Differences in spatial communities of European perch (Perca fluviatilis Linnaeus, 1758) fry in a canyon-shaped reservoir are not attributable to genetics

Czech Academy of Sciences Publication Activity Database

Kalous, L.; Kuříková, P.; Kohout, J.; Rylková, K.; Petrtýl, M.; Čech, Martin

2017-01-01

Roč. 33, č. 2 (2017), s. 306-313 ISSN 0175-8659. [European Congress of Ichthyology /15./. Porto, 07.09.2015-11.09.2015] R&D Projects: GA ČR GA206/06/1371; GA ČR GP206/09/P266; GA MŠk(CZ) 7F14316 Institutional support: RVO:60077344 Keywords : diel vertical migration * cross-species amplification * dna-sequence data * postglacial colonization * microsatellite loci Subject RIV: GL - Fishing OBOR OECD: Marine biology, freshwater biology, limnology Impact factor: 0.845, year: 2016

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

Science.gov (United States)

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

2015-05-11

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

Diel time-courses of leaf growth in monocot and dicot species: endogenous rhythms and temperature effects.

Science.gov (United States)

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.

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

NARCIS (Netherlands)

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

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

The diurnal vertical dynamics of cape hake and their potential prey ...

African Journals Online (AJOL)

cephalopods. Together with their cohabitant potential prey, hake are known to undertake diurnal vertical migrations, aggregating near the bottom during daylight, but migrating off the bottom at night. An attempt to determine the ... predation dominating. This may indicate a feeding strategy where vision is not important.

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

Science.gov (United States)

Stowe, G. Neil

2010-01-01

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

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

Science.gov (United States)

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

2016-01-21

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

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,.

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

Science.gov (United States)

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

2012-12-21

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

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.

Seasonal carbonate chemistry covariation with temperature, oxygen, and salinity in a fjord estuary: implications for the design of ocean acidification experiments.

Science.gov (United States)

Reum, Jonathan C P; Alin, Simone R; Feely, Richard A; Newton, Jan; Warner, Mark; McElhany, Paul

2014-01-01

Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008-2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems.

Diel cycle of iron, aluminum and other heavy metals in a volcano watershed in northern Taiwan

Science.gov (United States)

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

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....

Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio, Argentina

Science.gov (United States)

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.

Diel cycling of zinc in a stream impacted by acid rock drainage: Initial results from a new in situ Zn analyzer

Science.gov (United States)

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.

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

Science.gov (United States)

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

2015-12-18

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

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

Science.gov (United States)

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

2017-01-01

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

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

Science.gov (United States)

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

2016-04-15

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

Diel and seasonal movement pattern of the dusky grouper Epinephelus marginatus inside a marine reserve.

Science.gov (United States)

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.

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

DEFF Research Database (Denmark)

Juhl, M.; Tanner, David Ackland

2009-01-01

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

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

NARCIS (Netherlands)

Engberts, Jan B.F.N.

1995-01-01

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

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

NARCIS (Netherlands)

Engberts, J.B.F.N.

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

Diel and seasonal variation in food habits of Atlantic salmon parr in a small stream

Science.gov (United States)

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.

Lewis acid catalysis of a Diels-Alder reaction in water

NARCIS (Netherlands)

Otto, S; Bertoncin, F; Engberts, JBFN

1996-01-01

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

Vertically averaged approaches for CO 2 migration with solubility trapping

KAUST Repository

Gasda, S. E.; Nordbotten, J. M.; Celia, M. A.

2011-01-01

The long-term storage security of injected carbon dioxide (CO2) is an essential component of geological carbon sequestration operations. In the postinjection phase, the mobile CO2 plume migrates in large part because of buoyancy forces, following

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

NARCIS (Netherlands)

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

1994-01-01

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

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

NARCIS (Netherlands)

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

2002-01-01

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

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

Science.gov (United States)

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

2016-05-06

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

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

Science.gov (United States)

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

2013-10-30

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

Rhythmic diel pattern of gene expression in juvenile maize leaf.

Directory of Open Access Journals (Sweden)

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

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

Science.gov (United States)

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

2016-04-18

Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diel Variations in Optical Properties of Micromonas pusilla, a Prasinophyte

Science.gov (United States)

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.

Cs-137 migration in soil near NPPs

International Nuclear Information System (INIS)

Silant'ev, A.N.; Shkuratova, I.G.; Khatskevich, R.N.

1984-01-01

A convective-diffusion model has been employed for describing Cs-137 migration in soil. The migration parameters were determined by comparing the calculated vertical distribution profiles with the experimental ones. The migration parameters dependence on the soil state has been studied. Cs-137 penetration rate was found to be function of the soil type, surface state, soil wetness and orography. The obtained values are presented. A method is suggested for revealing the soil surface contamination by Cs-137 produced during NPP operation with distinguishing it from the global contamination background. For this purpose Cs-137 content in the upper 5 mm soil layer is estimated [ru

Migration of heavy metals in soils in a uranium mining area

International Nuclear Information System (INIS)

Hu Ruixia; Gao Bai; Hu Baoqun; Feng Jiguang

2009-01-01

Contents of several heavy metals (Zn,Ni,Cu,Cd,Pb) in soil samples collected from different depths of the soil sections in a uranium mining area were analyzed, and vertical migration dis-ciplines of heavy metals were obtained. The results show that the concents of heavy metals in vertical direction decrease as the soil increases in thickness and there is a trend of facies-cumulation for the heavy metals. The accumulation status of each heavy metal in soils differs, which is dependent on the content and migration velocity of the heavy metal itself, the local natural environment about the soil, etc. (authors)

Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system

Science.gov (United States)

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.

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

Science.gov (United States)

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

2009-09-03

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

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

DEFF Research Database (Denmark)

Johannsen, Mogens; Yao, Sulan; Graven, Anette

1998-01-01

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

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

Directory of Open Access Journals (Sweden)

Patrice Vanelle

2002-12-01

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

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

Science.gov (United States)

Palmer, David R. J.

2004-01-01

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

Influence of in-stream diel concentration cycles of dissolved trace metals on acute toxicity to one-year-old cutthroat trout (Oncorhynchus clarki lewisi)

Science.gov (United States)

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.

Pteropod Ecology and Physiology in Relation to Natural Variability in Carbonate Chemistry

Science.gov (United States)

Lawson, G. L.; Maas, A. E.; Wang, A. Z.; Bergan, A. J.; Wiebe, P. H.; Blanco-Bercial, L.; Lavery, A.; Copley, N. J.

2016-02-01

The thecosomatous pteropods are a group of aragonite-shelled zooplankton thought to be particularly vulnerable to ocean acidification. We seek to gain insight into both basic questions of pteropod biology and potential responses to ocean acidification by combining field sampling with shipboard experimental manipulations, capitalizing on natural spatial variability in modern-day carbonate chemistry between and within the Atlantic and Pacific Oceans. Two cruises were conducted, in 2011 and 2012, along open-ocean transects running between 35 and 50°N in the NW Atlantic and NE Pacific; strong differences in environmental conditions exist between these regions, as well as along the Pacific transect, notably in aragonite compensation and oxygen minimum depths. The transects overlapped with portions of WOCE/CLIVAR lines A20 and P17N and measurements of carbonate chemistry provided insight into rates of chemical change as well as information on the pteropods' chemical environment. The abundance and diversity of pteropods varied substantially within and between the study regions. Depth-stratified net sampling during day and night indicated that multiple pteropod species undertook the typical diel vertical migration employed by many zooplankton species as an anti-predation strategy; the amplitude of this migration differed among species as well as within sub-populations of certain cosmopolitan species found in both oceans. Shipboard experiments of short-duration (<18 hrs, intended to mimic the duration of diel vertical migrations to depth) exposing eight species of pteropod to high CO2 and low O2 found no effect of CO2 alone on metabolic rate and an effect of low O2 or interactive effect of CO2 and O2 only in two Atlantic species not known to naturally encounter low oxygen in their biogeographic range. The implications of these various findings to our understanding of the response of pteropods to environmental change will be discussed.

Fine-scale differences in diel activity among nocturnal freshwater planarias (Platyhelminthes: Tricladida

Directory of Open Access Journals (Sweden)

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

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

Directory of Open Access Journals (Sweden)

Felicia Megumi Ito

2009-09-01

Full Text Available The present study aimed to evaluate the ability for biotransformation of the Diels-Alder adduct tricyclo[6.2.1.0(2,7]undeca-4,9-dien-3,6-dione (1 and two synthetic derivatives by the saprobe fungus Mucor ramosissimus Samutsevitsch. Products from oxidation, isomerization and, regioselective and enantioselective reduction were achieved.Neste trabalho avaliou-se a capacidade de biotransformação do aduto de Diels-Alder triciclo[6.2.1.0(2-7]undeca-4,9-dien-3,6-diona (1 e dois derivados sintéticos pelo fungo sapróbio Mucor ramosissimus Samutsevitsch. Produtos de oxidação, isomerização e redução regiosseletiva e enantiosseletiva foram obtidos.

Behavioral, ecological and genetic differentiation in an open environment--a study of a mysid population in the Baltic Sea.

Directory of Open Access Journals (Sweden)

Martin Ogonowski

Full Text Available Diel vertical migration (DVM is often assumed to encompass an entire population. However, bimodal nighttime vertical distributions have been observed in various taxa. Mysid shrimp populations also display this pattern with one group concentrated in the pelagia and the other near the bottom. This may indicate alternative migratory strategies, resembling the seasonal partial migrations seen in birds, fishes and amphibians, where only a subset of the population migrates. To assess the persistence of these alternative strategies, we analyzed the nitrogen and carbon stable isotope signatures (as proxies for diet, biochemical indices (as proxies for growth condition, and genetic population divergence in the Baltic mysid Mysis salemaai collected at night in the pelagia and close to the bottom. Stable isotope signatures were significantly different between migrants (pelagic samples and residents (benthic samples, indicating persistent diet differences, with pelagic mysids having a more uniform and carnivorous diet. Sequencing of the mitochondrial cytochrome subunit I (COI gene showed genetic differentiation attributable to geographic location but not between benthic and pelagic groups. Divergent migration strategies were however supported by significantly lower gene flow between benthic populations indicating that these groups have a lower predisposition for horizontal migrations compared to pelagic ones. Different migration strategies did not convey measurable growth benefits as pelagic and benthic mysids had similar growth condition indices. Thus, the combination of ecological, biochemical and genetic markers indicate that this partial migration may be a plastic behavioral trait that yields equal growth benefits.

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

Science.gov (United States)

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

2012-01-11

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

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

Science.gov (United States)

Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

2015-09-23

Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

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.

Sardine (Sardina pilchardus) larval dispersal in the Iberian upwelling system, using coupled biophysical techniques

Science.gov (United States)

Santos, A. M. P.; Nieblas, A.-E.; Verley, P.; Teles-Machado, A.; Bonhommeau, S.; Lett, C.; Garrido, S.; Peliz, A.

2018-03-01

The European sardine (Sardina pilchardus) is the most important small pelagic fishery of the Western Iberia Upwelling Ecosystem (WIUE). Recently, recruitment of this species has declined due to changing environmental conditions. Furthermore, controversies exist regarding its population structure with barriers thought to exist between the Atlantic-Iberian Peninsula, Northern Africa, and the Mediterranean. Few studies have investigated the transport and dispersal of sardine eggs and larvae off Iberia and the subsequent impact on larval recruitment variability. Here, we examine these issues using a Regional Ocean Modeling System climatology (1989-2008) coupled to the Lagrangian transport model, Ichthyop. Using biological parameters from the literature, we conduct simulations that investigate the effects of spawning patchiness, diel vertical migration behaviors, and egg buoyancy on the transport and recruitment of virtual sardine ichthyoplankton on the continental shelf. We find that release area, release depth, and month of release all significantly affect recruitment. Patchiness has no effect and diel vertical migration causes slightly lower recruitment. Egg buoyancy effects are significant and act similarly to depth of release. As with other studies, we find that recruitment peaks vary by latitude, explained here by the seasonal variability of offshore transport. We find weak, continuous alongshore transport between release areas, though a large proportion of simulated ichthyoplankton transport north to the Cantabrian coast (up to 27%). We also show low level transport into Morocco (up to 1%) and the Mediterranean (up to 8%). The high proportion of local retention and low but consistent alongshore transport supports the idea of a series of metapopulations along this coast.

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

Science.gov (United States)

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

2017-05-05

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

Gold-Catalyzed Cyclization of Furan-Ynes bearing a Propargyl Carbonate Group: Intramolecular Diels-Alder Reaction with In Situ Generated Allenes.

Science.gov (United States)

Sun, Ning; Xie, Xin; Chen, Haoyi; Liu, Yuanhong

2016-09-26

Gold-catalyzed cyclization of various furan-ynes with a propargyl carbonate or ester moiety results in the formation of a series of polycyclic aromatic ring systems. The reactions can be rationalized through a tandem gold-catalyzed 3,3-rearrangement of the propargyl carboxylate moiety in furan-yne substrates to form an allenic intermediate, which is followed by an intramolecular Diels-Alder reaction of furan and subsequent ring-opening of the oxa-bridged cycloadduct. It was found that the steric and electronic properties of phosphine ligands on the gold catalyst had a significant impact on the reaction outcome. In the case of 1,5-furan-yne, the cleavage of the oxa-bridge in the cycloadduct with concomitant 1,2-migration of the R(1) group occurs to furnish anthracen-1(2H)-ones bearing a quaternary carbon center. For 1,4-furan-yne, a facile aromatization of the cycloadduct takes place to give 9-oxygenated anthracene derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2017-01-31

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

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

Science.gov (United States)

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

2016-11-18

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

Non-destructive measurement of soybean leaf thickness via X-ray computed tomography allows the study of diel leaf growth rhythms in the third dimension.

Science.gov (United States)

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

Integrity of clay till aquitards to DNAPL migration: Assessment using current and emerging characterization tools

DEFF Research Database (Denmark)

Fjordbøge, Annika Sidelmann; Janniche, Gry Sander; Jørgensen, Torben H.

2017-01-01

Field investigations were carried out to determine the occurrence of tetrachloroethene (PCE) dense non-aqueous phase liquid (DNAPL), the source zone architecture and the aquitard integrity at a 30-50 year old DNAPL release site. The DNAPL source zone is located in the clay till unit overlying......% of the total PCE mass. The data set, and associated data analysis, supported vertical migration of DNAPL through fractures in the upper part of the clay till, horizontal migration along high permeability features around the redox boundary in the clay till, and to some extent vertical migration through...... the fractures in the reduced part of the clay till aquitard to the underlying limestone aquifer. The aquitard integrity to DNAPL migration was found to be compromised at a thickness of reduced clay till of less than 2 m....

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

NARCIS (Netherlands)

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

2007-01-01

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

Specificity Responses of Grasshoppers in Temperate Grasslands to Diel Asymmetric Warming

Science.gov (United States)

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

Distribution and diel vertical movements of mesopelagic scattering layers in the Red Sea

KAUST Repository

Klevjer, Thor A.

2012-06-13

The mesopelagic zone of the Red Sea represents an extreme environment due to low food concentrations, high temperatures and low oxygen waters. Nevertheless, a 38 kHz echosounder identified at least four distinct scattering layers during the daytime, of which the 2 deepest layers resided entirely within the mesopelagic zone. Two of the acoustic layers were found above a mesopelagic oxygen minimum zone (OMZ), one layer overlapped with the OMZ, and one layer was found below the OMZ. Almost all organisms in the deep layers migrated to the near-surface waters during the night. Backscatter from a 300 kHz lowered Acoustic Doppler Current Profiler indicated a layer of zooplankton within the OMZ. They carried out DVM, yet a portion remained at mesopelagic depths during the night. Our acoustic measurements showed that the bulk of the acoustic backscatter was restricted to waters shallower than 800 m, suggesting that most of the biomass in the Red Sea resides above this depth. 2012 The Author(s).

Distribution and diel vertical movements of mesopelagic scattering layers in the Red Sea

KAUST Repository

Klevjer, Thor A.; Torres, Daniel J.; Kaartvedt, Stein

2012-01-01

The mesopelagic zone of the Red Sea represents an extreme environment due to low food concentrations, high temperatures and low oxygen waters. Nevertheless, a 38 kHz echosounder identified at least four distinct scattering layers during the daytime, of which the 2 deepest layers resided entirely within the mesopelagic zone. Two of the acoustic layers were found above a mesopelagic oxygen minimum zone (OMZ), one layer overlapped with the OMZ, and one layer was found below the OMZ. Almost all organisms in the deep layers migrated to the near-surface waters during the night. Backscatter from a 300 kHz lowered Acoustic Doppler Current Profiler indicated a layer of zooplankton within the OMZ. They carried out DVM, yet a portion remained at mesopelagic depths during the night. Our acoustic measurements showed that the bulk of the acoustic backscatter was restricted to waters shallower than 800 m, suggesting that most of the biomass in the Red Sea resides above this depth. 2012 The Author(s).

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

Science.gov (United States)

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

2015-12-04

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

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

Science.gov (United States)

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

2016-06-29

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

Variation in diel activity of ground beetles (Coleoptera: Carabidae) associated with a soybean field and coal mine remnant

Science.gov (United States)

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.

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

Science.gov (United States)

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

2017-09-15

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

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

Directory of Open Access Journals (Sweden)

Julio A. Alonso

2013-02-01

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

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

Science.gov (United States)

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

2017-11-01

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

Vertical ascending electrophoresis of cells with a minimal stabilizing medium

Science.gov (United States)

Omenyi, S. N.; Snyder, R. S.

1983-01-01

Vertical fractionation of a mixture of fixed horse and human red blood cells layered over a stabilizing support medium was done to give a valid comparison with proposed space experiments. In particular, the effects of sample thickness and concentration on zone migration rate were investigated. Electrophoretic mobilities of horse and human cells calculated from zone migration rates were compatible with those obtained by microelectrophoresis. Complete cell separation was observed when low power and effective cooling were employed.

Sequential aminodiene Diels-Alder approach to the ergoline skeleton.

Science.gov (United States)

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

2005-08-19

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

Vertical migratory rhythms of benthic diatoms in a tropical intertidal sand flat: Influence of irradiance and tides

Digital Repository Service at National Institute of Oceanography (India)

Mitbavkar, S.; Anil, A.C.

Vertical migratory behavior of benthic diatoms is one of the adaptive strategies employed for a life in intertidal habitats. Irradiance and tides are considered to be the key factors governing vertical migration. Experiments were carried out...

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

Science.gov (United States)

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

2015-01-01

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

Petroleum migration pathways and charge concentration: A three-dimensional model

Energy Technology Data Exchange (ETDEWEB)

Hindle, A.D. [Anadarko Algeria Corp., Middlesex (United Kingdom)

1997-09-01

Petroleum migration pathways through a basin are determined by the three-dimensional distribution of discontinuous sealing surfaces, which are usually parallel to bedding. The petroleum migrates below the sealing surface, taking the structurally most advantageous route. The three-dimensional distribution of migration pathways within the petroleum system can be modeled on a personal computer using a program based on the parameters discussed in this paper. Application of the model to the Paris and Williston basins demonstrates that a good correlation between predicted pathways and discovered accumulations can be made using simple models. Pathways form a dense network overlying generating areas in the central parts of basins. Toward the basin margins these routes commonly become increasingly focused into discrete pathways by the sealing-surface morphologies. Eventually, these pathways may reach the surface as seepages. It is important to integrate surface outcrops of migration routes (surface seepages) into migration modeling. Deflection of the pathways from the structurally most advantageous route below the sealing surface may be caused by lateral sealing barriers due to faces variation in the carrier rock below the seal, fault juxtaposition, or cross-formational seals such as salt intrusions. Deflection of pathways also occurs where there are hydrodynamic conditions in response to topography-driven groundwater flow. Zones of vertical migration are associated with facies changes along the horizon of the sealing surface into a nonsealing facies, or juxtaposition to nonsealing strata by faults. Vertical migration from either normally or abnormally pressured strata is most likely to occur into normally or lesser pressured strata at intrabasinal highs where hydrocarbons can be stored and transferred at times of temporary seal rupture.

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

Directory of Open Access Journals (Sweden)

Haghdadi Mina

2015-01-01

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

Ontogenetic behavior and migration of Atlantic sturgeon, Acipenser oxyrinchus oxyrinchus, and shortnose sturgeon, A. brevirostrum, with notes on social behavior

Science.gov (United States)

Kynard, B.; Horgan, M.

2002-01-01

Ontogenetic behavior of Hudson River Atlantic sturgeon and Connecticut River shortnose sturgeon early life intervals were similar during laboratory observations. After hatching, free embryos were photonegative and sought cover. When embryos developed into larvae, fish left cover, were photopositive, and initiated downstream migration. Free embryos may remain at the spawning site instead of migrating downstream because the risk of predation at spawning sites is low. The two species are sympatric, but not closely related, so the similarities in innate behaviors suggest common adaptations, not phylogenetlc relationship. Atlantic sturgeon migrated downstream for 12 days (peak, first 6 days), shortnose sturgeon migrated for 3 days, and year-0 juveniles of both species did not resume downstream migration. Short or long migrations of larvae may reflect different styles related to the total migratory distance from spawning sites to juvenile rearing areas. Atlantic sturgeon need to move a short distance to reach rearing areas and they had a long 1-step migration of 6-12 days. In contrast, shortnose sturgeon need to move a long distance to reach all rearing areas. This may be accomplished by a 2-step migration, of which the brief migration of larvae is only the first step. Early migrant Atlantic sturgeon were nocturnal, while late migrants were diurnal, and shortnose sturgeon were diurnal. These diel differences may also be adaptations for long (Atlantic sturgeon) or short (shortnose sturgeon) migrations. Cultured shortnose sturgeon, and possibly Atlantic sturgeon, have a dominance hierarchy with large fish dominant when competing for limited foraging space. Social behavior may be more important in the life history of wild sturgeons than is generally recognized.

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...

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.

Diels-Alder reactions onto fluorinated and hydrogenated graphene

Science.gov (United States)

Denis, Pablo A.

2017-09-01

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

Estimating dew formation in rice, using seasonally averaged diel patterns of weather variables

NARCIS (Netherlands)

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

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

KAUST Repository

Hadjichristidis, Nikolaos; Alkayal, Nazeeha

2015-01-01

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

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

Diel cycles in dissolved barium, lead, iron, vanadium, and nitrite in a stream draining a former zinc smelter site near Hegeler, Illinois

Science.gov (United States)

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

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

Science.gov (United States)

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

2016-07-15

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

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

Science.gov (United States)

Lee, Jihoon; Panek, James S

2014-06-20

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

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

NARCIS (Netherlands)

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

1998-01-01

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

Rhythmic behaviour of marine benthopelagic species and the synchronous dynamics of benthic communities

Science.gov (United States)

Aguzzi, Jacopo; Sbragaglia, Valerio; Tecchio, Samuele; Navarro, Joan; Company, Joan B.

2015-01-01

Light-intensity cycles drive the relentless motion of species in the oceans, and water column migrants may cyclically make contact with the seabed, hence influencing the temporal dynamism of benthic ecosystems. The influence of light on this process remains largely unknown to date. In this study, we focus on the occurrence of day-night changes in benthic communities on the western Mediterranean continental shelf (100 m depth) and slope (400 m depth) as a potential result of a behaviourally sustained benthopelagic coupling. We analysed fluctuations in species abundance based on trawling at hourly intervals over a 4-day period as a proxy of activity rhythms at the seabed. We also measured light in situ to assess how the depth-related decrease of its intensity influences species rhythms and the occurrence of the putative benthopelagic synchronisation. Temporal similarities in the catch patterns for different species were screened by dendrogram analysis. On the continental shelf, species performing diel migrations (i.e., over a 24 h period) that were either vertical (i.e., benthopelagic) or horizontal across depths (i.e., nektobenthic) clustered together separately from the more sedentary endobenthic and epibenthic species. At the same depth, waveform analysis showed a significant diurnal increase in the catch of water column species and benthic species at night. Such coupling was absent on the continental slope, where light intensity was several orders of magnitude lower than that on the shelf. Our data indicate that diel activity rhythms, which are well known for vertical pelagic migrators, are also evident in the benthos. We discuss the role of light as a major evolutionary driver shaping the composition and biodiversity of benthic communities via visual predation.

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 ...

IMPROVING VERTICAL AND LATERAL RESOLUTION BY STRETCH-FREE, HORIZON-ORIENTED IMAGING

Directory of Open Access Journals (Sweden)

Pérez Gabriel

2006-12-01

Full Text Available The pre-stack Kirchhoff migration is implemented for delivering wavelet stretch-free imaged data, if the migration is (ideally limited to the wavelet corresponding to a target horizon. Avoiding wavelet stretch provides long-offset imaged data, far beyond what is reached in conventional migration and results in images from the target with improved vertical and lateral resolution and angular illumination. Increasing the range of imaged offsets also increases the sensitivity to event-crossing, velocity errors and anisotropy. These issues must be addressed to fully achieve the greatest potential of this technique. These ideas are further illustrated with a land survey seismic data application in Texas, U.S.

Vertical sorting in bed forms - flume experiments with a natural and a tri-modal sediment mixture

NARCIS (Netherlands)

Blom, Astrid; Ribberink, Jan S.; de Vriend, Huib J.

2003-01-01

Two sets of flume experiments were conducted to examine grain size selective transport and vertical sorting in conditions with migrating bed forms and bed load transport. In the two sets of experiments we used a sediment mixture from the river Rhine and a trimodal mixture, respectively. The vertical

Alternative responses to predation in two headwater stream minnows is reflected in their contrasting diel activity patterns.

Science.gov (United States)

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

Alternative responses to predation in two headwater stream minnows is reflected in their contrasting diel activity patterns.

Directory of Open Access Journals (Sweden)

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

Vertical migration of fine-grained sediments from interior to surface of seabed driven by seepage flows-`sub-bottom sediment pump action'

Science.gov (United States)

Zhang, Shaotong; Jia, Yonggang; Wen, Mingzheng; Wang, Zhenhao; Zhang, Yaqi; Zhu, Chaoqi; Li, Bowen; Liu, Xiaolei

2017-02-01

A scientific hypothesis is proposed and preliminarily verified in this paper: under the driving of seepage flows, there might be a vertical migration of fine-grained soil particles from interior to surface of seabed, which is defined as `sub-bottom sediment pump action' in this paper. Field experiments were performed twice on the intertidal flat of the Yellow River delta to study this process via both trapping the pumped materials and recording the pore pressures in the substrate. Experimental results are quite interesting as we did observe yellow slurry which is mainly composed of fine-grained soil particles appearing on the seabed surface; seepage gradients were also detected in the intertidal flat, under the action of tides and small wind waves. Preliminary conclusions are that `sediment pump' occurs when seepage force exceeds a certain threshold: firstly, it is big enough to disconnect the soil particles from the soil skeleton; secondly, the degree of seabed fluidization or bioturbation is big enough to provide preferred paths for the detached materials to migrate upwards. Then they would be firstly pumped from interior to the surface of seabed and then easily re-suspended into overlying water column. Influential factors of `sediment pump' are determined as hydrodynamics (wave energy), degree of consolidation, index of bioturbation (permeability) and content of fine-grained materials (sedimentary age). This new perspective of `sediment pump' may provide some implications for the mechanism interpretation of several unclear geological phenomena in the Yellow River delta area.

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

Digital Repository Service at National Institute of Oceanography (India)

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

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

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

Science.gov (United States)

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

2015-06-07

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

Diel turbidity cycles in a headwater stream: evidence of nocturnal bioturbation?

OpenAIRE

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...

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

NARCIS (Netherlands)

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

2016-01-01

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

Temperature versus plant effects on diel dynamics of soil CO2 production and efflux: a controlled environment study

Science.gov (United States)

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

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

Science.gov (United States)

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

2016-08-05

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

Contaminant migration at two low-level radioactive waste sites in arid western United States - a review

International Nuclear Information System (INIS)

Wilshire, H.G.; Friedman, I.

1999-01-01

Contamination of the unsaturated zone and ground water at the Beatty, Nevada and Richland, Washington low-level radioactive waste sites shows that pathways exist for rapid lateral and vertical migration of contaminants through unconsolidated clastic sediments that comprise the 100 m-thick unsaturated zones of those arid disposal sites. Disposal of liquid wastes at the Beatty site until 1975 may have contributed to rapid migration of contaminants, but negligible amounts of liquid wastes reportedly were disposed at the Richland LLRW site and similar problems of contaminant migration exist. Pathways for vertical migration in the unsaturated zone include fractures and, at Richland, clastic dikes; lateral migration pathways likely are facies-controlled. Disturbance of the disposal sites contributed to increased infiltration of the unlined waste trenches after closure; simulations that used Beatty sample data show dramatic increases in recharge with disturbances necessary to develop the site. Because neither and arid climate nor presence of a thick unsaturated zone offer effective barriers to ground-water contamination, reliance on those factors at proposed sites such as Ward Valley, California and elsewhere is unwarranted. (orig.)

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...

The diel imprint of leaf metabolism on the δ13 C signal of soil respiration under control and drought conditions.

Science.gov (United States)

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.

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

Science.gov (United States)

Rivero, Uxía; Meuwly, Markus; Willitsch, Stefan

2017-09-01

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

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

Science.gov (United States)

Ho, Guo-Ming; Huang, Ci-Jhang; Li, Elise Yu-Tzu; Hsu, Sheng-Kai; Wu, Ti; Zulueta, Medel Manuel L.; Wu, Kevin Binchia; Hung, Shang-Cheng

2016-10-01

The Diels-Alder reaction is a useful tool for generating functionalized chiral molecules through the concerted cycloaddition of dienes and dienophiles leading to six-membered rings. Traditionally, the selective predictions of the products rely heavily on consideration of the secondary orbital interactions that stabilize the endo pathway. However, there remain some basic examples defying this notion and produce the exo-isomer as major product. Here we systematically evaluated of the structural features driving exo selectivity in thermal normal-electron-demand Diels-Alder reactions. Substitution at the Cβ position and the size and electronegativity of the electron-withdrawing group of the dienophile are contributing factors. Experimental and computational studies both point toward the steric and electrostatic forces between the substituents in both the diene and the dienophile that increase the likelihood of the exo pathway. For these substrates, the dominance of the endo pathway is reduced by transition state distortions and poor structural alignments of the reacting partners. We also noted the tilt of the dienophile with respect to the diene causing steric strain on the functionalities at the more advanced bond forming carbon-carbon position of the endo transition state. Insights into such factors may benefit synthetic planning and asserting control over this important named reaction.

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

Synthetic seismic monitoring using reverse-time migration and Kirchhoff migration for CO2 sequestration in Korea

Science.gov (United States)

Kim, W.; Kim, Y.; Min, D.; Oh, J.; Huh, C.; Kang, S.

2012-12-01

vertical CO2 migration at injection point, the reverse time migration yields better images than Kirchhoff migration does. On the other hand, Kirchhoff migration images horizontal CO2 migration clearer than the reverse time migration does. From these results, we can conclude that the reverse-time migration and Kirchhoff migration can complement with each other to describe the behavior of CO2 in the subsurface. Acknowledgement This work was financially supported by the Brain Korea 21 project of Energy Systems Engineering, the "Development of Technology for CO2 Marine Geological Storage" program funded by the Ministry of Land, Transport and Maritime Affairs (MLTM) of Korea and the Korea CCS R&D Center (KCRC) grant funded by the Korea government (Ministry of Education, Science and Technology) (No. 2012-0008926).

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

Czech Academy of Sciences Publication Activity Database

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

2012-01-01

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

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

Science.gov (United States)

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

2014-08-06

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

Diel variations in zooplankton and their biochemical composition from Vengurla to Ratnagiri, west coast of India

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...

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

Science.gov (United States)

Rowley, Christopher N.; Woo, Tom K.

2009-01-01

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

Pleistocene vertical motions of the Costa Rican outer forearc from subducting topography and a migrating fracture zone triple junction

Science.gov (United States)

Edwards, Joel H.; Kluesner, Jared W.; Silver, Eli A.; Bangs, Nathan L.

2018-01-01

Understanding the links between subducting slabs and upper-plate deformation is a longstanding goal in the field of tectonics. New 3D seismic sequence stratigraphy, mapped within the Costa Rica Seismogenesis Project (CRISP) seismic-reflection volume offshore southern Costa Rica, spatiotemporally constrains several Pleistocene outer forearc processes and provides clearer connections to subducting plate dynamics. Three significant shelf and/or slope erosional events at ca. 2.5–2.3 Ma, 1.95–1.78 Ma, and 1.78–1.19 Ma, each with notable differences in spatial extent, volume removed, and subsequent margin response, caused abrupt shifts in sedimentation patterns and rates. These shifts, coupled with observed deformation, suggest three primary mechanisms for Pleistocene shelf and slope vertical motions: (1) regional subaerial erosion and rapid subsidence linked to the southeastward Panama Fracture Zone triple-junction migration, with associated abrupt bathymetric variations and plate kinematic changes; (2) transient, kilometer-scale uplift and subsidence due to inferred subducting plate topography; and (3) progressive outer wedge shortening accommodated by landward- and seaward-dipping thrust faults and fold development due to the impinging Cocos Ridge. Furthermore, we find that the present-day wedge geometry (to within ∼3 km along strike) has been maintained through the Pleistocene, in contrast to modeled landward margin retreat. We also observe that deformation, i.e., extension and shortening, is decoupled from net margin subsidence. Our findings do not require basal erosion, and they suggest that the vertical motions of the Costa Rican outer forearc are not the result of a particular continuous process, but rather are a summation of plate to plate changes (e.g., passage of a fracture zone triple junction) and episodic events (e.g., subducting plate topography).

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

Science.gov (United States)

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

2017-02-01

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

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

Science.gov (United States)

Sousa, Carlos A. D.; Rodríguez-Borges, José E.; Freire, Cristina

2013-01-01

New L-serine derivative ligands were prepared and tested as cocatalyst in the Diels-Alder reactions between cyclopentadiene (CPD) and methyl acrylate, in the presence of several Lewis acids. The catalytic potential of the in situ formed complexes was evaluated based on the reaction yield. Bidentate serine ligands showed good ability to coordinate medium strength Lewis acids, thus boosting their catalytic activity. The synthesis of the L-serine ligands proved to be highly efficient and straightforward. PMID:24383009

Reverse time migration of prism waves for salt flank delineation

KAUST Repository

Dai, Wei; Schuster, Gerard T.

2013-01-01

In this paper, we present a new reverse time migration method for imaging salt flanks with prism wave reflections. It consists of four steps: (1) migrating the seismic data with conventional RTM to give the RTM image; (2) using the RTM image as a reflectivity model to simulate source-side reflections with the Born approximation; (3) zero-lag correlation of the source-side reflection wavefields and receiver-side wavefields to produce the prism wave migration image; and (4) repeating steps 2 and 3 for the receiver-side reflections. An advantage of this method is that there is no need to pick the horizontal reflectors prior to migration of the prism waves. It also separately images the vertical structures at a different step to reduce crosstalk interference. The disadvantage of prism wave migration algorithm is that its computational cost is twice that of conventional RTM. The empirical results with a salt model suggest that prism wave migration can be an effective method for salt flank delineation in the absence of diving waves.

Reverse time migration of prism waves for salt flank delineation

KAUST Repository

Dai, Wei

2013-09-22

In this paper, we present a new reverse time migration method for imaging salt flanks with prism wave reflections. It consists of four steps: (1) migrating the seismic data with conventional RTM to give the RTM image; (2) using the RTM image as a reflectivity model to simulate source-side reflections with the Born approximation; (3) zero-lag correlation of the source-side reflection wavefields and receiver-side wavefields to produce the prism wave migration image; and (4) repeating steps 2 and 3 for the receiver-side reflections. An advantage of this method is that there is no need to pick the horizontal reflectors prior to migration of the prism waves. It also separately images the vertical structures at a different step to reduce crosstalk interference. The disadvantage of prism wave migration algorithm is that its computational cost is twice that of conventional RTM. The empirical results with a salt model suggest that prism wave migration can be an effective method for salt flank delineation in the absence of diving waves.

Out of the dark: 350 million years of conservatism and evolution in diel activity patterns in vertebrates.

Science.gov (United States)

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.

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

Directory of Open Access Journals (Sweden)

Ronald N. Warrener

2000-12-01

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

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

International Nuclear Information System (INIS)

Hudhomme, P.

2006-01-01

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

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

Science.gov (United States)

Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath

We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.

Seismic chimneys in the Southern Viking Graben - Implications for palaeo fluid migration and overpressure evolution

Science.gov (United States)

Karstens, Jens; Berndt, Christian

2015-02-01

Detailed understanding of natural fluid migration systems is essential to minimize risks during hydrocarbon exploration and to evaluate the long-term efficiency of the subsurface storage of waste water and gas from hydrocarbon production as well as CO2. The Southern Viking Graben (SVG) hosts numerous focused fluid flow structures in the shallow (expressions of vertical fluid conduits are variously known as seismic chimneys or pipes. Seismic pipes are known to form large clusters. Seismic chimneys have so far been described as solitary structures. Here, we show that the study area in the SVG hosts more than 46 large-scale vertical chimney structures, which can be divided in three categories implying different formation processes. Our analysis reveals that seal-weakening, formation-wide overpressure and the presence of free gas are required to initiate the formation of vertical fluid conduits in the SVG. The presence of numerous vertical fluid conduits implies inter-stratigraphic hydraulic connectivity, which significantly affects the migration of fluids in the subsurface. Chimney structures are important for understanding the transfer of pore pressure anomalies to the shallow parts of the basin.

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

Science.gov (United States)

Silvestri, Michael G.; Dills, Charles E.

1989-01-01

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

A computer model for DNAPL potential migration study

International Nuclear Information System (INIS)

Yan, S.; Landry, G.R.; Tate, T.

1994-01-01

A computer model, named DNAPMIG (DNAPL Potential Migration), was developed to calculate the dense nonaqueous phase liquid (DNAPL) critical length required to initiate movement and direction of potential migration at locations within an area of interest. The model takes into consideration the potentiometric gradient, bottom structure elevation, DNAPL density, interfacial tension, contact angle, soil grain size, partitioning coefficient, effective solubility, and water saturation. The model is interfaced with SURFER graphics software to use vectors to indicate the DNAPL critical length and the potential migration direction. The potential for DNAPL existence and migration at a specific site can be estimated by relating chemical concentration in the ground water to its solubility limit and the DNAPL critical length. The possibility of vertical migration can also be determined. This model can be used to determine and compare the effectiveness of existing or alternative recovery well systems to capture a DNAPL plume or arrest its movement; to help determine optimum locations and pumping rates of recovery wells; and to help determine the optimum location of environmental borings to locate DNAPL. This paper presents two hypothetical examples and two site applications in south Louisiana

Is the poleward migration of tropical cyclone maximum intensity associated with a poleward migration of tropical cyclone genesis?

Science.gov (United States)

Daloz, Anne Sophie; Camargo, Suzana J.

2018-01-01

A recent study showed that the global average latitude where tropical cyclones achieve their lifetime-maximum intensity has been migrating poleward at a rate of about one-half degree of latitude per decade over the last 30 years in each hemisphere. However, it does not answer a critical question: is the poleward migration of tropical cyclone lifetime-maximum intensity associated with a poleward migration of tropical cyclone genesis? In this study we will examine this question. First we analyze changes in the environmental variables associated with tropical cyclone genesis, namely entropy deficit, potential intensity, vertical wind shear, vorticity, skin temperature and specific humidity at 500 hPa in reanalysis datasets between 1980 and 2013. Then, a selection of these variables is combined into two tropical cyclone genesis indices that empirically relate tropical cyclone genesis to large-scale variables. We find a shift toward greater (smaller) average potential number of genesis at higher (lower) latitudes over most regions of the Pacific Ocean, which is consistent with a migration of tropical cyclone genesis towards higher latitudes. We then examine the global best track archive and find coherent and significant poleward shifts in mean genesis position over the Pacific Ocean basins.

Long-term stability of tidal and diel-related patterns in mangrove creek fish assemblages in North Brazil

Science.gov (United States)

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

Seasonal Carbonate Chemistry Covariation with Temperature, Oxygen, and Salinity in a Fjord Estuary: Implications for the Design of Ocean Acidification Experiments

Science.gov (United States)

Reum, Jonathan C. P.; Alin, Simone R.; Feely, Richard A.; Newton, Jan; Warner, Mark; McElhany, Paul

2014-01-01

Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008–2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (aragonite were widespread (Ωar<1). We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal

Oxidative stress in deep scattering layers: Heat shock response and antioxidant enzymes activities of myctophid fishes thriving in oxygen minimum zones

Science.gov (United States)

Lopes, Ana Rita; Trübenbach, Katja; Teixeira, Tatiana; Lopes, Vanessa M.; Pires, Vanessa; Baptista, Miguel; Repolho, Tiago; Calado, Ricardo; Diniz, Mário; Rosa, Rui

2013-12-01

Diel vertical migrators, such as myctophid fishes, are known to encounter oxygen minimum zones (OMZ) during daytime in the Eastern Pacific Ocean and, therefore, have to cope with temperature and oxidative stress that arise while ascending to warmer, normoxic surface waters at night-time. The aim of this study was to investigate the antioxidant defense strategies and heat shock response (HSR) in two myctophid species, namely Triphoturus mexicanus and Benthosema panamense, at shallow and warm surface waters (21 kPa, 20-25 °C) and at hypoxic, cold (≤1 kPa, 10 °C) mesopelagic depths. More specifically, we quantified (i) heat shock protein concentrations (HSP70/HSC70) (ii) antioxidant enzyme activities [including superoxide dismutase (SOD), catalase (CAT) and glutathione-S-transferase (GST)], and (iii) lipid peroxidation [malondialdehyde (MDA) levels]. HSP70/HSC70 levels increased in both myctophid species at warmer, well-oxygenated surface waters probably to prevent cellular damage (oxidative stress) due to increased oxygen demand under elevated temperatures and reactive oxygen species (ROS) formation. On the other hand, CAT and GST activities were augmented under hypoxic conditions, probably as preparatory response to a burst of oxyradicals during the reoxygenation phase (while ascending). SOD activity decreased under hypoxia in B. panamense, but was kept unchanged in T. mexicanus. MDA levels in B. panamense did not change between the surface and deep-sea conditions, whereas T. mexicanus showed elevated MDA and HSP70/HSC70 concentrations at warmer surface waters. This indicated that T. mexicanus seems to be not so well tuned to temperature and oxidative stress associated to diel vertical migrations. The understanding of such physiological strategies that are linked to oxygen deprivation and reoxygenation phases may provide valuable information about how different species might respond to the impacts of environmental stressors (e.g. expanding mesopelagic hypoxia

Migration and speciation of heavy metal in salinized mine tailings affected by iron mining.

Science.gov (United States)

Zhang, Xu; Yang, Huanhuan; Cui, Zhaojie

2017-10-01

The negative effects of heavy metals have aroused much attention due to their high toxicity to human beings. Migration and transformation trend of heavy metals have a close relationship with soil safety. Researching on migration and transformation of heavy metals in tailings can provide a reliable basis for pollution management and ecosystem restoration. Heavy metal speciation plays an important role in risk assessment. We chose Anshan tailings for our study, including field investigations and laboratory research. Four typical heavy metal elements of mine tailings {Fe (373.89 g/kg), Mn (2,303.80 mg/kg), Pb (40.99 mg/kg) and Cr (199.92 mg/kg)} were studied via Tessier test in vertical and horizontal direction. The main speciation of heavy metals in Anshan tailings was the residual. However, heavy metals have a strong ability for migration and transformation in vertical and horizontal directions. Its tendency to change from stable to unstable speciation results in increasing bioavailability and potential bioavailability. Fe, Mn, Pb and Cr showed different ability in the migration and transformation process (Mn > Pb > Fe > Cr) depending on the characteristics of heavy metals and physicochemical properties of the environment.

The role of fluid migration system in hydrocarbon accumulation in Maichen Sag, Beibuwan Basin

Science.gov (United States)

Liu, Hongyu; Yang, Jinxiu; Wu, Feng; Chen, Wei; Liu, Qianqian

2018-02-01

Fluid migration system is of great significance for hydrocarbon accumulation, including the primary migration and secondary migration. In this paper, the fluid migration system is analysed in Maichen Sag using seismic, well logging and core data. Results show that many factors control the hydrocarbon migration process, including hydrocarbon generation and expulsion period from source rocks, microfractures developed in the source rocks, the connected permeable sand bodies, the vertical faults cutting into/through the source rocks and related fault activity period. The spatial and temporal combination of these factors formed an effective network for hydrocarbon expulsion and accumulation, leading to the hydrocarbon reservoir distribution at present. Generally, a better understanding of the hydrocarbon migration system can explain the present status of hydrocarbon distribution, and help select future target zones for oil and gas exploration.

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

Science.gov (United States)

Murase, Takashi; Horiuchi, Shinnosuke; Fujita, Makoto

2010-03-10

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

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...

When do predatory mites (Phytoseiidae) attack? Understanding their diel and seasonal predation patterns.

Science.gov (United States)

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.

Carbon cycling and exports over diel and flood-recovery timescales in a subtropical rainforest headwater stream

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. �

Carbon cycling and exports over diel and flood-recovery timescales in a subtropical rainforest headwater stream

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

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

Science.gov (United States)

Karunakaran, Jayachandran; Mohanakrishnan, Arasambattu K

2018-02-16

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

Diel variation of arsenic, molybdenum and antimony in a stream draining natural As geochemical anomaly

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

Geometric effects of 90-degree vertical elbows on local two-phase flow parameters

International Nuclear Information System (INIS)

Yadav, M.; Worosz, T.; Kim, S.

2011-01-01

This study presents the geometric effects of 90-degree vertical elbows on the development of the local two-phase flow parameters. A multi-sensor conductivity probe is used to measure local two-phase flow parameters. It is found that immediately downstream of the vertical-upward elbow, the bubbles have a bimodal distribution along the horizontal radius of the pipe cross-section causing a dual-peak in the profiles of local void fraction and local interfacial area concentration. Immediately downstream of the vertical-downward elbow it is observed that the bubbles tend to migrate towards the inside of the elbow's curvature. The axial transport of void fraction and interfacial area concentration indicates that the elbows promote bubble disintegration. Preliminary predictions are obtained from group-one interfacial area transport equation (IATE) model for vertical-upward and vertical-downward two-phase flow. (author)

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

NARCIS (Netherlands)

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

1997-01-01

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

Patterns of gravity induced aggregate migration during casting of fluid concretes

Energy Technology Data Exchange (ETDEWEB)

Spangenberg, J. [Department of Mechanical Engineering, Technical University of Denmark (DTU) (Denmark); Roussel, N., E-mail: Nicolas.roussel@lcpc.fr [Universite Paris Est, Laboratoire Central des Ponts et Chaussees (LCPC) (France); Hattel, J.H. [Department of Mechanical Engineering, Technical University of Denmark (DTU) (Denmark); Sarmiento, E.V.; Zirgulis, G. [Department of Structural Engineering, Norwegian University of Science and Technology (NTNU) (Norway); Geiker, M.R. [Department of Structural Engineering, Norwegian University of Science and Technology (NTNU) (Norway); Department of Civil Engineering, Technical University of Denmark (DTU) (Denmark)

2012-12-15

In this paper, aggregate migration patterns during fluid concrete castings are studied through experiments, dimensionless approach and numerical modeling. The experimental results obtained on two beams show that gravity induced migration is primarily affecting the coarsest aggregates resulting in a decrease of coarse aggregates volume fraction with the horizontal distance from the pouring point and in a puzzling vertical multi-layer structure. The origin of this multi layer structure is discussed and analyzed with the help of numerical simulations of free surface flow. Our results suggest that it finds its origin in the non Newtonian nature of fresh concrete and that increasing casting rate shall decrease the magnitude of gravity induced particle migration.

Patterns of gravity induced aggregate migration during casting of fluid concretes

International Nuclear Information System (INIS)

Spangenberg, J.; Roussel, N.; Hattel, J.H.; Sarmiento, E.V.; Zirgulis, G.; Geiker, M.R.

2012-01-01

In this paper, aggregate migration patterns during fluid concrete castings are studied through experiments, dimensionless approach and numerical modeling. The experimental results obtained on two beams show that gravity induced migration is primarily affecting the coarsest aggregates resulting in a decrease of coarse aggregates volume fraction with the horizontal distance from the pouring point and in a puzzling vertical multi-layer structure. The origin of this multi layer structure is discussed and analyzed with the help of numerical simulations of free surface flow. Our results suggest that it finds its origin in the non Newtonian nature of fresh concrete and that increasing casting rate shall decrease the magnitude of gravity induced particle migration.

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.

Acoustics Reveals the Presence of a Macrozooplankton Biocline in the Bay of Biscay in Response to Hydrological Conditions and Predator-Prey Relationships

Science.gov (United States)

Lezama-Ochoa, Ainhoa; Irigoien, Xabier; Chaigneau, Alexis; Quiroz, Zaida; Lebourges-Dhaussy, Anne; Bertrand, Arnaud

2014-01-01

Bifrequency acoustic data, hydrological measurements and satellite data were used to study the vertical distribution of macrozooplankton in the Bay of Biscay in relation to the hydrological conditions and fish distribution during spring 2009. The most noticeable result was the observation of a ‘biocline’ during the day i.e., the interface where zooplankton biomass changes more rapidly with depth than it does in the layers above or below. The biocline separated the surface layer, almost devoid of macrozooplankton, from the macrozooplankton-rich deeper layers. It is a specific vertical feature which ties in with the classic diel vertical migration pattern. Spatiotemporal correlations between macrozooplankton and environmental variables (photic depth, thermohaline vertical structure, stratification index and chlorophyll-a) indicate that no single factor explains the macrozooplankton vertical distribution. Rather a set of factors, the respective influence of which varies from region to region depending on the habitat characteristics and the progress of the spring stratification, jointly influence the distribution. In this context, the macrozooplankton biocline is potentially a biophysical response to the search for a particular depth range where light attenuation, thermohaline vertical structure and stratification conditions together provide a suitable alternative to the need for expending energy in reaching deeper water without the risk of being eaten. PMID:24505374

Acoustics reveals the presence of a macrozooplankton biocline in the Bay of Biscay in response to hydrological conditions and predator-prey relationships.

Directory of Open Access Journals (Sweden)

Ainhoa Lezama-Ochoa

Full Text Available Bifrequency acoustic data, hydrological measurements and satellite data were used to study the vertical distribution of macrozooplankton in the Bay of Biscay in relation to the hydrological conditions and fish distribution during spring 2009. The most noticeable result was the observation of a 'biocline' during the day i.e., the interface where zooplankton biomass changes more rapidly with depth than it does in the layers above or below. The biocline separated the surface layer, almost devoid of macrozooplankton, from the macrozooplankton-rich deeper layers. It is a specific vertical feature which ties in with the classic diel vertical migration pattern. Spatiotemporal correlations between macrozooplankton and environmental variables (photic depth, thermohaline vertical structure, stratification index and chlorophyll-a indicate that no single factor explains the macrozooplankton vertical distribution. Rather a set of factors, the respective influence of which varies from region to region depending on the habitat characteristics and the progress of the spring stratification, jointly influence the distribution. In this context, the macrozooplankton biocline is potentially a biophysical response to the search for a particular depth range where light attenuation, thermohaline vertical structure and stratification conditions together provide a suitable alternative to the need for expending energy in reaching deeper water without the risk of being eaten.

Acoustics reveals the presence of a macrozooplankton biocline in the Bay of Biscay in response to hydrological conditions and predator-prey relationships.

KAUST Repository

Lezama-Ochoa, Ainhoa; Irigoien, Xabier; Chaigneau, Alexis; Quiroz, Zaida; Lebourges-Dhaussy, Anne; Bertrand, Arnaud

2014-01-01

Bifrequency acoustic data, hydrological measurements and satellite data were used to study the vertical distribution of macrozooplankton in the Bay of Biscay in relation to the hydrological conditions and fish distribution during spring 2009. The most noticeable result was the observation of a 'biocline' during the day i.e., the interface where zooplankton biomass changes more rapidly with depth than it does in the layers above or below. The biocline separated the surface layer, almost devoid of macrozooplankton, from the macrozooplankton-rich deeper layers. It is a specific vertical feature which ties in with the classic diel vertical migration pattern. Spatiotemporal correlations between macrozooplankton and environmental variables (photic depth, thermohaline vertical structure, stratification index and chlorophyll-a) indicate that no single factor explains the macrozooplankton vertical distribution. Rather a set of factors, the respective influence of which varies from region to region depending on the habitat characteristics and the progress of the spring stratification, jointly influence the distribution. In this context, the macrozooplankton biocline is potentially a biophysical response to the search for a particular depth range where light attenuation, thermohaline vertical structure and stratification conditions together provide a suitable alternative to the need for expending energy in reaching deeper water without the risk of being eaten.

Acoustics reveals the presence of a macrozooplankton biocline in the Bay of Biscay in response to hydrological conditions and predator-prey relationships.

KAUST Repository

Lezama-Ochoa, Ainhoa

2014-02-04

Bifrequency acoustic data, hydrological measurements and satellite data were used to study the vertical distribution of macrozooplankton in the Bay of Biscay in relation to the hydrological conditions and fish distribution during spring 2009. The most noticeable result was the observation of a \\'biocline\\' during the day i.e., the interface where zooplankton biomass changes more rapidly with depth than it does in the layers above or below. The biocline separated the surface layer, almost devoid of macrozooplankton, from the macrozooplankton-rich deeper layers. It is a specific vertical feature which ties in with the classic diel vertical migration pattern. Spatiotemporal correlations between macrozooplankton and environmental variables (photic depth, thermohaline vertical structure, stratification index and chlorophyll-a) indicate that no single factor explains the macrozooplankton vertical distribution. Rather a set of factors, the respective influence of which varies from region to region depending on the habitat characteristics and the progress of the spring stratification, jointly influence the distribution. In this context, the macrozooplankton biocline is potentially a biophysical response to the search for a particular depth range where light attenuation, thermohaline vertical structure and stratification conditions together provide a suitable alternative to the need for expending energy in reaching deeper water without the risk of being eaten.

Unexpected Positive Buoyancy in Deep Sea Sharks, Hexanchus griseus, and a Echinorhinus cookei.

Science.gov (United States)

Nakamura, Itsumi; Meyer, Carl G; Sato, Katsufumi

2015-01-01

We do not expect non air-breathing aquatic animals to exhibit positive buoyancy. Sharks, for example, rely on oil-filled livers instead of gas-filled swim bladders to increase their buoyancy, but are nonetheless ubiquitously regarded as either negatively or neutrally buoyant. Deep-sea sharks have particularly large, oil-filled livers, and are believed to be neutrally buoyant in their natural habitat, but this has never been confirmed. To empirically determine the buoyancy status of two species of deep-sea sharks (bluntnose sixgill sharks, Hexanchus griseus, and a prickly shark, Echinorhinus cookei) in their natural habitat, we used accelerometer-magnetometer data loggers to measure their swimming performance. Both species of deep-sea sharks showed similar diel vertical migrations: they swam at depths of 200-300 m at night and deeper than 500 m during the day. Ambient water temperature was around 15°C at 200-300 m but below 7°C at depths greater than 500 m. During vertical movements, all deep-sea sharks showed higher swimming efforts during descent than ascent to maintain a given swimming speed, and were able to glide uphill for extended periods (several minutes), indicating that these deep-sea sharks are in fact positively buoyant in their natural habitats. This positive buoyancy may adaptive for stealthy hunting (i.e. upward gliding to surprise prey from underneath) or may facilitate evening upward migrations when muscle temperatures are coolest, and swimming most sluggish, after spending the day in deep, cold water. Positive buoyancy could potentially be widespread in fish conducting daily vertical migration in deep-sea habitats.

Nine-component vertical seismic profiling at Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Balch, A.H.; Erdemir, C.; Spengler, R.W.; Hunter, W.C.

1996-01-01

Nine-component vertical seismic profiling has been conducted at the UE-25 UZ No. 16 borehole at Yucca Mountain, Nevada, in support of investigation of the hydrologic significance of fault and fracture systems. A large data set from multi-component sources and receivers allows state-of-the-art advances in processing using polarization filtering and reverse time migration, for enhanced interpretation of geologic features

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

KAUST Repository

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

2014-01-01

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

Diel predator activity drives a dynamic landscape of fear

Science.gov (United States)

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.

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

Science.gov (United States)

Kowalczyk, Marcin; Lupton, David W

2014-05-19

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

Two-Way Outsourcing, International Migration, and Wage Inequality

OpenAIRE

Morihiro Yomogida; Laixun Zhao

2009-01-01

This paper develops a general equilibrium model with a vertical production structure to examine the relationship between offshore outsourcing and international migration,especially emphasizing their effects on the wages of skilled and unskilled workers. Two-way outsourcing (simultaneous insourcing and outsourcing) in skilled-labor intensive services arises due to product differentiation and scale economies, and outsourcing in unskilled-labor intensive processing occurs because of factor endow...

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

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

Science.gov (United States)

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

2007-04-25

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

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

Science.gov (United States)

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

2013-08-14

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

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

Science.gov (United States)

Jasiński, Radomir

2017-08-01

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

Testing the effects of the numerical implementation of water migration on models of subduction dynamics

Science.gov (United States)

Quinquis, M. E. T.; Buiter, S. J. H.

2013-10-01

Subduction of oceanic lithosphere brings water into Earth's upper mantle. Previous numerical studies have shown how slab dehydration and mantle hydration can impact the dynamics of a subduction system by allowing a more vigorous mantle flow and promoting localisation of deformation in lithosphere and mantle. The depths at which dehydration reactions occur in the hydrated portions of the slab are well constrained in these models by thermodynamic calculations. However, the mechanism by which free water migrates in the mantle is incompletely known. Therefore, models use different numerical schemes to model the migration of free water. We aim to show the influence of the numerical scheme of free water migration on the dynamics of the upper mantle and more specifically the mantle wedge. We investigate the following three migration schemes with a finite-element model: (1) element-wise vertical migration of free water, occurring independent of the material flow; (2) an imposed vertical free water velocity; and (3) a Darcy velocity, where the free water velocity is calculated as a function of the pressure gradient between water and the surrounding rocks. In addition, the material flow field also moves the free water in the imposed vertical velocity and Darcy schemes. We first test the influence of the water migration scheme using a simple Stokes flow model that simulates the sinking of a cold hydrated cylinder into a hot dry mantle. We find that the free water migration scheme has only a limited impact on the water distribution after 1 Myr in these models. We next investigate slab dehydration and mantle hydration with a thermomechanical subduction model that includes brittle behaviour and viscous water-dependent creep flow laws. Our models show how the bound water distribution is not greatly influenced by the water migration scheme whereas the free water distribution is. We find that a water-dependent creep flow law results in a broader area of hydration in the mantle

Biodiversity and diel variation of the benthohyponeuston: A case study of the Northeast Black Sea

Science.gov (United States)

Vereshchaka, Alexander L.; Anokhina, Ludmila L.

2015-12-01

The neustal is a specific habitat of oceans, which significantly differs in abiotic parameters from the waters below. One of the most significant components of the coastal neustonic fauna is the benthohyponeuston migrating diurnally between benthic and neustonic realms. Data on this fauna are fragmentary and contradictory, partly due to lack of the criteria to distinguish benthohyponeuston from other benthopelagic animals diurnally migrating to the bulk water from the seafloor. We propose a criterion to quantify the degree of aggregation/avoidance of the neustal zone, reveal four distinct ecological groups and describe patterns of their overnight dynamics. Benthohyponeuston appears in open water at sunset, its biomass most rapidly increases one hour after sunset. Cumaceans, mysids and polychaetes make significant contribution during first three hours after sunset. Decapods are important around midnight and 3 h later. Amphipods are significant overnight. By analogy with the benthopelagic species, we define the benthohyponeuston as benthic animals, which are associated with the neustal zone at least at one stage of their life cycle. This association is necessary for reproduction, dispersal or feeding - that represent three basic pathways connecting neustonic and benthic/benthopelagic coastal communities below. The data on benthohyponeuston and patterns of its overnight dynamics will help in a better understanding of vertical migrations in the coastal zone and in estimating diurnal fluxes of organic matter.

Diel resource partitioning among juvenile Atlantic Salmon, Brown Trout, and Rainbow Trout during summer

Science.gov (United States)

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.

Diastereoselective Synthesis of Novel Heterocyclic Scaffolds through Tandem Petasis 3-Component/Intramolecular Diels-Alder and ROM-RCM Reactions

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...

Trace elements and stable isotope ratios (δ13C and δ15N) in fish from deep-waters of the Sulu Sea and the Celebes Sea

International Nuclear Information System (INIS)

Asante, Kwadwo Ansong; Agusa, Tetsuro; Kubota, Reiji; Mochizuki, Hiroko; Ramu, Karri; Nishida, Shuhei; Ohta, Suguru; Yeh, Hsin-ming; Subramanian, Annamalai; Tanabe, Shinsuke

2010-01-01

Trace elements (TEs) and stable isotope ratios (δ 15 N and δ 13 C) were analyzed in fish from deep-water of the Sulu Sea, the Celebes Sea and the Philippine Sea. Concentrations of V and Pb in pelagic fish from the Sulu Sea were higher than those from the Celebes Sea, whereas the opposite trend was observed for δ 13 C. High concentrations of Zn, Cu and Ag were found in non-migrant fish in deep-water, while Rb level was high in fish which migrate up to the epipelagic zone, probably resulting from differences in background levels of these TEs in each water environment or function of adaptation to deep-water by migrant and non-migrant species. Arsenic level in the Sulu Sea fish was positively correlated with δ 15 N, indicating biomagnification of arsenic. To our knowledge, this is the first study on relationship between diel vertical migration and TE accumulation in deep-water fish.

Seasonal and Diel Activity Patterns of Eight Sympatric Mammals in Northern Japan Revealed by an Intensive Camera-Trap Survey.

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.

Assessment of brine migration risks along vertical pathways due to CO2 injection

Science.gov (United States)

Kissinger, Alexander; Class, Holger

2015-04-01

Global climate change, shortage of resources and the growing usage of renewable energy sources has lead to a growing demand for the utilization of subsurface systems. Among these competing uses are Carbon Capture and Storage (CCS), geothermal energy, nuclear waste disposal, 'renewable' methane or hydrogen storage as well as the ongoing production of fossil resources like oil, gas and coal. Additionally, these technologies may also create conflicts with essential public interests such as water supply. For example, the injection of CO2 into the subsurface causes an increase in pressure reaching far beyond the actual radius of influence of the CO2 plume, potentially leading to large amounts of displaced salt water. In this work we focus on the large scale impacts of CO2 storage on brine migration but the methodology and the obtained results may also apply to other fields like waste water disposal, where large amounts of fluid are injected into the subsurface. In contrast to modeling on the reservoir scale the spatial scale required for this work is much larger in both vertical and lateral direction, as the regional hydrogeology has to be considered. Structures such as fault zones, hydrogeological windows in the Rupelian clay or salt domes are considered as potential pathways for displaced fluids into shallow systems and their influence has to be taken into account. We put the focus of our investigations on the latter type of scenario, since there is still a poor understanding of the role that salt diapirs would play in CO2 storage projects. As there is hardly any field data available on this scale, we compare different levels of model complexity in order to identify the relevant processes for brine displacement and simplify the modeling process wherever possible, for example brine injection vs. CO2 injection, simplified geometries vs. the complex formation geometry and the role of salt induced density differences on flow. Further we investigate the impact of the

Geographic differences in vertical connectivity in the Caribbean coral Montastraea cavernosa despite high levels of horizontal connectivity at shallow depths.

Science.gov (United States)

Serrano, X; Baums, I B; O'Reilly, K; Smith, T B; Jones, R J; Shearer, T L; Nunes, F L D; Baker, A C

2014-09-01

The deep reef refugia hypothesis proposes that deep reefs can act as local recruitment sources for shallow reefs following disturbance. To test this hypothesis, nine polymorphic DNA microsatellite loci were developed and used to assess vertical connectivity in 583 coral colonies of the Caribbean depth-generalist coral Montastraea cavernosa. Samples were collected from three depth zones (≤10, 15-20 and ≥25 m) at sites in Florida (within the Upper Keys, Lower Keys and Dry Tortugas), Bermuda, and the U.S. Virgin Islands. Migration rates were estimated to determine the probability of coral larval migration from shallow to deep and from deep to shallow. Finally, algal symbiont (Symbiodinium spp.) diversity and distribution were assessed in a subset of corals to test whether symbiont depth zonation might indicate limited vertical connectivity. Overall, analyses revealed significant genetic differentiation by depth in Florida, but not in Bermuda or the U.S. Virgin Islands, despite high levels of horizontal connectivity between these geographic locations at shallow depths. Within Florida, greater vertical connectivity was observed in the Dry Tortugas compared to the Lower or Upper Keys. However, at all sites, and regardless of the extent of vertical connectivity, migration occurred asymmetrically, with greater likelihood of migration from shallow to intermediate/deep habitats. Finally, most colonies hosted a single Symbiodinium type (C3), ruling out symbiont depth zonation of the dominant symbiont type as a structuring factor. Together, these findings suggest that the potential for shallow reefs to recover from deep-water refugia in M. cavernosa is location-specific, varying among and within geographic locations likely as a consequence of local hydrology. © 2014 John Wiley & Sons Ltd.

Seismic patterns and migration history of submarine fan channels in deep-water area, Niger Delta, West Africa

Science.gov (United States)

Zhang, Guotao; Zhang, Shangfeng; Li, Yuan

2015-04-01

The channels of deep-water submarine fan under Niger delta slope are characterized by large dimensions special deposition positions and complex formation processes, its geographical location and sedimentary environment also hinder the research and exploration development. According to the strata slicing, RMS amplitude attribute and other techniques, we exhibit the platforms patterns of channels at different period, and based on the analysis of internal architecture and deformation history of channel-leveed systems, migration and evolution process of channel systems could be understood accurately. A great quantity of isolated channels develop in middle Miocene and aggrading streams in late Miocene, which generating because of large scale of turbidity caused by the drop of second order sea-level, which characterized by vertical accretion at smooth channel, while vertical accretion and lateral migration at bend. Evolution of channel systems can be divided into three stages: the initial erosion, erosion and filling alternately, and abandoned stage. With these three stages, the sinuosity of channel change from moderate to high, then decrease. Incision and filling of channels, being during the three development phases, is the driving force of meander-loops migration, which promote three kinds of migration patterns: lateral, down-system and combination migration. The research provides theoretical basis for high-precision prediction and evaluation of deep-water reservoir.

Effects of food type on diel behaviours of common carp Cyprinus carpio in simulated aquaculture pond conditions

NARCIS (Netherlands)

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

Effects of particle migration on the features of their transport by tidal currents in a region of freshwater influence

Science.gov (United States)

Korotenko, K. A.; Sentchev, A. V.

2008-10-01

Using a combined model that couples a three-dimensional ocean circulation model, a model for tidal currents, and a model for particle transport, the structure of the velocity field of the tidal current and the transport of particles migrating over the vertical were studied in the zone of the influence of the riverine runoff in the eastern part of the English Channel. It was found that the interaction between the tidal current and the baroclinic flow formed by the riverine runoff off the northeastern coast of France generates a steady-state intensive (˜0.3 m/s) residual current in the zone of the effect of the riverine runoff. In order to assess the influence of different types of particle migration (which simulate ichthyoplankton) on the processes of their transport in the region under consideration, we performed numerical experiments with particle clusters, for which parameterization of their migration was implemented on the basis of the field observations over the proper vertical movements of different types of ichthyoplankton. The experiments showed that the distribution of the fields of the particle concentrations and the velocities of their movements depend not only on the background hydrophysical conditions but also on the character of the vertical migration of the particles. In this paper, a comparison between the results of the modeling and those of the field observations in the region under consideration are presented.

Movement patterns and trajectories of ovigerous blue crabs Callinectes sapidus during the spawning migration

Science.gov (United States)

Carr, Sarah D.; Tankersley, Richard A.; Hench, James L.; Forward, Richard B.; Luettich, Richard A.

2004-08-01

Female blue crabs ( Callinectes sapidus Rathbun) migrate from low salinity estuarine regions to high salinity regions near the ocean to release larvae. During this migration, ovigerous females use ebb-tide transport, a vertical migratory behavior in which they ascend into the water column during ebb tides, to move seaward to larval release areas. In order to determine the relationship of ebb-tide vertical migrations to local currents and the influence of these vertical migrations on the horizontal transport of blue crabs in the estuary, ovigerous females with mature embryos (˜1-3 days from hatching) were tracked near Beaufort Inlet, North Carolina (USA), in July and August 2001 and 2002. Crabs were tagged and tracked using ultrasonic telemetry, and currents near the crabs were measured simultaneously with a shipboard acoustic Doppler current profiler. During the two seasons, eight crabs were successfully tracked for periods ranging from 3.9-37.0 h and for distances ranging from 1.9-10.6 km. All crabs migrated seaward during the tracking periods. Crabs moved episodically during all tidal phases with periods of movement on the order of minutes to an hour. They moved with local currents in terms of both speed and direction during ebb tides, consistent with ebb-tide transport, and moved down-estuary (seaward) in opposition to local currents during flood tides. The percentage of time that crabs were active was higher during night ebb tides than during day ebb tides or flood tides and increased with increasing ebb-tide current speed. Mean migratory speeds were 0.11, 0.04, 0.08 and 0.02 m s -1 during night ebb, night flood, day ebb and day flood tides, respectively, and net migratory speeds were on the order of 5 km day -1. Due to the episodic nature of the crabs' movements, the total distances that crabs traveled during ebb tides ranged from 10-40% of the distances that passive particles could have traveled under the same conditions.

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

Science.gov (United States)

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

2012-06-06

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

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

Science.gov (United States)

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

2018-02-16

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

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

Science.gov (United States)

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

2017-02-17

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

Testing the effects of basic numerical implementations of water migration on models of subduction dynamics

Science.gov (United States)

Quinquis, M. E. T.; Buiter, S. J. H.

2014-06-01

Subduction of oceanic lithosphere brings water into the Earth's upper mantle. Previous numerical studies have shown how slab dehydration and mantle hydration can impact the dynamics of a subduction system by allowing a more vigorous mantle flow and promoting localisation of deformation in the lithosphere and mantle. The depths at which dehydration reactions occur in the hydrated portions of the slab are well constrained in these models by thermodynamic calculations. However, computational models use different numerical schemes to simulate the migration of free water. We aim to show the influence of the numerical scheme of free water migration on the dynamics of the upper mantle and more specifically the mantle wedge. We investigate the following three simple migration schemes with a finite-element model: (1) element-wise vertical migration of free water, occurring independent of the flow of the solid phase; (2) an imposed vertical free water velocity; and (3) a Darcy velocity, where the free water velocity is a function of the pressure gradient caused by the difference in density between water and the surrounding rocks. In addition, the flow of the solid material field also moves the free water in the imposed vertical velocity and Darcy schemes. We first test the influence of the water migration scheme using a simple model that simulates the sinking of a cold, hydrated cylinder into a dry, warm mantle. We find that the free water migration scheme has only a limited impact on the water distribution after 1 Myr in these models. We next investigate slab dehydration and mantle hydration with a thermomechanical subduction model that includes brittle behaviour and viscous water-dependent creep flow laws. Our models demonstrate that the bound water distribution is not greatly influenced by the water migration scheme whereas the free water distribution is. We find that a bound water-dependent creep flow law results in a broader area of hydration in the mantle wedge, which

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.

An effective algorithm for approximating adaptive behavior in seasonal environments

DEFF Research Database (Denmark)

Sainmont, Julie; Andersen, Ken Haste; Thygesen, Uffe Høgsbro

2015-01-01

Behavior affects most aspects of ecological processes and rates, and yet modeling frameworks which efficiently predict and incorporate behavioral responses into ecosystem models remain elusive. Behavioral algorithms based on life-time optimization, adaptive dynamics or game theory are unsuited...... for large global models because of their high computational demand. We compare an easily integrated, computationally efficient behavioral algorithm known as Gilliam's rule against the solution from a life-history optimization. The approximation takes into account only the current conditions to optimize...... behavior; the so-called "myopic approximation", "short sighted", or "static optimization". We explore the performance of the myopic approximation with diel vertical migration (DVM) as an example of a daily routine, a behavior with seasonal dependence that trades off predation risk with foraging...

At-sea behavior varies with lunar phase in a nocturnal pelagic seabird, the swallow-tailed gull

Science.gov (United States)

Cruz, Sebastian M.; Hooten, Mevin; Huyvaert, Kathryn P.; Proaño, Carolina B.; Anderson, David J.; Afanasyev, Vsevolod; Wikelski, Martin

2013-01-01

Strong and predictable environmental variability can reward flexible behaviors among animals. We used long-term records of activity data that cover several lunar cycles to investigate whether behavior at-sea of swallow-tailed gulls Creagrus furcatus, a nocturnal pelagic seabird, varied with lunar phase in the Galápagos Islands. A Bayesian hierarchical model showed that nighttime at-sea activity of 37 breeding swallow-tailed gulls was clearly associated with changes in moon phase. Proportion of nighttime spent on water was highest during darker periods of the lunar cycle, coinciding with the cycle of the diel vertical migration (DVM) that brings prey to the sea surface at night. Our data show that at-sea behavior of a tropical seabird can vary with environmental changes, including lunar phase.

Scoping calculations for canister-tunnel migration of corrodants, oxidants and radionuclides

International Nuclear Information System (INIS)

Shaw, W.; Worth, D.

1992-03-01

This report presents the mathematical models and results obtained for a set of scooping calculations which estimate the possible extent of the vertical migration of canister corrodants, oxidants (forming a redox front) and radionuclides between a copper canister containing spent nuclear fuel, and an overlying emplacement tunnel. The KBS-3 concept for the disposal of spent nuclear fuel is copper canisters, vertically emplaced in deposition holes bored in the floor of a tunnel, situated deep underground. The deposition holes are filled with a buffer of bentonite and the tunnel is backfilled with a mixture of sand and bentonite. (au)

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

Science.gov (United States)

Pacheco, Joshua J.; Davis, Mark E.

2014-01-01

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

Diel hysteresis between soil respiration and soil temperature in a biological soil crust covered desert ecosystem.

Science.gov (United States)

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.

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

NARCIS (Netherlands)

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

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

On diel variability of marine sediment backscattering properties caused by microphytobenthos photosynthesis: Impact of environmental factors

Science.gov (United States)

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.

Parameters Affecting 137Cs Migration within Soil Profile

International Nuclear Information System (INIS)

Sefien, S.M.; Ibrahim, A.S.; Abdelmalik, W.E.Y.

2013-01-01

Some studies have been carried out on the adsorption, distribution and migration of 137 Cs within soils of the area in the vicinity of the Nuclear Research Centre, Egypt, and Ismailia Canal. The soil physicochemical and mineralogical characteristics were carried out and indicated that the soil samples consisted mainly of sand fraction (quartz) and silt fractions (semctite minerals). The kinetics of caesium adsorption and its adsorption isotherms for the tested soils were also studied. The sorption of 137 Cs on soil minerals markedly affects its migration rate. The natural background of both locations of study indicated that the amounts of 137 Cs present in the reactor site were found to be originated from the fallout and from the external contamination which affected the background level. The 137 Cs activity at the canal site was found to be 20.01 Bq/m 2 .cm, while that around the reactor site were found to be 231.15 Bq/m2.cm which may be originating from the fallout and from external contamination which affect the background level at that location. The activity in the canal soil which amounted to 20.01 Bq/m2/cm (0.87 Bq/kg) is about that of background.Based on the distribution data, the vertical distribution of 137 Cs has been studied for soil in both locations (the vicinity of the Nuclear Research Centre (NRC) and Ismailia canal). The vertical migration rates of 137 Cs were calculated for soil samples selected from different locations. These rates were found to be 0.056 and 0.031 cm/year for the reactor and canal site respectively.

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

Science.gov (United States)

Reiner, Thomas; Zeglis, Brian M

2014-04-01

The inverse electron-demand Diels-Alder (IEDDA) cycloaddition between 1,2,4,5-tetrazines and strained alkene dienophiles is an emergent variety of catalyst-free 'click' chemistry that has the potential to have a transformational impact on the synthesis and development of radiopharmaceuticals. The ligation is selective, rapid, high-yielding, clean, and bioorthogonal and, since its advent in 2008, has been employed in a wide variety of chemical settings. In radiochemistry, the reaction has proven particularly useful with (18)  F and has already been utilized to create a number of (18)  F-labeled agents, including the PARP1-targeting small molecule (18)  F-AZD2281, the αv β3 integrin-targeting peptide (18)  F-RGD, and the GLP-1-targeting peptide (18)  F-exendin. The inherent flexibility of the ligation has also been applied to the construction of radiometal-based probes, specifically the development of a modular strategy for the synthesis of radioimmunoconjugates that effectively eliminates variability in the construction of these agents. Further, the exceptional speed and biorthogonality of the reaction have made it especially promising in the realm of in vivo pretargeted imaging and therapy, and pretargeted imaging strategies based on the isotopes (111) In, (18)  F, and (64) Cu have already proven capable of producing images with high tumor contrast and low levels of uptake in background, nontarget organs. Ultimately, the characteristics of inverse electron-demand Diels-Alder click chemistry make it almost uniquely well-suited for radiochemistry, and although the field is young, this ligation has the potential to make a tremendous impact on the synthesis, development, and study of novel radiopharmaceuticals. Copyright © 2013 John Wiley & Sons, Ltd.

RADIALLY MAGNETIZED PROTOPLANETARY DISK: VERTICAL PROFILE

International Nuclear Information System (INIS)

Russo, Matthew; Thompson, Christopher

2015-01-01

This paper studies the response of a thin accretion disk to an external radial magnetic field. Our focus is on protoplanetary disks (PPDs), which are exposed during their later evolution to an intense, magnetized wind from the central star. A radial magnetic field is mixed into a thin surface layer, wound up by the disk shear, and pushed downward by a combination of turbulent mixing and ambipolar and ohmic drift. The toroidal field reaches much greater strengths than the seed vertical field that is usually invoked in PPD models, even becoming superthermal. Linear stability analysis indicates that the disk experiences the magnetorotational instability (MRI) at a higher magnetization than a vertically magnetized disk when both the effects of ambipolar and Hall drift are taken into account. Steady vertical profiles of density and magnetic field are obtained at several radii between 0.06 and 1 AU in response to a wind magnetic field B r ∼ (10 −4 –10 −2 )(r/ AU) −2 G. Careful attention is given to the radial and vertical ionization structure resulting from irradiation by stellar X-rays. The disk is more strongly magnetized closer to the star, where it can support a higher rate of mass transfer. As a result, the inner ∼1 AU of a PPD is found to evolve toward lower surface density. Mass transfer rates around 10 −8 M ⊙ yr −1 are obtained under conservative assumptions about the MRI-generated stress. The evolution of the disk and the implications for planet migration are investigated in the accompanying paper

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

Science.gov (United States)

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

2005-09-01

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

Unexpected Positive Buoyancy in Deep Sea Sharks, Hexanchus griseus, and a Echinorhinus cookei.

Directory of Open Access Journals (Sweden)

Itsumi Nakamura

Full Text Available We do not expect non air-breathing aquatic animals to exhibit positive buoyancy. Sharks, for example, rely on oil-filled livers instead of gas-filled swim bladders to increase their buoyancy, but are nonetheless ubiquitously regarded as either negatively or neutrally buoyant. Deep-sea sharks have particularly large, oil-filled livers, and are believed to be neutrally buoyant in their natural habitat, but this has never been confirmed. To empirically determine the buoyancy status of two species of deep-sea sharks (bluntnose sixgill sharks, Hexanchus griseus, and a prickly shark, Echinorhinus cookei in their natural habitat, we used accelerometer-magnetometer data loggers to measure their swimming performance. Both species of deep-sea sharks showed similar diel vertical migrations: they swam at depths of 200-300 m at night and deeper than 500 m during the day. Ambient water temperature was around 15°C at 200-300 m but below 7°C at depths greater than 500 m. During vertical movements, all deep-sea sharks showed higher swimming efforts during descent than ascent to maintain a given swimming speed, and were able to glide uphill for extended periods (several minutes, indicating that these deep-sea sharks are in fact positively buoyant in their natural habitats. This positive buoyancy may adaptive for stealthy hunting (i.e. upward gliding to surprise prey from underneath or may facilitate evening upward migrations when muscle temperatures are coolest, and swimming most sluggish, after spending the day in deep, cold water. Positive buoyancy could potentially be widespread in fish conducting daily vertical migration in deep-sea habitats.

Computational design of a Diels-Alderase from a thermophilic esterase: the importance of dynamics

Science.gov (United States)

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).

The innate origin of radial and vertical gradients in a simulated galaxy disc

Science.gov (United States)

Navarro, Julio F.; Yozin, Cameron; Loewen, Nic; Benítez-Llambay, Alejandro; Fattahi, Azadeh; Frenk, Carlos S.; Oman, Kyle A.; Schaye, Joop; Theuns, Tom

2018-05-01

We examine the origin of radial and vertical gradients in the age/metallicity of the stellar component of a galaxy disc formed in the APOSTLE cosmological hydrodynamical simulations. Some of these gradients resemble those in the Milky Way, where they have sometimes been interpreted as due to internal evolution, such as scattering off giant molecular clouds, radial migration driven by spiral patterns, or orbital resonances with a bar. Secular processes play a minor role in the simulated galaxy, which lacks strong spiral or bar patterns, and where such gradients arise as a result of the gradual enrichment of a gaseous disc that is born thick but thins as it turns into stars and settles into centrifugal equilibrium. The settling is controlled by the feedback of young stars; which links the star formation, enrichment, and equilibration time-scales, inducing radial and vertical gradients in the gaseous disc and its descendent stars. The kinematics of coeval stars evolve little after birth and provide a faithful snapshot of the gaseous disc structure at the time of their formation. In this interpretation, the age-velocity dispersion relation would reflect the gradual thinning of the disc rather than the importance of secular orbit scattering; the outward flaring of stars would result from the gas disc flare rather than from radial migration; and vertical gradients would arise because the gas disc gradually thinned as it enriched. Such radial and vertical trends might just reflect the evolving properties of the parent gaseous disc, and are not necessarily the result of secular evolutionary processes.

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

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

NARCIS (Netherlands)

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

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

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

Science.gov (United States)

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

2010-01-01

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

Migration characteristics and early clinical results of the NANOS® short-stem hip arthroplasty.

Science.gov (United States)

Kaipel, Martin; Grabowiecki, Phillip; Sinz, Katrina; Farr, Sebastian; Sinz, Günter

2015-05-01

Femoral short stems promise essential advantages in total hip arthroplasty. Up to now, only short- and midterm clinical studies exist. Data on early stem migration that could predict later aseptic loosening at an early stage are rare. The purpose of this study was to assess migration patterns and clinical outcome 2 years after hip replacement by a metaphyseal anchored cementless short stem. Migration data and clinical results were prospectively assessed in 49 patients. Clinical outcome was measured using the Harris Hip Score (HHS). Migration analyses were performed using the computer-assisted Einzel-Bild-Roentgen-Analyse (EBRA) system. At 2 years after surgery, none of the implants needed revision, and HHS increased from 47.9 up to 98.1. Of 49 patients, 5 (10%) showed increased vertical stem migration (1.5 mm/2a) that might predict late aseptic loosening. Of 49 stems, 44 (90%) showed stable migration patterns indicating a beneficial long-term outcome. Results of this study confirm the excellent clinical data of previous works. Migration patterns strongly suggest that short-stem arthroplasty is not only an innovative but also a reliable strategy in total hip replacement.

The use of satellite tags to redefine movement patterns of spiny dogfish (Squalus acanthias along the U.S. east coast: implications for fisheries management.

Directory of Open Access Journals (Sweden)

Amy E Carlson

Full Text Available Spiny dogfish (Squalus acanthias are assumed to be a highly migratory species, making habitual north-south migrations throughout their northwestern Atlantic United States (U.S. range. Also assumed to be a benthic species, spiny dogfish stock structure is estimated through Northeast Fisheries Science Center (NEFSC bottom-trawl surveys. Recent anomalies in population trends, including a recent four-fold increase in estimated spawning stock biomass, suggest alternative movement patterns could exist for this shark species. To obtain a better understanding of the horizontal and vertical movement dynamics of this species, Microwave Telemetry pop-up satellite archival X-Tags were attached to forty adult spiny dogfish at the northern (Gulf of Maine and southern (North Carolina extents of their core U.S. geographic range. Reconstructed geolocation tracks ranging in lengths from two to 12 months suggest that the seasonal migration patterns appear to be local in nature to each respective northern and southern deployment site, differing from previously published migration paradigms. Differences in distance and direction traveled between seasonal geolocations possibly indicate separate migratory patterns between groups. Kernel utilization distribution models also suggest strong separate core home ranges. Significant differences in seasonal temperature and depths between the two regions further substantiate the possibility of separate regional movement patterns between the two groups. Vertical utilization also suggests distinct diel patterns and that this species may not utilize the benthos as previously thought, potentially decreasing availability to benthic gear.

The use of satellite tags to redefine movement patterns of spiny dogfish (Squalus acanthias) along the U.S. east coast: implications for fisheries management.

Science.gov (United States)

Carlson, Amy E; Hoffmayer, Eric R; Tribuzio, Cindy A; Sulikowski, James A

2014-01-01

Spiny dogfish (Squalus acanthias) are assumed to be a highly migratory species, making habitual north-south migrations throughout their northwestern Atlantic United States (U.S.) range. Also assumed to be a benthic species, spiny dogfish stock structure is estimated through Northeast Fisheries Science Center (NEFSC) bottom-trawl surveys. Recent anomalies in population trends, including a recent four-fold increase in estimated spawning stock biomass, suggest alternative movement patterns could exist for this shark species. To obtain a better understanding of the horizontal and vertical movement dynamics of this species, Microwave Telemetry pop-up satellite archival X-Tags were attached to forty adult spiny dogfish at the northern (Gulf of Maine) and southern (North Carolina) extents of their core U.S. geographic range. Reconstructed geolocation tracks ranging in lengths from two to 12 months suggest that the seasonal migration patterns appear to be local in nature to each respective northern and southern deployment site, differing from previously published migration paradigms. Differences in distance and direction traveled between seasonal geolocations possibly indicate separate migratory patterns between groups. Kernel utilization distribution models also suggest strong separate core home ranges. Significant differences in seasonal temperature and depths between the two regions further substantiate the possibility of separate regional movement patterns between the two groups. Vertical utilization also suggests distinct diel patterns and that this species may not utilize the benthos as previously thought, potentially decreasing availability to benthic gear.

Evaluation of upward migration around a deep injection well

International Nuclear Information System (INIS)

Chia, Yeeping; Chiu, J.

1994-01-01

The long-term containment of injected wastes in the deep subsurface is expected to be achieved under suitable geologic and hydrologic conditions and by the use of competent engineering practices. Field experiences, however, indicate that waste containment may be affected by hydrologic conduits around the injection well. To assess the potential effects of these conduits, upward migration of injected waste is examined through the use of numerical models under various conditions. Test results indicate that without any preferential hydrologic conduits, most of the injected waste moves laterally in the injection interval, whereas only a small amount of waste migrates upward into the containment interval. When vertical fractures in the disturbed zone or defects in the cement seal around the wellbore exist, the contaminant can move rapidly upward along these conduits to an overlying aquifer, from which it migrates in the lateral direction. The contamination of the overlying aquifer that results from the upward migration of injected waste through these conduits cannot be impeded by a thick, low-permeability containment interval. However, when permeable interbeds exist within the containment interval, a significant portion of the waste migrating upward can be diverted laterally before reaching the overlying aquifer. The front of built-up pressure can reach the aquifer or permeable interbed immediately overlying the injection interval through the preferential hydrologic conduits shortly after the injection starts, but it cannot move farther upward because of pressure dissipation in the permeable formation. This study suggests that the injected waste has the potential to migrate upward into overlying formations through preferential migration conduits around the wellbore

Modeling dissolution and volatilization of LNAPL sources migrating on the groundwater table.

Science.gov (United States)

Kim, Jeongkon; Corapcioglu, M Yavuz

2003-08-01

A vertically averaged two-dimensional model was developed to describe areal spreading and migration of light nonaqueous-phase liquids (LNAPLs) introduced into the subsurface by spills or leaks from underground storage tanks. The NAPL transport model was coupled with two-dimensional contaminant transport models to predict contamination of soil gas and groundwater resulting from a LNAPL migrating on the water table. Numerical solutions were obtained by using the finite-difference method. Simulations and sensitivity analyses were conducted with a LNAPL of pure benzene to study LNAPL migration and groundwater contamination. The model was applied to subsurface contamination by jet fuel. Results indicated that LNAPL migration were affected mostly by volatilization. The generation and movement of the dissolved plume was affected by the geology of the site and the free-product plume. Most of the spilled mass remained as a free LNAPL phase 20 years after the spill. The migration of LNAPL for such a long period resulted in the contamination of both groundwater and a large volume of soil.

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

Science.gov (United States)

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

2012-09-07

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

Resolution limits of migration and linearized waveform inversion images in a lossy medium

KAUST Repository

Schuster, Gerard T.; Dutta, Gaurav; Li, Jing

2017-01-01

The vertical-and horizontal-resolution limits Delta x(lossy) and Delta z(lossy) of post-stack migration and linearized waveform inversion images are derived for lossy data in the far-field approximation. Unlike the horizontal resolution limit Delta x proportional to lambda z/L in a lossless medium which linearly worsens in depth z, Delta x(lossy) proportional to z(2)/QL worsens quadratically with depth for a medium with small Q values. Here, Q is the quality factor, lambda is the effective wavelength, L is the recording aperture, and loss in the resolution formulae is accounted for by replacing lambda with z/Q. In contrast, the lossy vertical-resolution limit Delta z(lossy) only worsens linearly in depth compared to Delta z proportional to lambda for a lossless medium. For both the causal and acausal Q models, the resolution limits are linearly proportional to 1/Q for small Q. These theoretical predictions are validated with migration images computed from lossy data.

Resolution limits of migration and linearized waveform inversion images in a lossy medium

KAUST Repository

Schuster, Gerard T.

2017-03-10

The vertical-and horizontal-resolution limits Delta x(lossy) and Delta z(lossy) of post-stack migration and linearized waveform inversion images are derived for lossy data in the far-field approximation. Unlike the horizontal resolution limit Delta x proportional to lambda z/L in a lossless medium which linearly worsens in depth z, Delta x(lossy) proportional to z(2)/QL worsens quadratically with depth for a medium with small Q values. Here, Q is the quality factor, lambda is the effective wavelength, L is the recording aperture, and loss in the resolution formulae is accounted for by replacing lambda with z/Q. In contrast, the lossy vertical-resolution limit Delta z(lossy) only worsens linearly in depth compared to Delta z proportional to lambda for a lossless medium. For both the causal and acausal Q models, the resolution limits are linearly proportional to 1/Q for small Q. These theoretical predictions are validated with migration images computed from lossy data.

Larval biology of the crab Rhithropanopeus harrisii (Gould): a synthesis.

Science.gov (United States)

Forward, Richard B

2009-06-01

This synthesis reviews the physiological ecology and behavior of larvae of the benthic crab Rhithropanopeus harrisii, which occurs in low-salinity areas of estuaries. Larvae are released rhythmically around the time of high tide in tidal estuaries and in the 2-h interval after sunset in nontidal estuaries. As in most subtidal crustaceans, the timing of larval release is controlled by the developing embryos, which release peptide pheromones that stimulate larval release behavior by the female to synchronize the time of egg hatching. Larvae pass through four zoeal stages and a postlarval or megalopal stage that are planktonic before metamorphosis. They are retained near the adult population by means of an endogenous tidal rhythm in vertical migration. Larvae have several safeguards against predation: they undergo nocturnal diel vertical migration (DVM) and have a shadow response to avoid encountering predators, and they bear long spines as a deterrent. Photoresponses during DVM and the shadow response are enhanced by exposure to chemical cues from the mucus of predator fishes and ctenophores. The primary visual pigment has a spectral sensitivity maximum at about 500 nm, which is typical for zooplankton and matches the ambient spectrum at twilight. Larvae can detect vertical gradients in temperature, salinity, and hydrostatic pressure, which are used for depth regulation and avoidance of adverse environmental conditions. Characteristics that are related to the larval habitat and are common to other crab larval species are considered.

Observations of the Hawaiian Mesopelagic Boundary Community in Daytime and Nighttime Habitats Using Estimated Backscatter

Directory of Open Access Journals (Sweden)

Comfort CM

2017-07-01

Full Text Available The Hawaiian mesopelagic boundary community is a slope-associated assemblage of micronekton that undergoes diel migrations along the slopes of the islands, residing at greater depths during the day and moving upslope to forage in shallower water at night. The timing of these migrations may be influenced by environmental factors such as moon phase or ambient light. To investigate the movements of this community, we examined echo intensity data from acoustic Doppler current profilers (ADCPs deployed at shallow and deep sites on the southern slope of Oahu, Hawaii. Diel changes in echo intensity (and therefore in estimated backscatter were observed and determined to be caused, at least in part, by the horizontal migration of the mesopelagic boundary community. Generalized additive modeling (GAM was used to assess the impact of environmental factors on the migration timing. Sunset time and lunar illumination were found to be significant factors. Movement speeds of the mesopelagic boundary community were estimated at 1.25–1.99 km h-1 (35–55 cm s-1. The location at which the migrations were observed is the future site of a seawater air conditioning system, which will cause artificial upwelling at our shallow observation site and may cause animal entrainment at the seawater intake near our deep water observation site. This study is the first to observe the diel migration of the mesopelagic boundary community on southern Oahu in both deep and shallow parts of the habitat, and it is also the first to examine migration trends over long time scales, which allows a better assessment of the effects of seasons and lunar illumination on micronekton migrations. Understanding the driving mechanisms of mesopelagic boundary community behavior will increase our ability to assess and manage coastal ecosystems in the face of increasing anthropogenic impacts.

Estimates of potential radionuclide migration at the Bullion site

International Nuclear Information System (INIS)

Brikowski, T.H.

1992-04-01

The Bullion site in Area 20 of the Nevada Test Site has been selected for an intensive study of the hydrologic consequences of underground testing, including subsequent radionuclide migration. The bulk of the chimney and cavity lie in zeolitized tuffs of low hydraulic conductivity, while the base of the cavity may extend downward into more conductive rhyolite flows. A mathematical analog to the Bullion setting is used here to estimate expected radionuclide migration rates and concentrations. Because of a lack of hydrologic data at the site, two contrasting scenarios are considered. The first is downward-transport, in which downward hydraulic gradients flush chimney contents into the conductive underlying units, enhancing migration. The other is upward-transport, in which upward gradients tend to drive chimney contents into the low-conductivity zeolitized tuffs, discouraging migration. In the downward-transport scenario, radionuclide travel times and concentrations are predicted to be similar to those encountered at Cheshire, requiring approximately 10 years to reach a proposed well 300 m downgradient. The upward transport scenario yields predicted travel times on the order of 2,000 years to the downgradient well. The most likely scenario is a combination of these results, with vertical movement playing a limited role. Radionuclides injected directly into the rhyolites should migrate laterally very quickly, with travel times as in the downward-transport scenario. Those in the zeolitized tuff-walled portion of the chimney should migrate extremely slowly, as in the upward-transport scenario

Hypoxia Tolerance and Metabolic Suppression in Oxygen Minimum Zone Euphausiids: Implications for Ocean Deoxygenation and Biogeochemical Cycles

KAUST Repository

Seibel, Brad A.

2016-08-10

The effects of regional variations in oxygen and temperature levels with depth were assessed for the metabolism and hypoxia tolerance of dominant euphausiid species. The physiological strategies employed by these species facilitate prediction of changing vertical distributions with expanding oxygen minimum zones and inform estimates of the contribution of vertically migrating species to biogeochemical cycles. The migrating species from the Eastern Tropical Pacific (ETP), Euphausia eximia and Nematoscelis gracilis, tolerate a Partial Pressure (PO2) of 0.8 kPa at 10 °C (∼15 µM O2) for at least 12 h without mortality, while the California Current species, Nematoscelis difficilis, is incapable of surviving even 2.4 kPa PO2 (∼32 µM O2) for more than 3 h at that temperature. Euphausia diomedeae from the Red Sea migrates into an intermediate oxygen minimum zone, but one in which the temperature at depth remains near 22 °C. Euphausia diomedeae survived 1.6 kPa PO2 (∼22 µM O2) at 22 °C for the duration of six hour respiration experiments. Critical oxygen partial pressures were estimated for each species, and, for E. eximia, measured via oxygen consumption (2.1 kPa, 10 °C, n = 2) and lactate accumulation (1.1 kPa, 10 °C). A primary mechanism facilitating low oxygen tolerance is an ability to dramatically reduce energy expenditure during daytime forays into low oxygen waters. The ETP and Red Sea species reduced aerobic metabolism by more than 50% during exposure to hypoxia. Anaerobic glycolytic energy production, as indicated by whole-animal lactate accumulation, contributed only modestly to the energy deficit. Thus, the total metabolic rate was suppressed by ∼49–64%. Metabolic suppression during diel migrations to depth reduces the metabolic contribution of these species to vertical carbon and nitrogen flux (i.e., the biological pump) by an equivalent amount. Growing evidence suggests that metabolic suppression is a widespread strategy among migrating

Studies on the migration rule and mechanism of radon and its daughters

International Nuclear Information System (INIS)

Jia Wenyi; Fang Fang; Zhou Rongsheng; Ma Yingjie; Qiu Yuande; Hou Xinsheng; Wu Yunping; Zu Xiulan; Wang Xiaoqin

2000-01-01

By using very precise, highly sensitive, static accumulated, easily repeated CD-1 α-cup, the migration rule and mechanism of radon and its daughters was studied. Significant results were obtained: (1) Under laboratory conditions, the vertical component of migration of radon and its daughters was much greater than the horizontal component, the former was over 90% and the latter was less than 10%. (2) Despite the very big specific gravity of radon and its daughters, the descending component of migration was less than 45%, while the ascending component was more than 45%. (3) After α-particles (emitted from radon and its daughters) being slowed down. 4 He combined with the radon and its daughters to form clusters. When the density of the cluster was less than that of the air, the self-ascending would occur

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

Science.gov (United States)

Imada, Yasushi; Okada, Yohei; Chiba, Kazuhiro

2018-01-01

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

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

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.

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

Science.gov (United States)

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

2009-12-07

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

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

Directory of Open Access Journals (Sweden)

Mujeeb A. Sultan

2016-01-01

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

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

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.

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

Science.gov (United States)

Baar, Marsha R.; Wustholz, Kristin

2005-01-01

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

Organizing vertical layout environments: a forward-looking development strategy for high-rise building projects

Science.gov (United States)

Magay, A. A.; Bulgakova, E. A.; Zabelina, S. A.

2018-03-01

The article highlights issues surrounding development of high rise buildings. With the rapid increase of the global population there has been a trend for people to migrate into megacities and has caused the expansion of big city territories. This trend, coupled with the desire for a comfortable living environment, has resulted in numerous problems plaguing the megacity. This article proposes that a viable solution to the problems facing megacities is to create vertical layout environments. Potential options for creating vertical layout environments are set out below including the construction of buildings with atriums. Further, the article puts forth suggested spatial organization of the environment as well as optimal landscaping of high-rise buildings and constructions for the creation of vertical layout environments. Finally, the persuasive reasons for the adoption of vertical layout environments is that it will decrease the amount of developed urban areas, decrease traffic and increase environmental sustainability.

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

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.

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

Science.gov (United States)

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

2018-01-01

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

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

Science.gov (United States)

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

2017-09-20

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

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

KAUST Repository

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

2011-01-01

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

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

KAUST Repository

Li, Jinling

2011-11-14

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

RADIALLY MAGNETIZED PROTOPLANETARY DISK: VERTICAL PROFILE

Energy Technology Data Exchange (ETDEWEB)

Russo, Matthew [Department of Physics, University of Toronto, 60 St. George St., Toronto, ON M5S 1A7 (Canada); Thompson, Christopher [Canadian Institute for Theoretical Astrophysics, 60 St. George St., Toronto, ON M5S 3H8 (Canada)

2015-11-10

This paper studies the response of a thin accretion disk to an external radial magnetic field. Our focus is on protoplanetary disks (PPDs), which are exposed during their later evolution to an intense, magnetized wind from the central star. A radial magnetic field is mixed into a thin surface layer, wound up by the disk shear, and pushed downward by a combination of turbulent mixing and ambipolar and ohmic drift. The toroidal field reaches much greater strengths than the seed vertical field that is usually invoked in PPD models, even becoming superthermal. Linear stability analysis indicates that the disk experiences the magnetorotational instability (MRI) at a higher magnetization than a vertically magnetized disk when both the effects of ambipolar and Hall drift are taken into account. Steady vertical profiles of density and magnetic field are obtained at several radii between 0.06 and 1 AU in response to a wind magnetic field B{sub r} ∼ (10{sup −4}–10{sup −2})(r/ AU){sup −2} G. Careful attention is given to the radial and vertical ionization structure resulting from irradiation by stellar X-rays. The disk is more strongly magnetized closer to the star, where it can support a higher rate of mass transfer. As a result, the inner ∼1 AU of a PPD is found to evolve toward lower surface density. Mass transfer rates around 10{sup −8} M{sub ⊙} yr{sup −1} are obtained under conservative assumptions about the MRI-generated stress. The evolution of the disk and the implications for planet migration are investigated in the accompanying paper.

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

NARCIS (Netherlands)

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

2015-01-01

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

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

Science.gov (United States)

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

2015-11-15

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

Seasonal carbonate chemistry covariation with temperature, oxygen, and salinity in a fjord estuary: implications for the design of ocean acidification experiments.

Directory of Open Access Journals (Sweden)

Jonathan C P Reum

Full Text Available Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall. pCO2 exceeded the 2008-2011 mean atmospheric level (392 µatm at all depths and seasons sampled except for the near-surface waters (< 10 m in the summer. Further, undersaturated conditions with respect to the biogenic carbonate mineral aragonite were widespread (Ωar<1. We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31, was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight

Influence of mesoscale features on micronekton and large pelagic fish communities in the Mozambique Channel

Science.gov (United States)

Potier, Michel; Bach, Pascal; Ménard, Frédéric; Marsac, Francis

2014-02-01

We investigated the diversity and distribution of two communities, micronekton organisms and large predatory fishes, sampled in mesoscale features of the Mozambique Channel from 2003 to 2009, by combining mid-water trawls, stomach contents of fish predators and instrumented longline fishing surveys. The highest species richness for assemblages was found in divergences and fronts rather than in the core of eddies. Despite an unbalanced scheme, diversity indices did not differ significantly between cyclonic and anticyclonic eddies, divergences and fronts. We found that eddies and associated physical cues did not substantially affect the distribution of micronektonic species which are mainly driven by the diel vertical migration pattern. Top predators exhibited a more complex response. Swordfish (Xiphias gladius) associated better with mesoscale features than tunas, with a clear preference for divergences which is consistent with the diel vertical migrations and occurrence of its main prey, the flying squids Sthenoteuthis oualaniensis (Ommastrephidae). On the other hand, the probability of presence of yellowfin tuna was not tied to any specific eddy structure. However, the highest values of positive yellowfin CPUEs were associated with low horizontal gradients of sea-level anomalies. We also showed a non-linear response of positive yellowfin CPUEs with respect to the depth of the minimal oxygen content. The larger the distance between the hooks and the minimal oxygen layer, towards the surface or at greater depths, the higher the CPUE, highlighting that yellowfin congregated in well-oxygenated waters. Micronekton sampled by mid-water trawls and stomach contents exhibited different species composition. The highly mobile organisms were not caught by trawling whereas they remain accessible to predators. The combination of stomach contents and mid-water trawls undoubtedly improved our understanding of the micronekton assemblage distribution. Our results provide some

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.

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

Science.gov (United States)

Qi, Jun; Roush, William R.

2008-01-01

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

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

International Nuclear Information System (INIS)

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

2009-01-01

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

Vertical distribution of radionuclides in soil

International Nuclear Information System (INIS)

Bikit, I.; Slivka, J.; Krmar, M.; Chonkic, Lj.; Veskovic, M.; Hadzhic, V.

1990-01-01

Pedological profiles were opened at selected representative locations on different geomorphic types and in certain soil layers down to 3 m depth. The mechanical composition, hydro physical and chemical features were studied. The vertical distribution of naturally occurring radionuclides and 137 Cs was analyzed during 1988 and 1989. The parameter alpha of the exponential dependence of activity concentration vs. depth were calculated for the three soil types, as well as the activity concentration of 137 Cs at depths of 1 and 3 m. The extent of 137 Cs migration was evaluated at these depths and it is shown that the coefficient α is proportional to the reciprocal of the time elapsed from the surface contamination. (author)

Diel periodicity of pheromone release by females of Planococcus citri and Planococcus ficus and the temporal flight activity of their conspecific males

Science.gov (United States)

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.

Forty years of 9Sr in situ migration: importance of soil characterization in modeling transport phenomena

International Nuclear Information System (INIS)

Fernandez, J.M.; Piault, E.; Macouillard, D.; Juncos, C.

2006-01-01

In 1960 experiments were carried out on the transfer of 9 Sr between soil, grapes and wine. The experiments were conducted in situ on a piece of land limited by two control strips. The 9 Sr migration over the last 40 years was studied by performing radiological and physico-chemical characterizations of the soil on eight 70 cm deep cores. The vertical migration modeling of 9 Sr required the definition of a triple layer conceptual model integrating the rainwater infiltration at constant flux as the only external factor of influence. Afterwards the importance of a detailed soil characterization for modeling was discussed and satisfactory simulation of the 9 Sr vertical transport was obtained and showed a calculated migration rate of about 1.0 cm year -1 in full agreement with the in situ measured values. The discussion was regarding some of the key parameters such as granulometry, organic matter content (in the Van Genuchten parameter determination), Kd and the efficient rainwater infiltration. Besides the experimental data, simplifying assumptions in modeling such as water-soil redistribution calculation and factual discontinuities in conceptual model were examined

Functional biology and ecological role of krill in Northern marine ecosystems

DEFF Research Database (Denmark)

Agersted, Mette Dalgaard

Krill is an understudied key group of zooplankton, which transfers energy through the food web by linking lower and higher trophic levels. Furthermore, krill play an important role in the biological pump by transporting carbon out of the euphotic zone to depth by diel vertical migration (DVM...... to be the key factor determining the trophic position of a species, where the largest species had the highest trophic position. The species were feeding on the same food items, which could lead to competition for food. However, there is a difference between the two functional groups, represented by M. norvegica...... for the two dominating species within the fjord, T. inermis and T. raschii. The krill grazed community at this time of year. Yet, the grazing impact was similar to the copepods’, which are normally...

At-sea behavior varies with lunar phase in a nocturnal pelagic seabird, the swallow-tailed gull.

Directory of Open Access Journals (Sweden)

Sebastian M Cruz

Full Text Available Strong and predictable environmental variability can reward flexible behaviors among animals. We used long-term records of activity data that cover several lunar cycles to investigate whether behavior at-sea of swallow-tailed gulls Creagrus furcatus, a nocturnal pelagic seabird, varied with lunar phase in the Galápagos Islands. A Bayesian hierarchical model showed that nighttime at-sea activity of 37 breeding swallow-tailed gulls was clearly associated with changes in moon phase. Proportion of nighttime spent on water was highest during darker periods of the lunar cycle, coinciding with the cycle of the diel vertical migration (DVM that brings prey to the sea surface at night. Our data show that at-sea behavior of a tropical seabird can vary with environmental changes, including lunar phase.

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

Science.gov (United States)

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

2015-05-01

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

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

Science.gov (United States)

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

2015-01-01

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

Krill (Meganyctiphanes norvegica) swim faster at night

KAUST Repository

Klevjer, Thor A.

2011-05-01

Krill are key members in marine food webs, and measurement of swimming speed is vital to assess their bioenergetic budgets, feeding, and encounters with predators. We document a consistent and marked diel signal in swimming speed of krill in their natural habitat that is not related to diel vertical migration. The results were obtained using a bottom-mounted, upward-looking echo sounder at 150-m depth in the Oslofjord, Norway, spanning 5 months from late autumn to spring at a temporal resolution of ~1–2 records s−1. Swimming speed was assessed using acoustic target tracking of individual krill. At the start of the registration period, both daytime and nocturnal average swimming speeds of Meganyctiphanes norvegica were ~ 3.5 cm s−1 (~ 1 body lengths ([bl] s−1) in waters with oxygen concentrations of ~ 15–20% O2 saturation. Following intrusion of more oxygenated water, nocturnal average swimming speeds increased to ~ 10 cm s−1 (~ 3 bl s−1), i.e., more than double that of daytime swimming speeds in the same period. We hypothesize that krill activity during the first period was limited by oxygen, and the enhanced swimming at night subsequent to the water renewal is due to increased feeding activity under lessened danger of predation in darkness.

Krill (Meganyctiphanes norvegica) swim faster at night

KAUST Repository

Klevjer, Thor A.; Kaartvedt, Stein

2011-01-01

Krill are key members in marine food webs, and measurement of swimming speed is vital to assess their bioenergetic budgets, feeding, and encounters with predators. We document a consistent and marked diel signal in swimming speed of krill in their natural habitat that is not related to diel vertical migration. The results were obtained using a bottom-mounted, upward-looking echo sounder at 150-m depth in the Oslofjord, Norway, spanning 5 months from late autumn to spring at a temporal resolution of ~1–2 records s−1. Swimming speed was assessed using acoustic target tracking of individual krill. At the start of the registration period, both daytime and nocturnal average swimming speeds of Meganyctiphanes norvegica were ~ 3.5 cm s−1 (~ 1 body lengths ([bl] s−1) in waters with oxygen concentrations of ~ 15–20% O2 saturation. Following intrusion of more oxygenated water, nocturnal average swimming speeds increased to ~ 10 cm s−1 (~ 3 bl s−1), i.e., more than double that of daytime swimming speeds in the same period. We hypothesize that krill activity during the first period was limited by oxygen, and the enhanced swimming at night subsequent to the water renewal is due to increased feeding activity under lessened danger of predation in darkness.

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

Science.gov (United States)

Kotha, Sambasivarao; Ravikumar, Ongolu

2015-01-01

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

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

Science.gov (United States)

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

2012-01-01

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

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

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.

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)

Diel cycles of hydrogen peroxide in marine bathing waters in Southern California, USA: In situ surf zone measurements

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.

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

Science.gov (United States)

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

2015-11-01

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

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

Directory of Open Access Journals (Sweden)

2008-08-01

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

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

Science.gov (United States)

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

2017-05-22

We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this Au I -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simulating the Oceanic Migration of Silver Japanese Eels.

Directory of Open Access Journals (Sweden)

Yu-Lin Chang

Full Text Available The oceanic migration of silver Japanese eels starts from their continental growth habitats in East Asia and ends at the spawning area near the West Mariana Ridge seamount chain. However, the actual migration routes remain unknown. In this study, we examined the possible oceanic migration routes and strategies of silver Japanese eels using a particle tracking method in which virtual eels (v-eels were programmed to move vertically and horizontally in an ocean circulation model (Japan Coastal Ocean Predictability Experiment 2, JCOPE2. Four horizontal swimming strategies were tested: random heading, true navigation (readjusted heading, orientation toward the spawning area (fixed heading, and swimming against the Kuroshio. We found that all strategies, except random swimming, allowed v-eels swimming at 0.65 m s-1 to reach the spawning area within eight months after their departure from the south coast of Japan (end of the spawning season. The estimated minimum swimming speed required to reach the area spawning within eight months was 0.1 m s-1 for true navigation, 0.12 m s-1 for constant compass heading, and 0.35 m s-1 for swimming against the Kuroshio. The lowest swimming speed estimated from tracked Japanese eels at sea was 0.03 m.s-1, which would not allow them to reach the spawning area within eight months, through any of the tested orientation strategies. Our numerical experiments also showed that ocean circulation significantly affected the migration of Japanese v-eels. A strong Kuroshio could advect v-eels further eastward. In addition, western Pacific ocean currents accelerated the migration of navigating v-eels. The migration duration was shortened in years with a stronger southward flow, contributed by a stronger recirculation south of Japan, an enhanced subtropical gyre, or a higher southward Kuroshio velocity.

Simulating the Oceanic Migration of Silver Japanese Eels.

Science.gov (United States)

Chang, Yu-Lin; Miyazawa, Yasumasa; Béguer-Pon, Mélanie

2016-01-01

The oceanic migration of silver Japanese eels starts from their continental growth habitats in East Asia and ends at the spawning area near the West Mariana Ridge seamount chain. However, the actual migration routes remain unknown. In this study, we examined the possible oceanic migration routes and strategies of silver Japanese eels using a particle tracking method in which virtual eels (v-eels) were programmed to move vertically and horizontally in an ocean circulation model (Japan Coastal Ocean Predictability Experiment 2, JCOPE2). Four horizontal swimming strategies were tested: random heading, true navigation (readjusted heading), orientation toward the spawning area (fixed heading), and swimming against the Kuroshio. We found that all strategies, except random swimming, allowed v-eels swimming at 0.65 m s-1 to reach the spawning area within eight months after their departure from the south coast of Japan (end of the spawning season). The estimated minimum swimming speed required to reach the area spawning within eight months was 0.1 m s-1 for true navigation, 0.12 m s-1 for constant compass heading, and 0.35 m s-1 for swimming against the Kuroshio. The lowest swimming speed estimated from tracked Japanese eels at sea was 0.03 m.s-1, which would not allow them to reach the spawning area within eight months, through any of the tested orientation strategies. Our numerical experiments also showed that ocean circulation significantly affected the migration of Japanese v-eels. A strong Kuroshio could advect v-eels further eastward. In addition, western Pacific ocean currents accelerated the migration of navigating v-eels. The migration duration was shortened in years with a stronger southward flow, contributed by a stronger recirculation south of Japan, an enhanced subtropical gyre, or a higher southward Kuroshio velocity.

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

Science.gov (United States)

Fernández, Israel; Bickelhaupt, F Matthias

2016-12-06

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

Numerical modeling of fracking fluid migration through fault zones and fractures in the North German Basin

Science.gov (United States)

Pfunt, Helena; Houben, Georg; Himmelsbach, Thomas

2016-09-01

Gas production from shale formations by hydraulic fracturing has raised concerns about the effects on the quality of fresh groundwater. The migration of injected fracking fluids towards the surface was investigated in the North German Basin, based on the known standard lithology. This included cases with natural preferential pathways such as permeable fault zones and fracture networks. Conservative assumptions were applied in the simulation of flow and mass transport triggered by a high pressure boundary of up to 50 MPa excess pressure. The results show no significant fluid migration for a case with undisturbed cap rocks and a maximum of 41 m vertical transport within a permeable fault zone during the pressurization. Open fractures, if present, strongly control the flow field and migration; here vertical transport of fracking fluids reaches up to 200 m during hydraulic fracturing simulation. Long-term transport of the injected water was simulated for 300 years. The fracking fluid rises vertically within the fault zone up to 485 m due to buoyancy. Progressively, it is transported horizontally into sandstone layers, following the natural groundwater flow direction. In the long-term, the injected fluids are diluted to minor concentrations. Despite the presence of permeable pathways, the injected fracking fluids in the reported model did not reach near-surface aquifers, either during the hydraulic fracturing or in the long term. Therefore, the probability of impacts on shallow groundwater by the rise of fracking fluids from a deep shale-gas formation through the geological underground to the surface is small.

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

Science.gov (United States)

Sexton, Thomas; Kraka, Elfi; Cremer, Dieter

2016-02-25

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

Vertical Motion Changes Related to North-East Brazil Rainfall Variability: a GCM Simulation

Science.gov (United States)

Roucou, Pascal; Oribe Rocha de Aragão, José; Harzallah, Ali; Fontaine, Bernard; Janicot, Serge

1996-08-01

The atmospheric structure over north-east Brazil during anomalous rainfall years is studied in the 11 levels of the outputs of the Laboratoire de Météorologie Dynamique atmospheric general circulation model (LMD AGCM). Seven 19-year simulations were performed using observed sea-surface temperature (SST) corresponding to the period 1970- 1988. The ensemble mean is calculated for each month of the period, leading to an ensemble-averaged simulation. The simulated March-April rainfall is in good agreement with observations. Correlations of simulated rainfall and three SST indices relative to the equatorial Pacific and northern and southern parts of the Atlantic Ocean exhibit stronger relationships in the simulation than in the observations. This is particularly true with the SST gradient in the Atlantic (Atlantic dipole). Analyses on 200 ;hPa velocity potential, vertical velocity, and vertical integral of the zonal component of mass flux are performed for years of abnormal rainfall and positive/negative SST anomalies in the Pacific and Atlantic oceans in March-April during the rainy season over the Nordeste region. The results at 200 hPa show a convergence anomaly over Nordeste and a divergence anomaly over the Pacific concomitant with dry seasons associated with warm SST anomalies in the Pacific and warm (cold) waters in the North (South) Atlantic. During drought years convection inside the ITCZ indicated by the vertical velocity exhibits a displacement of the convection zone corresponding to a northward migration of the ITCZ. The east-west circulation depicted by the zonal divergent mass flux shows subsiding motion over Nordeste and ascending motion over the Pacific in drought years, accompanied by warm waters in the eastern Pacific and warm/cold waters in northern/southern Atlantic. Rainfall variability of the Nordeste rainfall is linked mainly to vertical motion and SST variability through the migration of the ITCZ and the east-west circulation.

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

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

Science.gov (United States)

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

2018-02-16

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

Vegetation induced diel signal and its meaning in recharge and discharge regions

Science.gov (United States)

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

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

Science.gov (United States)

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

2016-10-24

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

Metabolic profiles and cDNA-AFLP analysis of Salvia miltiorrhiza and Salvia castanea Diel f. tomentosa Stib.

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

Regulation of nif gene expression and the energetics of N2 fixation over the diel cycle in a hot spring microbial mat.

Science.gov (United States)

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.

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

Science.gov (United States)

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

2017-12-11

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

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

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.

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

Science.gov (United States)

Sizemore, Nicholas; Rychnovsky, Scott D

2014-02-07

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

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

Science.gov (United States)

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

2016-09-23

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

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.

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

Science.gov (United States)

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

2016-02-04

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

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

Science.gov (United States)

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

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

Science.gov (United States)

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

2016-08-26

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

Determinations of vertical stroke V{sub cb} vertical stroke and vertical stroke V{sub ub} vertical stroke from baryonic Λ{sub b} decays

Energy Technology Data Exchange (ETDEWEB)

Hsiao, Y.K. [Shanxi Normal University, School of Physics and Information Engineering, Linfen (China); National Tsing Hua University, Department of Physics, Hsinchu (China); Geng, C.Q. [Shanxi Normal University, School of Physics and Information Engineering, Linfen (China); National Tsing Hua University, Department of Physics, Hsinchu (China); Hunan Normal University, Synergetic Innovation Center for Quantum Effects and Applications (SICQEA), Changsha (China)

2017-10-15

We present the first attempt to extract vertical stroke V{sub cb} vertical stroke from the Λ{sub b} → Λ{sub c}{sup +}l anti ν{sub l} decay without relying on vertical stroke V{sub ub} vertical stroke inputs from the B meson decays. Meanwhile, the hadronic Λ{sub b} → Λ{sub c}M{sub (c)} decays with M = (π{sup -},K{sup -}) and M{sub c} =(D{sup -},D{sup -}{sub s}) measured with high precisions are involved in the extraction. Explicitly, we find that vertical stroke V{sub cb} vertical stroke =(44.6 ± 3.2) x 10{sup -3}, agreeing with the value of (42.11 ± 0.74) x 10{sup -3} from the inclusive B → X{sub c}l anti ν{sub l} decays. Furthermore, based on the most recent ratio of vertical stroke V{sub ub} vertical stroke / vertical stroke V{sub cb} vertical stroke from the exclusive modes, we obtain vertical stroke V{sub ub} vertical stroke = (4.3 ± 0.4) x 10{sup -3}, which is close to the value of (4.49 ± 0.24) x 10{sup -3} from the inclusive B → X{sub u}l anti ν{sub l} decays. We conclude that our determinations of vertical stroke V{sub cb} vertical stroke and vertical stroke V{sub ub} vertical stroke favor the corresponding inclusive extractions in the B decays. (orig.)

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.

Migration of radionuclides in the soil-crop-food product system and assessment of agricultural countermeasures

International Nuclear Information System (INIS)

Bogdevitch, I.; Ageyets, V.

1996-01-01

Studies on dynamics of redistribution of radionuclides through of profile of the different soils on uncultivated agricultural lands of Belarus during the 1986-1995 period show that vertical migration occurs with low rate. In arable soils the radionuclides are distributed in comparatively uniform way through the whole depth of the 25-30 cm cultivated layer. Investigations on migration of radionuclides with wind erosion on the drained series of wet sandy and peat soils and water erosion on sloping lands show that one should take into consideration the secondary contamination of soils while forecasting a possible accumulation of radionuclides in farm products

Using diel movement behavior to infer foraging strategies related to ecological and social factors in elephants.

Science.gov (United States)

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

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

Science.gov (United States)

Celius, Tevye C.

2010-01-01

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

The measurement of the vertical component of hydraulic conductivity in single cased and uncased boreholes

International Nuclear Information System (INIS)

Black, J.H.; Noy, D.J.; Brightman, M.A.

1986-11-01

The project summarised in the paper aimed to assess the different existing methods of measuring vertical hydraulic conductivity in single boreholes by carrying out some actual field testing. The measurements are relevant to the disposal of radioactive waste into argillaceous rocks, where the primary geological barrier to potential leachate migration is the mudrock. Also the prime parameter of interest in the assessment of mudrocks is the vertical component of hydraulic conductivity. A description of the methods of test analysis and interpretation is given. The experimental programme for open borehole testing and cased borehole testing is described, along with the practical and theoretical considerations. (U.K.)

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

Science.gov (United States)

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

2016-07-04

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

Sea level driven marsh expansion in a coupled model of marsh erosion and migration

Science.gov (United States)

Kirwan, Matthew L.; Walters, David C.; Reay, William G.; Carr, Joel

2016-01-01

Coastal wetlands are among the most valuable ecosystems on Earth, where ecosystem services such as flood protection depend nonlinearly on wetland size and are threatened by sea level rise and coastal development. Here we propose a simple model of marsh migration into adjacent uplands and couple it with existing models of seaward edge erosion and vertical soil accretion to explore how ecosystem connectivity influences marsh size and response to sea level rise. We find that marsh loss is nearly inevitable where topographic and anthropogenic barriers limit migration. Where unconstrained by barriers, however, rates of marsh migration are much more sensitive to accelerated sea level rise than rates of edge erosion. This behavior suggests a counterintuitive, natural tendency for marsh expansion with sea level rise and emphasizes the disparity between coastal response to climate change with and without human intervention.

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

Directory of Open Access Journals (Sweden)

Mujeeb A. Sultan

2016-09-01

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

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

Science.gov (United States)

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

2016-01-01

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

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

Science.gov (United States)

Beniwal, Vijay; Manna, Arpan; Kumar, Anil

2016-07-04

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

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

Science.gov (United States)

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

2018-03-01

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

Correlation of molecular expression with diel rhythm of oviposition in Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae) and implications for forensic entomology.

Science.gov (United States)

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.

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

Directory of Open Access Journals (Sweden)

Hamzehloueian Mahshid

2014-01-01

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

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

Science.gov (United States)

Cheng, Mei-Fun; Li, Wai-Kee

2003-01-01

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

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

KAUST Repository

Yang, Limin

2014-08-01

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

Seasonal and diel variation in xylem CO2 concentration and sap pH in sub-Mediterranean oak stems.

Science.gov (United States)

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.

Following a Foraging Fish-Finder: Diel Habitat Use of Blainville's Beaked Whales Revealed by Echolocation

Science.gov (United States)

Arranz, Patricia; de Soto, Natacha Aguilar; Madsen, Peter T.; Brito, Alberto; Bordes, Fernando; Johnson, Mark P.

2011-01-01

Simultaneous high resolution sampling of predator behavior and habitat characteristics is often difficult to achieve despite its importance in understanding the foraging decisions and habitat use of predators. Here we tap into the biosonar system of Blainville's beaked whales, Mesoplodon densirostris, using sound and orientation recording tags to uncover prey-finding cues available to echolocating predators in the deep-sea. Echolocation sounds indicate where whales search and encounter prey, as well as the altitude of whales above the sea-floor and the density of organisms around them, providing a link between foraging activity and the bio-physical environment. Tagged whales (n = 9) hunted exclusively at depth, investing most of their search time either in the lower part of the deep scattering layer (DSL) or near the sea-floor with little diel change. At least 43% (420/974) of recorded prey-capture attempts were performed within the benthic boundary layer despite a wide range of dive depths, and many dives included both meso- and bentho-pelagic foraging. Blainville's beaked whales only initiate searching when already deep in the descent and encounter prey suitable for capture within 2 min of the start of echolocation, suggesting that these whales are accessing prey in reliable vertical strata. Moreover, these prey resources are sufficiently dense to feed the animals in what is effectively four hours of hunting per day enabling a strategy in which long dives to exploit numerous deep-prey with low nutritional value require protracted recovery periods (average 1.5 h) between dives. This apparent searching efficiency maybe aided by inhabiting steep undersea slopes with access to both the DSL and the sea-floor over small spatial scales. Aggregations of prey in these biotopes are located using biosonar-derived landmarks and represent stable and abundant resources for Blainville's beaked whales in the otherwise food-limited deep-ocean. PMID:22163295

Following a foraging fish-finder: diel habitat use of Blainville's beaked whales revealed by echolocation.

Directory of Open Access Journals (Sweden)

Patricia Arranz

Full Text Available Simultaneous high resolution sampling of predator behavior and habitat characteristics is often difficult to achieve despite its importance in understanding the foraging decisions and habitat use of predators. Here we tap into the biosonar system of Blainville's beaked whales, Mesoplodon densirostris, using sound and orientation recording tags to uncover prey-finding cues available to echolocating predators in the deep-sea. Echolocation sounds indicate where whales search and encounter prey, as well as the altitude of whales above the sea-floor and the density of organisms around them, providing a link between foraging activity and the bio-physical environment. Tagged whales (n = 9 hunted exclusively at depth, investing most of their search time either in the lower part of the deep scattering layer (DSL or near the sea-floor with little diel change. At least 43% (420/974 of recorded prey-capture attempts were performed within the benthic boundary layer despite a wide range of dive depths, and many dives included both meso- and bentho-pelagic foraging. Blainville's beaked whales only initiate searching when already deep in the descent and encounter prey suitable for capture within 2 min of the start of echolocation, suggesting that these whales are accessing prey in reliable vertical strata. Moreover, these prey resources are sufficiently dense to feed the animals in what is effectively four hours of hunting per day enabling a strategy in which long dives to exploit numerous deep-prey with low nutritional value require protracted recovery periods (average 1.5 h between dives. This apparent searching efficiency maybe aided by inhabiting steep undersea slopes with access to both the DSL and the sea-floor over small spatial scales. Aggregations of prey in these biotopes are located using biosonar-derived landmarks and represent stable and abundant resources for Blainville's beaked whales in the otherwise food-limited deep-ocean.

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

NARCIS (Netherlands)

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

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

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

Czech Academy of Sciences Publication Activity Database

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

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

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

Science.gov (United States)

Kotha, Sambasivarao; Gunta, Rama

2015-01-01

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

Behavioral Strategies of Lanternfishes (Family Myctophidae) in a High-Latitude Fjord and the Tropical Red Sea

KAUST Repository

Dypvik, Eivind

2012-12-01

The diel vertical migration (DVM) and feeding periodicity of myctophids (lanternfishes) were studied in the high-latitude Masfjorden, Norway, and the tropical Red Sea. In Masfjorden, a bottom-mounted echo sounder permitted continuous studies throughout the year, and revealed a diverse seasonal DVM behavior. During spring and summer, when zooplankton peaks in the epipelagic zone, migrating glacier lanternfish performed normal DVM (NDVM), ascending to the epipelagic zone during night and residing below ~200m during daytime. During autumn and winter, when Calanus overwinters between ~150–300 m, migrating glacier lanternfish mainly performed inverse DVM (IDVM), ascending to feed on Calanus in mid-waters during daytime. Non migrating (NoDVM) individuals were present all year below ~300 m in Masfjorden. In the Red Sea, where zooplankton has an epipelagic distribution, the whole population of skinnycheek lanternfish performed NDVM, feeding in the epipelagic zone at night, while residing at ~500–750 m during daytime. The warm waters of the Red Sea were hypothesized to limit the time individuals can stay in the mesopelagic zone without migrating to feed in the epipelagic layers. The DVM behavior of myctophids largely seemed to relate to the distribution of zooplankton, and it was hypothesized that NDVM will prevail with epipelagic distribution of prey, while IDVM and NoDVM are common in areas where zooplankton migrate seasonally to mesopelagic depths. Potential predators were continuously present, found to apparently attack glacier lanternfish, at mesopelagic depth in Masfjorden. Thus, myctophids are under threat of predation even at mesopelagic depth.

Role of access charges in the migration from copper to FTTH

OpenAIRE

Jeanjean, François; Liang, Julienne

2011-01-01

We consider a horizontally and vertically differentiated duopoly model in order to analyze both intra- and inter-platform competition in an always corvered broadband access market (Copper-Copper, Copper-FTTH and FTTH-FTTH competitions). The model is purely static and does not address dynamic efficiency issues. It shows that the access charges play a significant role in the migration from copper to FTTH and in FTTH investment incentives, provided that consumers are segmented. In FTTH-infrastru...

Upward migration of radio-cesium and strontium in a sand-filled lysimeter

International Nuclear Information System (INIS)

Sanford, W.E.; Larsen, I.L.; McConnell, J.W.; Rogers, R.D.

1998-01-01

The upward migration of 134 Cs, 137 Cs, and 90 Sr was observed in a silica sand-filled lysimeter at the Field Lysimeter Investigations: Low Level Waste Data Base Development experiment site at Oak Ridge National Laboratory. The source of the radionuclides first observed on the surface was identified from isotopic analysis as being from the buried waste. Cores of the sand were collected and analyzed for the vertical distribution of the radionuclides. Results of analyses revealed that pulses (elevated levels) in the activity of the Cs and Sr radioisotopes occurred at the same depths. During the sectioning of the sand core collected from directly above the buried waste form it was discovered that a fine root from an unidentified plant was present throughout all but the upper few centimeters of the core. Because the upward migration was unexpected, information that may lead to the determination of a definitive mechanism of migration was not preserved. The distribution of the radionuclides coupled with the presence of the root suggest that Cs and Sr migrated upward in the evapotranspiration stream of the root. Further study must be undertaken to confirm this phenomenon. Upward migration of radionuclides as observed here could result in direct exposures and offsite releases from underground storage facilities. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

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

Science.gov (United States)

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

2018-05-02

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

Vertical contamination in the unconfined groundwater at the Hanford Site, Washington

International Nuclear Information System (INIS)

Eddy, P.A.; Myers, D.A.; Raymond, J.R.

1978-08-01

Disposal to the ground at Hanford of large volumes of low- and intermediate-level wastes in the local unconfined groundwater flow system has raised concern about the movement and distribution of this waste. Previous work produced information on the horizontal movement of the waste, but little or no information exists on its vertical distribution within the unconfined groundwater flow system. In 1975 Phase I of a study was started to determine the vertical distribution of contaminants in three existing wells (699-28-40, 699-31-31, and 699-37-43). Because of negative results, only one well that produced positive results (699-31-31) was chosen for Phase II. Phase II consisted of tests conducted on this well by a testing company, with samples cross-checked by two different laboratories. Phase III was a cooperative study with Rockwell Hanford Operations, which included the installation, testing, and sampling of piezometers. The data were then analyzed using predictive codes and models in order to determine if vertical movement did occur. The present groundwater flow system shows some vertical contamination. However, concentrations are relatively higher near the surface of the flow system, indicating possible radial flow patterns from the groundwater mounds known to have developed under the chemical processing area disposal sites. Upward flow from deeper aquifers may be diluting the contaminant and masking a possible downward migration of contaminants

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

Science.gov (United States)

Sauvage, Xavier; Delaude, Lionel

2008-01-01

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

GAUGING THE VERTICAL SPECIALIZATION IN EU TRADE

Directory of Open Access Journals (Sweden)

IULIA MONICA OEHLER-SINCAI

2014-11-01

Full Text Available The purpose of this paper is threefold. First, we review the mechanisms and determinants of vertical specialization (VS, as this has gradually become the dominant characteristic of international trade. Second, we underline that there is a rich literature regarding VS in EU trade, at aggregate and individual levels and research is advancing together with the instruments used to measure trade in value added. Third, our investigation brings to the forefront a classification of EU countries according to their GVC participation index, taking into consideration both upstream and downstream links. As a conclusion, the VS analyses help us better understand the interconnectedness among countries and industries by means of foreign direct investment, trade, labour migration and technology transfer.

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

Science.gov (United States)

Zhao, Pei; Zhao, Xiang; Ehara, Masahiro

2016-09-16

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